DE112020000018T5 - IMMOBILIZED CHALCOGEN AND ITS USE IN A RECHARGEABLE BATTERY - Google Patents

Abstract

A system or mass of immobilized chalcogen includes a mixture or combination of chalcogen and carbon. The carbon can have the shape of a carbon framework. The chalcogen can include oxygen, sulfur, selenium, or tellurium, or a combination of two or more of oxygen, sulfur, selenium, and tellurium. The activation energy for chalcogen to escape the system or the mass of immobilized chalcogen is ≥ 96 kJ / mol.

Description

CROSS REFERENCE TO RELATED APPLICATION

This registration is a partial continuation of U.S. Patent Application No. 15 / 434,655 , filed February 16, 2017, and also claims U.S. Provisional Patent Application No. 62 / 802,929 , filed February 8, 2019. The disclosures of the above applications are incorporated herein by reference in their entirety.

GENERAL STATE OF THE ART

Field of invention

The present application relates to the field of high energy density lithium secondary batteries. In particular, the application relates to a method for preparing carbon-selenium nanocomposite materials and their applications. The present invention also relates to immobilized chalcogen, which includes chalcogen and carbon. Immobilized chalcogen herein can comprise combinations of oxygen, sulfur, selenium and tellurium. It also relates to a method for producing and using the immobilized chalcogen. One of the uses of immobilized chalcogen is in a rechargeable battery. The present application also relates to a rechargeable battery that can perform high-rate discharge-charge cycling (e.g. 10C rate) with a minimum level of capacity fading while being able to maintain its electrochemical performance such as specific capacity substantially recover when charged at a low rate such as a 0.1C rate.

Description of the prior art

In view of the increasing human demand for energy, secondary batteries with high mass specific energy and high volumetric energy density such as lithium-sulfur batteries and lithium-selenium batteries have attracted widespread interest. Group 6A elements in the table of the periodic table, such as sulfur and selenium, have set out two-electron reaction mechanisms in the electrochemical reaction process with lithium. Although the theoretical mass specific capacity of selenium (675 mAh / g) is lower than that of sulfur (1675 mAh / g), selenium has a higher density (4.82 g / cm ³ ) than sulfur (2.07 g / cm ^{3 3} ). Therefore, the theoretical volumetric energy density of selenium (3253 mAh / cm ³ ) is close to the theoretical volumetric energy density of sulfur (3467 mAh / cm ³ ). At the same time, compared to sulfur, which is close to an electrically insulating material, selenium is electrically semiconducting and shows better electrical conductivity properties. Compared to sulfur, selenium can therefore exhibit a higher level of activity and better usage efficiency even at a higher charge level, resulting in battery systems with high energy and power density. In addition, a selenium-carbon composite material can have a further improvement in electrical conductivity compared to sulfur-carbon composite material, in order to obtain an electrode material with higher activity.

As disclosed in Patent Publication No. CN104393304A described, when hydrogen-selenium gas is allowed to pass through a graphene dispersion solution, the solvent heat reduces the graphene oxide in graphene, while it oxidizes the hydrogen-selenium in selenium. The selenium-graphene electrode material prepared in this way is paired with an ether electrolyte system, 1.5M lithium-bi-trifluoromethane-sulfonimide (LiTFSI) / 1,3-dioxolane (DOL) + dimethyl ether (DME) (volume ratio 1: 1); the specific charging capacity reaches 640 mAh / g (and approaches the theoretical specific capacity of selenium) in the first cycle. During the charge-discharge process, however, polyselenium ions dissolve in the electrolyte and show significant amounts of pendulum effect, which causes the subsequent decline in capacity. At the same time, the procedures for preparing the graphene oxide raw material used in this process are complicated and not suitable for industrial production.

The patent CN104201389B discloses a lithium selenium battery cathode material employing a current collector having a nitrogenous layered porous carbon composite material mixed with selenium. When preparing the current collector with nitrogen-containing layered porous carbon composite material, nitrogen-containing conductive polymer is first deposited or grown on the surface of a piece of paper, which is followed by alkali activation and high-temperature carbonization, which is achieved in a current collector with nitrogen-containing layered porous carbon composite material with carbon fiber as a network structure self carries, results; and such a current collector with nitrogen-containing layered porous carbon composite material is then further mixed with selenium. The Deposition processes for preparing a conductive polymer are complicated, and the process of film formation or growth is difficult to control. The preparation process is complicated, which goes hand in hand with undesirably high costs.

In addition, the demand for a long life, high energy density, high power density rechargeable battery with the ability to be charged and discharged at a rapid rate is increasing in electronics, electric / hybrid vehicle, air / space / drone, U -Boat and other industrial, military, and consumer applications are constantly increasing. Lithium-ion batteries are examples of rechargeable batteries in the above mentioned applications. However, the need for better performance and cycling ability has not been met with lithium-ion batteries as lithium-ion battery technology has matured.

Atomic oxygen has an atomic mass of 16 and an ability for 2 electron transfers. A rechargeable lithium-oxygen battery was tested for the purpose of making batteries with high energy density by weight fraction, 6 580 W.hr / oxygen with an assumption of a Li-O battery voltage of 2.0 V. When a battery involves an oxygen cathode paired with lithium or sodium metal as an anode, it will have the greatest stoichiometric energy density. Much of the technical problems with the Li // Na oxygen battery remain unsolved, such as (i) the involvement of more than one chemical transport during the electrochemical discharge and charge process, for example (a) lithium / sodium -Ion transport from the anode to the cathode during the battery discharge process and vice versa during the battery charging process, which is very similar to that of a lithium-ion battery, and (b) the oxygen transport from the gas phase to the cathode surface, and the conversion into solid-like superoxides , Peroxides and oxides during the battery discharging process, and converting back during the battery charging process, (ii) an extremely corrosive nature of the intermediates formed during the discharging process, particularly superoxides and peroxides, for inactive cathode materials; (iii) Nucleophilic attack on the battery electrolyte by the intermediate products formed (superoxides or peroxides). A number of discoveries, therefore, were required in order to successfully master electrochemical behaviors using oxygen as an active electrochemical material in a rechargeable battery.

Elemental sulfur is also in the chalcogen group and has the second highest energy density (by weight) when paired with a lithium or sodium metal anode, 2,961 W.hr/kg-S with the assumption of a Li S battery voltage of 1.8 V. A lithium-sulfur or a sodium-sulfur battery has been extensively studied for the same purpose. However, a Li / Na-S battery can still have more than one chemical transport during the electrochemical discharge and charge process, at least (a) lithium / sodium ion transport from the anode to the cathode during the battery discharge process and vice versa during the battery charging process, which is very similar to a lithium-ion battery, and (b) elemental sulfur during the battery discharging process, which is converted into an intermediate polysulfide ion, which dissolves in the electrolyte solution and shuttles from cathode to anode. Upon reaching the anode, a polysulfide anion reacts with the lithium or sodium metal, resulting in a loss of energy density that converts electrochemical energy into heat, which is undesirable and requires additional thermal management for a battery system. In addition, it is known that a Li / Na-S rechargeable battery is difficult to discharge or charge at a rapid rate due to the extremely low electrical conductivity of sulfur.

Elemental selenium is another chalcogen element that has an energy density less than that of sulfur and oxygen by weight, 1,350 W.hr / kg-Se. However, selenium has a higher mass density (4.8 g / cm ³ ) than sulfur (2.0 g / cm ³ ) and oxygen (1.14 g / cm ³ ) in a cryogenic form (would be much lower if it were in gaseous form). This has the effect that the selenium energy density by volume is at a level that is that of sulfur and oxygen, 6,480 W.hr/l-Se vs. 5,922 W.hr/lS and 7,501 W.hr/l oxygen is similar. In addition, elemental selenium is more electrically conductive than sulfur, which can allow a Li / Na-Se battery to operate at a higher rate of cycling. A Li / Na-Se battery, however, can still involve more than one chemical transport during the electrochemical discharge and charge process, at least (a) lithium / sodium ion transport from the anode to the cathode during the battery discharge process and vice versa during the battery charging process, which is very similar to a lithium-ion battery, and (b) during the battery discharging process, converting an elemental selenium into a polyselenide ion as an intermediate product, which dissolves in the electrolyte solution and shuttles from cathode to anode; on reaching the anode, a polyselenide anion reacts with lithium or sodium metal, which results in a loss of energy density, converting the electrochemical energy into heat, which is undesirable and requires additional thermal management for a battery system.

Elemental tellurium is the heaviest chalcogen element that is not radioactive; it has an energy density of only 742 W.hr / kg, with the assumption that the voltage of the Li-Te battery is the same as that for a Li-S battery, namely 1.8 V. Tellurium has a mass density of 6.24 g / cm ³ resulting in a theoretical energy density of 4.630 W.hr/1-Te, which is only about 1/3 lower than Li-Oxygen, Li-S and Li-Se, that of 5,922 W.hr/l to 7 501 W.hr/1 range. Interest in a Li / Na-Te battery is not as great as in Li-oxygen and Li-Se batteries because of its intrinsically low energy density, both by weight and volume. Tellurium is more electrically conductive than selenium, which can allow the Li-Te battery to cycle at a higher rate.

SUMMARY OF THE INVENTION

A process for preparing a two-dimensional carbon nanomaterial having a high degree of graphitization is disclosed herein. The two-dimensional carbon nanomaterials are mixed with selenium to obtain a carbon-selenium composite material, which is used as a cathode material, which is paired with an anode material containing lithium, resulting in a lithium-selenium battery having high Has energy density and stable electrochemical performances. A similar process can be used to further assemble a pouch cell that also exhibits excellent electrochemical properties.

A method of preparing selenium-carbon composite material with readily available raw materials and simple preparation procedures is also disclosed.

• (1) Organische Alkali-Metallsalze oder organische Erdalkali-Metallsalze werden bei hohen Temperaturen karbonisiert und dann mit verdünnter Salzsäure oder anderen Säuren gewaschen und getrocknet, um ein zweidimensionales Carbonmaterial zu erhalten;
• (2) Das zweidimensionale Carbonmaterial, das in Schritt (1) erhalten wurde, wird mit Selen in organischer Lösung vermischt, erhitzt, und das organische Lösemittel wird verdampft, und dann wird das Vermischen von Selen mit dem zweidimensionalen Carbonmaterial durch eine mehrstufige Wärmerampen- und Durchwärmungsvorgehensweise abgeschlossen, um Carbon-Selen-Verbundmaterial zu erhalten.

The selenium-carbon composite material described herein can be obtained with a preparatory process comprising the following steps:

• (1) Organic alkali metal salts or organic alkaline earth metal salts are carbonized at high temperatures and then washed with dilute hydrochloric acid or other acids and dried to obtain a two-dimensional carbon material;
• (2) The two-dimensional carbon material obtained in step (1) is mixed with selenium in organic solution, heated, and the organic solvent is evaporated, and then the mixing of selenium with the two-dimensional carbon material is carried out by a multi-stage heat ramp and Soak procedure completed to obtain carbon-selenium composite.

In step (1), the organic alkali metal salt can be selected from one or more of potassium citrate, potassium gluconate and sucrose acid sodium. The organic alkaline earth metal salt can be selected from either or both of calcium gluconate and sucrose acid calcium. The high temperature carbonization can be carried out at 600 to 1000 ° C, desirably 700 to 900 ° C; Carbonization time 1 to 10 hours, desirably 3 to 5 hours.

In step (2), the organic solvent can be selected from one or more of ethanol, dimethyl sulfoxide (DMSO), tolulene, acetonitrile, N, N-dimethylformamide (DMF), carbon tetrachloride and diethyl ether or ethyl acetate; the multi-stage heat ramp and soak section can be called a ramp rate of 2 to 10 ° C / min., desirably 5-8 ° C / min., followed by a temperature between 200 and 300 ° C, desirably between 220 and 280 ° C soaking at the temperature for 3 to 10 hours, desirably 3 to 4 hours; then continue heating to 400 to 600 ° C, desirably 430 to 460 ° C, followed by soaking for 10 to 30 hours, desirably 15 to 20 hours.

A lithium-selenium secondary battery comprising the carbon-selenium composite materials is also disclosed herein. The lithium selenium secondary battery may further include: an anode containing lithium, a separator, and an electrolyte.

The lithium-containing anode can be one or more of lithium metal, lithiated graphite anode, and lithiated silicon-carbon anode materials (by assembling the graphite and silicon-carbon anode materials and lithium anode into a half-cell battery, discharging to make the lithiated graphite anode and to prepare lithiated silicon-carbon anode materials). The separator (membrane) can be a commercially available membrane such as, without limitation, a Celgard membrane, a Whatman membrane, a cellulose membrane, or a polymer membrane. The electrolyte can be one or more of a carbonate electrolyte, an ether electrolyte, and ionic liquids.

The carbonate electrolyte can be selected from one or more of diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylene carbonate (EC), ethyl methyl carbonate (EMC), and propylene carbonate (PC); and the solute can be selected from one or more of lithium hexafluorophosphate (LiPF ₆ ), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium perchlorate (LiClO ₄ ), and lithium bis (fluorosulfonyl) imide (LiFSI ).

For the electrolytic ether solution, the solvent can be selected from one or more of 1,3-dioxolane (DOL), ethylene glycol dimethyl ether (DME), and triethylene glycol dimethyl ether (TEGDME); and the solute can be selected from one or more of lithium hexafluorophosphate (LiPF ₆ ), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium perchlorate (LiClO ₄ ), and lithium bis-fluorosulfonylimide (LiFSI).

For ionic liquids, the ionic liquid can be one or more of ionic liquid at room temperature Sulfonimide salt), [PP13] NTf2 (N-propyl-methylpiperidine-alkoxy-N-bis-trifluoromethane-sulfonimide salt); and the solute can be selected from one or more of lithium hexafluorophosphate (LiPF ₆ ), bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium perchlorate (LiClO ₄ ), and lithium bis-fluorosulfonylimide (LiFSI).

This also describes a lithium-selenium pouch cell battery which comprises the carbon-selenium composite material.

Compared with the prior art, referring to the method for preparing selenium-carbon composite material disclosed herein, the two-dimensional carbon material has advantages that the raw materials are easily available at low cost, the preparation process simple, high is practical and suitable for mass production, and the obtained selenium-carbon composite material exhibits excellent electrochemical properties.

Also disclosed herein is immobilized selenium (an immobilized selenium mass) comprising selenium and a carbon backbone. The immobilized selenium comprises at least one of the following aspects: (a) It requires the recovery of sufficient energy for a selenium particle to have a kinetic energy of ≥ 9.5 kJ / mol, ≥ 9.7 kJ / mol, ≥ 9.9 kJ / mol, ≥ 10.1 kJ / mol, ≥ 10.3 kJ / mol or ≥ 10.5 kJ / mol reached in order to escape the immobilized selenium system; (b) a temperature of 490 ° C or higher, ≥ 500 ° C, ≥ 510 ° C, ≥ 520 ° C, ≥ 530 ° C, ≥ 540 ° C, ≥ 550 ° C or ≥ 560 ° C is required for this Selenium particles gain enough energy to escape the immobilized selenium system; (c) the carbon skeleton has a surface (with pores less than 20 angstroms) of ≥ 500 m ² / g, ≥ 600 m ² / g, ≥ 700 m ² / g, ≥ 800 m ² / g, ≥ 900 m ² / g or ≥ 1,000 m ² / g; (d) the carbon framework has a surface area (for pores between 20 Angstroms and 1000 Angstroms) of 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, 2% or less, 1 % or less of the total surface.

A cathode or a rechargeable battery comprising immobilized selenium is also disclosed herein. The selenium can be doped with other elements, such as, but not limited to, sulfur.

This also discloses a composite material that contains selenium and carbon, which comprises a platelet morphology with an aspect ratio of ≥ 1, 2, 5, 10 or 20.

This also discloses a cathode which contains a composite material which comprises selenium and carbon and comprises a platelet morphology with an aspect ratio of ≥ 1, 2, 5, 10 or 20. Also disclosed herein is a rechargeable battery that includes a composite material comprising selenium and carbon and having a platelet morphology having the aspect ratio above.

Also disclosed herein is a rechargeable battery that includes a cathode, an anode, a separator, and an electrolyte. The rechargeable battery can be charged at 0.1C, 0.2C, 0.5C, 1C, 1.5C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, 9C, 10C or faster. The cathode can comprise at least one element of a chalcogen group, such as selenium, sulfur, tellurium and oxygen The anode can contain at least one element of an alkali metal, Alkaline earth metal and a metal or metals of Group IIIA. The separator can comprise an organic or an inorganic separator, the surface of which can optionally be modified. The electrolyte may comprise at least one of an alkali metal, an alkaline earth metal and a metal or group IIIA metals. The solvent in the electrolyte solution can comprise organic solvents, based on carbonate, ether or ester.

The rechargeable battery can have a specific capacity of 400 mAh / g or higher, 450 mAh / g or higher, 500 mAh / g or higher, 550 mAh / g or higher, or 600 mAh / g or higher. The rechargeable battery may be capable of electrochemical cycling for 50 cycles or more, 75 cycles or more, 100 cycles or more, 200 cycles or more, and so on. The rechargeable battery can have a specific capacity of the battery greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70% or greater than 80% of the second specific discharge capacity at a cycling rate of 0.1C performing charge-discharge cycling at high C rate (e.g. 5 cycles at 0.1C, 5 cycles at 0.2C, 5 cycles at 0.5C, 5 cycles at IC, 5 cycles at 2C, 5 cycles at 5C and cycles with 10C). The rechargeable battery can have a Coulomb efficiency of ≥ 50%, ≥ 60%, ≥ 70%, ≥ 80% or ≥ 90%. The rechargeable battery can be used for electronics, an electric or hybrid vehicle, an industrial application, a military application such as a drone, an aerospace application, a marine application, and so on.

Immobilized chalcogen and its properties, processes for producing immobilized chalcogen and the use of immobilized chalcogen in a rechargeable battery are also disclosed therein.

Various preferred and non-limiting examples or aspects of the present invention will now be described and set forth in the following numbered clauses.

• eine Aktivierungsenergie für ein Chalkogenteilchen zum Entkommen aus der immobilisierten Chalkogen-Masse ≥ 96 kJ/mol, ≥ 99 kJ/mol, ≥ 102 kJ/mol, ≥ 105 kJ/mol, ≥ 108 kJ/mol oder ≥ 111 kJ/mol;
• einen Pre-Exponential-log-Faktor (LogA) ≥7,0, ≥7,1, ≥7,3, ≥7,4 oder ≥7,5;
• eine Stoßfrequenz ≥ 1,0×10⁷, ≥ 1,3×10⁷, ≥ 1,6×10⁷, ≥ 2,6×10⁷ oder ≥ 3,2×10⁷;
• eine kinetische Energie, damit das Chalkogenteilchen der immobilisierten Chalkogen-Masse entkommt von 1 840.3x² + 90,075x + D, wobei x das Schwefel-Gew.-% des gesamten Selens und Schwefels in einer immobilisierten Chalkogen-Masse ist, und D ≥ 9 500 J/mol ≥ 9 700 J/mol ≥ 9 900 J/mol ≥ 10 000 J/mol, 10 200 J/mol, 10 400 J/mol oder ≥ 10 600 J/mol betragen kann;
• eine mittlere Gewichtsverlusttemperatur der immobilisierten Chalkogen-Masse = 147,57 x² + 7,2227 x + C, wobei C ≥ 510 °C, ≥ 520 °C, ≥ 530 °C, ≥ 540 °C, ≥ 550 °C, 560 °C oder ≥ 570 °C betragen kann und x der Gew.-%-Anteil von Schwefel in den Gesamtmengen von Selen und Schwefel in der immobilisierten Chalkogen-Masse ist;
• eine Beständigkeit gegenüber Umgebungsoxidation mit einer Haltbarkeit von ≥ 3 Monaten, ≥ 6 Monaten, ≥ 9 Monaten, ≥ 12 Monaten, ≥ 15 Monaten, ≥ 18 Monaten, ≥ 21 Monaten, oder ≥ 24 Monaten, bestimmt durch einen exothermen Gewichtsverlust zwischen 200 und 250 °C ≤ 2,0 Gew.-%, ≤ 1,8 Gew.-%, ≤ 1,6 Gew.-% ≤ 1,4 Gew.-% ≤ 1,2 Gew.-% oder 1,0 Gew.-% bei einer TGA-Analyse unter einem Argonstrom;
• eine d-Spacing-Schwindung von Carbon ≥ 0,5 Å, ≥ 0,6 Å, ≥ 0,7 Å, ≥ 0,8 Å oder ≥ 0,9 Å;
• eine Steigerung der D-Band-Raman-Verschiebung des Carbons um ≥2 cm^-1, ≥3 cm^-1, ≥4 cm^-1, ≥5 cm^-1 oder ≥6 cm^-1.
• eine Steigerung der G-Band-Raman-Verschiebung um ≥1 cm^-1, ≥2 cm^-1 oder ≥₃ cm^-1.
• das Carbon ist bei Umgebungsbedingungen hoch aktiv, nachdem es unter einem Inertgasstrom, wie Argon, unter erhöhten Temperaturen, zum Beispiel ≥ 400 °C, ≥ 500 °C, ≥ 600 °C, ≥ 700 °C oder ≥ 800 °C, behandelt wurde, wobei das Carbongerüst zum Beispiel unter einem Inertgasstrom bei den erwähnten Temperaturen von selbst bei Exposition mit Umgebungsbedingungen zu brennen beginnen kann, wie bei Umgebungsluft bei Raumtemperatur (zum Beispiel zwischen etwa 13 °C und 27 °C);
• Wasser wird ≥100 ppm, ≥200 ppm, ≥300 ppm, ≥400 ppm, oder ≥500 ppm, nach Gewicht freigesetzt, wenn die immobilisierte Chalcogen-Masse bis 400 °C erhitzt wird;
• Kohlendioxid wird ≥1.000 ppm, ≥1.200 ppm, ≥1.400 ppm, ≥1.600 ppm oder ≥1.800 ppm, nach Gewicht freigesetzt, wenn die immobilisierte Chalkogen-Masse bis 600 °C erhitzt wird;
• Kohlenmonoxid wird ≥1.000 ppm, ≥1.200 ppm, ≥1.400 ppm, ≥1.600 ppm oder ≥1.800 ppm oder ≥2.000, in Gewicht freigesetzt, wenn die immobilisierte Chalkogen-Masse bis 800 °C erhitzt wird;
• eine wiederaufladbare Batterie, die immobilisierte Chalkogen-Masse umfasst, weist einen einstufigen Entladeprozess auf, was ein Mindestniveau von Polychalkogenidbildung während des Entladeprozesses nahelegt;
• die wiederaufladbare Batterie, die eine Batterie-Zyklisierungseffizienz von ≥90 %, ≥95 %, ≥97 %, ≥98 oder ≥99 % aufweist, wobei kein Pendeln auftritt, wenn die Zyklisierungseffizienz = 100 %, wobei eine hohe Zyklisierungseffizienz nahelegen kann, dass ein Mindestniveau von Polychalkogenidbildung besteht und/oder Polychalkogenid sich sogar während des Entladeprozesses bildet, wobei das Polychalkogenid auf der Kathode verankert ist;
• die wiederaufladbare Batterie, die eine mittlere Entladespannung von ≥1,2 V, ≥1,3 V, ≥1,4 V, ≥1,5V oder ≥1,5V bei einer C-Rate von 1 aufweist, wobei eine höhere mittlere Spannung wünschenswert ist, da sie nahelegt, dass die interne Batteriespannung niedrig ist, was eine hohe C-Rate für das Entladen und Laden der Batterie erlaubt; und oder
• die wiederaufladbare Batterie, die eine immobilisierte Chalkogen-Masse umfasst, die eine spezifische Kapazität von 50 % der theoretischen Kapazität von Chalkogen für ≥50 Zyklen, ≥100 Zyklen, ≥150 Zyklen, ≥200 Zyklen oder ≥250 Zyklen aufweist;

Clause 1: An immobilized chalcogen mass comprises a mixture of chalcogen and carbon, for example a carbon skeleton. The chalcogen includes oxygen, sulfur, selenium, tellurium or a mixture thereof. The immobilized chalcogen mass comprises at least one of the following:

• an activation energy for a chalcogen particle to escape from the immobilized chalcogen mass ≥ 96 kJ / mol, ≥ 99 kJ / mol, ≥ 102 kJ / mol, ≥ 105 kJ / mol, ≥ 108 kJ / mol or ≥ 111 kJ / mol;
• a pre-exponential log factor (LogA) ≥7.0, ≥7.1, ≥7.3, ≥7.4, or ≥7.5;
• a shock frequency ≥ 1.0 × 10 ⁷ , ≥ 1.3 × 10 ⁷ , ≥ 1.6 × 10 ⁷ , ≥ 2.6 × 10 ⁷ or ≥ 3.2 × 10 ⁷ ;
• a kinetic energy for the chalcogen particle to escape the immobilized chalcogen mass of 1,840.3x ² + 90.075x + D, where x is the sulfur wt% of the total selenium and sulfur in an immobilized chalcogen mass, and D ≥ 9 500 J / mol ≥ 9 700 J / mol ≥ 9 900 J / mol ≥ 10 000 J / mol, 10 200 J / mol, 10 400 J / mol or ≥ 10 600 J / mol;
• a mean weight loss temperature of the immobilized chalcogen mass = 147.57 x ² + 7.2227 x + C, where C ≥ 510 ° C, ≥ 520 ° C, ≥ 530 ° C, ≥ 540 ° C, ≥ 550 ° C, 560 ° C or ≥ 570 ° C and x is the% by weight fraction of sulfur in the total amounts of selenium and sulfur in the immobilized chalcogen mass;
• a resistance to ambient oxidation with a shelf life of ≥ 3 months, ≥ 6 months, ≥ 9 months, ≥ 12 months, ≥ 15 months, ≥ 18 months, ≥ 21 months, or ≥ 24 months, determined by an exothermic weight loss between 200 and 250 ° C ≤ 2.0% by weight, ≤ 1.8% by weight, ≤ 1.6% by weight ≤ 1.4% by weight ≤ 1.2% by weight or 1.0% by weight -% in a TGA analysis under a stream of argon;
• a d-spacing shrinkage of carbon ≥ 0.5 Å, ≥ 0.6 Å, ≥ 0.7 Å, ≥ 0.8 Å, or ≥ 0.9 Å;
• an increase in the D-band Raman shift of the carbon by ≥2 cm ^-1 , ≥3 cm ^-1 , ≥4 cm ^-1 , ≥5 cm ^-1 or ≥6 cm ^-1 .
• an increase in the G-band Raman shift by ≥1 cm ^-1 , ≥2 cm ^-1 or ≥ ₃ cm ^-1 .
• the carbon is highly active at ambient conditions after it has been treated under a stream of inert gas such as argon at elevated temperatures, for example ≥ 400 ° C, ≥ 500 ° C, ≥ 600 ° C, ≥ 700 ° C or ≥ 800 ° C wherein, for example, under a stream of inert gas at the temperatures mentioned, the carbon framework can start to burn by itself upon exposure to ambient conditions, such as ambient air at room temperature (for example between about 13 ° C and 27 ° C);
• Water is released ≥100 ppm, ≥200 ppm, ≥300 ppm, ≥400 ppm, or ≥500 ppm, by weight, when the immobilized chalcogen mass is heated to 400 ° C;
• Carbon dioxide is released ≥1,000 ppm, ≥1,200 ppm, ≥1,400 ppm, ≥1,600 ppm or ≥1,800 ppm, by weight, when the immobilized chalcogen mass is heated to 600 ° C;
• Carbon monoxide is released ≥1,000 ppm, ≥1,200 ppm, ≥1,400 ppm, ≥1,600 ppm or ≥1,800 ppm or ≥2,000 by weight when the immobilized chalcogen mass is heated to 800 ° C;
• a rechargeable battery comprising immobilized chalcogen mass has a one-step discharge process suggesting a minimum level of polychalcogenide formation during the discharge process;
• the rechargeable battery, which has a battery cycling efficiency of ≥90%, ≥95%, ≥97%, ≥98, or ≥99%, with no hunting when the cycling efficiency = 100%, and high cycling efficiency may suggest that there is a minimum level of polychalcogenide formation and / or polychalcogenide forms even during the discharge process, the polychalcogenide being anchored on the cathode;
• the rechargeable battery, which has a mean discharge voltage of ≥1.2V, ≥1.3V, ≥1.4V, ≥1.5V or ≥1.5V at a C-rate of 1, with a higher mean voltage is desirable as it suggests that the internal battery voltage is low, allowing a high C-rate for discharging and charging the battery; and or
• the rechargeable battery comprising an immobilized chalcogen mass having a specific capacity of 50% of the theoretical capacity of chalcogen for ≥50 cycles, ≥100 cycles, ≥150 cycles, ≥200 cycles, or ≥250 cycles;

Clause 2: The immobilized chalcogen mass of Clause 1 may form a coordination bond or an electron donor acceptor bond.

Clause 3: The immobilized chalcogen mass of Clause 1 or 2, wherein the carbon that forms the carbon backbone may contain a chemical deactivation function group that has an ability to withdraw an electron from the delocalized Extremely Massive Aromatic Conjugated (EMAC) - Has π bonding system of the carbon frame.

Clause 4: The immobilized chalcogen mass according to any one of Clauses 1 to 3, wherein the carbon backbone can have a carbon cation center on the EMAC π bonding system.

Clause 5: The immobilized chalcogen mass according to any one of Clauses 1 to 4, wherein the chemical deactivation function group is an oxygen-containing group ≥0.1 mmol O / g, ≥0.5 mmol O / g, ≥1.0 mmol O / g, May contain ≥1.5 mmol O / g, ≥2.0 mmol O / g, ≥2.5 mmol O / g, ≥3.0 mmol O / g.

Clause 6: The immobilized chalcogen composition of any one of Clauses 1 to 5, wherein the chemical deactivating functional group comprising oxygen may include at least one of the following: -CHO (formyl group or aldehyde group), -COR (acyl group or ketone group), -COOH (Carboxyl group or carboxylic acid group) or its salt (-COO ^- ), -COOR (a carboxylate group or ester group), an anhydride group or a carbonyl group (-CO-).

Clause 7: The immobilized chalcogen mass according to any one of Clauses 1 to 6, wherein the chemical deactivation function group is a nitrogen-containing group ≥0.1 mmol N / g, ≥0.5 mmol N / g, ≥1.0 mmol N / g, May contain ≥1.5 mmol N / g, ≥2.0 mmol N / g, ≥2.5 mmol N / g, ≥3.0 mmol N / g.

Clause 8: The immobilized chalcogen composition of any of Clauses 1 to 7, wherein the chemical deactivating functional group comprising nitrogen may include at least one of the following: a nitro group, -NO ₂ , a nitroso group, -NO, an ammonium group, -N ⁺ R ₃ , where R can be an alkyl group, an aryl group or an H, a cyano group (-CN), a thiocyanate group (-SCN) or an isothiocyanate group (-NCS).

Clause 9: The immobilized chalcogen mass according to any one of Clauses 1 to 8, wherein the chemical deactivation function group is a sulfur-containing group ≥0.1 mmol S / g, ≥0.5 mmol S / g, ≥1.0 mmol S / g, May contain ≥1.5 mmol S / g, ≥2.0 mmol S / g, ≥2.5 mmol S / g, ≥3.0 mmol S / g.

Clause 10: The immobilized chalcogen composition of any of Clauses 1 to 9, wherein the chemical deactivating functional group comprising sulfur may include at least one of the following: -SO ₃ H- (a sulfonic acid) group or its salt (-SO ₃ ^- ), -SCN (a thiocyanate group), -SO ₂ R (a Sulfonyl ester) group, where R can be an alkyl group, aryl group or halogen, -SO ₂ CF ₃ (a trifluoromethyl sulfonyl ester group), -SO ₂ -OR, or a sulfonium group (-S ⁺ R ₂ ), where R is an alkyl group, May be aryl group or other organic functional group and R may not be the same.

Clause 11: The immobilized chalcogen mass according to any one of Clauses 1 to 10, wherein the chemical deactivation function group is a phosphorus-containing group ≥0.1 mmol P / g, ≥0.5 mmol P / g, ≥1.0 mmol N / g, May contain ≥1.5 mmol P / g, ≥2.0 mmol P / g, ≥2.5 mmol P / g, ≥3.0 mmol P / g.

Clause 12: The immobilized chalcogen composition of any of Clauses 1 through 11, wherein the chemical deactivating functional group comprising phosphorus may include at least one of the following: a phosphonic acid group (-PO ₃ H ₂ ) or its salt (-PO ₃ H ^- , - PO ₃ ^2- ), a phosphonate (-PO ₃ R ₂ , -PO ₃ HR or -PO ₃ R ^- ) or a phosphonyl group (-POR2), where R is an arkyl, aryl or any organic functional group is. The chemical deactivation functional group can be a phosphonium group (-P ⁺ R ₃ ).

Clause 13: The immobilized chalcogen mass according to one of Clauses 1 to 12, where the chemical deactivation function group is a halogen-containing group ≥0.1 mmol X / g, ≥0.5 mmol X / g, ≥1.0 mmol X / g, ≥1.5 mmol X / g, ≥2.0 mmol X / g, ≥2.5 mmol X / g, ≥3.0 mmol X / g, where the halogen (X) fluorine, chlorine, bromine and / or iodine.

Clause 14: The immobilized chalcogen composition of any one of Clauses 1 to 13, wherein the chemical deactivating functional group comprising halogen may include at least one of the following: F, Cl, Br, I, -CF ₃ , -CCl ₃ , -CBr ₃ , -Cl ₃ and or a strongly halogenated alkyl group with more than one carbon.

Figure list

• 1 Fig. 5 is a 50,000X scanning electron microscope photograph of the carbon material of Example 1;
• 2 Fig. 13 is a 0.1C charge and discharge curve of the lithium selenium battery of Example 1;
• 3 Fig. 13 is a 0.1C charge and discharge curve of the lithium selenium battery of Comparative Example 2;
• 4th Fig. 13 is an optical image of a pouch cell battery of Example 1;
• 5 Fig. 13 is a 0.05C charge and discharge curve of the pouch cell battery of Example 1;
• 6th Figure 13 is a flow diagram of a process for making immobilized selenium;
• 7th Fig. 13 is a scanning electron microscope image of a carbon skeleton prepared by the process of Example 9;
• 8th are X-ray diffraction patterns of the carbon skeleton prepared by the process of Example 9;
• 9 Fig. 13 is a Raman spectrum of the carbon skeleton prepared by the process of Example 9;
• 10A Figure 13 is a graph of cumulative and incremental surface area for the carbon framework prepared using the process of Example 9;
• 10B Figure 13 is a graph of cumulative and incremental volume for the carbon skeleton prepared using the process of Example 9;
• 11A Figure 13 is a TGA analysis graph for the immobilized selenium prepared by the process of Example 10;
• 11B Figure 13 is a graph of TGA analysis for non-immobilized selenium samples prepared by the process of Example 10 using Se-Super-P-Carbon and Se-Graphite;
• 11C is a graph of a TGA analysis of the non-immobilized selenium sample obtained using the Se-Super-P-Carbon ( 11B) under a stream of argon gas and at heating rates of 16 ° C / min. and 10 ° C / min. is prepared;
• 11D Figure 13 is a graph of rate constants for non-immobilized selenium (Se-Super-P composite (solid line) and 2 different samples of immobilized selenium (228-110 (dotted line) and 115-82-2 (dashed line)), as determined by the Process of Example 10 is prepared;
• 12 Fig. 13 is a graph of a Raman spectrum of the immobilized selenium prepared by the process of Example 10;
• 13 Fig. 13 is a graph of X-ray diffraction patterns for the immobilized selenium prepared by the process of Example 10;
• 14th Fig. 10 is an SEM image of the immobilized selenium prepared by the process of Example 10;
• 15th Fig. 13 is an exploded view of a coin cell battery including a cathode prepared according to the process of Example 11 or Example 13;
• 16 are graphs of cycling test results for a first lithium selenium button cell battery (0.1C) ( 16A - left) and a second lithium selenium button cell battery (0.1C and then 1C) ( 16A - right) of the type in 15th prepared using the process of Example 12;
• 17th are graphs of cycling tests for a lithium selenium button cell battery of the type shown in 15th is shown prepared using the process of Example 12 at different cycling rates;
• 18th are graphs of 0.1C cycling test results for a lithium-sulfur-doped selenium button cell battery of the type shown in 15th is shown; made in accordance with Example 13 with a polymer separator;
• 19th are graphs of IC cycling test results for a lithium-sulfur doped selenium coin cell battery of the type shown in 15th made in accordance with Example 13 with a polymer separator.
• 20A Figure 3 is a model of an EMAC π bonding system of a carbon framework;
• 20B is the model of 20A bonded with an electron withdrawal chemical deactivation functional group, resulting in an electron deficient carbon cation center at para and / or ortho position of the EMAC π bonding system by resonances;
• 20C is the model of 20B Showing the Carbon Cation Center moveable by resonances;
• 20D is the model of 20C Figure 13 shows immobilized chalcogen in which the chalcogen donates lone pairs to a lone pair acceptor at a carbon cation center;
• 20E is a model of a carbon-cation center that is created by the presence of a carbonyl group or an anhydride group as part of the EMAC-π-bonding system via resonances, the carbon-cation centers in the EMAC-π-bonding system being movable via resonances ;
• 20F Figure 3 is a model of d-spacing shrinkage of a carbon scaffold in immobilized chalcogen;
• 21st Figure 10 shows TGA and DSC graphs of immobilized selenium sample C-Se478 (dotted lines) analyzed 4 months after its preparation and immobilized selenium sample C-SE100 (solid lines) analyzed 28 months after its preparation;
• The 22A-22B are respective TGA and DSC graphics of C-Se composites made with activated Carbon Elite C (available from Calgon Carbon, Pittsburgh, PA) analyzed 27 months after the C-Se composites were prepared;
• 23 Fig. 10 shows X-ray diffraction (XRD) patterns for raw materials Se, S, SeS _2, and carbons, including multi-walled carbon nanotubes (MWCNT), and a carbon scaffold comprising a chemical deactivation functional group comprising oxygen;
• The 24A-24C show XRD patterns for autoclave-treated mixtures of sulfur and selenium ( 24A) , Sulfur powder ( 24B) and selenium powder ( 24C ) all without the presence of a carbon backbone comprising a chemical deactivating functional group comprising oxygen;
• 25A shows Raman scattering spectra for starting materials Se, S, SeS ₂ , carbons (Example 15) and multi-walled carbon nanotube materials between 0 to 4000 cm ^-1 , the Raman spectrum for sulfur being divided by 150;
• 25B FIG. 13 is a single enlarged view of the Raman scattering spectra of FIG 25A between 100 and 800 cm ^-1;
• 26A shows Raman scattering spectra for autoclaved selenium, sulfur, and their mixtures without the presence of the carbon backbone comprising a chemical deactivation function group comprising oxygen (with some of the Raman spectra being divided (1 / X) as shown in the figure) between 0 and 4000 cm ^-1 ,
• 26B FIG. 13 is a single enlarged view of the Raman scattering spectra of FIG 26A between 100 and 800 cm ^-1 ,
• 27 Figure 13 shows XRD patterns for immobilized chalcogen comprising a carbon backbone comprising a chemical deactivating functional group; which includes oxygen; for different percentage combinations of selenium and sulfur together with an XRD pattern for a carbon framework for comparison;
• 28 Figure 13 shows Raman scattering spectra for immobilized chalcogen comprising a carbon backbone; comprising a chemical deactivation functional group; which includes oxygen, for different percentage combinations of selenium and sulfur;
• 29 Figure 12 shows XRD patterns for three MWCNT-SeS ₂ composites (upper three patterns) and one immobilized chalcogen (SeS ₂ - lower pattern), each comprising a carbon backbone comprising a chemical deactivation functional group comprising oxygen, the two upper patterns prepared in air at 160 ° C for 16 hours, and the two lower samples were prepared in flowing argon at 130 ° C for 1.5 hours;
• 30th shows Raman scattering spectra for three control MWCNT-SeS ₂ composites (upper three samples) and immobilized SeS ₂ (lower sample), the two upper samples being prepared in air at 160 ° C for 16 hours and the two lower in flowing argon at 130 ° C for 1.5 hours;
• 31A shows a TGA analysis of the immobilized chalcogen with different contents of selenium, sulfur and a carbon structure at a heating rate of 10 ° C / min .;
• 31B shows a TGA analysis (a heating rate of 10 ° C / min.) of immobilized SeS ₂ (38% by weight) and control C-SeS ₂ composite materials made from multi-walled carbon nanotubes MWCNT), the MWCNT-1-SeS ₂ (70% by weight and the MWCNT-5_SeS ₂ (70% by weight) being prepared in air at 160 ° C. for 16 hours, and the MWCNT-5_SeS ₂ (38 wt%) were prepared in a flow of argon at 130 ° C for 1.5 hours;
• 32A shows a mean weight loss temperature (in the TGA analysis in 31A) compared to sulfur wt .-% of the total Se and S in immobilized chalcogen, the solid circles representing measurement data, the dashed line the desirable mean weight loss temperature (at or above the dashed line) and the solid triangles control C-SeS ₂ - Represent composite materials prepared with MWCNT materials;
• 32B shows a kinetic energy of mean weight loss (in the TGA analysis in 31A) compared to sulfur wt .-% of the total Se and S in immobilized chalcogen, the solid circles representing measurement data, the dashed line the desirable mean weight loss temperature (at or above the dashed line) and the solid triangles control C-SeS ₂ - Represent composite materials prepared with MWCNT materials;
• 33A shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 0 wt .-% Se_100 wt .-% S and carbon skeleton;
• 33B shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 85 wt .-% S_15 wt .-% Se and carbon skeleton;
• 33C shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 68 wt .-% S_32 wt .-% Se and carbon skeleton;
• 33D shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 51 wt .-% S_49 wt .-% Se and carbon skeleton;
• 33E shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 34% by weight S_66% by weight Se and carbon skeleton;
• 33F shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 17 wt .-% S_83 wt .-% Se and carbon skeleton;
• 33G shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 8.5 wt.% S_91.5 wt.% Se and carbon skeleton;
• 33H shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with 0 wt .-% S_100 wt .-% Se and carbon skeleton;
• 331 shows activation energy (solid line) and pre-exponential log factor (dashed line) of immobilized chalcogen with SeS ₂ and carbon skeleton;
• 33J shows activation energy (solid line) and pre-exponential log factor (dashed line of MWCNT-5_SeS ₂ (38 wt%) prepared in a flow of argon at 130 ° C for 1.5 hours;
• 33K shows activation energy (solid line) and pre-exponential log factor (dashed line of MWCNT-5_SeS ₂ (70 wt%) prepared in air at 160 ° C for 16 hours;
• 33L shows activation energy (solid line and pre-exponential log factor (dashed line of MWCNT-1_SeS ₂ (70% by weight) prepared in air at 160 ° C for 16 hours;
• 34A shows a gas chromatograph analysis (GC analysis) of immobilized chalcogen for water release when heated in a helium stream, the solid triangles representing H ₂ O, which is released from the immobilized chalcogen with 83 wt .-% Se_17 wt .-% S, the continuous triangles Squares represent H ₂ O released from the immobilized chalcogen with 100 wt% Se_0 wt% S, and the open circles represent the calculated released H ₂ O;
• 34B Figure 10 shows a gas chromatograph (GC) analysis of immobilized chalcogen for CO ₂ release when heated in a stream of helium, with solid triangles representing CO ₂ obtained from the immobilized chalcogen with 83 wt% Se _17 wt% S is released, the solid squares representing CO ₂ released from the immobilized chalcogen containing 100 wt.% Se_0 wt.% S, and the open circles representing the calculated released CO ₂ ;
• 34C shows a gas chromatograph analysis (GC analysis) of immobilized chalcogen for CO release when heated in a helium stream, the solid triangles representing CO, which is released from the immobilized chalcogen with 83 wt .-% Se_17 wt .-% S, the continuous triangles Squares represent CO released from the immobilized chalcogen with 100 wt% Se_0 wt% S, and the open circles represent the calculated released CO;
• 35 shows graphical representations (voltage V compared to specific capacity mAh / g - chalcogen with a C-rate of 1) of the 10th discharge and charge cycle of a number of different batteries that comprise immobilized chalcogens that contain different weight% combinations ( Wt% combinations) of selenium and sulfur, the theoretical specific capacity 675 mA / g-Se and 1,645 mAh / gS being used to determine the electrical current at a specified C-rate; and
• 36 Fig. 13 shows graphs of cycling performances of a number of different batteries comprising immobilized chalcogens having different wt% combinations (wt% combinations) of selenium and sulfur, the solid lines showing specific capacity versus number of cycles, and the dashed line represents coulombic efficiency versus number of cycles.

DESCRIPTION OF THE INVENTION

In connection with the specific examples, the present invention is further described below. Unless otherwise specified, the experimental procedures in the following examples are all conventional; the reagents and materials are all available from commercial sources.

Example 1:

Preparation of selenium-carbon composite material

After crushing and grinding, an appropriate amount of potassium citrate is calcined at 800 ° C. for 5 hours under an inert atmosphere and cooled to room temperature. It is washed to neutral pH with dilute hydrochloric acid; filtered and dried to give a two-dimensional carbon nanomaterial (1); according to the mass ratio of 50:50, the two-dimensional carbon material and selenium are weighed and then evenly stirred and mixed with the selenium ethanol solution; after Evaporation of the solvent, the mixture is dried in a drying oven; the dried mixture was at 5 ° C / min. heated to 240 ° C and warmed through for 3 hours; then continue at 5 ° C / min. heated to 450 ° C; Soaked for 20 hours, cooled to room temperature, resulting in the selenium-carbon composite.

Preparation of the selenium-carbon composite cathode

The selenium-carbon composite materials prepared above are mixed with Carbon Black Super P (TIMCAL) and binder CMC / SBR (weight ratio: 1: 1) together with water by means of a fixed formulation by crushing, coating, drying and other procedures to produce a selenium -Carbon composite cathode.

Put together lithium selenium battery

The selenium-carbon composite material cathode prepared above, lithium foil as anode, Celgard membrane as separator and 1M LiPF ₆ in EC / DMC as the electrolyte were assembled into a lithium-selenium button cell battery and a lithium-selenium pouch cell battery ( 4th ).

Lithium selenium battery test

A charge-discharge device is used to perform a constant current charge-discharge test on the lithium selenium button cell battery and the lithium selenium pouch cell battery. The test voltage range is 1.0-3.0 V and the test temperature is 25 ° C. The specific discharge power and the level of the charge-discharge current are calculated based on the selenium mass according to the standard. The charge-discharge current is 0.1C or 0.05C. The lithium selenium button charge and discharge curve is in 2 The specific test results are shown in Table 1 below. The lithium selenium pouch cell test results are in 5 shown.

Example 2:

The conditions are the same as in Example 1, except that the raw material that is carbonized for the two-dimensional carbon is sodium citrate. The battery test results are summarized in Table 1 below.

Example 3:

The conditions are the same as in Example 1, except that the raw material that is carbonized for the two-dimensional carbon is potassium gluconate. The battery test results are summarized in Table 1 below.

Example 4:

The conditions are the same as in Example 1, with the exception that the high temperature carbonization temperature for the carbon material is 650 ° C. The battery test results are summarized in Table 1 below.

Example 5:

The conditions are the same as in Example 1, with the exception that the dried mixture at 5 ° C / min. heated to 300 ° C and warmed through at this temperature for 3 hours. The battery test results are summarized in Table 1 below.

Example 6:

The conditions are the same as in Example 1, with the exception that the dried mixture at 5 ° C / min. heated to 240 ° and warmed through at this temperature for 3 hours, then further heated to 600 ° C and warmed through at this constant temperature for 20 hours. The battery test results are summarized in Table 1 below.

Example 7:

The conditions are the same as in Example 1, except that the lithium Se battery was packed with a lithiated graphite anode in place of the lithium anode sheet. The battery test results are summarized in Table 1 below.

Example 8:

The conditions are the same as in Example 1, except that the lithium Se battery was packed with a lithiated silicon-carbon anode in place of the lithium anode sheet. The battery test results are summarized in Table 1 below.

Comparative example 1:

The conditions are the same as in Example 1, except that polyacrylonitrile is used as the raw material. The battery test results are summarized in Table 1 below.

Comparative example 2:

The conditions are the same as in Example 1; except that a one-step composite process is used to prepare the selenium and carbon composite. In this example, the dried selenium-carbon mixture at 5 ° C / min. Heated to 500 ° C and warmed through at this temperature for 23 hours to obtain selenium-carbon composite material. The charge-discharge curve of a battery made of the selenium-carbon composite material thus obtained is shown in FIG 3 shown; the battery test results are summarized in Table 1 below. Table 1 - Summarized Battery Test Results numbering The discharge capacity of the first cycle (mAh / g) The charge capacity of the first cycle / the discharge capacity of the first cycle (%) The capacity of the 50th cycle (mAh / g) example 1 1050 78.1 756 Example 2 940 74.6 672 Example 3 962 75.3 683 Example 4 987 72.1 680 Example 5 936 73.2 653 Example 6 972 70 661 Example 7 836 72.5 580 Example 8 910 73 600 Comparative example 1 635 55 350 Comparative example 2 980 40.8 386

After describing a method for preparing a selenium-carbon composite material, a method for preparing immobilized selenium and the use of the immobilized selenium in, for example, a rechargeable battery will be described.

Selenium is an element in the same group as oxygen and sulfur, namely group 6 of the table of the periodic table. Selenium can be advantageous over oxygen and sulfur in terms of its substantially high electrical conductivity. US 2012/0225352 discloses making rechargeable Li-selenium and Na-selenium batteries with good capacity and cycling ability. However, a certain level of polyselenide anions oscillates between the cathodes and anodes of such batteries, which results in additional electrochemical performances which have to be improved significantly for practical uses. Literature relevant to this area includes:

"Electrode Materials for Rechargeable Batteries," Ali Aboulmrane and Khalil Amine, US patent application 2012/0225352 , September 6, 2012.

"Lithium-Selenium Secondary Batteries Having non-Flammable Electrolyte", Hui He, Bor Z. Jang, Yanbo Wang, and Aruna Zhamu, U.S. Patent Application 2015/0064575, March 5, 2015 .

"Electrolyte Solution and Sulfur-based or Selenium-based Batteries including the Electrolyte Solution", Fang Dai, Mei Cai, Qiangfeng Xiao, and Li Yang, U.S. Patent Application 2016/0020491, Jan. 21, 2016 .

"A New Class of Lithium and Sodium Rechargeable Batteries Based on Selenium and Selenium-Sulfur as a Positive Electrode", Ali Abouimrane, Damien Dambournet, Kerena W. Chapman, Peter J. Chupa, Wei Wang and Khalil Amine, J. Am. Chem. Soc. 2012, 134, 4505-4508 .

"A Free-Standing and Ultralong-life Lithium-Selenium Battery Cathode Enabled by 3D Mesoporous Carbon / Graphene Hierachical Architecture", Kai Han, Zhao Liu, Jingmei Shen, Yuyuan Lin, Fand Dai, and Hongqi Ye, Adv. Funct. Mater., 2015, 25, 455-463 .

"Micro- and Mesoporous Carbide-Derived Carbon-Selenium Cathodes for High-Performance Lithium Selenium Batteries", Jung Tai Lee, Hyea Kim, Marin Oschatz, Dong-Chan Lee, Feixiang Wu, Huan-Ting Lin, Bogdan Zdyrko, Wan Il Chao, Stefan Kaskel and Gleb Yushin, Adv. Energy Mater. 2014, 1400981 .

"High-Performance Lithium Selenium Battery with Se / Microporous Carbon Composite Cathode and Carbonate-Based Electrolyte", Chao Wu, Lixia Yuan, Zhen Li, Ziqi Yi, Rui Zeng, Yanrong Li and Yunhui Huang, Sci. China Mater. 2015, 58, 91-97 .

"Advanced Se-C Nanocomposites: a Bifunctional Electrode Material for both Li-Se and Li-ion Batteries", Huan Ye, Ya-Xia Yin, Shuai-Feng Zhang and Yu-Guo Guo, J. Mater. Chem. A., May 23, 2014 .

"Lithium Iodide as a Promising Electrolyte Additive for Lithium-Sulfur Batteries: Mechanisms of Performance Enhancement", Feixiang Wu, Jung Tae Lee, Naoki Nitta, Hyea Kim, Oleg Borodin and Gleb Yushin, Adv. Mater. 2015, 27, 101-108 .

"A Se / C Composite as Cathode Material for Rechargeable Lithium Batteries with Good Electrochemical Performance", Lili Li, Yuyang Hou, Yaqiong Yang, Minxia Li, Xiaowei Wang and Yuping Wu, RSC Adv., 2014, 4, 9086-9091 .

"Elemental Selenium for Electrochemical Energy Storage", Chun-Peng Yang, Ya-Xia Yin and Yu-Guo Guo, J. Phys. Chem. Lett. 2015, 6, 256-266 .

"Selenium @ mesoporous Carbon Composite with Superior Lithium and Sodium Storage Capacity", Chao Luo, Yunhua Xu, Yujie Zhu, Yihang Liu, Shiyou Zheng, Ying Liu, Alex Langrock and Chunsheng Wang, ACSNANO, Volume 7, No. 9, 8003-8010 .

Immobilized selenium comprising selenium and carbon is also disclosed herein. Immobilized selenium can have an elemental form of selenium or a selenium mixture form. Selenium can be doped with another element such as, but not limited to, sulfur. The immobilized selenium enables the location of elementary selenium atoms that function properly electrochemically without oscillating between a cathode and anode of a battery. Immobilizing selenium enables an elementary selenium atom to gain two electrons during a discharge process and to form a selenium anion at the point where the selenium molecule / atom is immobilized. The selenium anion can then donate two electrons during a charging process to form an elementary selenium atom. Immobilized selenium can thus work as an electrochemical active agent for a rechargeable battery that has a specific capacity that can go up to a stoichiometric level, a coulombic efficiency that can be ≥ 95%, ≥ 98% or up to 100% and can achieve significantly improved long-term cycling ability.

In a battery made with immobilized selenium, the electrochemical behaviors of elemental selenium atoms and selenide anions during charging are processes that are desirable to function properly. Carbon skeletons that have Sp ² carbon-carbon bonds have delocalized electrons that have aromatic π bonds via a conjugated six-membered ring local graph-like G-band networks bound by D-band carbon are shared. If there is an electrical potential, such delocalized electrons can flow over the carbon skeleton with little or no electrical resistance. Selenium immobilization can also compress the Sp ² carbon-carbon bonds of a carbon backbone, resulting in stronger carbon-carbon bonds, possibly leading to improved electronic conductivity within the carbon backbone network. At the same time, the selenium immobilization can also lead to the compression of selenium particles, which results in stronger chemical and physical selenium-selenium interactions, which possibly lead to improved electrical conductivity among immobilized selenium particles. When both carbon-carbon bonds and Se-Se bonds are improved due to selenium immobilization, carbon-selenium interactions are also improved by the compression in addition to the presence of a stabilized selenium portion to which the carbon backbone can bind. This portion of selenium can act as an interface layer for a carbon scaffold to successfully immobilize the stabilized selenium portion. Electrons can consequently flow in the carbon skeleton and the immobilized selenium, whereupon the electrochemical charge / discharge processes can function efficiently in a rechargeable battery. This in turn allows the rechargeable battery to maintain near stoichiometric specific capacity and have the ability to cycle at almost any practical rate with a low level of degradation in the electrochemical performance of the battery.

A carbon framework can be porous and can be doped with a different composition. The pore size distributions of the carbon skeleton can range from sub-Angstroms to a few micrometers or up to a pore size that a pore size distribution instrument using nitrogen, argon, CO ₂ or some other absorbent as the test molecule can characterize. The porosity of the carbon framework can comprise a pore size distribution that reaches a peak value in the range of at least one of the following: between sub-angstroms and 1000 angstroms or between one angstrom and 100 angstrom or between one angstrom and 50 angstrom or between one and 30 angstrom Angstrom and or between one angstrom and 20 angstrom. The porosity of the carbon skeleton can further comprise pores which have a pore size distribution with more than one peak in the regions described in the explanation above. Immobilized selenium can favor a carbon backbone that has small pore sizes in which electrons are rapidly delivered and recovered with minimal electrical resistance, which can allow selenium to function better electrochemically in a rechargeable battery. The small pore size can also provide more carbon framework surface, wherein the first portion of the selenium can form a first cut surface layer for a second portion of selenium immobilization. Additionally, the presence in a carbon backbone that has a certain proportion of medium-sized pores and a certain proportion of large-sized pores can also be beneficial for effective delivery of solvent lithium ions from bulk solvent media to an area with small pores where lithium ions can lose their coordinated solvent molecules and are transported in lithium selenide solid phase.

The pore volume of the carbon framework can be as low as 0.01 ml / g and as high as 5 ml / g or can be between 0.01 ml / g and 3 ml / g or can be between 0.03 ml / g and 2, 5 ml / g or can be between 0.05 ml / g and 2.0 ml / g. The pore volume, which has pore sizes smaller than 100 Å or smaller than 50 Å, or smaller than 30 Å or smaller than 20 Å, can be larger than 30% or larger than 40% or larger than 50% or larger than 60% or larger than 70% or greater than 80% of the total measurable pore volume that can be measured using a BET instrument with nitrogen, CO ₂ , argon and other test gas molecules. The surface of the carbon determined by BET can be greater than 400 m ² / g or greater than 500 m ² / g or greater than 600 m ² / g or greater than 700 m ² / g or greater than 800 m ² / g or greater than 900 m ² / g or greater than 1000 m ² / g.

The carbon can also be substantially amorphous or it can have a very broad peak feature centered on a d-spacing about 5 angstroms.

The carbon may comprise Sp ² carbon-carbon bonds that have Raman peak shifts with a D-band and a G-band. In one example, the Sp ² carbon-carbon bonds of the carbon have a D-band centered at 1364 + 100 cm ^-1 with a FWHM about 296 ± 50 cm ^-1 and a G-band center at 1589 ± 100 cm ^-1 with an FWHM of about 96 ± 50 cm ^-1 in the Raman spectrum. The ratio of the area of the D-band to that of the G-band can range from 0.01 to 100, or from 0.1 to 50, or from 0.2 to 20.

The carbon can have any desired morphology, namely platelets, spheres, fibers, needles, tubes, irregular, coherent, agglomerated, single or any solid particles. Platelet, fiber, Needle, tube, or a morphology that has a certain level of aspect ratio can be beneficial for achieving better contact between particles, resulting in better electrical conductivity, possibly improving the performance of the rechargeable battery.

The carbon can have any particle size, with an average particle size from a nanometer to a few millimeters or from a few nanometers to less than 1000 micrometers or from 20 nm to 100 micrometers.

The property of a carbon framework can affect selenium immobilization, and interactions between the carbon framework surface and the selenium particles can affect the performance of a rechargeable battery. The location of Sp ² carbon in a carbon skeleton can help achieve Se immobilization. Sp ² carbon from small carbon scaffold pores may be preferred, which can be quantified by the NLDFT surface method as discussed in Example 9 herein. The surface of carbon skeleton pores less than 20 angstroms may ≥ 500 m ² / g, ≥ 600 m ² / g, ≥ 700 m ² / g, ≥ 800 m ² / g, ≥ 900 m ² / g or ≥ 1,000 m ² / amount g . The surfaces of the carbon framework pores between 20 Angstroms and 1000 Angstroms can be 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, 2% or less, or 1% or less of the total surface area of the carbon framework turn off.

Immobilized selenium may include selenium that vaporizes at a temperature higher than that of elemental selenium, with reference to the following definition of selenium evaporation: Elemental selenium in a Se-Super-P composite loses 50% of its weight in one Temperature of 480 ° C, elemental selenium in an Se / graphite composite material loses 50% of its weight in contained selenium at a temperature of 471 ° C. Immobilized selenium loses 50% of its weight at a temperature higher than 480 ° C, for example at a temperature ≥ 490 ° C, ≥ 500 ° C, ≥ 510 ° C, ≥ 520 ° C, ≥ 530 ° C, ≥ 540 ° C , ≥ 550 ° C, ≥ 560 ° C, ≥ 570 ° C or ≥ 580 ° C or more. Selenium in the immobilized selenium can have a kinetic energy of ≥ 9.5 kJ / mol, ≥ 9.7 kJ / mol, ≥ 9.9 kJ / mol, ≥ 10.1 kJ / mol, ≥ 10.3 kJ / mol or ≥ 10.5 kJ / mol or more to overcome the connection and / or intermolecular forces in the immobilized selenium system and to escape to the gas phase. In one example, the last portion of the immobilized selenium that evaporates may require kinetic energy of ≥ 11.635 joules / mol (≥ 660 ° C) to escape the carbon backbone and may be critical for selenium immobilization and as an interface material between the Carbon skeleton and most of the immobilized selenium molecules work. This part of the element, which requires a kinetic energy of ≥ 11.635 Joule / mol, is called interface selenium. The amount of interfacial selenium in the immobilized selenium can be 1.5%, 2.0%, 5% or 3.0% of the total immobilized selenium.

Immobilized selenium may comprise selenium which has an activation energy higher than that for conventional (non-immobilized) selenium to overcome for the selenium to escape from the immobilized Se-C composite material system. The activation energy for non-immobilized selenium (Se-Super-P composite system) was determined to be about 92 kJ / mol according to the ASTM E1641-16 method. The activation energy for selenium in the immobilized selenium, which comprises selenium and carbon, is ≥ 95 kJ / mol, ≥ 98 kJ / mol, ≥ 101 kJ / mol, ≥ 104 kJ / mol, ≥107 kJ / mol or ≥ 110 kJ / mol. The activation energy for selenium in the immobilized selenium comprising selenium and carbon is ≥ 3%, ≥ 6%, ≥ 9%, ≥ 12%, ≥ 15% or ≥ 18% more than for selenium in the Se-Super-P -Composite material. The immobilized selenium may be more persistent than non-immobilized selenium, which is why the battery that includes immobilized selenium is better able to electrochemically cycle, probably due to the minimization (or elimination) of selenium shuttling between the cathode and anode, which as a result, selenium is immobilized in the Se-C composite material.

Immobilized selenium can include selenium that is Raman inactive or Raman active, typically having a Raman peak at 255 ± 25 cm ^-1 or at 255 ± 15 cm ^-1 or at 255 ± 10 cm ^-1 . Relative Raman peak strength is defined as the area of the Raman peaks at 255 cm ^-1 with respect to the area of the D-band peak of the carbon Raman spectrum. Immobilized carbon can comprise selenium, which has a relative Raman peak strength of ≥ 0.1%, ≥ 0.5%, ≥ 1%, ≥ 3%, ≥ 5%. Immobilized carbon can contain ≥ 5% selenium, ≥ 10% selenium, ≥ 20% selenium, ≥ 30% selenium, ≥ 40% selenium, ≥ 50% selenium, ≥ 60% selenium or ≥ 70% selenium.

Immobilized selenium can include selenium that is red-shifted from the Raman peak of pure selenium. A redshift is defined by a positive difference between the Raman peak position for the immobilized selenium and that for pure selenium. Pure selenium typically has a Raman peak at around 235 cm ^-1 . Immobilized selenium can include selenium, which is redshift of the Raman peak by ≥ 4 cm ^-1 , ≥ 6 cm ^-1 , ≥ 8 cm ^-1 ,> 10 cm ^-1 , ≥ 12 cm ^-1 , ≥ 14 cm ^-1 or ≥ 16 cm ^-1 . A redshift of the Raman peak suggests that there is compression on the selenium particles.

Immobilized selenium can include carbon, which can be under compression. Under compression, electrons can flow with minimal resistance, which facilitates rapid electron delivery to selenium and from selenium anions for electrochemical processes during discharge-charge processes for a rechargeable battery. D-band and / or G-band in the Raman spectrum for the Sp ² carbon-carbon bonds of the carbon skeleton, which comprise the immobilized selenium, can have a redshift of ≥ 1 cm ^-1 , ≥ 2 cm ^-1 , ≥ 3 cm ^-1 , ≥ 4 cm ^-1 or ≥ 5 cm ^-1 .

Immobilized selenium includes selenium, which may have a higher shock frequency than non-immobilized selenium. Such a high shock frequency can result from the fact that selenium is under compression in the immobilized Se-C system. The collision frequency for selenium in unimmobilized selenium was determined to be 2.27 × 10 ⁵ according to the ASTM E1641-16 method. The collision frequency for selenium in the immobilized selenium comprising selenium and carbon is ≥ 2.5 × 10 ⁵ , ≥ 3.0 × 10 ⁵ , ≥ 3.5 × 10 ⁵ , ≥ 4.0 × 10 ⁵ , ≥ 4 , 5 × 10 ⁵ , ≥ 5.0 × 10 ⁵ , ≥ 5.5 × 10 ⁵ , ≥ 6.0 × 10 ⁵ or ≥ 8.0 × 10 ⁵ . The immobilized selenium can have a shock frequency ≥ 10%, ≥ 30%, ≥ 50%, ≥ 80%, ≥ 100%, ≥ 130%, ≥ 150%, ≥ 180% or ≥ 200% higher than that for non-immobilized selenium in the Se-C composite material. This can lead to better electron conductivity in the immobilized selenium system due to more collisions among selenium species. The immobilized selenium in Se-C composite would also have a higher impact frequency against the wall of the carbon host (e.g. a carbon framework), which can result in better electron delivery or electron yield from the carbon framework during electrochemical cycling, resulting in a battery (the immobilized selenium) which has improved cycling performances such as achieving more cycles or cycling at a much higher C-rate, which is highly desirable.

Immobilized selenium includes selenium, which has less of a tendency to leave its host material (carbon) as it has a kinetic rate constant that is ≤ 1: 5, ≤ 1:10, ≤ 1:50, ≤ 1: 100, ≤ 1 : 500 or ≤ 1: 1000 of the kinetic rate constant for non-immobilized / conventional selenium. In our example, the immobilized selenium comprises selenium, which tends less to leave its host material (carbon) because (at 50 ° C) it has a kinetic rate constant of ≤ 1 × 10 ^-10 , ≤ 5 × 10 ^-11 , ≤ 1 × 10 ^-11 , ≤ 5 × 10 ^-12 or ≤ 5 × 10 ^-13 .

Immobilized selenium can include selenium, which can be amorphous as determined by x-ray diffraction measurements. A diffraction peak that has ad spacing of about 5.2 Angstroms is relatively smaller or weaker, for example 10% weaker, 20% weaker, 30% weaker, or 40% weaker than that for the carbon framework.

Immobilized selenium can be prepared by physically mixing carbon and selenium, followed by melting and homogenizing (or mixing or blending) selenium molecules to achieve selenium immobilization. Physical mixing can be achieved by ball milling (dry or wet), mortar and pestle (dry or wet) mixing, jet milling, horizontal milling, attritor milling, high shear mixing in slurry, conventional slurry mixing with a blade, etc. The physically mixed mixture of selenium and carbon can be heated to a temperature that is at or above the melting point of selenium and lower than the melting point of carbon. The heating can be carried out in an inert gas environment such as, but not limited to, argon, helium, nitrogen, etc. The heating environment can include air or a reactive environment. Immobilization of selenium can be achieved by impregnating dissolved selenium in carbon, followed by evaporation of the solvent. The solvent for dissolving selenium may include an alcohol, an ether, an ester, a ketone, a hydrocarbon, a halogenated hydrocarbon, a nitrogen-containing composite, a phosphorus-containing composite, a sulfur-containing composite, water, and so on.

Immobilized selenium can be achieved by melting a large amount of selenium in the presence of carbon followed by removal of excess, non-immobilized selenium.

An immobilized selenium system or an immobilized selenium mass can comprise immobilized selenium with 30%, 40%, 50%, 60%, 70%, 80% or 90% of the total amount of selenium in the system or the mass. The non-immobilized selenium can evaporate at a temperature lower than that of the immobilized selenium.

An immobilized selenium system or an immobilized selenium mass can comprise immobilized selenium which is doped with one or more additional / other elements of group 6 of the table of the periodic table, such as sulfur and / or tellurium. The dopant level can range from as low as 100 ppm by weight to as high as 85% of the weight of the immobilized selenium system or mass of selenium.

An exemplary process for making immobilized selenium is in 6th illustrated. During the process, selenium and carbon are mixed together under dry or wet conditions (S1). The mixture can optionally be dried to a powder (S2), followed by optional pelletizing of the dried powder ( S3 ). The results of the step S1 and optionally the steps S2 and S3 result in a carbon framework that is a starting material for step S4 is. At step S4 Selenium is melted into the carbon structure. It is the selenium that is melted into the carbon backbone being allowed to dry, thereby immobilizing the selenium of the step S5 is produced. The preparation and characterization of the immobilized selenium are described below in connection with Example 10.

The immobilized selenium can be used as a cathode material for a rechargeable battery. To make a cathode, the immobilized selenium can be dispersed in a liquid medium, such as, but not limited to, water or organic solvent. The cathode comprising the immobilized selenium may comprise a binder, optionally another binder, optionally an electrical conductivity enhancer, and a current charge collector. The binder can be organic or organic. An organic binder can consist of a natural product such as CMC or a synthetic product such as an SBR rubber latex. An electrical conductivity promoter can be a type of carbon, such as small particles derived from graphite, graphene, carbon nanotubes, carbon nanosheet, carbon black, etc. An electrical charge collector can, for example, be an aluminum foil, a copper foil, a carbon foil, a carbon fabric or other metallic foils his. The cathode can be by coating an immobilized selenium containing slurry (or slurries) on the charge collector, followed by a typical drying process (air drying, oven drying, vacuum oven drying, etc.). The immobilized selenium slurry or slurries can be prepared by a high-shear mixer, a conventional mixer, a planetary mixer, a double planetary mixer, a ball mill, a vertical attritor, a horizontal mill, and so on. The cathode, which comprises immobilized selenium, can be pressed or roll milled (or calendered) prior to use in a battery assembly.

A rechargeable battery that includes immobilized selenium may include a cathode that includes immobilized selenium, an anode, a separator, and an electrolyte. The anode can comprise lithium, sodium, silicon, graphite, magnesium, tin and / or a desirable element and / or a desirable element or a combination of elements from Group IA, Group IIA, Group IIIA, etc. of the table of the periodic table. The separator can comprise an organic separator, an inorganic separator or a solid electrolyte separator. An organic separator can comprise a polymer such as polyethylene, polypropylene, polyester, a halogenated polymer, a polyether, a polyketone, etc. An inorganic separator can comprise a glass or quartz fiber, a solid electrolyte separator. An electrolyte may include a lithium salt, a sodium salt or other salt, a Group IA salt of the Periodic Table, a Group IIA salt of the Periodic Table, and an organic solvent. The organic solvent can comprise an organic carbonate mixture, an ether, an alcohol, an ester, a hydrocarbon, a halogenated hydrocarbon, a lithium-containing solvent and so on.

A rechargeable battery comprising immobilized selenium can be used for electronics, an electric or hybrid vehicle, an industrial application, a military application such as a drone, an aerospace application, a marine application, and so on.

A rechargeable battery comprising immobilized selenium can have a specific capacity of 400 mAh / g active amount of selenium or higher, 450 mAh / g or higher, 500 mAh / g or higher, 550 mAh / g or higher, or 600 mAh / g or higher exhibit. A rechargeable battery comprising immobilized selenium may be able to be subjected to electrochemical cycling for 50 cycles or more, 75 cycles or more, 100 cycles or more, 200 cycles or more, and so on.

A rechargeable battery comprising immobilized selenium may be capable of charging 0.1C, 0.2C, 0.5C, 1C, 1.5C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, 9C, 10C or to be loaded faster. After performing extensive charge-discharge cycling at high C-rate for 30 or more cycles (e.g., 5th Cycles at 0.1C, 5 cycles at 0.2C, 5 cycles at 0.5C, 5 cycles at 1C, 5 cycles at 2C, 5 cycles at 5C and 5 cycles at 10C), a rechargeable battery that includes immobilized selenium can , a specific battery capacity>30%,>40%,>50%,>60%,>70%,> 80% of the 2nd specific discharge capacity at a cycling rate of 0.1C.

Several examples follow below to illustrate the spirit of the inventions. However, these examples should not be construed in a limiting sense.

EXAMPLES

Characterization method

Scanning electron microscopy (SEM) images were collected on a Tescan Vega scanning electron microscope equipped with an Energy Dispersive Analysis X-ray detector (EDX detector).

Raman spectra were collected with a Renishaw-in-Via (confocal) Raman microscope. Laser Raman spectroscopy is widely used as a standard for characterizing carbon and diamond, and provides readily distinguishable signatures of each of the various forms (allotropes) of carbon (e.g. diamond, graphite, buckyballs, etc.). Combined with photoluminescence (PL) technology, it offers a non-destructive way of examining various properties of a diamond, including phase purity, crystal size and orientation, defect level and structure, impurity type and concentration, and stress and strain. In particular, the width (full-width-half-maximum, FWHM) of the Raman diamond peak at 1332 cm ^-1 , as well as the Raman strength ratio between diamond peak and graphitic peaks (D-band at 1350 cm ^-1 and G-band at 1600 cm ^-1 ), is a direct indicator of diamond quality or the quality of other carbon materials. Furthermore, stress and strain levels in diamond or other carbon grains and foils can be estimated from the Raman diamond peak shift. It has been reported that the Raman diamond peak displacement rate under hydrostatic stress is about 3.2 cm ^-1 / GPa, with a peak shift to a lower wavenumber under tensile stress and a higher wavenumber under compressive stress. The Raman spectra discussed herein were collected using a Renishaw-in-Via Raman spectroscope with an excitation laser at 514 nm. More information on the use of Raman spectroscopy to characterize diamond is also in the references (1) AM Zaitsev, Optical Properties of Diamond, 2001, Springer and (2) S. Prawer, RJ Nemanich, Phil. Trans. R. Soc. Lond. A (2004) 362, 2537-2565 , available.

The data for BET surface and pore size distributions of carbon samples were measured by nitrogen absorption and CO ₂ absorption with a 3Flex (Mircomeritics) equipped with a Smart-VacPrep for sample degassing preparations. The sample is typically degassed in Smart-Vac-Prep at 250 ° C. for 2 hours under vacuum before the CO ₂ and N ₂ absorption measurements. The nitrogen absorption is used to determine the BET surface area. Nitrogen absorption data and CO ₂ absorption data were combined to calculate pore size distributions of a carbon sample. For details on combining both N ₂ and CO ₂ absorption data to determine pore size distributions for carbon materials, see "Dual Gas Analysis of Microporous Carbon Using 2D-NLDFT Heterogeneous Surface Model and Combined Adsorption Data of N ₂ and CO ₂ ", Jacek Jagiello, Conchi Ania, Jose B. Parra and Cameron Cook, Carbon 91, 2015, pages 330 to 337 , draw.

The data for thermogravimetric analysis (TGA) and dynamic differential calorimetry (DSC) for samples from immobilized selenium and the control samples were measured with the Netzsch Thermal Analyzer. The TGA analysis was performed under an argon flow rate of -200 ml / min., A heating rate of 16 ° C / min., 10 ° C / min., 5 ° C / min., 2 ° C / min., 1 ° C / Min. and other heating rates. In terms of consistency, a typical amount of immobilized selenium sample for TGA analysis was about 20 mg.

Activation energy and impact frequency of the immobilized selenium and non-immobilized selenium were determined by TGA following the procedures outlined in the procedure ASTM E1641-16 are described.

X-ray diffraction results for different carbon, Se-carbon samples and immobilized selenium were collected on a Philip diffractometer.

Battery cycling performances for rechargeable batteries comprising immobilized selenium were tested on a Lanhe CT2001A Battery Cycling Tester. Charge and discharge currents of the rechargeable batteries including immobilized selenium were determined by an amount of selenium contained in the immobilized selenium and a cycling rate (0.1C, 0.5C, 1C, 2C, 3C, 4C, 5C, 10C, etc. .) certainly.

Example 9: Synthesis and characterization of a carbon skeleton

To form an initial residue, a batch of 260 grams of potassium citrate was placed in a crucible and the crucible was placed in a quartz tube inside a tube furnace. A stream of argon gas was admitted into the furnace and the furnace was started at 5 ° C / min. heated from room temperature (~ 20 to 22 ° C) to 600 ° C. The furnace was held at this temperature for 60 minutes with a shutdown of the furnace and removal of the batch from the crucible after the furnace had cooled to yield 174.10 grams of processed residue. To form the second and third processed residues, the same process as that described for the first residue was repeated separately for batches of 420 and 974 grams of potassium citrate. The resulting second and third processed residues weighed 282.83 grams and 651.93 grams, respectively.

1108.9 grams from these three processed residues were combined in a crucible that was placed in the quartz tube inside the tube furnace and a flow of argon gas was admitted into the furnace. The oven was running at 5 ° C / min. heated to 800 ° C. The oven was held at 800 ° C for 1 hour. The furnace was allowed to cool, after which the crucible was removed from the quartz tube, and then 1085.74 grams of an initial final residue was recovered.

Then, following the same procedure as in this example (800 ° C), a batch of 120 grams of potassium residue introduced into the oven yielded about 77 grams of a second final residue (800 ° C).

The combination of the first and second final residues resulted in approximately 1163 grams of a third final residue.

The 1163 grams of the third final residue was then mixed with 400 ml of water to form a slurry which was roughly evenly separated into four two liter beakers. The pH of each slurry was determined to be greater than 13 by measurement. Thereafter, a concentrated hydrochloric acid solution was added to each beaker with a violent evolution of carbon dioxide, which precipitated with a pH less than about 5. More hydrochloric acid solution was added to maintain a pH of about 1.9. These slurries were then filtered and washed into filter cakes which were dried in an oven at 120 ° C for about 12 hours, followed by vacuum drying at 120 ° C for 24 hours, resulting in four carbon skeleton samples totaling about 61.07 grams.

These carbon framework samples were characterized using SEM, XRD, Raman, BET / pore size distributions. The SEM result for a carbon framework is in 7th shown. Surface morphologies of typical carbon backbone particles prepared in the process described in this example had sheet-like morphology associated with their sheet edges, with sample thicknesses between 500 nm and 100 nm, and the sample width (or length) between 0.5 and 2 µm, consequently with an aspect ratio (defined as the ratio of the longest dimension of the sample width (or layer length) to the sample thickness ≥ 1, for example with an aspect ratio ≥ 5 or larger or an aspect ratio ≥ 10.

X-ray diffraction pattern of a carbon framework shown in 8th show that the carbon backbone is essentially in the amorphous phase. However, this shows a broad diffraction peak centered about 20 from about 17 °, indicating a d-spacing of about 5.21 Angstroms.

Raman scattering spectroscopic results for a carbon framework are shown in 9 showing Sp ² carbon showing a D-band at about 1365 cm ^-1 (curve 1) and G-band at about 1589 cm ^-1 (curve 2) with an FWHM of 296 and 96 cm ^-1, respectively having. Both the D-band and the G-band show a mixture of Gaussian and Lorenz distributions; the D-band has about 33% Gaussian distributions and the G-band has about 61% Gaussian distributions. The ratio of the area for the D-band to the area for the G-band is about 3.5.

The BET surface area of the carbon framework was measured to be 1,205 m2 / g by nitrogen absorption. The incremental pore surface area compared to the pore size is in 10A using the NLDFT method and shows a cumulative pore surface area (Cumulative Pore Surface Area) of 1,515 m ² / g. The discrepancy between the BET surface area and the NLDFT surface area may arise from the fact that NLDFT distributions are calculated using both nitrogen and CO ₂ absorption data; CO ₂ molecules can penetrate into the pores, which are smaller than the pores into which nitrogen molecules can penetrate. The NLDFT surface area in the pores, peaking at 3.48 angstroms, is 443 m ² / g, is 859 m ² / g at 5.33 angstroms, and is 185 at 11.86 angstroms (up to 20 angstroms) m ² / g, a total of 1,502 m ² / g for the pores at 20 Angstroms or smaller, while the NLDFT surface area of the pores between 20 Angstroms and 1000 Angstroms is only 7.5 m ² / g, and the surface area of the pores to 20 Angstroms or greater is only about 0.5% of the total surface.

The pore size distributions of the carbon skeleton sample were determined by nitrogen absorption and CO ₂ absorption. The absorption results of nitrogen absorption and CO ₂ absorption were combined to obtain the pore size distribution shown in 10B is shown to generate. The relationship between Incremental Pore Volume (ml / g) versus pore size (Angstroms) shows that there are three large peaks located at 3.66 Angstroms, 5.33 Angstroms and 11.86 Angstroms; the relationship of Cumulative Pore Volume (ml / g) versus pore width (Angstroms) shows that there are about 0.080 ml / g pores below the peak of 3.66 Angstroms, about 0.240 ml / g pores below the Peak of 5.33 angstroms, about 0.108 ml / g pores below the peak of 11.86 angstroms, with 0.43 ml / g pores of 20 angstroms or smaller, 0.042 ml / g pores between 20 and 100 angstroms and a sum of 0.572 ml / g pores up to 1000 angstroms.

Example 10: Preparation and characterization of immobilized selenium

Place 0.1206 grams of selenium (with bulk properties of selenium) in an agate mortar and pestle set, and add 0.1206 grams of the carbon scaffold prepared in accordance with Example 9 to the same agate mortar and mortar pod. Grind the mixture of selenium and carbon skeleton by hand for about 30 minutes and transfer the milled mixture of selenium and carbon skeleton into a stainless steel die (10 mm diameter). Press the mixture into the die at a pressure of about 10 MPa to form a pellet of the mixture. Then load the pellet into a sealed container in the presence of an inert environment (argon) and place the sealed container containing the pellet in an oven. Heat the furnace containing the sealed container containing the pellet to 240 ° C (above the melting temperature of selenium) for, for example, 12 hours. However, any combination of time and temperature above the melting temperature of selenium is contemplated that is sufficient to cause selenium and carbon to react, either partially or completely, and to form immobilized selenium which has some or all of the characteristics present in it Application are described, has. The pellet is then removed from the container after allowing the pellet to cool to room temperature. The removed pellet is the immobilized selenium of this Example 10.

The immobilized selenium of this example 10 was characterized by TGA-DSC and TGA. The TGA-DSC analysis results were for the immobilized selenium under an argon gas flow of 200 ml / min. at a heating rate of 10 ° C / min. collected. There is no noticeable endothermic DSC peak at temperatures near the melting point of selenium (about 230 ° C) indicating that the immobilized selenium of this Example 10 is different from the bulk form of selenium molecules / atoms which have a melting point of about 230 ° C at which an endothermic peak should occur.

Research has shown that the TGA-DSC data may not be reliable if the heating temperature reaches a point where selenium molecules begin to leak out of the TGA-DSC sample crucible (graphite or ceramics). To this end, selenium molecules (from the sample crucible) enter the argon carrier gas stream in gas phase and appear to react with the TGA-DSC platinum sample holder, distorting actual TGA-DSC thermochemical behaviors. Since the released selenium molecules from the sample crucible react with the platinum sample holder, this leads to less weight loss in this temperature range. The selenium-platinum composite material in the platinum sample holder is then released in the gas phase when the heating temperature reaches a point that is above 800 ° C. Complete selenium release can occur at 1000 ° C. This investigation consumed the majority of the immobilized selenium sample of this Example 10. Thus, a new sample of the immobilized selenium (~ 16 grams) was prepared using the same process as described above in the initial part of this Example 10.

The thermodynamic behaviors of this new sample of immobilized selenium were investigated by TGA analysis which uses a ceramic sample holder that covers a very small thermocouple that is used for TGA analysis. The TGA analysis results for this new sample of immobilized selenium are in 11A together with the TGA analysis results ( 11B) for selenium-carbon composites (made from 50-50 Se-Super-P-Carbon composite and Se-graphite (ground graphite) shown in the same process as the preparation of the immobilized selenium of this Example 10. Super P is a commercially available carbon black which is widely used for the lithium-ion battery industry. The ground graphite was prepared by grinding Poco 2020 graphite. The TGA analysis data is also summarized in Table 2 below. Table 2 Se-graphite composite. Se-Super-P composite. Immobilized Se in Example 10 Mean weight loss temperature Temperature down at head weight loss Final temperature of the TGA-Expt. Mean weight loss temperature, ° C 471 480 595 660 1000 Mean weight loss temperature, K 744 753 868 933 1273 Kinetic energy, joules / mol 9,278 9,391 10,825 11,635 15,876

Immobilized selenium can have an initial weight loss temperature starting at about 400 ° C, compared to 340 ° C for Se-Super-P carbon composite and the Se-graphite-carbon composite; a midpoint weight loss temperature for immobilized selenium may be about 595 °, compared to 480 ° C for the Se-Super-P-carbon composite and 471 ° C for the Se-graphite composite; and a major weight loss complete at 544 ° C for the Se-super-P-carbon composite and Se-graphite composite, and at 660 ° C for the immobilized selenium. The Se-Super-P-Carbon composite and the Se-graphite composite show less than 0.6% weight loss between 560 ° C and 780 ° C, while the immobilized selenium shows a weight loss of about 2.5% from below Shows major weight loss (-660 ° C to 1000 ° C). These results suggest that non-immobilized selenium (Se-Super-P-Carbon composite material and Se-graphite composite material) comprises ≤ 1.2% of the total selenium that can escape from the composite material at a temperature of ≥ 560 ° Celsius , while the immobilized selenium comprises about 5.0% of the total selenium that can escape from the carbon structure at a temperature of ≥ 660 ° C. The following details are provided to give examples that provide insight into the thermodynamic behaviors. However, these details should not be construed in a limiting sense.

Using the TGA midpoint weight loss temperature data as examples of thermochemical behaviors as the heating temperature increases, the kinetic energy of the selenium molecules in the Se-super-P-carbon composite and the Se-graphite composite increases to a level at which these selenium molecules have enough energy to overcome the intermolecular interactions among selenium molecules and to escape from the liquid phase of selenium. Here kinetic energy = 3RT / 2, where: R is the gas constant and T is the temperature in Kelvin.

It was observed that the average kinetic energy of selenium molecules for Se-Super-P-Carbon composite was measured as 9,391 Joules / mol when the selenium molecules escape from the Se-Super-P-Carbon composite mixture. However, the immobilized selenium has to gain more energy in order to have an average kinetic energy of about 10,825 joules / mol for selenium to leave the carbon structure to form gas-phase selenium molecules. It is believed that the selenium in immobilized selenium can chemically interact with selenium and the carbon backbone beyond intermolecular interactions of selenium in either an atomic form, or a molecular form, or any form. In addition, the last portion of selenium that escapes from the carbon structure between 660 ° C. and 1000 ° C. has an average kinetic energy in the range of 11,635 joules / mol to 15,876 joules / mol or more. This suggests that selenium in the immobilized selenium is more stable than the selenium in conventional selenium-carbon composites. The stabilized selenium in the immobilized selenium this Example 10 enhances the ability of selenium to remain within the carbon framework either as atomic forms, molecular forms, or in any form during electrochemical processes, such as during the charge and discharge cycling of a rechargeable battery comprised of immobilized selenium. In one example, this last portion of selenium may require kinetic energy ≥ 11,635 joules / mol (≥ 660 ° C) to escape the carbon backbone and can be critical for selenium immobilization and as an interface material between the carbon backbone and most of the immobilized Selenium molecules work. The proportion of interfacial selenium in the immobilized selenium can be 1.5%, 2.0%, 2.5% or 3.0% of the total immobilized selenium.

11A Also shows the TGA studies immobilized selenium at a heating rate of 16 ° C / min., with a temperature of 628 ° C for the midpoint weight loss of contained selenium. As in 11C shown, the temperature at the midpoint weight loss is the contained Se at a heating rate of 16 ° C / min. for Se-Super-P-Carbon composite material 495 ° C. With different heating rates (for example 16 ° C / min., 10 ° C / min., 5 ° C / min., 2.5 ° C / min. And 1 ° C / min.) The activation energy and impact frequency can be determined and using known methods such as ASTM E1641-16 and E2958-14. The temperatures at 15% weight loss for different heating rates are shown in tabular form in Table 3 below. Table 3 β (° C / min.) Temperature (° C) Immobilized Se prepared by the process of Example 10 (228-110) Immobilized Se prepared by the process of Example 10 (155-82-2) Se-Super-P composite. 16 590.65 570.13 471.08 10 560.82 544.86 456.61 5 535.57 515.09 413.37 2.5 506.66 493.27 397.21 1 478.48 462.18 365.02 Activation energy, kJ / mo 1 120.7 120.0 92.3 2.27 x 10 ⁵ Shock frequency 12.4 x 10 ⁵ 18.3 × 10 ⁵

The activation energy for selenium (non-immobilized or conventional) in the Se-Super-P-Carbon composite was determined to be 92.3 kJ / mol with an impact frequency of 2.27 × 10 ⁵ . The activation energy for selenium in immobilized selenium (228 to 110 above) was also determined to be 120.7 kJ / mol with a collision frequency of 12.4 × 10 ⁵ . In another example of immobilized selenium (155-82-2 above), which was prepared using the same procedures as Example 10, an activation energy of 120.0 kJ / mol and an impact frequency of 18.3 × 10 ^{5 were also} determined by measurement.

wobei k die Geschwindigkeitskonstante ist, E_a die Aktivierungsenergie ist, A die Stoßfrequenz ist, R die Gaskonstante ist, und T die Temperatur in Kelvin ist.The kinetic rate constant for selenium is calculated using the Arrhenius equation, $$k=\mathrm{A.}{e}^{-{\mathrm{E.}}_a\text{/}\mathrm{R.}T}$$

where k is the rate constant, E _{a is} the activation energy, A is the impact frequency, R is the gas constant, and T is the temperature in Kelvin.

With reference to 11D With the activation energy and impact frequency determined above, the kinetic rate constant was calculated using the Arrhenius equation at different temperatures. 11D shows that non-immobilized selenium (Se-Super-P composite - solid line) has a much higher rate constant than that for immobilized selenium (228-110 (dotted line) and 115-82-2 (dashed line)) used for the Example is four orders of magnitude larger at 35 ° C, and about three orders of magnitude larger at 100 ° C. In one example, at 50 ° C the rate constant for non-immobilized selenium (Super P) is 2.668 × 10 ^-10 , while immobilized selenium has a rate constant of 7.26 × 10 ^-14 (155-82-2) and 3.78 × 10 ^-14 (228- 110). Selenium, which has a lower kinetic rate constant, has less of a tendency to leave the host material (carbon), resulting in better battery cycling performance.

12 14 shows the spectrum of immobilized selenium with Raman peaks of the D band at 1368 cm ^-1 and the G band at 1596 cm ^-1 , with a ratio of the area for the D band to the area for the G band of FIG ,8th. Compared to the Raman spectrum of the carbon backbone shown in 9 , shown, selenium immobilization shifts both Raman peaks to a higher wavenumber, about 3 cm ^-1 redshift for the D band and 7 cm ^-1 redshift for the G band, suggesting that the binding strength of Sp ² -Carbon is reinforced in the carbon frame, with a redshift of about 4 cm ^-1 for the D-band and a redshift of about 8 cm ^-1 for the G-band. At the same time, the ratio of the area for the D-band to the area for the G-band also decreased from about 3.4 to 2.8, which suggests that either the D-band is relatively weaker or that the G-band is relatively stronger becomes. A stronger G-band may be desirable because the G-band may be related to a type of carbon that allows the carbon backbone to conduct electrons more easily, which may be desirable for electrochemical performance when used in a rechargeable battery. Bulk or pure selenium typically shows a sharp Raman shift peak at around 235 cm ^-1 . For immobilized selenium, the Raman spectrum in 12 a broad Raman peak at about 257 cm ^-1 (~ 12.7% of the G-band in area) and a new broad hump at about 500 cm ^-1 (about 3.0% of the G-band area). Selenium immobilization is believed to change the Raman characteristics for both the carbon skeleton and selenium, with all Raman peaks shifted to a higher wavenumber, suggesting that both the carbon-carbon Sp ² -Bonds for the carbon skeleton and the selenium-selenium bonds of selenium are under compression.

The compression that results from selenium immobilization strengthens both the carbon-carbon Sp ² bonds for the carbon backbone and the Se-Se bonds for selenium, creating stronger selenium-selenium and carbon-selenium interactions. It would therefore require more kinetic energy for selenium to overcome the stronger Se-Se bond and stronger carbon-selenium interactions, which is what the observations in the TGA analysis of the immobilized selenium compared to Se-Super-P composite and Se-graphite -Composite explained.

Furthermore, the carbon framework under compression would then have a better ability to conduct electrons at the bond level; and under compression, selenium atoms or molecules would also have better ability to conduct electrons.

Stabilized selenium for the immobilized selenium, together with improved electron conductivity via the carbon skeleton and selenium can be desirable in electrochemical processes, such as, for example, improved specific capacity for the active material with a minimum level of pendulum, improved cyclability due to immobilization, a capability with a higher level Rate of being charged and discharged, etc. However, this should not be construed in a limiting sense.

X-ray diffraction patterns for the immobilized selenium prepared in accordance with Example 10 presented in 13 show a decrease in the strength of the broad diffraction peak from the carbon backbone with ad spacing to about 5.21 Angstroms, only about 1/3 the strength, suggesting that immobilized selenium also renders the carbon backbone more disordered or more damaging the order of the carbon framework. One example assumes that this is due to the compressive forces being applied to the carbon-carbon Sp ² bonds.

14th FIG. 13 shows a SEM image for the immobilized selenium prepared in accordance with Example 10 showing layer-like morphologies, same as the image in FIG 7th for the carbon frame. Although there is about 50% selenium immobilized in the carbon backbone, there are no observable selenium particles on the surfaces of the carbon backbone, except that the compounds within the layer have been destroyed, resulting in many flat layers that have high aspect ratios . These layer-like morphologies can be highly desirable for forming aligned coatings that are aligned along the flat layer directions, creating layer surface to layer surface contacts, resulting in improved electrical conductivity within the layer, which can result in higher electrical performance for electrochemical processes, like a rechargeable battery.

Example 11: Preparation of the Se cathode

56 mg of the immobilized selenium prepared in accordance with Example 10; 7.04 mg Super-P; 182 µl carboxymethyl cellulose solution (CMC solution) (which contains 1 mg dry CMC for every 52 µl CMC solution); 21.126 µl SBR latex dispersion (which contains 1 mg dry SBR latex for each 6.036 µl SBR latex dispersion); and put 200 µl of deionized water in a mortar with a pestle stick. Hand grind the particles, binder, and water into a slurry for 30 minutes to create a cathode slurry. The cathode slurry was then applied to one side of a piece of electrically conductive substrate, for example a foil, and air dried. In one example, the conductive substrate or foil can be aluminum foil (Al foil). However, this is not to be interpreted in a limiting sense as the use of any convenient and / or desirable electrically conductive material of any shape or form is contemplated. For the purpose of description only, the use of an Al foil to form a selenium cathode is described herein. However, this should not be interpreted in a limiting sense.

The slurry-coated Al foil was then placed in a drying oven and heated to a temperature of 55 ° C. for 12 hours, resulting in a selenium cathode consisting of a dried layer of immobilized selenium on one side of the Al foil where the Al foil on the other side was uncoated, i.e. bare aluminum.

The selenium cathode was then punched into cathode disks, each 10 mm in diameter. Some of these cathode disks have been used as cathodes for rechargeable batteries.

Example 12: Li-Se rechargeable battery assembly and testing

The cathode disks of Example 11 were used to power spiral-wound Li-Se rechargeable batteries in the manner discussed in the example described next and in FIG 15th is shown joining. In this example, a cathode disk 4 from Example 11 with a diameter of 10 mm was placed on a base 2 of a button battery made of stainless steel 2032, which is used as the positive case of the button cell (“positive case” in 15th ) functions with the layer 5 of immobilized selenium facing up, away from the base 2 of the positive housing, and with the bare Al side facing and in contact with the base of the positive housing. Then, a battery separator 6 (19 mm in diameter and 25 micrometers thick) was placed on top of the cathode disk 4 in contact with the layer 5 of immobilized selenium. In one example, the battery separator 6 may be an organic separator or an inorganic separator or a solid electrolyte separator. An organic separator can be a polymer such as polyethylene, polypropylene, polyester, a halogenated polymer, a polyether, a polyketone, etc. The inorganic separator can be made of glass and / or quartz fiber.

Then 240 μl of electrolyte 7, the LiPF ₆ (1M) in ethylene carbonate (EC) and dimethyl carbonate (DMC) solution (50 parts by weight each) were included; inserted into the positive housing 2, followed by placing a lithium foil disk 8 (15.6 mm in diameter and 250 micrometers thick) on a side of the separator 6 opposite to the cathode disk 4. Then, a stainless steel (SS) spacer 10 was placed on one side of the lithium foil disk 8, opposite the separator 6, followed by placing one or more foam disks 12 made of, for example, nickel on one side of the SS spacer 10 the lithium foil disk 8 are made opposite. The lithium foil 8, the SS spacer 10 and / or the foam disk 12 can act as an anode. Finally, a housing 14, made from 2032 stainless steel 14, was designed to function as the negative side of the button cell (the "negative housing" in 15th ) on one side of the nickel foam disc (s) 12, opposite the SS spacer 10 and the collar of the positive housing 2. The positive housing 2 and negative housing 14 were then sealed together under high pressure, for example 1000 psi. Sealing the positive and negative housings (2, 14) under high pressure also caused compression of the stack which (from bottom to top in 15th ) comprises the cathode disk 4, the separator 6, the lithium foil 8, the SS spacer 10 and the Ni foam disk (s) 12. More than a dozen coin cell batteries have been assembled using the battery separators described above and fiberglass separators. The assembled coin cell batteries were then tested under the following conditions.

Some of the assembled coin cell batteries were tested at charge-discharge rates of 0.1C and 1C using a Lanhe CT2001A battery tester. Each coin cell battery has been tested: (1) resting for 1 hour; (2) discharge to 1V; (3) rest for 10 minutes; (4) charge to 3V; (5) rest for 10 minutes; Repeat steps (2) through (5) to repeat the cycling test.

16A (left) shows the cycling test results (313 cycles with a charge-discharge rate of 0.1C) for a button cell made in accordance with Example 12 using the cathode prepared in accordance with Example 11, which demonstrates excellent cycling stability , with a specific capacity of 633.7 mAh / g after 313 cycles, which corresponds to a remaining of 93.4% of the initial specific capacity. The first specific discharge capacity was higher than the stoichiometric value, possibly due to some side reactions on the cathode and anode surfaces. From the second cycle, the specific capacity initially decreased with cycling; however, the specific capacity increased slightly from about 30 cycles to about 120 cycles before becoming stable at about 180 cycles and then decreasing. 16B (right) also shows excellent cycling stability (100 cycles at 0.1C and then 500 cycles at 1C) for another button cell that has a specific capacity of 462.5 mAh / g at the 600th cycle, giving a remaining 66, 0% of the capacity of the 2nd cycle at 0.1C or a remaining 80.3% of the capacity of the 105th cycle at 1C. The Coulomb efficiency can be ≥ 95%, ≥ 98% or even 100%, which suggests that no discernible amount of selenium oscillated between the cathode and anode. It is believed that this electromechanical performance is the result of the immobilized selenium in the cathode, which prevents the selenium from being dissolved and shuttling from the cathode 14 to the anode 2.

17th shows cycling test results at different discharge-charge cycling rates (between 0.1C and 10C) for a button cell which was assembled with a polymer separator as described in Example 12. The test protocols were similar to the tests described above, except for the cycling rates (0.1C, 0.2C, 0.5C, 1C, 2C, 5C, and 10C); five charge and discharge cycles were performed for each C-rate; then the cycling rate was reset to 0.1C cycle. At the 0.1C rate, the battery exhibited a specific capacity around the stoichiometric value. In addition, the battery exhibited good cycling durability for cycling rates of 0.2C, 0.5C, IC, and 2C. The battery also exhibited fast charging - and discharge capacity, cycled 56% of the stoichiometric capacity at the 10C rate, although it showed a decreasing specific capacity during cycling. In other words, at the 10C rate, it took the battery 3.3 minutes to charge and discharge to / from a capacity of 56% of stoichiometric value. A conventional battery would not be expected to survive such a rapid cycling rate.

The Li-Se battery comprising immobilized selenium; can regain its specific capacity to 670 mAh / g, 98% of its full capacity, when cycled at a 0.1C rate at the start of the test. It is believed that (1) the stabilization of selenium in the immobilized selenium cathode prevents selenium from exiting the carbon framework, prevents the selenium from shuttling between the cathode and anode during cycling, which enables the battery to improve To exhibit cycling performance; (2) Sp ² carbon-carbon bonds as well as carbon skeleton, selenium-selenium bonds and carbon-selenium interactions can be under compression, which may result in higher electrical conductivity within the carbon skeleton, within the selenium particles and under the carbon and selenium cut surfaces, which can aid in achieving the observed cycling performance at high C-rates.

• (a) eine kinetische Energie, die erforderlich ist, damit ein Selenteilchen dem immobilisierten Selen entkommt, kann ≥ 9,5 kJ/mol ≥ 9,7 kJ/mol ≥ 9,9 kJ/mol ≥ 10,1 kJ/mol ≥ 10,3 kJ/mol oder ≥ 10,5 kJ/mol betragen;
• (b) eine Temperatur, die erforderlich ist, damit ein Selenteilchen dem immobilisierten Selen entkommen kann, kann ≥ 490 °C, ≥ 500 °C, ≥ 510°C, ≥ 520 °C, ≥ 530 °C, ≥ 540 °C, ≥ 550 °C oder ≥ 560 °C betragen;
• (c) das Carbon kann eine Oberfläche (für Poren kleiner als 20 Angström) von ≥ 500 m²/g, ≥ 600 m²/g, ≥ 700m²/g, ≥ 800 m²/g, ≥ 900 m²/g oder ≥ 1.000 m²/g betragen;
• (d) das Carbon kann eine Oberfläche (für Poren zwischen 20 Ångström und 1000 Angström) von ≤ 20 %, ≤ 15 %, ≤ 10 %, ≤ 5 %, ≤ 3 %, ≤ 2 %, ≤ 1 % der gesamten Oberfläche aufweisen;
• (e) das Carbon und/oder das Selen kann unter Kompression stehen. Vorteile des immobilisierten Selens, bei dem das Carbon und/oder das Selen unter Kompression stehen, gegenüber einem Carbon-Selen-System, bei dem das Carbon und/oder das Selen nicht unter Kompression stehen, können aufweisen: verbesserten Elektronenfluss, reduzierten Widerstand gegen Elektronenfluss oder beides, was die Elektronenlieferung zu Selen und von den Selen-Anionen während des Ladens und Entladens einer wiederaufladbaren Batterie, die eine Kathode aufweist, die aus dem immobilisierten Selen besteht, erleichtern kann;
• (f) das immobilisierte Selen kann Selen umfassen, das eine Aktivierungsenergie aufweist, die höher ist als die für herkömmliches (nicht immobilisiertes) Selen, damit das Selen aus dem immobilisierten Se-C-Verbundmaterialsystem entweicht. Bei einem Beispiel wurde die Aktivierungsenergie für nicht-immobilisiertes Selen (Se-Super-P-Verbundmaterialsystem) als 92 kJ/mol gemäß dem Verfahren ASTM E1641-16 bestimmt. Dagegen kann die Aktivierungsenergie für Selen in dem immobilisierten Selen, das Selen und Carbon umfasst, ≥ 95 kJ/mol, ≥ 98 kJ/mol, ≥ 101 kJ/mol, ≥ 104 kJ/mol, ≥107 kJ/mol oder ≥ 110 kJ/mol betragen. Bei einem anderen Beispiel kann die Aktivierungsenergie für Selen in dem immobilisierten Selen, das Selen und Carbon umfasst, ≥ 3 %, ≥ 6 %, ≥ 9 %, ≥ 12 %, ≥ 15 % oder ≥ 18 % > größer sein als für Selen in dem Se-Super-P-Verbundmaterial;
• (g) das immobilisierte Selen kann Selen umfassen, das eine höhere Stoßfrequenz aufweist als nicht immobilisiertes Selen. Bei einem Beispiel wurde die Stoßfrequenz für nicht immobilisiertes Selen gemäß dem Verfahren ATSM E1641-16 als 2,27×10⁵ bestimmt. Dagegen kann bei einem anderen Beispiel die Stoßfrequenz für Selen in immobilisiertem Selen, das Selen und Carbon umfasst, ≥ 2,5×10⁵, ≥ 3,0×10⁵, ≥ 3,5×10⁵, ≥ 4,0×10⁵, ≥ 4,5×10⁵, ≥ 5,0×10⁵, ≥ 5,5×10⁵, ≥ 6,0×10⁵ oder ≥ 8,0×10⁵ betragen. Das immobilisierte Selen kann eine Stoßfrequenz ≥ 10 %, ≥ 30 %, ≥ 50 %, ≥ 80 %, ≥ 100 %, ≥ 130 %, ≥ 150 %, ≥ 180 % oder ≥ 200 % als die für nicht immobilisiertes Selen in einem Se-C-Verbundmaterial aufweisen; und
• (h) das immobilisierte Selen kann Selen, das eine kinetische Geschwindigkeitskonstante umfasst, die ≤ 1:5, ≤ 1:10, ≤ 1:50, ≤ 1:100, ≤ 1:500 oder ≤ 1:1000 der Geschwindigkeitskonstante für nicht-immobilisiertes/herkömmliches Selen beträgt, umfassen. Bei einem Beispiel kann das immobilisierte Selen Selen umfassen, das eine Geschwindigkeitskonstante (bei 50 °C) von ≤ 1×10^-10, ≤ 5×10^-11, ≤ 1×10^-11, ≤ 5×10^-12 oder ≤ 5×10^-13 aufweist.

The mass of immobilized selenium comprising selenium and carbon that is prepared in accordance with the concepts described herein may include one or more of the following features:

• (a) a kinetic energy that is necessary for a selenium particle to escape the immobilized selenium can be ≥ 9.5 kJ / mol ≥ 9.7 kJ / mol ≥ 9.9 kJ / mol ≥ 10.1 kJ / mol ≥ 10 , 3 kJ / mol or ≥ 10.5 kJ / mol;
• (b) a temperature required for a selenium particle to escape the immobilized selenium can be ≥ 490 ° C, ≥ 500 ° C, ≥ 510 ° C, ≥ 520 ° C, ≥ 530 ° C, ≥ 540 ° C, Be ≥ 550 ° C or ≥ 560 ° C;
• (c) the carbon can have a surface (for pores less than 20 angstroms) ² / g of ≥ 500 m, ≥ 600 m ² / g, ≥ 700 m ² / g, ≥ 800 m ² / g, ≥ 900 m ² / g or ≥ 1,000 m ² / g;
• (d) the carbon can have a surface area (for pores between 20 Angstroms and 1000 Angstroms) of ≤ 20%, ≤ 15%, ≤ 10%, ≤ 5%, ≤ 3%, ≤ 2%, ≤ 1% of the total surface ;
• (e) the carbon and / or the selenium can be under compression. Advantages of the immobilized selenium, in which the carbon and / or the selenium are under compression, compared to a carbon-selenium system, in which the carbon and / or the selenium are not under compression, can have: improved electron flow, reduced resistance to electron flow, or both, which may facilitate electron delivery to selenium and from the selenium anions during charging and discharging of a rechargeable battery having a cathode comprised of the immobilized selenium;
• (f) the immobilized selenium may comprise selenium which has an activation energy higher than that for conventional (non-immobilized) selenium in order for the selenium to escape from the immobilized Se-C composite material system. In one example, the activation energy for non-immobilized selenium (Se-Super-P composite system) was determined to be 92 kJ / mol according to method ASTM E1641-16. In contrast, the activation energy for selenium in the immobilized selenium comprising selenium and carbon can be 95 kJ / mol, 98 kJ / mol, J 101 kJ / mol, 104 kJ / mol, 107 kJ / mol or oder 110 kJ / mol. In another example, the activation energy for selenium in the immobilized selenium comprising selenium and carbon can be ≥ 3%, ≥ 6%, ≥ 9%, ≥ 12%, ≥ 15% or ≥ 18%> greater than for selenium in FIG the Se-Super-P composite material;
• (g) the immobilized selenium may comprise selenium which has a higher collision frequency than non-immobilized selenium. In one example, the shock frequency for non-immobilized selenium was determined to be 2.27 × 10 ⁵ according to the ATSM E1641-16 method. On the other hand, in another example, the collision frequency for selenium in immobilized selenium including selenium and carbon can be ≥ 2.5 × 10 ⁵ , ≥ 3.0 × 10 ⁵ , ≥ 3.5 × 10 ⁵ , ≥ 4.0 × 10 ⁵ , ≥ 4.5 × 10 ⁵ , ≥ 5.0 × 10 ⁵ , ≥ 5.5 × 10 ⁵ , ≥ 6.0 × 10 ⁵ or ≥ 8.0 × 10 ⁵ . The immobilized selenium can have a shock frequency ≥ 10%, ≥ 30%, ≥ 50%, ≥ 80%, ≥ 100%, ≥ 130%, ≥ 150%, ≥ 180% or ≥ 200% than that for non-immobilized selenium in a Se -C composite material; and
• (h) the immobilized selenium can be selenium which comprises a kinetic rate constant that is ≤ 1: 5, ≤ 1:10, ≤ 1:50, ≤ 1: 100, ≤ 1: 500 or ≤ 1: 1000 of the rate constant for non- immobilized / conventional selenium. In one example, the immobilized selenium may comprise selenium which has a rate constant (at 50 ° C.) of 1 × 10 ^-10 , 5 × 10 ^-11 , 1 × 10 ^-11 , 5 × 10 ^-12 or 5 × 10 ^-13 .

With the carbon and / or selenium of the immobilized selenium under compression, the D-band and / or the G-band of the Raman spectrum for the Sp ² -CC bonds of the carbon (or carbon skeleton, which is defined by the carbon) of the immobilized selenium demonstrate a (positive) red shift, for example by ≥ 1 cm ^-1 , ≥ 2 cm ^-1 , ≥ 3 cm ^-1 , ≥ 4 cm ^-1 or ≥ 5 cm ^-1 from a carbon starting material.

With the carbon and / or selenium of the immobilized selenium under compression, the selenium can exhibit a (positive) red shift from the Raman peak of pure selenium (235 cm ^-1 ), for example by ≥ 4 cm ^-1 , ≥ 6 cm ^-1 , ≥ 8 cm ^-1 , ≥ 10 cm ^-1 , ≥ 12 cm ^-1 , ≥ 14 cm ^-1 or ≥ 16 cm ^-1 , whereby the redshift may suggest compression on the selenium particles.

The immobilized selenium can be an elemental form of selenium and / or a selenium mixture.

The immobilized selenium, which comprises selenium and carbon, can also be doped with one or more additional elements from group 6 of the table of the periodic table (referred to below as “additional G6 element (s)”), including for example and without limitation sulfur and / or tellurium. The dopant level can range from as low as 100 ppm by weight to as high as 85% of the total weight of the immobilized selenium. In one example, the immobilized selenium can comprise 15% to 70% carbon and 30% to 85% selenium and optionally additional G6 element (s). In one example, the immobilized selenium can comprise a mixture of (1) 15% to 70% carbon and (2) 30% to 85% selenium + (a) an additional / additional G6 element (s). In the mixture comprising selenium + an additional G6 element (s), the additional G6 element (s) can constitute between 0.1% and 99% of the mixture and selenium can constitute between 1% and Make up 99.9% of the mixture. However, these areas of selenium + additional / additional G6 element (s) must not be interpreted in a restrictive sense.

The immobilized selenium can contain ≥ 5% selenium, ≥ 10% selenium, ≥ 20% selenium, ≥ 30% selenium, ≥ 40% selenium, ≥ 50% selenium, ≥ 60% selenium, or ≥ 70% or a higher percentage of selenium .

The immobilized selenium may optionally include another element such as sulfur, tellurium, etc.

The immobilized selenium can be Raman-inactive or Raman-active. If it is Raman-active, the immobilized selenium can have a relative Raman peak strength at 255 + 25 cm ^-1 , at 255 + 15 cm ^-1 or at 255 + 10 cm ^-1 .

The immobilized selenium can comprise selenium which has a relative Raman peak strength of 0.1%, 0.5%, 1%, 3% or 5%, here being the relative Raman peak strength is defined as the area of the Raman peak at 255 cm ^-1 with respect to the area of the D-band peak of the carbon Raman spectrum.

The carbon comprising the immobilized selenium can be used as a carbon skeleton for selenium immobilization. The carbon backbone can have Sp ² carbon-carbon bonds with a Raman D-band at 1365 ± 100 cm ^-1 and G-band at 1589 ± 100 cm ^-1 ; a D-band at 1365 + 70 cm ^-1 and a G-band at 1589 + 70 cm ^-1 , a D-band at 1365 + 50 cm ^-1 and a G-band at 1589 ± 50 cm ^-1 , a D -Band at 1365 ± 30 cm ^-1 and a G-Band at 1589 ± 30 cm ^-1 , or a D-Band at 1365 ± 20 cm ^-1 and a G-Band at 1589 ± 20 cm ^-1 .

The carbon of the immobilized selenium may include Sp ² carbon-carbon bonds that have Raman peaks that include a D-band and a G-band. A ratio of the area of the D-band to the G-band can range from 0.01 to 100, from 0.1 to 50, or from 0.2 to 20.

The carbon of the immobilized selenium may include Sp ² carbon-carbon bonds that have Raman peaks that include a D-band and a G-band. Each of the D-band and the G-band may have a shift to a higher wavenumber ≥ 1 cm ^-1 , ≥ 2 cm ^-1, or more.

The carbon of the immobilized selenium can be doped with one or more other elements of the table of the periodic table.

The carbon of the immobilized selenium can be porous. The pore size distribution of the carbon framework can be between one Angstrom and a few micrometers. The pore size distribution may have at least one peak located between one Angstrom and 1000 Angstrom, between one Angstrom and 100 Angstrom, between one Angstrom and 50 Angstrom, between one Angstrom and 30 Angstrom or between one Angstrom and 20 Angstrom. The porosity of the carbon framework can have pore size distributions with more than one peak in the above ranges.

The carbon of the immobilized selenium can have a pore volume between 0.01 ml / g and 5 ml / g; between 0.01 ml / g and 3 ml / g; between 0.03 ml / g and 2.5 ml / g; or between 0.05 ml / g and 2.0 ml / g.

The carbon of the immobilized selenium can have a pore volume (which has a pore size <100 Angstroms, <50 Angstroms, <30 Angstroms or <20 Angstroms) which is> 30%,> 40%,> 50%,> 60%,> 70 % or> 80% of the total measurable pore volume.

The carbon of the immobilized selenium can have a surface area> 400 m ² / g,> 500 m ² / g,> 600 m ² / g,> 700 m ² / g,> 800 m ² / g,> 900 m ² / g or > 1000 m ² / g.

The carbon of the immobilized selenium can be amorphous and can have a broad peak centered at a d-spacing about 5.2 angstroms.

The carbon of the immobilized selenium can have any desired morphology, namely platelets, spheres, fibers, needles, tubes, irregular, contiguous, agglomerated, single or any solid particles. Platelet, fiber, needle, tube, or a morphology that has a certain aspect ratio may be beneficial for achieving better contact between particles, resulting in improved electrical conductivity (versus immobilized selenium made from a different aspect ratio), which for an electrochemical cell, such as a rechargeable battery, can be inexpensive.

The carbon of the immobilized selenium can have any particle size, with an average particle size between 1 and 9 nanometers and 2 millimeters, between 1 and 9 nanometers to <1000 micrometers or between 20 nanometers and 100 micrometers.

The selenium of the immobilized selenium can be amorphous, as determined, for example, by X-ray diffraction. The diffraction peak of the selenium of the immobilized selenium that ad-spaced around 5.2 Angstroms may have, can be weaker than the diffraction peak for the carbon framework, for example 10% weaker, 20% weaker, 30% weaker or 40% weaker.

• (a) physisches Mischen von Carbon und Selen. Das physische Mischen kann durch (trockenes oder nasses) Kugelmühlenmahlen, (trockenes oder nasses) Mischen mit Mörser und Mörserkeule, Strahlmühlenmahlen, horizontales Mahlen, Attritionsmahlen, Mischen mit hoher Scherwirkung in Slurries, herkömmliches Slurry-Mischen mit einer Klinge usw. erfolgen.
• (b) das physisch gemischte Carbon und Selen des Schritts (a) können bis zu der Schmelztemperatur des Selens oder darüber erhitzt werden. Das Erhitzen des Gemischs aus Carbon und Selen kann bei Anwesenheit einer Inertgasumgebung erfolgen, wie, ohne darauf beschränkt zu sein, Argon, Helium, Stickstoff usw. oder in einer Luft- oder reaktiven Umgebung.
• (c) optional Homogenisieren oder Vermengen des erhitzten Carbons und Selens, um Selen-Immobilisation zu erzielen.
• (d) Abkühlen des immobilisierten Selens des Schritts (c) auf Umgebungs- oder Raumtemperatur.

In one example, the method for preparing the immobilized selenium can include:

• (a) physically mixing carbon and selenium. The physical mixing can be done by ball milling (dry or wet), mortar and pestle (dry or wet) mixing, jet milling, horizontal milling, attrition milling, high shear mixing in slurries, conventional slurry mixing with a blade, etc.
• (b) The physically mixed carbon and selenium of step (a) can be heated to or above the melting temperature of the selenium. The heating of the mixture of carbon and selenium can be in the presence of an inert gas environment, such as, but not limited to, argon, helium, nitrogen, etc., or in an air or reactive environment.
• (c) optionally homogenizing or blending the heated carbon and selenium to achieve selenium immobilization.
• (d) cooling the immobilized selenium of step (c) to ambient or room temperature.

In another example, the immobilized selenium can be prepared by dissolving selenium on carbon followed by evaporation. The solvent for dissolving selenium may be an alcohol, an ether, an ester, a ketone, a hydrocarbon, a halogenated hydrocarbon, a nitrogen-containing composite material, a phosphorus-containing composite material, a sulfur-containing composite material, water, and so on.

In another example, the immobilized selenium can be prepared by melting selenium on carbon followed by removing extra or excess unimmobilized selenium.

• (a) Vermischen von Selen und Carbon unter trockenen oder nassen Bedingungen;
• (b) optional Trocknen des Gemischs des Schritts (a) bei einer hohen Temperatur;
• (c) optional Pelletieren des getrockneten Gemischs des Schritts (b);
• (d) Schmelzen des Selens in das Carbon, um das immobilisierte Selen zu erzeugen.

In one example, the method of making the immobilized selenium can include:

• (a) mixing selenium and carbon under dry or wet conditions;
• (b) optionally drying the mixture of step (a) at a high temperature;
• (c) optionally pelletizing the dried mixture of step (b);
• (d) melting the selenium into the carbon to produce the immobilized selenium.

Immobilized selenium can be used as a cathode material for a rechargeable battery. The cathode can contain an inorganic or an organic binder. The inorganic binder can consist of a natural product, such as, for example, CMC, or of a synthetic product, for example, an SBR rubber latex. The cathode may include an optional promoter of electrical conductivity, such as particles derived from graphite, graphene, carbon nanotubes, carbon nanosheets, carbon blacks, etc. Finally, the cathode may include a charge collector, such as aluminum foil, copper foil, carbon foil, carbon cloth or other metallic foil.

The method of making the cathode may involve coating an immobilized selenium-containing slurry on the charge collector, followed by drying the slurry that has been applied to the charge collector (e.g., air drying, oven drying, vacuum oven drying, etc.). The immobilized selenium can be dispersed in the slurry, which can be prepared by a high-shear mixer, a conventional mixer, a planetary mixer, a double planetary mixer, a ball mill, a vertical attritor, a horizontal mill, and so on. The slurry can be applied to the charge collector followed by drying in air or in vacuum. The coated cathode can then be pressed or roll milled (or calendered) prior to use in a rechargeable battery.

A rechargeable battery can be manufactured by using the immobilized selenium described herein. The rechargeable battery may include a cathode comprising the immobilized selenium, an anode, and a separator that separates the anode and the cathode. The anode, the cathode and the separator can be immersed in an electrolyte such as LiPF ₆ . The anode can be made of lithium, sodium, silicon, graphite, magnesium, tin, etc.

The separator can consist of an organic separator, an inorganic separator or a solid electrolyte separator. The organic separator can comprise a polymer, such as Polyethylene, polypropylene, polyester, a halogenated polymer, a polyether, a polyketone, etc. The inorganic separator may comprise a glass or quartz fiber or a solid electrolyte separator.

The electrolyte can comprise a lithium salt, a sodium salt or another salt from Group IA, IIA and IIIA in an organic solvent. The organic solvent can consist of an organic carbonate mixture, an ether, an alcohol, an ester, a hydrocarbon, a halogenated hydrocarbon, a lithium-containing solvent, etc.

The rechargeable battery can be used for electronics, an electric or hybrid vehicle, an industrial application, a military application such as a drone, an aerospace application, a marine application, and so on.

The rechargeable battery can have an electrochemical capacity of ≥ 400 mAh / g of active amount of selenium, ≥ 450 mAh / g of active amount of selenium, ≥ 500 mAh / g of active amount of selenium, ≥ 550 mAh / g of active amount of selenium or ≥ 600 mAh / g of active amount of selenium.

The rechargeable battery can experience electrochemical cycling for ≥ 50 cycles, ≥ 75 cycles, ≥ 100 cycles, ≥ 200 cycles, and so on.

The rechargeable battery can be charged and / or discharged at 0.1C, 0.2C, 0.5C, 1C, 1.5C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, 9C, 10C or faster.

The rechargeable battery can have a specific capacity of the battery> 30%,> 40%,> 50%,> 60%,> 70% or> 80% of the 2nd specific discharge capacity at a cycling rate of 0.1C after charging Discharge cycling at a high C rate (for example 5 cycles at 0.1C, 5 cycles at 0.2C, 5 cycles at 0.5C, 5 cycles with IC, 5 cycles at 2C, 5 cycles at 5C and 5 cycles with 10C).

The rechargeable battery can have a Coulomb efficiency of 50%, 60%, 70%, 80% or 90% or even about 100%.

Wobei η_c die coulombsche Effizienz (%) istThe coulomb efficiency of a battery is defined as follows: $${\eta }_c=\frac{Q_{Out}}{Q_{in}}$$

Where η _{c is} the Coulomb efficiency (%)

Q _{out is} the amount of charge leaked from the battery during a discharge cycle.

Q _{in is} the amount of charge that enters the battery during a charge cycle.

The rechargeable battery can be charged at a C rate of 0.1C, 0.2C, 0.5C, 1C, 1.5C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, 9C, 10C or faster. A C-rate is a measure of the rate at which a battery is discharged from its maximum capacity. For example, a rate of 1C means that the discharge current will discharge the entire battery in 1 hour. For a battery with a capacity of 100 Ah, for example, this corresponds to a discharge current of 100 A. A rate 5C for the same battery would be 500A, and a rate 0.5C would be 50 A.

The cathode of the rechargeable battery can comprise one or more elements of a chalcogen group, such as selenium, sulfur, tellurium and oxygen.

The anode of the rechargeable battery may include at least one of alkali metal, alkaline earth metals, and Group IIIA metals.

The separator of the rechargeable battery may comprise an organic separator or an inorganic separator.

The electrolyte of the rechargeable battery may include at least one of alkali metals, alkaline earth metals, and Group IIIA metals; and a solvent of the electrolyte may comprise an organic solvent based on carbon, ether or ester.

The rechargeable battery can have a specific capacity of ≥ 400 mAh / g, ≥ 450 mAh / g, ≥ 500 mAh / g, ≥ 550 mAh / g or ≥ 600 mAh / g.

The rechargeable battery can experience electrochemical cycling for ≥ 50 cycles, ≥ 75 cycles, ≥ 100 cycles, ≥ 200 cycles, and so on.

The rechargeable battery can have a specific capacity of the battery> 30%,> 40%,> 50%,> 60%,> 70% or> 80% of the 2nd specific discharge capacity at a cycling rate of 0.1C after charging High C-rate discharge cycling (5 cycles at 0.1C, 5 cycles at 0.2C, 5 cycles at 0.5C, 5 cycles at 1C, 5 cycles at 2C, 5 cycles at 5C and 5 cycles at 10C) exhibit.

The rechargeable battery can have a Coulomb efficiency of ≥ 50%, ≥ 60%, ≥ 70%, ≥ 80% or ≥ 90%.

A composite material comprising selenium and carbon is disclosed herein, wherein the composite material can have a platelet morphology with an aspect ratio of 1 1, 2, 5, 10 or 20.

The selenium of the immobilized selenium can be amorphous, for example as determined by X-ray diffraction. The diffraction peak of the selenium of the immobilized selenium, which can have ad-spacing around 5.2 angstroms, can be weaker than that for a carbon framework, for example 10% weaker, 20% weaker, 30% weaker or 40% weaker than the carbon frame.

• (a) physisches Mischen von Carbon und Selen. Das physische Mischen kann durch (trockenes oder nasses) Kugelmühlenmahlen, (trockenes oder nasses) Mischen mit Mörser und Mörserkeule, Strahlmühlenmahlen, horizontales Mahlen, Attritionsmahlen, Mischen mit hoher Scherwirkung in Slurries, herkömmliches Slurry-Mischen mit einer Klinge usw. erfolgen;
• (b) das physisch vermischte Carbon und Selen des Schritts (a) können auf die Schmelztemperatur von Selen oder höher erhitzt werden, und das Erhitzen kann in Anwesenheit einer Inertgasumgebung auftreten, wie zum Beispiel Argon, Helium, Stickstoff usw., oder in einer Luft- oder reaktiven Umgebung; und
• (c) das erhitzte Carbon und Selen des Schritts (b) können als eine Unterstützung des Erzielens von Selen-Immobilisation homogenisiert oder vermengt werden.

In one example, the method for preparing the composite material may include:

• (a) physically mixing carbon and selenium. The physical mixing can be done by ball mill (dry or wet) milling, mortar and pestle (dry or wet) mixing, jet milling, horizontal milling, attrition milling, high shear mixing in slurries, conventional slurry mixing with a blade, etc .;
• (b) the physically mixed carbon and selenium of step (a) can be heated to the melting temperature of selenium or higher, and the heating can occur in the presence of an inert gas environment such as argon, helium, nitrogen, etc., or in air - or reactive environment; and
• (c) The heated carbon and selenium of step (b) can be homogenized or blended as an aid in achieving selenium immobilization.

In another example, the composite material can be prepared by dissolving selenium on carbon followed by evaporation. The solvent for dissolving selenium may include an alcohol, an ether, an ester, a ketone, a hydrocarbon, a halogenated hydrocarbon, a nitrogen-containing composite, a phosphorus-containing composite, a sulfur-containing composite, water, and so on.

The composite material can be prepared by melting the selenium on (or in) the carbon, followed by removal of extra or excess non-immobilized selenium.

• (a) Vermischen von Selen und Carbon unter trockenen oder nassen Bedingungen;
• (b) optional Trocknen des Gemischs des Schritts (a) bei einer hohen Temperatur;
• (c) optional Pelletieren des getrockneten Gemischs des Schritts (b);
• (d) Schmelzen des Selens in das Carbon, um das immobilisierte Selen zu erzeugen.

In one example, a method for preparing the composite material may include:

• (a) mixing selenium and carbon under dry or wet conditions;
• (b) optionally drying the mixture of step (a) at a high temperature;
• (c) optionally pelletizing the dried mixture of step (b);
• (d) melting the selenium into the carbon to produce the immobilized selenium.

The composite material can be used as a cathode material for a cathode of a rechargeable battery. The cathode can contain an inorganic or an organic binder. The inorganic binder can be a natural product such as CMC, or a synthetic product such as SBR rubber latex. The cathode may include an optional promoter of electrical conductivity, such as small particles derived from graphite, graphene, carbon nanotubes, Carbon nanosheets, carbon blacks, etc. Finally, the cathode can include a current charge collector, such as an aluminum foil, a copper foil, a carbon foil, a carbon fabric or other metallic foil.

The method of making the cathode may include coating an immobilized selenium-containing slurry on the charge collector followed by drying the slurry that has been applied to the charge collector (e.g., air drying, oven drying, vacuum oven drying, etc.). The immobilized selenium can be dispersed in the slurry, which can be prepared by a high-shear mixer, a conventional mixer, a planetary mixer, a double planetary mixer, a ball mill, a vertical attritor, a horizontal mill, and so on. The slurry can be applied to the charge collector followed by drying in room air or in a vacuum. The coated cathode can then be pressed or roll milled (or calendered) prior to use in a rechargeable battery.

A rechargeable battery can be manufactured by using the composite material described above. The rechargeable battery can be charged at 0.1C, 0.2C, 0.5C, 1C, 1.5C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, 9C, 10C or faster.

Example 13: Preparation of the immobilized selenium doped with sulfur, electrode and batteries thereof

In accordance with the concepts and procedures described in Example 10, 5 atomic% (at%) selenium, 20 at% selenium, 35 at% selenium, and 50 at% selenium were immobilized separately by sulfur in the synthesis of the sulfur doped selenium, which is set out in detail in Table 4 below. Samples of the sulfur-doped immobilized selenium were synthesized with the carbon backbone prepared in accordance with the concepts and procedures described in Example 9. Table 4 Sample ID Se, at% S, at% Se, wt% S, wt% Se95S5 95 5 97.9 2.1 Se80S20 80 20th 90.8 9.2 Se65S35 65 35 82.1 17.9 Se50S50 50 50 71.1 28.9

The immobilized sulfur-doped selenium samples thus prepared were then used to prepare a number of cathodes 4 comprising immobilized sulfur-doped selenium according to the concepts and procedures described in Example 11 for the immobilized selenium.

The cathodes so prepared, comprising immobilized sulfur-doped selenium, were then used in this example to prepare button cell batteries in accordance with the concepts and procedures described in Example 12.

The assembled coin cell batteries in this example were then tested in the battery tester described in Example 12 following the same test protocols described in Example 12 at 0.1C and 1C charge and discharge cycling rates.

The electrochemical cycling results at 0.1C for button cell batteries containing a cathode composed of the selenium cathode of immobilized sulfur-doped selenium made with an immobilized sulfur-doped selenium sample (Se50S50 in Table 4) are in 18th shown with a 2nd cycle discharge capacity of 821 mAh / g (which is considered good), and a consistent coulombic efficiency ≥ 95%, typically ≥ 98% (which is also considered good) or even 100%.

If selenium is assumed to have a stoichiometric specific capacity of 675 mAh / g at the 0.1C cycling rate, the sulfur specific capacity would be assumed to be around 1,178 mAh / g (which is considered good for sulfur). The Coulomb efficiency of ≥ 95%, ≥ 98% or even 100% indicates that there is no discernible amount of sulfur oscillating between the cathode and anode. Sulfur species in the battery with immobilized sulfur-doped selenium work in one Electrolyte that includes carbonate is good. Typically, sulfur is not expected to work well in a Li-S battery that has carbonate as an electrolyte; a conventional Li-S battery typically uses an electrolyte based on ether. Carbonate-based electrolyte is typically used in current lithium-ion batteries. Carbonate-based electrolyte is more economical and much more readily available on the market than ether-based electrolyte.

The electrochemical cycling results at the 1C cycling rate for button cell batteries containing a cathode composed of the selenium cathode of immobilized sulfur-doped selenium made with an immobilized sulfur-doped selenium sample (Se50S50 in Table 4) are in 19th shown with a discharge capacity of the 2nd cycle of 724 mAh / g and a consistent coulombic efficiency ≥ 95%, typically ≥ 98% or even 100%.

If selenium is assumed to have a specific capacity of 625 mAh / g at the 1C cycling rate, the sulfur specific capacity would be assumed to be around 966 mAh / g (which is also unexpected). Sulfur is an insulator and has a very low electrical conductivity. Typically, a Li-S battery cannot cycle well at a fast cycling rate, such as a 1C rate.

As can be seen, when immobilized sulfur-doped selenium is used as a cathode material in a rechargeable battery, it overcomes two fundamental problems associated with Li-S batteries, namely pendulum effect and low cycling rate. When these two problems are solved, a battery including a cathode made of immobilized sulfur-doped selenium can have high energy density and high power density in real applications.

As can be seen in one example, an immobilized sulfur-doped selenium system or mass can be formed by the process which comprises: (a) mixing selenium, carbon and sulfur to form a selenium-carbon-sulfur mixture; (b) heating the mixture of step (a) to a temperature above the melting temperature of selenium; and (c) causing the heated mixture of step (b) to cool to ambient or room temperature, thereby forming the mass of immobilized sulfur-doped selenium.

The bulk of the immobilized sulfur-doped selenium of step (c) can comprise selenium and sulfur in a carbon backbone.

Step (a) can be done under a dry or a wet condition.

Step (b) can involve homogenizing or blending the mixture.

Step (a) can include forming the selenium-carbon-sulfur mixture in a bulk. Step (b) can include heating the mass to a temperature above the melting temperature of selenium. Step (c) may include causing the mass or allowing the mass to cool to ambient or room temperature.

Step (b) may involve heating the mixture for a time sufficient for the selenium and carbon and sulfur to fully or partially react.

In another example, a method for preparing a system or mass of immobilized sulfur-doped selenium may include: (a) forming a carbon scaffold; and (b) melting selenium and sulfur into the carbon skeleton.

In another example, a method of forming a system or mass of immobilized sulfur-doped selenium may include: (a) mixing selenium and carbon and sulfur; and (b), following step (a), causing selenium and sulfur to dissolve on the carbon, thereby forming the system or mass of immobilized sulfur-doped selenium.

A solvent for dissolving the selenium and sulfur can be an alcohol, an ether, an ester, a ketone, a hydrocarbon, a halogenated hydrocarbon, a nitrogen-containing composite material, a phosphorus-containing composite material, a sulfur-containing composite material, or water. The solvent can be added to one or more of the selenium, sulfur or carbon before step (a), during step (a) or during step (b).

The method may further include (c) removing excess non-immobilized selenium, non-immobilized sulfur, or both from the system or bulk of immobilized sulfur-doped selenium.

There is also disclosed a rechargeable battery comprising: a cathode comprised of immobilized sulfur-doped selenium deposited on an electrically conductive substrate; a separator disposed in direct contact with the electrically conductive substrate and in contact with the immobilized sulfur-doped selenium, and an anode spaced from the cathode by the separator.

The rechargeable battery may further include the anode that is spaced from the separator by lithium. In one example, the lithium can be in the form of a lithium foil.

The rechargeable battery may further include the cathode, the separator, the anode, and the lithium immersed in an electrolyte.

In the rechargeable battery, the immobilized sulfur-doped selenium may comprise a selenium-carbon-sulfur mixture, the selenium and the sulfur having been melted into the carbon skeleton.

In the rechargeable battery, the separator can be formed from an organic material, an inorganic material, or a solid electrolyte.

The rechargeable battery can have a Coulomb efficiency of ≥ 95%.

Discussion of the immobilized chalcogen

Immobilized chalcogen (system or both) includes chalcogen and a carbon framework. The immobilization of the chalcogen can involve the pairing of the electron donor and electron acceptor of a free electron pair. The amount of chalcogen in the immobilized chalcogen can be 1% by weight, 5% by weight, 10% by weight, 15% by weight or% by weight. The lower end of the chalcogen weight percentage may be more desirable for a light chalcogen element such as oxygen or sulfur. Chalcogen, which includes oxygen, sulfur, selenium and / or tellurium, can behave as an electron donor and donate a free electron pair to an electron acceptor. Chalcogen can be in elemental form or in a mixture form, such as a chalcogenide or polychalcogenide. Chalcogen, which has a lone pair of electrons, a formal negative or partially negative charge (δ ^- ), behaves as a nucleophile. A chemical species, like a molecule or ion, that donates a pair of electrons to form a new covalent bond is called a nucleophile, which means “nucleus-loving” in Greek. A carbon framework can behave like an electron acceptor. A carbon backbone that includes a carbon cation center can act as an acceptor for electrons donated by chalcogen. A carbon backbone that includes centers that can accept electrons behaves as an electrophile. A molecule or ion that donates electrons to form a new covalent bond is called an electrophile, which means “electron-loving” in Greek.

Immobilized chalcogen can present many advantages, namely: (1) the C = C bond can be strengthened with a carbon plane for improved electron conduction; (2) the d-spacing of the carbon framework can dwindle, which can result in improved electron conduction between the carbon planes; (3) Chalcogen in the immobilized chalcogen has a higher activation energy, suggesting that there are strong chemical interactions between the chalcogen and the carbon skeleton, so that chalcogen is strongly anchored by donating a lone pair of electrons to the carbon skeleton, the lone pair of electrons of the chalcogen can be part of the π-bonding system, which is responsible for electron conduction, which is why electron flows between chalcogen and carbon are largely improved, which fundamentally removes the limitation of chalcogen in its electrical conductivity, especially for a light chalcogen such as oxygen, sulfur and selenium ; (4) Chalcogen immobilization can prevent a polychalcogenide ion from forming, which has an electrochemical process in one step during the battery charge-discharge process, no shuttling of a chalcogenide ion between anode and cathode, which eliminates the dangers of cathode material, such as carbon, is oxidized by a polychalcogenide ion; (5) immobilized chalcogen can have a higher collision frequency, which can improve the electron flows between chalcogen and carbon; and (6) immobilized chalcogen can provide better environmental oxidation resistance for improved lifetime and better electrochemical RedOx Have resistance to higher cycling performances of a rechargeable chalcogen battery comprising immobilized chalcogen.

A carbon framework can be one level of an Extremely Massive Aromatic Conjugated (EMAC) -π bonding system, as in a simplified model in 20A shown include. The carbo-cation center can be on the EMAC π bonding system, as indicated by the “+” symbols in 20B shown. The EMAC-π bonding system can have a large number of resonances that stabilize a carbo-cation center. The carbo cation center can be used in the EMAC π bonding system by the large number of resonances, as in 20C shown to be very mobile. In other words, the carbon cation center in the carbon skeleton provides a mobile site as an electron acceptor and a location wherever there is a nucleophile that forms a chemical bond via an electron donor and an electron acceptor. The bond via electron donor and electron acceptor is a coordination bond.

A mobile carbon cation center on the EMAC π bonding system is created by the presence of a chemical deactivation function group on the EMAC π bonding system of the carbon framework, as in the 20B-20C shown, created. A chemical deactivation function group can withdraw an electron (s) from the EMAC-n bonding system, resulting in a reduced electron density for a carbon that is at a para or ortho position in an aromatic ring by a carbo cation center is formed which has an insufficient amount of electrons. Such a carbo-cation center is along the EMAC-π-bonding system by resonances, as in 20C shown mobile.

20D shows that chalcogen can be anchored on a carbon framework through an electron donor – acceptor binding mechanism. Immobilized chalcogen comprises a carbon backbone that includes or includes a chemical deactivation functional group, desirably ≥ 0.1 millimole / gram (mmol / g), ≥ 0.5 mmol / g, ≥ 1.0 mmol / g, ≥ 1.5 mmol / g, ≥ 2.0 mmol / g, ≥ 2.5 mmol / g or ≥ 3.0 mmol / g.

It is believed that the mobile carbocation center of the EMAC π bonding system of a carbon backbone may be an acid because of its ability to accept a lone pair of electrons from the chalcogen. The mobile carbo-cation center can also be a soft acid due to its high mobility in the EMAC-π bonding system. The stability of the coordination bond formed or the stability of the free electron donor acceptor bond of chalcogen as a ligand and carbo-cation of the EMAC-π bonding system as a soft acid follows the order O «S ≤ Se ≈ Te. The lone pair of electrons can be attached to the carbo-cation center of the EMAC-π-bonding system via shoulder-to-shoulder or head-to-head bonding, as in 20D shown. Such direct participation in the EMAC-π bonding system can be advantageous for electron conduction during an electrochemical battery process (discharge or charge process) by overcoming a disadvantage of some chalcogen members, such as sulfur or oxygen, namely that they are viewed as an electrical insulator can. Immobilized chalcogen can allow a rechargeable chalcogen battery to cycle at a high C-rate.

A chemical deactivation function group on the EMAC π bonding system of the carbon backbone itself can have a center that is electron poor, as in FIG 20B to 20E shown and behave as an electrophile.

In the presence of a chemical deactivation group on the EMAC π bonding system, the carbon backbone itself can be an electrophile that is essentially harmless to electrophilic attack; consequently, an electrophilic carbon backbone can be more chemically resistant to an electrophile.

It may be desirable to have an immobilized chalcogen that includes a carbon backbone that includes or includes a chemical deactivation functional group on the EMAC π bonding system, which is in the presence of a mobile carbo cation center along the EMAC π bonding system which is most desirable for providing a lone pair site that accepts the electrons from a donor, for example a chalcogen such as oxygen, sulfur, selenium or tellurium.

In one example, the chemical deactivating functional group can be a nitrogen-containing group. Immobilized chalcogen can comprise a carbon backbone that comprises a chemical deactivation functional group that contains nitrogen, for example ≥ 0.1 mmol N / g, ≥ 0.5 mmol N / g, ≥ 1.0 mmol N / g, ≥ 1.5 mmol N / g, ≥ 2.0 mmol N / g, ≥ 2.5 mmol N / g or ≥ 3.0 mmol N / g. A nitrogen-containing group can be a Nitro group, -NO ₂ or a nitroso group, -NO. A nitrogen-containing group can be an ammonium group, -N ⁺ R ₃ , where R can be an alkyl group, an aryl group or an H. A nitrogen-containing group can be a cyano group (-CN), a thiocyanate group (-SCN) or an isothiocyanate group (-NCS).

In one example, the chemical deactivating functional group can be a sulfur-containing group. Immobilized chalcogen can comprise a carbon backbone that comprises a chemical deactivation functional group that comprises sulfur, for example ≥ 0.1 mmol S / g, ≥ 0.5 mmol S / g, ≥ 1.0 mmol S / g, ≥ 1.5 mmol S / g, ≥ 2.0 mmol S / g, ≥ 2.5 mmol S / g or ≥ 3.0 mmol S / g. The chemical deactivating functional group comprising sulfur may be -SO ₃ H (a sulfonic acid) group or its salt (-SO ₃ ^- ), -SCN (a thiocyanate group), -SO ₂ R (a sulfonyl ester) group, where R is a Alkyl group, aryl group or halogen, -SO ₂ CF ₃ (a trifluoromethyl sulfonyl ester group), -SO ₂ -OR or a sulfonium group (-S ⁺ R ₂ ), where R can be an alkyl group, aryl group or other organic functional group and R may not be the same. In one example, the chemical deactivating functional group can be a trihalomethyl group, -CX ₃ , where X can be F, Cl, Br, and I. The chemical functional group of -CF ₃ can be more favorable than functional groups of -CCl ₃ , -CBr ₃ or -Cl ₃ . A highly halogenated alkyl group with more than one carbon can also be a chemical deactivation function group that withdraws an electron from the EMAC π bonding system of a carbon backbone. Immobilized chalcogen can comprise a carbon skeleton which comprises a deactivation functional group which comprises halogen (X), for example ≥ 0.1 mmol X / g, ≥ 0.5 mmol X / g, ≥ 1.0 mmol X / g, ≥ 1 , 5 mmol X / g, ≥ 2.0 mmol X / g, ≥ 2.5 mmol X / g or ≥ 3.0 mmol X / g.

In one example, the chemical deactivating functional group can be a phosphorus-containing group. The phosphorus-containing group can be a phosphonic acid group (-PO ₃ H ₂ ) or its salt (-PO ₃ H ^- , -PO ₃ ^2- ), a phosphonate (-PO ₃ R ₂ , -PO ₃ HR or -PO ₃ R ^- ) or a phosphonyl group (-POR2), where R is an arkyl, aryl or any organic functional group. The chemical deactivation functional group can be a phosphonium group (-P ⁺ R ₃ ). Immobilized chalcogen comprises a carbon backbone that comprises a chemical deactivation functional group that comprises phosphorus, for example ≥ 0.1 mmol P / g, ≥ 0.5 mmol P / g, ≥ 1.0 mmol P / g, ≥ 1.5 mmol P / g, ≥ 2.0 mmol P / g, ≥ 2.5 mmol P / g or ≥ 3.0 mmol P / g.

In one example, the chemical deactivation functional group can be an oxygen-containing functional group. The oxygen-containing group can be a carbonyl-containing group such as -CHO (formyl group or aldehyde group), -COR (acyl group or ketone group), -COOH (carboxyl group or carboxylic acid group) or its salt, -COOR (a carboxylate group or ester group), etc. The chemical deactivation group can also be located within the EMAC π bonding system, as in 20E with a carbonyl group or an anhydride group, as an example, being part of the EMAC π bonding system. Such an electron withdrawal effect can also generate carbo-cation centers through resonances. The carbo cation centers are also mobile in the EMAC π bonding system due to a massive number of resonances. Immobilized chalcogen comprises a carbon framework that comprises a chemical deactivation functional group that comprises oxygen, for example ≥ 0.1 mmol O / g, ≥ 0.5 mmol O / g, ≥ 1.0 mmol O / g,> 1.5 mmol O / g, ≥ 2.0 mmol O / g, ≥ 2.5 mmol O / g or ≥ 3.0 mmol O / g.

In one example, the amount of chemical deactivating functional group, for example an oxygen-containing group, or groups, in the EMAC π bonding system of a carbon scaffold can be characterized by the amount of oxygen content. The oxygen-containing chemical deactivating group may be capable of releasing carbon monoxide, carbon dioxide and water at high temperatures in an inert gas stream such as argon, helium or nitrogen. When the temperature reaches around 400 ° C, most of the water is released; and when the temperature reaches about 600 ° C, most of the carbon dioxide is released, but it is believed that even at a high temperature of about 800 ° C, carbon monoxide is still released at a rate similar to or higher than that at 600 ° C becomes. An immobilized chalcogen can comprise an oxygen-containing functional group that releases at high temperature under a stream of inert gas as water (desirably ≥ 100 ppm, ≥ 200 ppm, ≥ 300 ppm, ≥ 400 ppm or ≥ 500 ppm, by weight) when it reaches 400 ° C is heated; as carbon dioxide (desirable ≥ 1,000 ppm, ≥ 1,200 ppm, ≥ 1,400 ppm, ≥ 1,600 ppm or ≥ 1,800 ppm or ≥ 2,000 ppm, by weight) when heated to 600 ° C, and / or as carbon monoxide (desirable ≥ 1,000 ppm, ≥ 1,200 ppm, ≥ 1,400 ppm, ≥ 1,600 ppm or ≥ 1,800 ppm or ≥ 2,000 ppm, by weight) when heated to 800 ° C. The complete or partial elimination of the deactivating group comprising oxygen species (likely partial elimination) from the EMAC π bonding system of a carbon skeleton makes the EMAC π bonding system of the carbon skeleton by electron withdrawal volatile enough for the remaining or remaining electron deactivating groups. The carbon framework can therefore become very reactive to the environment. In one example, a carbon framework of a chemically deactivated functional group for air became sufficiently active to start burning by itself if there was room air at room temperature (~ 13 ° C to ~ 26 ° C) was exposed. The fire became self-sustaining and red-hot. The presence of an electron-withdrawing deactivating group can thus be critical and highly desirable for the carbon backbone of immobilized chalcogen. As understood, immobilized chalcogen desirably comprises a carbon backbone that is highly active towards ambient conditions after being treated under a stream of inert gas such as argon at high temperatures, e.g., ≥ 400 ° C, ≥ 500 ° C, ≥ 600 ° C , ≥ 700 ° C or ≥ 800 ° C. More specifically, the carbon skeleton, which is treated under a stream of inert gas at the temperatures mentioned above, can start to burn by itself while exposed to air.

Immobilized chalcogen includes chalcogen which has a lone pair of electrons and a carbon backbone capable of accepting lone pairs from the lone pair donor, in this case from the chalcogen. Chalcogen lone pairs of electrons are donated by resonances to the carbo cation centers, which are mobile in the EMAC π bonding system. This donor-acceptor lone pair bond system in immobilized chalcogen leads to a higher concentration of electron density in the EMAC π bonding system of the carbon backbone, which results in a stronger C = C bond in the EMAC π bonding system. Strengthening the C = C bond in the immobilized chalcogen can increase electron conduction in the plane of the EMAC π bonding system of the carbon framework.

Immobilized chalcogen desirably has an increase in the D-band Raman scattering peak of ≥ 2 cm ^-1 , ≥ 3 cm ^-1 , ≥ 4 cm ^-1 , ≥ 5 cm ^-1 or ≥ 6 cm ^-1 . An immobilized chalcogen, particularly for immobilized chalcogen comprising sulfur, desirably has an increase in the wavenumber of the D-band Raman scattering peak and / or the G-band Raman scattering peak by 1 cm ^-1 , 2 cm ^-1 or ≥ 3 cm ^-1 . Herein, an increase in the wavenumber when used in conjunction with immobilized chalcogen relates to a corresponding wavenumber (D-band, G-band, etc. of the carbon itself, that is to say without chalcogen, which comprises the immobilized chalcogen).

The carbon backbone can have both D-band and G-band Raman shifts; where the D-band relates to disordered C = C bonds and the G-band relates to more ordered graphitic C = C bonds. The carbo cation center that is present on the D-band related EMAC π bonding system may be a softer acid than the carbo cation center that is present in the G band related EMAC π bonding system Carbon frame is present. Selenium is easier to polarize and a softer ligand; Sulfur is a small atom and more difficult to polarize, so it's a harder ligand. A softer ligand can preferably bind to a softer acid site, while a harder ligand can preferably bind to a harder acid site. Selenium thus appears to be more strengthening in the C = C bond in the D band than sulfur, and sulfur appears to be more strengthening in the C = C bond in the G band. Even with a large amount of chalcogen, which is sulfur, the presence of a smaller amount of selenium may be able to significantly strengthen the C = C bond in the D-band.

In other words, the C = C bond in the EMAC π bonding system of the immobilized chalcogen system becomes stronger as the chalcogen is able to donate free electron pairs, which improves the electronic conductivity in the plane of the EMAC π bonding system of a carbon framework can. Elemental sulfur or a reduced form of sulfur such as S ^2- (sulfide), and S _n ^2- (polysulfide) etc. have lone pairs of electrons. Sulfur has an electronic structure [Ne] 3s ² 3p ⁴ , selenium has an electronic structure [Ar] 3d ¹⁰ 4s ² 4p ⁴ , and tellurium has an electronic structure [Kr] 4d ¹⁰ 5s ² 5p ⁴ . Lone pairs of electrons in selenium and its reduced forms, for example selenide (Se ^2- ) and polyselenide (Se _n ^2- ), are further away from the nucleus (or nuclei) of the selenium atom than those in sulfur atoms. The lone pairs of electrons in selenium may be capable of being donated, which may result in a stronger donor-acceptor bond system in immobilized selenium than in immobilized sulfur. It is worth pointing out that immobilized (immobilized) Se / S shows that the strength of the donor-acceptor bond of a lone pair increases in the presence of selenium. Lone pairs in tellurium are further away from the nucleus than those in selenium. The lone pairs of electrons in tellurium may be more capable of donating lone pairs of electrons to the acceptor, which can lead to an even stronger donor-acceptor bond system in immobilized tellurium than in immobilized selenium, immobilized sulfur or immobilized oxygen.

Tellurium can be more nucleophilic than selenium, which can be more nucleophilic than sulfur, which can be more nucleophilic than oxygen

Furthermore, oxygen has an electronic structure [He] 2s ² 2p ⁴ . Lone pairs of electrons in oxygen and its reduced forms (O ^2- ), peroxide (O ₂ ^2- ), and superoxide (O ₂ ^- ) are closer to its core (or nuclei) of the oxygen atom than those in sulfur. It is known that peroxide or superoxide is highly active is; it is a strong oxidizer that can oxidize carbon. In a prior art lithium-oxygen or lithium-air battery, achieving chemical resistance to the cathode material involving carbon can be difficult because lithium peroxide or lithium superoxide proves to be an intermediate chemical species during the electrochemical cycling process of a rechargeable lithium-oxygen battery. and lithium air battery can form. It is known that peroxide or superoxide is highly active and has a strong oxidizing power, especially for carbon or other cathode materials.

From the same perspective, a polychalcogenide anion comprising chalcogen, a peroxide ion or a superoxide ion can also behave similarly when the cathode material is oxidized, such as carbon. Accordingly, it may be desirable to avoid or prevent polychalcogenide formation during the electrochemical process of a rechargeable battery that includes chalcogen.

wobei nur ein elektrochemischer Entladeprozess bestehtDischarging is one of the electrochemical processes in a battery, while the chalcogen at the cathode gains electrons. It is desirable that the chalcogen gain electrons and form chalcogenide in one step: $${\text{n chalcogen or chalcogen}}_{\text{n}}+2{\text{n e}}^{-}={\text{n chalcogen}}^{2-},$$

where there is only one electrochemical discharge process

oder $$\begin{array}{l}{\text{n Chalkogen oder Chalkogen}}_{\text{n}}+{\text{ e}}^{-}={\text{Chalkogen}}_{\text{n}}{}^{-}\\ {\text{ Chalkogen}}_{\text{n}}{}^{-}+2\left(n-1\right)e^{-}={\text{n Chalkogen}}^{2-}\end{array}$$

wobei mehr als ein elektrochemischer Prozess während der Entladung anwesend ist. Polychalkogenid ist aufgrund seines Pendeleffekts (Pendel zwischen Kathode und Anode) nicht wünschenswert, da ein Polychalkogenid-Ion in einem Batterieelektrolyt löslich sein kann; Pendeleffekt führt zu einer niedrigeren elektrochemischen Effizienz, weniger als 100 %, wobei die elektrochemische Energie in Hitze umgewandelt wird, was zusätzliche Herausforderungen bei einer Chalkogen-Batterie aufweist. Polychalkogenid ist zum Beispiel auch aufgrund seiner Fähigkeit zum Oxidieren des Hostmaterials nicht wünschenswert. In einer elektrochemischen Umgebung kann zum Beispiel Polychalkogenid elektrochemisch aktiver sein, eine noch stärkere Oxidationsfähigkeit gegenüber einem Hostmaterial, insbesondere Carbon, oder einem Binder in der Kathode aufweisen. Die Oxidation des Kathodenmaterials, wie Carbon oder eines Binders, ist für eine wiederaufladbare Batterie nicht wünschenswert, resultiert in Beschädigung einer Chalkogen-Kathode, was schlussendlich in Versagen der Zyklisierungsfähigkeit einer wiederaufladbaren Chalkogen-Batterie resultiert.However, it is not desirable for chalcogen to gain electrons and form polychalcogenide $$\begin{array}{l}{\text{n chalcogen or chalcogen}}_{\text{n}}+2{\text{n e}}^{-}={\text{Chalcogen}}_{\text{n}}{}^{2-}\\ {\text{Chalcogen}}_{\text{n}}{}^{2-}+2\left(n-1\right)e^{-}={\text{n chalcogen}}^{2-}\end{array}$$

or $$\begin{array}{l}{\text{n chalcogen or chalcogen}}_{\text{n}}+{\text{e}}^{-}={\text{Chalcogen}}_{\text{n}}{}^{-}\\ {\text{Chalcogen}}_{\text{n}}{}^{-}+2\left(n-1\right)e^{-}={\text{n chalcogen}}^{2-}\end{array}$$

with more than one electrochemical process being present during the discharge. Polychalcogenide is undesirable because of its pendulum effect (pendulum between cathode and anode), since a polychalcogenide ion can be soluble in a battery electrolyte; Pendulum effect results in lower electrochemical efficiency, less than 100%, with the electrochemical energy being converted into heat, which presents additional challenges for a chalcogen battery. Polychalcogenide, for example, is also undesirable because of its ability to oxidize the host material. In an electrochemical environment, for example, polychalcogenide can be more electrochemically active, have an even stronger oxidizing ability compared to a host material, in particular carbon, or a binder in the cathode. The oxidation of the cathode material, such as carbon or a binder, is undesirable for a rechargeable battery, results in damage to a chalcogen cathode, which ultimately results in failure of the cycling ability of a rechargeable chalcogen battery.

In immobilized chalcogen, free electron pairs of the chalcogen interact with the corresponding acceptor, a carbo-cation center of the EMAC-π-bonding system of the carbon skeleton or a cationic center that is located in the deactivation function group by forming a chemical coordination bond. The donor-acceptor binding system may not affect the RedOx ability of the chalcogen, allows the chalcogen element to acquire electrons, be reduced and form chalcogenide, and allows the chalcogenide to lose electrons, be oxidized and add elemental chalcogen form to complete an electrochemical RedOx cycle, making it possible for a rechargeable battery application. Polychalcogenide allows a rechargeable battery application to be an intermediate between elemental chalcogen and the chalcogenide. Both chalcogenide and polychalcogenide have a free electron pair and can also be immobilized in the immobilized chalcogen, just like chalcogen in its elemental form.

Immobilization of chalcogen can disorder or destroy the chalcogen crystal structure. A crystalline chalcogen, such as selenium, sulfur, tellurium, or a combination thereof, can become disordered, lose its crystallinity, which is illustrated in X-ray diffraction studies. Immobilized chalcogen changes the crystal structure of the chalcogen.

The immobilization of chalcogen can destroy the chemical bond between chalcogen atoms. An elementary sulfur-sulfur bond shows strong Raman shifts at 154 cm ^-1 , 217 cm ^-1 , 221 cm ^-1 , 473 cm ^-1 . In a system or mass of immobilized sulfur, the sulfur-sulfur bond may change somehow and not be shown in the Raman spectrum. In the immobilized Se / S, no S-Se bond is shown in Raman spectra for a sulfur content between 8.5% by weight and 100% by weight of S and SS.

The sulfur molecules, mainly S ₈ , with over 30 allotropes, such as cyclic S ₆ , S ₇ , S ₁₂ or even S ₁₈ , can exist in crystalline forms. With quenching, sulfur can be amorphous. But the amorphous form of sulfur typically converts to a crystalline form of sulfur. In the immobilized chalcogen comprising sulfur, either alone or as a mixture (immobilized Se / S), sulfur is no longer arranged in a crystalline form. Selenium is also no longer arranged in a crystalline form in immobilized selenium.

By donating the chalcogen lone pair of electrons to an electron-deficient carbo-cation center in the EMAC π bonding system of a carbon framework that includes a deactivating group that withdraws electrons, the chalcogen atom lone pair of electrons can become part of an EMAC π bonding system. The number of delocalized electrons in the EMAC π bonding system is large; the large number of delocalized electrons in the EMAC π-bonding system in the immobilized chalcogen thus shields the interactions between the chalcogen nucleus and the valence electrons in the chalcogen. The chalcogen-chalcogen bond is weakened to such a level that chalcogen behaves like an atom, not a molecule, in a reduction-oxidation process (RedOx process) by gaining two electrons to generate a chalcogenide anion (2nd ^- ) directly, which in turn loses two electrons and forms elemental chalcogen directly without forming an intermediate species such as a polychalcogenide anion. Immobilized chalcogen can exhibit only one step of electrochemical behavior during its use as a cathode in a rechargeable battery. It should be noted that there can be more than one charging or discharging behavior in a chalcogen battery if chalcogen is attached to an intermediate element, in particular a polychalcogenide, such as polysulfide (S _n ^2- ), polyselenide (Se _n ^2- ) etc., forms. The immobilized chalcogen described herein can overcome the problem with rechargeable chalcogenide batteries such as Li-S and Li-Se batteries, especially the pendulum effect of a polychalcogenide ion between the cathode and the anode during the discharge-charge process Battery. The most beneficial solution for the pendulum effect of the polychalcogenide anion is to prevent it from forming or to anchor it if it is formed by chalcogen immobilization in an immobilized chalcogen, the chalcogen and a carbon backbone that includes a chemical deactivating functional group becomes. As far as one understands, immobilized chalcogen appears to show only an electrochemical process during discharge between 3 V and 1 V.

It is known in the art that chalcogen, such as sulfur and selenium, forms polychalcogenide, such as polysulfide (S _n ^2- ) and polyselenide (Se _n ^2- ), which in a carbonate electrolyte in a rechargeable Li-S or Li Se battery that uses a carbonate electrolyte are soluble. In one example, an ether based electrolyte can be used to minimize the pendulum effect. Polychalcogenide ions have a relatively low solubility in an ether-based electrolyte compared to a carbonate-based electrolyte. It should be noted that carbonate-based electrolyte is the current standard in lithium-ion batteries, which is commercially available and less expensive than an ether-based electrolyte. The approach of minimizing the solubility of polychalcogenide in an ether electrolyte may not be an optimal solution and therefore a chalcogenide battery for its commercialization still faces challenges in overcoming the pendulum effect.

However, if a chemical activation function group were present on an EMAC π bonding system, the chemical activation function group would donate electron (s) to the EMAC π bonding system, resulting in an increase in electron density for a carbon attached to a Para or ortho position is in an aromatic ring that forms a carb anion center that has (an) extra electron (s). Such a carb anion center is also movable along the EMAC π bonding system by resonance, which may have one or more of the following results, which may be undesirable: (1) The center of an electron-rich carb anion is prone to electrophilic attack what in one The result is a carbon skeleton, which is chemically less stable compared to the resistance of the carbon which does not have a chemical activation functional group or has a carbon cation in an EMAC-π bonding system of a carbon skeleton; and / or (2) the presence of a carb anion provides a center for electron transfer to adsorbed species such as O ₂ , S ₈ , Se ₈ , etc. by adding O ₂ ^2- , S _n ^2- , Se _n ^2-, etc. ., which has a strong catalytic oxidation activity in addition to its high solubility in an electrolyte solution, particularly in a conventional carbonate electrolyte solution. From this perspective, a chalcogen molecule in an adsorbed form may be undesirable in view of its facile conversion to a polychalcogenide ion; an adsorbed form of a chalcogen molecule can form if the interactions of chalcogen and carbon are stronger than physical interactions, with a chemisorption level (defined below as having activation energy less than 95 kJ / mol but higher than 40 kJ / mol), however no chemical bond level (which is defined below as having an activation energy of ≥ 96 kJ / mol) is achieved.

In one example, immobilized chalcogen may be persistent in an environment, e.g., a lifetime (at room temperature) of ≥ 3 months, ≥ 6 months, ≥ 9 months, ≥ 12 months, ≥ 15 months, ≥ 18 months, ≥ 21 months, or ≥ 24 months during which the exothermic weight loss between 200 and 250 ° C ≤ 2.0% by weight, ≤ 1.8% by weight, ≤ 1.6% by weight, ≤ 1.4% by weight , 1.2 wt% or 1.0 wt%, as determined by TGA analysis under a stream of inert gas such as argon.

The presence of a deactivating group in the EMAC π bonding system is desirable for immobilized chalcogen, which comprises chalcogen and a carbon backbone. As a comparative example, Elite C, an activated carbon available from Calgon Carbon of Pittsburgh, Pennsylvania, has an oxygen content of about 1.3% by weight. This commercially available carbon was used to produce selenium at a melting difference amount of selenium (various amounts of Se, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.% And 70 wt.% Se) to host in the pores of the activated carbon Elite C. About 28 months later it was discovered that the Elite C-Se composites were deteriorating. It is believed that this degradation is due to chemical attack by ambient air at room temperature as revealed by TGA-DSC analysis. The degraded Elite C-Se composites with 50 wt%, 55 wt%, 60 wt%, 65 wt% and 70 wt% selenium all showed severe weight loss between 200 and 250 ° C for TGA analysis in a stream of inert gas (argon) with an exothermic peak (measured by DSC analysis on the same TGA-DSC runs). An analysis of the oxygen content was carried out for some of these degraded Elite-C-Se samples, and the results showed that the degraded Elite-C-Se composites at 50% and 65% by weight had an oxygen content of around 24, 0% for both samples at approximately the same time frame on TGA-DSC analysis. The 50 wt% Se degraded Elite C-Se sample had a weight loss of about .32.0 wt% between 200 and 250 ° C; the Elite C-Se sample with 55 wt% Se had a weight loss of 27.5%; the Elite C-Se sample with 60 wt% Se had a weight loss of about 24.4% and the Elite C-Se sample with 70 wt% Se had a weight loss of 17.7 wt. -% on. It is believed that the weight loss between 200 and 250 ° C for the degraded C-Se composites made with Elite-C is related to carbon content. The higher the carbon content (or the lower the Se content), the greater the weight loss between 200 and 250 ° C. This suggests that the carbon in the Elite-C-Se composites was oxidized by the surrounding oxygen at room temperatures, which is undesirable.

It was also noted that the freshly made C-Se composites with Elite-C showed no noticeable weight loss between 200 and 250 ° C (certainly no observable exothermic behaviors) when analyzed freshly by TGA-DSC in an argon stream.

As another comparative example, Maxsorb MSP20X, an activated carbon available from Kansai Coke Chemicals Co., LTD, Japan (hereinafter “Kansai”) also has an oxygen content of about 1.5% by weight and was used to to prepare a C-Se composite material with a selenium content of 65% by weight. About 18 months later, this C-Se composite also showed an exothermic weight loss of about 2.4% at temperatures between 200 and 250 ° C, in the same environment as the Elite C-Se composites described above. This environmental degraded Maxsorb C-Se composite also showed an oxygen content of about 14% by weight.

The discoveries in the comparative examples above show that a C-SE composite made with carbon containing less than 2% oxygen is undesirable and is prone to exothermic weight loss due to environmental conditions such as, without limitation, Ambient oxygen or humidity at room temperatures. As far as one understands, the exothermic weight loss at temperatures between 200 ° C and 250 ° C may be related to the percentage of carbon in the C-Se composite, suggesting that carbon in the C-Se composites depends on the ambient oxygen or moisture was attacked, which is also evidenced by the significant increase in oxygen content in the deteriorated C-Se samples. It has been observed that the oxygen level of freshly made C-Se composites is typically close to a number equal to multiplying the oxygen content of the carbon starting material by the percentage of carbon in the C-Se composite. The activated Elite-C carbons and Maxsorb 20X have also been observed to withstand ambient conditions. The selenium used to make the C-Se composites is chemically pure, typically greater than 99.5% by weight. The low oxygen content of Elite-C or Maxsorb-MSP-20X-Carbon may be directly related to the lack of the chemical deactivation functional group, which includes oxygen in the EMAC-π-bonding system of a carbon scaffold.

In another example, an immobilized selenium sample comprising selenium and a carbon backbone comprising a chemical deactivation functional group was prepared with a carbon backbone comprising an oxygen content of about 9%. It was observed that the immobilized selenium sample still behaved the same in the TGA-DSC analysis in an argon stream; after about 26 months there was a noticeable weight loss between 200 and 250 ° C, and there was no observable exothermic behavior in this temperature range. The presence of the chemical deactivating functional group in this example, which comprises oxygen in a carbon backbone, can be critical to the successful immobilization of the chalcogen.

In an immobilized chalcogen, the chalcogen is chemically immobilized. The lone pair donor-acceptor bonding system in the immobilized chalcogen anchors itself as an element, chalcogenide or polychalcogenide, which requires a much higher energy for chalcogen to overcome the strong activation energy barrier and escape.

The van der Waals forces and capillary force are typically present in an SC composite material, a C-Se composite material, or a T-Se composite material in which a chalcogen as a guest molecule is cast into porous carbon that acts as a host material is working. Van der Waals forces are typically around 4 kJ / mol, and the strongest van der Waals forces can reach 40 kJ / mol. Interactions between Van Dder Waals forces and capillary force are typically physical, not chemical. Physical interactions do not involve any changes in the electronic state of the guest and host molecules, i.e. no chemical bonding. For a physically entrapped C-chalcogen composite material, the chalcogen is entrapped by physical interactions such as van der Waals interactions and capillary force or surface tension due to curvatures of the pores of the carbons.

When the forces involved in the interactions among the guest molecules and the host reach levels that reach an activation energy of 96 kJ / mol or higher (or 1 eV) to overcome and escape, the interactions between the guest molecules are and host molecules define and reach a level of chemical interactions. Chemical interactions typically involve changes in the electronic state of the molecules or atoms. Such changes can involve breaking an existing chemical bond, forming a new chemical bond, or strengthening an existing chemical bond, or weakening an existing chemical bond. The forces that involve the guest and host at levels between 40 and 95 kJ / mol are transient, a possible combination of physical interactions and chemical adsorption. In a state of chemical absorption, chalcogen still exists as a chalcogen molecule, for example as an adsorbed form of O ₂ , S ₈ or Se ₈ , which in turn can accept electrons during a battery discharge process that a polychalcogenide ion, such as O ₂ ^2- , S _n ^2- or Se _n ^2- , which are undesirable.

An activation energy (at 15 wt.% Loss) that is required to overcome an immobilized chalcogen system consisting of chalcogen and a carbon skeleton, which results in the breaking of a donor-acceptor bond of the lone pair between chalcogen and the Carbon skeleton can be ≥ 96 kJ / mol, ≥ 99 kJ / mol, ≥ 102 kJ / mol, ≥ 105 kJ / mol, ≥ 108 kJ / mol or ≥ 111 kJ / mol. A higher activation energy for the immobilized chalcogen can ensure that chalcogen is properly anchored by strong chemical interactions and is difficult to leave the immobilized chalcogen system, which is desirable for consistent cycling performance for a rechargeable battery comprising immobilized chalcogen. A higher activation energy can also suggest the presence of strong chemical interactions between chalcogen and carbon skeleton, which ensures a minimum level of polychalcogenide formation.

The Log_Pre exponential constant (shock frequency) for an immobilized chalcogen is desirably ≥ 7.0, ≥ 7.2, ≥ 7.4, ≥ 7.6 or ≥ 7.8. Immobilized chalcogen can have a high impact frequency; the chalcogen can thus have more interactions with the carbon backbone for improved electrical conduction during electrochemical processes.

In order to escape an immobilized chalcogen system, the chalcogen in the immobilized system requires sufficient kinetic energy. In one example, the midpoint kinetic weight loss energy may be -1,840.3x ² + 90.075x + D, where x is the sulfur weight percentage of the total selenium and sulfur in the immobilized chalcogen system; D can be ≥ 9,500 J / mol, ≥ 9,700 J / mol, ≥ 9,900 J / mol, ≥ 10,000 J / mol, 10,200 J / mol, 10,400 J / mol or ≥ 10,600 J / mol; the midpoint weight loss temperature is -147.57 x ² + 7.2227 x + C, where C ≥ 510 ° C, ≥ 520 ° C, ≥ 530 ° C, ≥ 540 ° C, ≥ 550 ° C, 560 ° C or ≥ 570 ° C.

It is believed that the carbon scaffold d-spacing in the immobilized chalcogen disappears, as in FIG 20F shown. It has been observed that a sheet-like structure material such as carbon has the sheet-like structure disclosed in, for example, US Pat 20A to 20C is shown. The spacing between the carbon sheets, d-spacing, can be determined by X-ray diffraction. D-spacing expansion is typically observed for graphite used as an anode in a lithium-ion battery, due to the lithium interposed between the graphite-carbon sheets. The same phenomenon applies to inserted tone, a d-spacing expansion. It has been observed that immobilized chalcogen exhibits d-spacing shrinkage, suggesting that there are (strong) chemical interactions that pull planes of the EMAC-π bonding system of the carbon scaffold. In one example, it may be desirable to have a d spacing shrinkage of ≥ 0.5 Å, ≥ 0.6 Å, ≥ 0.7 Å, ≥ 0.8 Å, or ≥ 0.9 Å.

Immobilized chalcogen can be used in a battery, capacitor, or energy storage device. A battery that includes immobilized chalcogen can be a primary battery or a secondary (or rechargeable) battery. A battery that includes immobilized chalcogen can include a cathode, an anode, a separator, and an electrolyte. Immobilized chalcogen can also be used as a cathode material in a battery. The anode can be a metallic material, for example a Group IA metal (an alkali metal such as Li, Na, K, etc.), a Group IIA metal (alkaline earth such as Mg, Ca, Ba, etc.), a Group IIA metal (such as Al, Ga or In), a group IVA metal (such as Sn or Pb), a group V metal (such as Sb or Bi), a semiconductor metal (such as Si, Ge or As), a transition metal or a rare earth metal, as shown in the table of the periodic table. Graphite can also be used as an anode material. An organic polymer film or an inorganic film can be used as a separator. The surface of an inorganic polymer film can be modified for desirable properties in a battery. An organic electrolyte or an aqueous electrolyte can be used in a battery comprising immobilized chalcogen. An example of an organic electrolyte can be a carbonate-based electrolyte, an ether-based electrolyte, or a special organic electrolyte. It should be noted that a carbonate-based electrolyte is a common electrolyte used in current lithium-ion rechargeable batteries. An example of an inorganic electrolyte can be a solid electrolyte. A battery comprising immobilized chalcogen may have a hybrid electrolyte in which a solid electrolyte is used with a dual function, one that allows ions to pass through the solid electrolyte membrane and the other that prevents the transport of certain undesirable ions , whereby dendrite formation is avoided or prevented.

In one example, immobilized chalcogen can be applied or laminated to a charge collector, such as aluminum foil, followed by assembling a battery with a lithium metal anode, a carbonate-based electrolyte, and a polymer separator, resulting in a battery comprising immobilized chalcogen . A battery comprising immobilized chalcogen may be able to discharge to a voltage as low as is practically desirable. This battery may have a single level of voltage-specific discharge capacity profile under a constant current with a C-rate of 0.001 to 100C-rate or above, suggesting that chalcogen directly gains two electrons to form chalcogenide, and a Coulomb efficiency in cycling of ≥ 90 %, ≥ 95%, ≥ 97%, ≥ 98% or ≥ 99%. This battery can have a multi-level voltage-specific discharge capacity profile, which may be undesirable, but as long as the Coulomb cycling efficiency is ≥ 90%, ≥ 95%, ≥ 97%, ≥ 98% or ≥ 99% because the polychalcogenide ion in the immobilized chalcogen system is anchored, it is difficult for him to escape the mass or the system of immobilized chalcogen and to commute to the anode.

At a C-rate of 1, a battery that includes chalcogen can have a specific capacity of ≥ 50%, ≥ 55%, ≥ 60%, ≥ 65% or ≥ 70% of its theoretical specific capacity at its tenth cycle and can be capable of be able to retain 70% of their capacity after ≥ 50 cycles, ≥ 100 cycles, ≥ 150, ≥ 200 cycles or ≥ 250 cycles.

With a C-rate of 1, a battery comprising chalcogen may have a midpoint discharge voltage of ≥1.2V, ≥1.3V, ≥1.4V, ≥1.5V, or ≥1.5V .

A battery comprising immobilized chalcogen may be able to discharge at a C-rate of ≥ 0.1, ≥ 0.3, ≥ 0.5, ≥ 1.0, ≥ 2.0, or ≥ 5.0.

A battery that includes immobilized chalcogen can maintain a 50% specific capacity of the theoretical specific capacity of the chalcogen in the battery for ≥ 50 cycles, ≥ 100 cycles, ≥ 150 cycles, ≥ 200 cycles, or ≥ 250 cycles.

Examples:

The DSC / TGA system, available from TA Instruments, New Castle, Delaware, TGA-DSC was used to characterize thermal behaviors of samples. For the temperature it was calibrated with Zn. A modulated mode was used to calculate the activation energy and pre-exponential factor of carbon-selenium, carbon-sulfur, carbon-selenium / sulfur and other samples in argon flows at a heating rate of 3.5 ° C / min. to be determined with graphite crucibles (without lid). The TGA analysis was carried out in argon flows at a heating rate of 10 ° C./min. with alumina crucibles with lids (alumina) on top. Raman spectra were collected on a confocal Raman microscope with argon laser at 488 nm, available from Renishaw-PLC with an office in West Perdue, Illinois. X-ray diffraction results were collected on the Philips PD5000 system with a copper target. The BET surface area and pore size distributions of the carbon were collected separately on a Micromeritics brand BET analyzer with nitrogen and CO ₂ as test molecules, and the results were combined.

Examples of preparations of a carbon skeleton including a chemical deactivating functional group including oxygen.

Example 14: Carbon Scaffold Comprising a Deactivating Functional Group Comprising Oxygen (9-10 wt%) - Large Crucible under Static Conditions

Potassium citrate (1 kg) was placed in a stainless steel crucible (boat shape, 4.5 "diameter and 24" length). The crucible was then placed in a stainless steel tubular reactor 6 inches in diameter. In the presence of a flow of argon, the reactor at a heating rate of 5 ° C / min. heated to 600 ° C, warmed through or held at 600 ° C for one hour (for carbonization) and ramping at 3 ° C / min. Heated further up to 800 ° C and warmed through or held at 800 ° C for two hours (for activation). The reactor was then cooled to 180 ° C and the argon flow was switched to a nitrogen flow that was bubbled through a water stirrer to pick up water molecules. The nitrogen flow carried the water molecules into the reactor to react with metallic potassium that formed during the carbon manufacturing process to prevent the metallic potassium from igniting when exposed to ambient conditions.

The resulting mixture of the carbon skeleton with decomposed salts (mainly potassium carbonate) was optionally slurried (mixed) in water together with an alkali (potassium hydroxide). Hydrochloric acid was used to neutralize the slurry with excess to achieve a pH around 1. The carbon slurry was filtered with a filter press and washed with water up to a conductivity of 10 µS / cm or lower.

The washed carbon was then loaded from the filter press and dried in an oven at a temperature of ~ 120 ° C, resulting in a carbon backbone comprising a deactivating group that had oxygen levels at a level of about 9-10% by weight, which was surprisingly high.

Note that it was observed that the oxygen content in the carbon skeleton apparently depends on a batch size of the potassium citrate. A small batch of potassium citrate can result in a carbon backbone formed therefrom, which has an oxygen content at a level of about 5% by weight.

Example 15: Carbon Scaffold Comprising a Deactivating Functional Group Comprising Oxygen (~ 12 to 14 wt%) - Continuously in a rotary kiln.

Potassium citrate was fed from a bunker at the rate of about 9 pounds per hour with an auger feeder into a 6 inch diameter rotary kiln with a stainless steel rod therein for mixing and scraping. The oven contained four heating zones and was heated with the following temperature settings: the last temperature zone (zone 4) was controlled to 600 ° C; the temperature for zone 3 was set at 400 ° C; and the temperature for the first two zones (zone 2 and zone 1) was set at 150 ° C. When the steady state is reached, the temperatures in zones 3, 2 and 1 are typically higher than the setpoints, for example between 400 and 500 ° C for zone 3 and between 300 and 400 ° C for zone 1 and zone 2, due to the Heat conducted from zone 4 to zone 3 and on to zone 2 and on to zone 1. Zone 4 can be the only one that has been actively heated. The furnace is rotated through an angle of about 1 ° at a speed of about 6 revolutions per minute. A flow of argon was dehydrated against the flow direction of the potassium citrate while the potassium citrate was carbonized. The potassium citrate was fed from the bunker in zone 1, and the rotation of the rotary kiln gradually moved the potassium citrate through zones 2 to 4 of the rotary kiln to discharge the carbonized potassium citrate and the decomposed salts from zone 4 into a metal container. About 4 hours after unloading into the metal container, the reactions reached a steady state and the mixture produced contained the carbonized carbon mixture for the next step in the process, namely activation.

Then the carbonized carbon mixture produced was fed in the steady state from the carbonization at a similar rate into the rotary kiln from zone 1 to zone 4 a second time for activation at high temperatures, all zones were brought to 800 ° C at a speed of 4 revolutions per minute controlled, tilted by 1 °, with an argon flow against the flow direction of the carbonized carbon mixture. The mixture collected from the activation process contained the carbon framework for further processing.

Then, the mixture collected from the activation process was slurried (mixed), followed by mixing with hydrochloric acid, filtering and washing in a filter press, and drying in an oven at -120 ° C. The carbon thus produced is a carbon skeleton comprising a chemical deactivating function group which was analyzed to have an oxygen content of 12 wt%, which is higher than the carbon skeleton materials produced from the large crucible under static conditions.

Examples of the immobilization of chalcogen

Example 16: Immobilization of selenium with a carbon skeleton comprising a chemical deactivation function group comprising oxygen (oxygen content about 9 to 10%).

Selenium powder (2.4 g) and a carbon skeleton with an oxygen content of 9.29 g, 2 g (60 wt.% Se and 40 wt.% Carbon skeleton) were weighed into a ball mill jar. The jar was then capped and ground in a double planetary mill for 40 minutes. The ground mixture was then dried under vacuum at 80 ° C. overnight, and then transferred to an autoclave in an argon glove box with a tight lid. The autoclave was then transferred to a heating furnace to be heated at a temperature set at 230 ° C for 24 hours. The resulting sample is the immobilized chalcogen, in the present case immobilized selenium. The analysis showed an oxygen content of 2.6% by weight of the sample.

Example 17: Immobilization of selenium with a carbon backbone comprising a chemical deactivation functional group comprising oxygen (oxygen content about 12% by weight).

Using a procedure similar to that described in Example 16, immobilized chalcogen, in this case immobilized selenium, was made with a carbon structure (50% by weight Se powder (2 g) and 50% by weight carbon structure), which is produced continuously in a rotary kiln, which is described in Example 15, with 2 grams of a carbon structure that has an oxygen content of 12%, prepared. Three months after its preparation, an analysis revealed that the immobilized selenium had an oxygen content of 4.8% by weight.

Examples 16 and 17 show that the immobilized chalcogen, in the present case immobilized selenium, comprises chalcogen, carbon and oxygen.

Example 18: Stability of the immobilized chalcogen, in the present case the immobilized selenium, under ambient air.

Following a similar procedure as described in Examples 16 and 17, two immobilized selenium samples were prepared separately at intervals of about two years, that is, the second immobilized selenium sample (broken line) was prepared about two years after the first (solid line) has been. These immobilized selenium samples were analyzed by TGA-DSC as described in 21st which shows that there is no aging effect on the TGA-DSC behaviors of the two samples after aging the samples under ambient conditions for more than two years and about four months each, focusing in particular on the temperature between 200 ° C and 250 ° C for the two samples.

Comparative example 3: Preparation of carbon-Se composite materials with selenium and commercially available carbons with an oxygen content of less than 2% (for example Elite-C and Maxsorb MSP20X)

Following a procedure similar to that described in Examples 16 and 17, using the commercially available Carbon Elite C having an oxygen content of 1.19 wt.%, C-Se composites having an Se content of 50 wt. -%, 55% by weight, 60% by weight, 65% by weight and 70% by weight prepared and stored in an environment, for example ambient air at room temperature, pressure and humidity. About 26 to 27 months later, these C-Se composite samples were analyzed for their TGA-DSC behaviors in an argon stream. The TGA-DSC results for 50 wt% Se, 60 wt% Se, 70 wt% Se are in 22A (TGA) and 22B (DSC) shown. As from the 22A and 22B can be seen, there is a significant weight loss between 200 and 250 ° C in the TGA analysis ( 22A) after about two years of aging in the area; the temperatures associated with the weight loss correspond to an exothermic peak on DSC ( 22B) . The level of weight loss correlates well with the strength of the exothermic peak. The higher the weight loss at 200 to 250 ° C, the higher the exothermic peak in this temperature range. It is also found that the higher the carbon content for the Elite-C-Se composite material (or the lower the selenium content for Elite-C-Se), the higher the degree of exothermic weight loss between 200 and 250 ° C . This suggests that the carbon is being attacked by the environment somehow.

About 26 months after its preparation, the Elite C-Se composite was analyzed to have 65 wt% Se as having an oxygen content of about 24 wt%. This suggests that Elite-C-Se composites are not stable under ambient conditions, somehow oxygen or moisture in the environment will attack the carbon in the presence of selenium in the Elite-C-Se composites. The activated carbon in the Elite-C has a low oxygen content, which can be a determining factor as (due to its low oxygen content) it is not stabilized by the presence of a chemical deactivation group that includes oxygen.

In another example, another commercially available activated carbon, Maxsorb MSP20X, which analysis showed an oxygen content of 1.33% by weight, was used to prepare the first and second C-Se composites, the first being C-Se The composite material had an Se content of 65% by weight Se and the second C-Se composite material had an Se content of 60% by weight Se. The second C-Se composite was prepared about 17 months after the first C-Se composite. Both samples were analyzed in TGA-DSC at the time the second C-Se composite was prepared for the purpose of studying the environmental aging resistance of these composites made with commercially available carbon materials. It was discovered that the first C-Se composite exhibited an exothermic weight loss at temperatures between 200-250 ° C, with an exothermic weight loss (approximately 5% weight loss) similar to that of the thermal behaviors of the Elite C-Se composites described above is very similar. It was also discovered that the first C-Se composite made with Maxsorb MSP20X had an oxygen content of up to 14% by weight after about 17 to 18 months of aging under ambient conditions. The first C-Se composite was also oxidized by the ambient oxygen, which confirms the discoveries made with the C-Se composites made from activated elite C-carbon described above.

From the examples of Elite-C-Se composites and Maxsorb-Se composites, it is believed that both of these carbons have low oxygen content, while the carbon skeleton materials of the examples described above have significantly higher oxygen content. As far as one can understand, the resistance to immobilization of chalcogen can be greatly affected by the presence of a chemical deactivating group, which includes oxygen.

Comparative Example 4: Preparations of carbon-SeS ₂ composite materials with SeS ₂ (selenium disulfide) and multi-walled carbon nanotube materials, as described in Ali Abouimrane et al., J. Am. Chem. Soc. 2012, 134, 4505-4508.

In their work, Abouimrane et al. C-SeS ₂ composite materials by using multi-walled nanotube materials (MWCNT) and SeS ₂ at 160 ° C for 12 hours in air with 70 wt .-% SeS ₂ charge (30 wt .-% MWCNT). There are two MWCNT materials, namely MWCNT-1 and MWCNT-5.

Using a procedure similar to that described in Comparative Example 3, examples of MWCNT-1 and MWCNT-5 materials were weighed, 1.2 g and placed in separate milling jars, followed by adding 2.8 g of SeS ₂ separately to each Vessel with SeS ₂ drawer aiming at 70 wt% (30 wt% MWCNT). The mixtures were ball milled for 15 minutes and separated from the milling vessels. The samples were then placed in two separate crucibles, placed in a conventional oven at 160 ° C for 12 hours in air, resulting in MWCNT-1_SeS ₂ (70 wt%) and MWCNT-5-SeS ₂ (70 wt%). %) resulted.

The MWCNT-5 material was also used to make a C-SeS ₂ composite material with a loading target of 38 wt% SeS ₂ (62 wt% MWCNT-5), same as immobilized chalcogen materials in accordance with Example 19 (described below) have been prepared. In this example, 2.48 grams of MWCNT-5 was weighed into a grinding jar along with 1.52 grams of SeS ₂ powders, followed by ball milling for 40 minutes. The milled mixture was then separated, pelleted, and placed in a glass tube reactor ~ 1 inch in diameter. The mixture was then poured in place with an argon flow of about 600 ml / min. dried for 3 hours. The reactor was then with flowing argon at a rate of 10 ° C / min. heated to a temperature of 130 ° and the temperature was held there for 1.5 hours. The prepared C-SeS ₂ composite sample was then cooled to room temperature and identified as MWCNT-5-_SeS ₂ , a C-SeS ₂ composite made with MWCNT-5.

Comparative Example 5: Autoclave treatment of raw material selenium powders, raw material sulfur powders and mixtures of selenium and sulfur produced by ball mills according to the following Table 5 without the presence of a carbon skeleton comprising a chemical deactivation function group including oxygen. Table 5 Sample ID 258-50-1 258-50-2 258-50-3 258-50-4 251-70-2 258-46-1 258-46-2 258-46-3 258-46-4 Active weight% 62% 55% 50% 42% 38% 36% 32% 28% 26% S% by weight in active 0% 8.5% 17% 34% 45% * 51% 68% 85% 100% Se% by weight in active 100% 91.5% 83% 66% 55% 49% 32% 15% 0% Carbon (example 15), g 3.80 4.47 5.00 5.81 6.20 6.39 6.84 7.18 7.43 Sulfur, g 0 0.47 0.85 1.42 1.84 2.15 2.40 2.57 Selenium, g 6.20 5.06 4.15 2.77 1.77 1.01 0.42 0 SeS, 3.80 Overall, g 10 10 10 10 10 10 10 10 10 Specific capacity mAh / g 418 419 420 421 422 422 422 423 423 Temp. ° C 230 130 130 130 130 130 130 130 130 * SeS ,: 55wt% Se and 45wt% S

Table 5 shows a number of immobilized chalcogens (10 g each), which are listed according to sample ID, with the listed amounts of Se, S, SeS ₂ and carbon skeleton with a relatively constant specific capacity (418-423 mAh / g) a temperature of 230 ° C for 100% Se sample and 130 ° C for the rest of the samples.

In order to better illustrate the immobilization of chalcogen, the same mixtures as in Comparative Example 4 without the carbon skeleton were prepared as control examples according to Table 5 without the presence of a carbon skeleton. The appropriate amounts of selenium and sulfur were weighed into a grinding jar, followed by 40 minutes of ball milling in a double planetary ball mill. Each milled mixture was separated from the milling balls and transferred to a separate ceramic crucible. A group of these selenium / sulfur mixtures and the starting raw materials (selenium powder and sulfur powder) were then placed in their respective crucibles in an autoclave in an argon glove box. The autoclave was then transferred to a heating furnace and the furnace was heated to 130 ° and held at 130 ° for 24 hours. The corresponding samples were unloaded in ambient air at room temperature and placed in sample containers with corresponding labels.

In these included examples, it was observed that the grain size of the selenium powders appeared to grow, which is understandable since the melting point of selenium is 220 ° C. Selenium powder should therefore not melt, but should experience grain growth during heating (Oswalt ripening phenomenon). It was also found that both the mixture of 8.5% by weight sulfur and 91.5% by weight selenium and that of 17% by weight sulfur and 83% by weight did not melt at 130.degree , but showed some grain growth at this temperature. The mixtures of S-Se with sulfur contents of 34% by weight, 51% by weight, 68% by weight and 85% by weight and with the residual selenium all melted at 130.degree. Of course, sulfur powder also melted at 130 ° C.

23 shows X-ray diffraction patterns for the raw materials, and selenium powder, sulfur powder and SeS ₂ powder are all crystalline materials.

The 24A to 24C show X-ray diffraction patterns (XRD patterns) for mixtures of sulfur and selenium autoclaved at 130 ° C ( 24A) , Sulfur powder ( 24B) and selenium powder ( 24C ), all without the presence of a carbon backbone comprising a chemical deactivation functional group comprising oxygen. The 24B to 24C show that the selenium and sulfur powders autoclaved at 130 ° C are still in crystalline form, although sulfur may have changed from one phase to another. 24A shows that the autoclave-treated sulfur / selenium mixtures thereof are crystalline, although the autoclave-treated mixtures are 34 wt% sulfur and 51 wt% sulfur less crystalline, possibly the XRD patterns of selenium disulfide in FIG 23 similar.

The 25A to 25B show Raman scattering spectra for the starting materials and selenium powder, sulfur powder and SeS ₂ powder, all of which are Raman scattering active, indicating the presence of a Se-Se bond (237 cm ^-1 ), SS bond (154 cm ^-1 , 217 cm ^-1 , 221 cm ^-1 , and 473 cm ^-1 ) and Se-S bond (255 cm ^-1 , 353 cm ^-1 and 454 cm ^-1 ) in these starting materials.

The 26A and 26B show Raman scattering spectra for selenium autoclaved at 130 ° C, sulfur and mixtures of selenium and sulfur. These figures suggest the existence of a Se-Se bond at 237 cm ^-1 from pure selenium down to a mixture of 66% selenium; they also suggest the existence of a SS bond from pure sulfur down to a mixture containing 68% sulfur. These results suggest that there may be a reaction of sulfur and selenium which forms selenium disulphide for these mixtures between 83% selenium and 32% selenium or between 68% sulfur and 17% sulfur.

Example 19: Immobilization of chalcogen comprising selenium, selenium and sulfur, SeS ₂ or sulfur with a carbon skeleton comprising a deactivating function group comprising oxygen (oxygen content between 12 and 14%).

A number of samples of the immobilized selenium, immobilized sulfur, immobilized SeS ₂ and immobilized mixture of Se and sulfur were prepared according to the following procedures and formulations listed in Table 5 with the aim of an almost constant specific capacity, which in a rechargeable Battery is used, namely a specific capacity between 418 mAh / g for immobilized chalcogen, which is based on pure selenium, and 423 mAh / g for immobilized chalcogen, which is based on pure sulfur. The carbon framework for this example was produced in a continuous process in a rotary kiln, which is described in example 15, to prepare the immobilized chalcogen. It should be noted that this carbon backbone contained higher amounts of a chemical deactivating function group comprising oxygen (12-14%).

The amounts of carbon plus selenium, SeS ₂ and / or sulfur were weighed separately and placed in their own ball mill jar, in which the grinding balls were located. Then each sample of carbon plus selenium, SeS ₂ and / or sulfur was ground in a double planetary mill for 40 minutes. Each milled mixture was then separated from the milling balls and pressed into pellets (which is optional; pellets often break). The mixture was then transferred to the same glass reactor that was described in the second part of Comparative Example 4. A stream of argon gas (-600 ml / min.) Then flowed through the mixture in the glass reactor for 3 hours to remove any physically absorbed water. The glass reactor was then at a heating rate of 10 ° C / min. heated to 130 ° C, and the temperature was maintained at 130 ° C for 1.5 hours while the argon gas flowed continuously. After cooling, the reacted mixture is the immobilized chalcogen. The detailed compositions of these immobilized chalcogens are identified in Table 5 above. In Table 5, Example 248-70-2 is immobilized SeS ₂ containing 45% sulfur, which can be directly compared to the C-SeS ₂ composites prepared with multi-walled carbon nanotubes as described in Comparative Example 4. It should be noted that the preparation temperature for the pure selenium was 258-50-1.230 ° C.

27 Fig. 13 shows X-ray diffraction patterns for samples of immobilized chalcogen shown in Table 5 prepared from carbon skeleton (s) comprising a chemical deactivating functional group comprising oxygen and elemental selenium, elemental sulfur or the combination of the includes elemental selenium and elemental sulfur. Sample 251-70-2 in Table 5 is in 27 not shown. The results show the absence of crystalline chalcogen, which strongly suggests that selenium or sulfur atoms are no longer arranged in an ordered manner, for example ordered in a crystalline manner. In contrast, in this comparative example 5, the selenium which had been autoclaved at 130 ° C., the sulfur or its mixtures were still essentially in crystalline form. This surprising result suggests that the chemical bond between Se-SE, SS or Se-S may not have changed. The chalcogen molecules with several atoms chained in a cyclic form cannot be present in the immobilized chalcogen system. In addition, it is still incomprehensible how selenium and sulfur get into the carbon structure and form immobilized chalcogen of 8.5% by weight S_91.5% by weight Se and 17% by weight S_83% by weight Se at 130 ° C because the mixtures of S and Se did not melt at 130 ° C in the absence of a carbon backbone (as discussed above).

27 also shows the d-spacing shrinkage of samples of the immobilized chalcogen in Table 5. The carbon framework has an EMAC π bonding system along the carbon plane; an individual carbon plane can also be viewed as a single-walled graphene sheet. When the planes of the EMAC π bonding system are stacked, there is d-spacing, as in FIG 20F shown. The XRD results of the 27 for the carbon skeleton show a diffraction peak at a 2 theta of about 17.1 °, which corresponds to a d-spacing of about 5.18 Å. After immobilizing the chalcogen within the carbon skeleton, the lone pair of electrons of the chalcogen can be donated to a carbon cation center of the EMAC-π bonding system of the carbon skeleton, so that an electron donor-acceptor bond or a coordination bond is formed between the chalcogen and the carbon skeleton becomes. If such a type of donor-acceptor bond is strong, the immobilized chalcogen planes of the EMAC π bonding system can draw closer. The stronger the bond, the closer the spacing between planes of the EMAC π bonding system. As discussed above, selenium may be better able to donate a lone pair of electrons to the carbo-cation center of the EMAC π-bonding system than sulfur. Immobilized selenium would consequently have more d-spacing shrinkage than immobilized sulfur. Surprisingly, it was discovered that the 2 theta of the XRD peak for immobilized selenium (100 wt% selenium) increased from 17.1 ° C to about 25.3 °, which corresponds to the d-spacing of about 5.18 Å of the carbon backbone shrink to about 3.52 Ä, i.e. a d-spacing Shrinkage of about 1.64 Å; the 2 theta of the XRD peak for immobilized sulfur (100% sulfur) increased from 17.1 ° to 23.4 °, which caused the d-spacing to disappear from about 5.18 Å to about 3.80 angstroms, i.e. a d -Spacing shrinkage of about 1.38 Å. As can also be understood from the above, as the selenium percentage is increased, the d-spacing shrinkage increases from 1.38 Å to 1.64 Å. In addition to the d-spacing shrinkage, the immobilization of chalcogen can also disorder the carbon skeleton, which shows a broader XRD peak. The reduced XRD strength may be due to the fact that the carbon backbone is thinned by the presence of chalcogen in an immobilized chalcogen system.

Table 6 shows D-band and G-band Raman scattering locations, their displacements, activation energy, LogA and d-spacing for immobilized chalcogen and control C-chalcogen composite materials prepared with MWCNT materials.

28 Figure 13 shows Raman scattering spectra for samples of the immobilized chalcogen of Table 5 prepared with a carbon backbone comprising a chemical deactivating function group comprising oxygen. Sample 251-70-2 in Table 5 is in 28 not shown. Chalcogen donates a lone pair of electrons to a carbocation center on the EMAC π bonding system of the carbon backbone, which comprises a chemical deactivation function group comprising oxygen. The donor-acceptor bond strengthens the C = C bond in the EMAC π bonding system of the carbon framework. It was surprisingly discovered that the Raman diffraction peaks of the C = C bonds increased for both D-band and G-band, i.e. direct evidence of the strengthening of the C = C bond. The Raman peaks of the 28 were determined by curve fitting and behave as listed in Table 6.

Selenium in the immobilized chalcogen appears to have more significant wavenumber increase in the D-band, from 8.1 cm ^-1 to 12.8 cm ^-1 , than for pure sulfur (4.7 cm ^-1 ), as shown in Table 6 above . In one example, sulfur in immobilized chalcogen appears to have more of an effect on the G-band shift to a higher wavenumber, although the degree of G-band shift may be less than the degree of D-band shift, as shown in Table 6 . Combined with the d-spacing shrinkage, the D-band Raman shift to a higher wavenumber, and / or the G-band shift to a higher wavenumber, it appears that the chalcogen is in an immobilized chalcogen system or an immobilized Chalcogen mass donates its electrons to the EMAC of a carbon framework, which strengthens the C = C bond and contracts the planes of the EMAC-π bonding system of the carbon framework. This type of donor-acceptor binding system in immobilized chalcogen is desirable.

The electrons of the chalcogen take part directly in the EMAC π bonding system of the carbon framework, with the delocalized π electrons being responsible for the electron conduction. This suggests that the chalcogen lone pair of electrons participates directly in electron conduction during an electrochemical process, such as a discharging process or a battery charging process that causes the Limitation of the chalcogen in its electrical insulation properties overcomes, especially for a light chalcogen such as oxygen and sulfur.

It was amazing to find that a battery comprising immobilized sulfur is capable of charging and discharging at a high C-rate as discussed below in connection with immobilized chalcogen used as a cathode of a rechargeable battery. It is also advantageous that the lone pair of electrons of each chalcogen participates in electron conduction during an electrochemical battery process, which is not influenced by the valence state of the chalcogen in its elemental state or in a reduced state (-2). In addition, d-spacing shrinkage of the carbon backbone in an immobilized chalcogen is also highly desirable because it allows electron flow to flow more freely under the planes of the EMAC π bonding system of a carbon backbone.

28 also shows the disappearance of Raman scattering peak features of the sulfur-sulfur bond or selenium-sulfur bond, while the peak for selenium-selenium bonds at 237 cm ^-1 shifts to a higher wavenumber, about 258 cm ^-1 ( please refer 28 , for example the graphs for 100% Se - 0%; 91.5% Se - 8.5% S; and 83% Se - 17% S). The redirection or disappearance of SS and S-Se bonds suggests that chemical interactions such as donor-acceptor bonding or coordination bonding may dissociate to atomic form or to a level at which polysulfide ions cannot form has been. It is assumed that the Se-Se bond may also have been influenced in such a way that no polyselenide ions can form.

29 shows XRD results for multi-walled carbon nanotube (MWCNT) and SeS ₂ composite materials prepared in accordance with Comparative Example 4. By comparing the XRD results of the 29 with the XRD results of the 23 one can see that the XRD results for the starting materials of MWCNT ( 23 ) show no significant d-spacing shrinkage for the three MWCNT samples shown in Table 6. In Table 6 (MWCNT-5 in Table 6 is for two samples that have different d-spacing) the immobilized SeS _{2 shows} a d-spacing shrinkage of ~ 5.18 Å for the carbon framework of Example 15 alone to -3, 75 Å for immobilized chalcogen, with 55 wt% Se and 45 wt% S, a d-spacing shrinkage of about 1.43 Å, which agrees well with the immobilized chalcogen presented above. Additionally, as shown in Table 6, there are still separate XRD patterns used for SeS ₂ for the MWCNT-5-SeS ₂ (70 wt%) and the MWCNT-1-SeS ₂ (70 wt% ), which were produced in air at 160 ° C for 16 hours, and there are also detectable XRD patterns that may be related to features of SeS ₂ for the sample MWCNT-5 / SeS ₂ (38% by weight) , which was produced in flowing argon at 130 ° C for 1.5 hours.

30th shows XRD results for multi-walled carbon nanotube (MWCNT) and SeS ₂ composite materials prepared in accordance with Comparative Example 4. When comparing the Raman results in 30th with the Raman results in 25A to 25B for the starting materials MWCNT-1, MWCNT-5 and SeS ₂ , one can see that the characteristics of SeS _{2 appeared} for all MWCNT-SeS ₂ composite materials ( 30th ), suggesting that the chemical bonding of SeS ₂ may not have been altered by MWCNT in these MWCNT-SeS ₂ composites. There is no observable increase in wavenumber in the D-band and no observable increase in wavenumber for the G-band, and if there were, that wavenumber (s) would decrease, suggesting that SeS ₂ may not be a significant chemical Has an effect on C = C bonding in MWCNT. The interactions of the guest molecules, SeS _2, and the host material, in this case MWCNT, may not reach a chemical level. The immobilized SeS ₂ , however, shows a wavenumber increase of 4.8 cm ^-1 for D-band, and 2.9 cm ^-1 for G-band. Both the results of XRD ( 27 ) as well as from Raman ( 30th ) advocate that immobilized chalcogen can have strong bonds between chalcogen and carbon backbone, possibly through electron donor and acceptor bonds or coordination bonds, resulting in a stronger C = C bond and a shorter spacing between the planes of the EMAC π bonding system of the carbon skeleton can result.

It has been observed that immobilized chalcogen can have strong chemical interactions between chalcogen and a carbon backbone, which is highly desirable for its application in a rechargeable battery. Immobilized chalcogen means that chalcogen is immobilized during an electrochemical battery process, such as a discharging process and a charging process, which can overcome the challenges faced by a rechargeable chalcogen battery, namely (1) forming a polychalcogenide ion, which, especially for a heavier element, such as sulfur, selenium, or tellurium, is soluble in an electrolyte and shuttles to the anode during the battery discharge process, reacting with the anode, in one aspect consuming electrical energy and converting chemical energy into heat that needs to be disposed of or managed; followed by a loading process in which can again form polychalcogenide at the anode, which is then dissolved in the electrolyte and shuttles back to the cathode, which further oxidizes the elemental chalcogen; the electrochemical Coulomb cycling efficiency is reduced during the shuttle process, which is undesirable; and (2) the formation of polychalcogenide, which can be detrimental to the chemical resistance of cathode materials, such as carbon, polychalcogenide, such as O _n ^2, S _n ² , Se _n ² , Te _n ² , or mixed thereof Heavily oxidize mold, especially for a lighter element, which may be one reason a prior art chalcogenide battery is unable to cycle well as a battery, especially for oxygen and sulfur.

J/mol, wobei T die Temperatur (K) und R die Gaskonstante 8,314 J/mol-K ist.The immobilization of chalcogen is achieved by having stronger chemical interactions or bonds or electron donor acceptor bonds or coordination bonds between chalcogen and a carbon skeleton. The level of such chemical bonding or interactions can be characterized by the kinetic energy required by chalcogen to escape from an immobilized chalcogen system. Kinetic energy for a chemical species is characterized by temperature: $\text{KE}=\frac{3\text{<figure-callout id="2" label="RT" filenames="DE112020000018T5\_0008.png,DE112020000018T5\_0013.png" state="{{state}}">RT</figure-callout>}}{2}$

J / mol, where T is the temperature (K) and R is the gas constant 8.314 J / mol-K.

In immobilized chalcogen, chalcogen is bound to a carbon framework, for example via a coordination bond or an electron donor acceptor bond. Chalcogen must therefore gain sufficient kinetic energy to break this chemical bond or overcome the chemical interactions, in addition to physical interactions between the chalcogen and the carbon framework, in order to escape from the immobilized chalcogen system or ultimately from the carbon framework. This can be determined by a TGA analysis. For each TGA analysis, a sample of approximately 15 mg immobilized chalcogen was placed in an alumina crucible with a lid and placed in the TGA analyzer oven chamber. The furnace chamber was closed with two separate argon gas flows, one at 100 ml / min. and the other at 50 ml / min. The sample was dewatered in the argon gas flows for 10 minutes, followed by ramping up from room temperature to 1000 ° C at a heating rate of 10 ° C / min. While TGA data was acquired.

31A shows the TGA analysis results for immobilized chalcogen with different percentages of sulfur and selenium, from pure selenium to pure sulfur. The midpoint weight loss temperature is the temperature halfway through the total weight loss for each immobilized chalcogen sample. The results appear to indicate that the midpoint weight loss temperature of selenium or sulfur is content dependent. The higher the sulfur content, the lower the midpoint weight loss temperature. The midpoint weight loss temperature for (neat) immobilized sulfur is 460 ° C (surprisingly high), which suggests that the sulfur actually binds to the carbon backbone in immobilized sulfur and requires a midpoint kinetic weight loss energy of 9.14 kJ / mol to achieve the To overcome binding and to escape from the carbon structure. The midpoint weight loss temperature for (pure) immobilized selenium is 605.7 ° C, which is higher than that disclosed above (595 ° C in Table 2), which may be due to the newly disclosed immobilized selenium having a carbon backbone includes, which has higher amounts of oxygen. It was noted that a carbon frame made from a continuous process with a rotary kiln (Example 15) has a higher oxygen content than that for the carbon frame made under stationary conditions in a stainless steel crucible (Example 14), and is higher than that for carbon frameworks made from a smaller batch of potassium citrate. Although it is not well understood why oxygen levels increase with batch size and from a stationary process to a continuous process, it is believed that an immobilized chalcogen that includes a carbon backbone that includes a higher amount of a chemical deactivator, that includes oxygen, is stronger may have chemical interactions between the chalcogen and the carbon skeleton, which may be the reason why the newly prepared immobilized selenium requires a higher level of mid-point kinetic weight loss energy (10.96 kJ / mol) to escape from the immobilized chalcogen system.

The midpoint weight loss temperatures for another immobilized chalcogen with different percentages of selenium and sulfur are also in 31A shown. 31B shows the analysis of immobilized SeS ₂ and a number of control samples. The data that is in the 31A to 31B are shown in the 32A to 32B graphically represented. In 32A was the midpoint weight loss temperature vs. Sulfur percentage fitted using a quadratic model described by the following equation T = -147.57 x ² + 7.2227x + C, where C is a constant, in this case 610.31 ° C, T is the midpoint weight loss temperature, x is the weight percentage of sulfur based on the total weight of selenium and sulfur.

The chalcogen may require a midpoint kinetic weight loss energy of -1840.3 x ² + 90.075 x + DJ / mol to overcome the chemical interactions and escape from the immobilized chalcogen, where D is 11,018 J / mol and x is the weight percentage of sulfur of all of the sulfur and selenium is in the immobilized chalcogen.

As described above, chalcogen immobilization is achieved by having stronger chemical interactions or bonds or electron donor acceptor bonds or coordination bonds between chalcogen and a carbon skeleton. The level of such chemical bonding or interactions can be characterized by activation energy, an energy barrier that a chalcogen molecule must overcome in order to escape the immobilized chalcogen system. Details relating to activation energy, pre-exponential factor (a kinetic parameter - shock frequency) and Arrhenius law are known in the art.

Herein, the activation energy and the pre-exponential factor of the immobilized chalcogen and the control samples, such as carbon-chalcogen MWCNT-SeS ₂ composites, were determined by a temperature modulation TGA method, each sample having two separate after placing in the oven Flows of argon gas in the furnace, one for equalization flushing (100 ml / min.), And the other specifically for measurement (50 ml / min). Each sample was placed under the argon flow for 30 minutes to remove physical water that may be absorbed on the sample. The temperature of the oven was set to modulate at an amplitude of 5 ° C with a period of 200 seconds, and the temperature of the sample was raised from room temperatures to 150 ° C and held isothermal for 5 minutes to equilibrate. The temperature was then increased from 150 ° C. to 700 ° C. at a heating rate of 3.5 ° C./min. ramped up while the temperature was modulating the amplitude of 5 ° C for a period of 200 seconds. The modulated TGA data were collected between 150 ° C and 700 ° C for the activation energy and pre-exponential factor in the temperature range between 150 ° C and 700 ° C. The weight loss was demonstrated to be 100% of the weight loss between temperatures of 200 ° C and 700 ° C. For further information one should (1) "Obtaining Kinetic Parameters by Modulated Thermogravimetry", RL Blaine and BK Hahn, J. Thermal Analysis, Vol. 54 (1998) 695-704 , and (2) Modulated Thermogravimetric Analysis: A new approach for obtaining kinetic parameters, TA-237, TA Instruments, Thermal Analysis & Rheology, a subsidiary of Waters Corporation.

The 33A to 33L show the results for activation energy and LogA or logarithm of the pre-exponential factor for immobilized chalcogen (such as sulfur, pure selenium, mixtures of sulfur and selenium and SeS ₂ ). The figures also show the results for activation energy and LogA for the control samples of carbon-chalcogen composite materials, which were prepared with SeS ₂ and multi-walled carbon nanotubes, in two different processes, which are described in Comparative Example 4. The modulated TGA analysis method described above was observed to produce two separate curves for Ea (activation energy, kJ / mol) and LogA (log pre-exponential factor (1 / min)) vs. Produced weight loss. In keeping with ASTM E1641-16 and E2954-14 and the disclosure above, the data for activation energy and LogA at 15% weight loss for immobilized chalcogen and control C-SeS ₂ samples were also prepared and tabulated in Table 6 which shows the activation energy for immobilized chalcogen from 137.3 kJ / mol to 144.9 kJ / mol. Immobilized SeS ₂ comprising a carbon skeleton comprising a chemical deactivation functional group comprising oxygen has an activation energy of 140 kJ / mol. The C-SeS ₂ composite materials (70% by weight), which were prepared with two multi-walled carbon nanotubes MWCNT-5 and MWCNT-1 in air at 160 ° C. for 16 hours (described in Comparative Example 4), however, each have an activation energy of 85.6 kJ / mol and 79.1 kJ / mol. The control sample MWCNT-5-SeS ₂ composite material (38% by weight), which was prepared in flowing argon at 130 ° C. for 1.5 hours, has an activation energy of 78.3 kJ / mol. As can be seen from Table 6, the interactions in the control composites do not reach a level of chemical interaction with a threshold of 96 kJ / mol. Namely, the immobilized chalcogen reached a chemical interaction level of 96 kJ / mol or above.

LogA (Log Pre-Exponential Factor, a measurement of the impact frequency) for each sample of immobilized chalcogen and for control C-SeS ₂ prepared with multi-walled carbon nanotubes are also in the 33B to 331 and 33J to 33L and tabulated in Table 6. The control samples show a LogA of 5.50 to 6.42, which corresponds to a pre-exponential factor between 3.16 × 10 ⁵ and 6.76 × 10 ⁵ . Immobilized chalcogen shows a LogA between 8.25 and 10.2, which corresponds to a pre-exponential factor between 1.79 × 10 ⁸ and 1.58 × 10 ¹⁰ . And immobilized SeS ₂ has a LogA 9.17, which corresponds to a collision frequency A of 1.48 × 10 ⁹ .

Additional samples were also prepared using the same procedures as described in Example 19 above. An example is an immobilized chalcogen with 34 wt .-% active material (chalcogen), 100 wt .-% consisting of sulfur; it has a theoretical specific capacity of 559 mAh / g-immobilized chalcogen, an increase of 32% in specific capacity compared to that (423 mAh / g-immobilized chalcogen) for the sample with a 26% by weight active material (chalcogen ) in which 100% by weight is sulfur; this new sample was also characterized for the activation energy (127.5 kJ / mol) and LogA (9.29). Another example is an immobilized chalcogen with 42 wt .-% active material (chalcogen), 51 wt .-% consisting of sulfur, with an 8% increase in the specific capacity from 422 mA / g to 490 mAh / g- immobilized_Chalkogen, compared to a sample with 36 wt .-% active material (chalcogen), 51 wt .-% consisting of sulfur. The sample with 42 wt% active material was measured for its activation energy (131.2 kJ / mol) and LogA (9.02). The next sample is an immobilized chalcogen with 55 wt .-% active material (chalcogen), with 100 wt .-% being selenium, with a 12% reduction in specific capacity from 418 mAh / g to 374 mAh / g- immobilized_chalkogen, and its activation energy and LogA of the immobilized chalcogen were each measured to be 138.9 kJ / mol with a LogA of 7.99. These additional examples with either an increase in active material (or active charge) or a decrease in active material (or active charge) demonstrate that immobilized chalcogen has strong interactions that exceed a level of chemical interactions (coordination bond or donor-acceptor bond) with an activation energy that is 96 kJ / mol or more and a collision frequency (A) of 1 × 10 ⁷ or more.

The experimental data of both the activation energy and LogA (which can be translated to A, pre-exponential factor, or collision frequency) by 10 ^{LogA demonstrate} that immobilized chalcogen has strong interactions of chalcogen and carbon, resulting in a level of chemical interactions, 96 kJ / mol, as well as a higher collision frequency. A high activation energy and / or a high shock frequency are highly desirable; Chalcogen is essentially anchored and is prevented from escaping from the immobilized chalcogen system or carbon framework; Chalcogen has a high frequency of collision with itself and the carbon framework; this would prevent the chalcogenide ion pendulum from occurring, since chalcogen is anchored, and result in better electron conduction between chalcogen and carbon.

Surprisingly, it is discovered that the immobilized chalcogen described herein has an activation energy 11 to 25 kJ / mol higher than immobilized selenium, which was described earlier herein, and also has an impact frequency 1 to 3 orders of magnitude higher. It is believed that this is due to the fact that the carbon skeleton is produced in a continuous process in a rotary kiln which has a higher amount of chemical deactivation functional group including oxygen.

An additional experiment for activation energy and log pre-exponential factor for the SeS ₂ powder was also carried out. The activation energy and the log pre-exponential factor for 15% by weight loss of pure SeS ₂ were determined to be 80.8 kJ / mol and 6.1, respectively.

Immobilized chalcogen includes chalcogen and a carbon backbone that includes a chemical deactivation functional group that includes or may include oxygen. Immobilized chalcogen can release water molecules, CO ₂ molecules and / or CO molecules at high temperatures. For example, a sample of immobilized chalcogen may first be dried at room temperature in a flow of inert gas such as helium to remove physically absorbed water. The sample can then be rapidly heated from room temperature to a preset temperature by placing it (in a reactor with a flowing helium stream) in a preheated oven and holding it at the preset temperature for 30 minutes. During this 30 minute period, a nitrogen cold trap can be used to trap water, CO _2, or other condensable chemical species. Untrapped species, such as CO, pass through the cold trap and flow with the carrier gas (flowing helium) directly to a gas chromatograph detector (GC detector). The amounts of released water, CO ₂ , CO or another chemical species such as COS can be quantified (weight ppm). The 34A to 34C show the results of the cumulative amounts of released water (H ₂ O), CO ₂ and CO from room temperature to 800 ° C for immobilized chalcogen, 100% by weight Se_0% by weight S and 83% by weight Se_17% by weight S, along with the corresponding amounts calculated from the starting materials.

34A shows that a large part of the water molecules from immobilized chalcogen is released in a temperature range between room temperatures and 400 ° C. The total amounts of water released between room temperatures and 800 ° C were found to be about 3,257 ppm (by weight) for the immobilized chalcogen with 100 wt% Se_0 wt% S and 4,690 ppm for the immobilized Chalcogen with 83 wt .-% Se_17 wt .-% S analyzed. It is believed that the presence of sulfur increases the amount of water released. In addition, it should be noted that the total amount of water released was projected to be about 1,652 ppm, as about 1/3 to 1/2 the actual amount of water released from the immobilized chalcogen. This can be additional evidence that immobilized chalcogen has strong chemical interactions between chalcogen and the carbon framework, which can affect the results of persistence of a chemical water-generating functional group.

34B shows that a large part of the CO ₂ molecules from immobilized chalcogen is released in a temperature range between room temperatures and 600 ° C. The total amounts of CO _{2 released} between room temperatures and 800 ° C were found to be about 10,595 ppm for the immobilized chalcogen with 100 wt .-% Se_0 wt .-% S and 18,799 ppm for the immobilized chalcogen with 83 wt .-% Se_17 wt% S projected. It is believed that the presence of sulfur also increases the amount of CO ₂ released. It should be noted that the total amounts of CO ₂ released were projected to be about 11.102 ppm, which is about the same as for immobilized chalcogen with 100 wt% Se_0 wt% S, but only about one Half of that for immobilized chalcogen with 83 wt% Se_17 wt% S is. This can be further evidence that immobilized chalcogen has strong chemical interactions between chalcogen and the carbon backbone, which in particular can influence the results of the resistance of a chemical CO ₂ -generating functional group with the presence of sulfur.

34C shows that CO molecules continue to be released from immobilized chalcogen between room temperature and 800 ° C with a tendency above 800 ° C. The total amounts of CO released between room temperature and 800 ° C were found to be about 11,618 ppm for the immobilized chalcogen with 100 wt% Se_0 wt% S and 8,690 ppm for the immobilized chalcogen with 83 wt% Se_17 Wt% S projected. It is believed that the presence of sulfur may not change the amount of CO released. It must be noted that the amounts of CO released at temperatures between room temperature and 400 ° C matched the calculated amounts of released CO. If the temperature is higher than 400 ° C, the amounts of CO released are significantly lower than the calculated (23,755 ppm for CO released between room temperatures and 800 ° C). This can be further evidence that chalcogen immobilization stabilizes the chemical functional group that forms CO through chemical interactions.

How to get out of the 34A to 34C understands, in immobilized chalcogen, for example a mass or a system of immobilized chalcogen, chemical interactions of chalcogen and carbon skeleton affect the durability of the chemical deactivation functional group (which may include oxygen) by removing water molecules, CO ₂ molecules and CO molecules at high temperatures are formed.

Example 20: A Battery Comprising Immobilized Chalcogen - Manufacture, Testing, and Performances.

Immobilized chalcogen can be used as a cathode material for a battery, a capacitor, or an energy storage device. A battery comprising immobilized chalcogen used as a cathode material can be made with different anode materials, for example with a metallic material (such as an alkali metal, an alkaline earth metal, a group IIIA metal, a group IVA metal and a group metal VA, and a transition metal), graphite, semiconductor material (such as silicon, germanium, arsenic, etc.) or a rare earth metal in the table of the periodic table.

A battery that includes immobilized chalcogen may have an organic electrolyte or an aqueous electrolyte. The organic electrolyte can be a carbonate or ether based or other organic electrolyte. A battery comprising immobilized chalcogen can have a separator, which can be an organic polymer, an inorganic membrane, or a solid electrolyte, which can also function as a separator of the battery.

A battery that includes immobilized chalcogen vs. Controls in the following examples, used lithium metal as an anode, a carbonate-based electrolyte (a conventional electrolyte in lithium-ion batteries), and a polymer separator.

A Li-chalcogen battery that includes immobilized chalcogen vs. Control C-SeS ₂

Immobilized chalcogen and control C-SeS ₂ composite chalcogen coin cell batteries tabulated in Table 6 were prepared and tested in accordance with processes similar to those described in Example 12 above. It should be noted that a battery can exhibit a rapid specific capacity lag in the early cycles. 35 Figure 10 shows the 10th cycle discharge and charge results for a battery prepared with immobilized chalcogen and control C-SeS ₂ composites made with MWCNT materials at rate 1. It should be noted that the cycling current for battery discharging or charging was determined using the theoretical specific capacity of 675 mAh / g-Se and 1,645 mAh / gS. Because of its low electrical conduction, sulfur is typically considered an electrical insulator and therefore a battery primed with sulfur will typically cycle at a very low C-Rate, 0.1C-Rate, and occasionally as low as 0.05C-Rate probably due to its intrinsically high internal electrical resistivity, resulting in an internal voltage drop. The higher the C-rate, the higher the internal voltage drop. Surprisingly, it is found that the battery comprising immobilized chalcogen, especially for those that have a high content of sulfur, for example 51 wt% sulfur, 68 wt% sulfur, 85 wt% S or even 100 wt% sulfur, can discharge at an IC rate with a midpoint voltage greater than 1.69 V and provide a specific capacity of 70% to 90% of a theoretical specific capacity. It has also been found that there is only one stage of discharge, suggesting that either sulfur or selenium gains 2 electrons and from sulfide or selenide in a single electrochemical step. There is no intermediate step, which suggests that no polychalcogenide ions, such as polysulfide or polyselenide ions, formed during the discharge process. 35 also shows that the batteries made with control C-SeS ₂ prepared with MWCNT materials all have a very low specific capacity (both discharge and charge) on their tenth cycle, for example a specific one Discharge capacity of 61 mAh / g for MWCNT-5-SeS ₂ (70% by weight) and 8.3 mAh / g for MWCNT_SeS ₂ (38% by weight).

35 also shows that a battery comprising immobilized chalcogen has a specific capacity (at the 10th cycle, mAh / g) 667 for 91.5 wt% Se_8.5 wt% S with a midpoint voltage of 1.853 V; 718.7 for 83 wt% Se_17 wt% S with a midpoint voltage of 1.8235 V; 869.7 for 66 wt% Se_34 wt% S with a midpoint voltage of 1.8269 V; 967.7 for 49 wt% Se_51 wt% S with a midpoint voltage of 1.8059 V; 944.4 for 32 wt% Se_68 wt% S with a midpoint voltage of 1.6587 V; 1,150.6 for 15 wt% Se_85 wt% S with a midpoint voltage of 1.7101 V; and 1,291.4 for 0 wt% Se_100 wt% S with a midpoint voltage of 1.6865V. Batteries made from C-SeS ₂ composite materials prepared with MWCNT-5, the sample prepared at 70 wt% (prepared in air) and the sample prepared at 38 wt% (prepared in argon flow) have only one tenth cycle specific capacities of 8.3 and 61.1 mAh / g, with midpoint voltages of 1.1523 V and 1.2636 V, respectively; the batteries prepared with MWCNT_C-SeS ₂ composite materials showed poor performance. It should be noted that the theoretical specific capacity for SeS _{2 is} 1,115 mAh / g. A battery that includes chalcogen provides 88%, 85.6%, 86.6%, 82.7%, 70.8%, 76.7%, and 78.5% of the theoretical specific capacities on its tenth cycle a voltage greater than 1.6V and a C-rate of 1 for the immobilized chalcogen batteries discussed in this paragraph.

36 also shows the cycling efficiency (Coulombic efficiency) data for batteries comprising immobilized chalcogen, all about 100% for after less than 10 cycles, suggesting that the battery comprising immobilized chalcogen did not have a pendulum effect of a polychalcogenide ion, which corresponds to a electrochemical process in one step from voltage vs. Specific capacity discharge curve. It should be noted that the batteries made in the current examples use carbonate-based LiPF ₆ electrolyte, which is the same electrolyte system as a lithium-ion battery. A Li-S battery would typically not work due to the formation of polysulfide. The literature teaches the use of ether based electrolyte to reduce the pendulum effect of the polysulfide ion. However, the presence of the polysulfide ion can also slowly degrade the carbon in the cathode, which is an analogy to the presence of peroxide or superoxide (in a lithium-air or lithium-oxygen battery), which is highly oxidizing for carbon materials in the cathode . Thus, it is difficult to achieve desirable cycling performances for a Li-S battery even if the hunting is minimized by using an ether-based electrolyte with low polysulfide solubility. In other words, minimizing the polysulfide solubility may not be a thorough solution to the root cause, more likely a compromised one, let alone its intrinsic property in its ability to oxidize the carbon materials on the cathode during the Can slowly oxidize battery cycles. The batteries prepared with MWCNT-5_SeS ₂ composite materials and carbonate-based electrolyte show a low coulombic efficiency, for example 77% for MWCNT-5_SeS ₂ (70% by weight) and 91% for MWCNT-5_SeS (38 Wt .-%) at 10 cycles, and these batteries delivered less than 10% of the theoretical specific capacity of the SeS ₂ (1112 mAh / g), which essentially did not work.

36 also shows the cycling performances of batteries comprising immobilized chalcogen compared to control batteries made with C-SeS ₂ composites prepared with MWCNT materials. It is surprising that a battery comprising immobilized chalcogen cycled well at a 1C rate after 300 cycles, while the control batteries prepared with MWCNT materials barely functioned as a rechargeable battery. It is also surprising to see a Li-S battery capable of delivering a specific capacity of more than 1,210 mA / gS at cycle 391, which is about 73.5% of the theoretical capacity (1,645 mAh / g) for a C rate equals 1. A battery prepared with immobilized chalcogen (15 wt% Se_85 wt% S) delivered 1,058 mAh / g at cycle 388, which is about 70.5% of the theoretical specific capacity (1,500 mAh / g) for a C rate equals 1. A battery prepared with immobilized chalcogen (SeS ₂ ) delivered 877.2 mAh / g at cycle 49, which corresponds to about 78.9% of the theoretical capacity (1112 mAh / g). A battery prepared with immobilized chalcogen (83 wt% Se_17 wt% S) delivered 614.2 mAh / g at cycle 55, which corresponds to 73.1% of a theoretical specific capacity (840 mAh / g) . Other batteries comprising immobilized chalcogen still perform well for their theoretical specific capacity, although cycling tests are still ongoing at the time of this disclosure.

The examples have been described with reference to the accompanying figures. Changes and modifications may arise for other people when reading and understanding the above examples. The above examples should therefore not be construed as limiting the disclosure.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (16)

A system or mass of immobilized chalcogen comprising: a mixture of chalcogen and a carbon, the activation energy for a chalcogen particle to escape from the system or the mass of immobilized chalcogen being ≥ 96 kJ / mol. System or mass of immobilized chalcogen after Claim 1 , wherein the chalcogen comprises one or more of the following: oxygen, sulfur, selenium and / or tellurium. System or mass of immobilized chalcogen after Claim 1 , wherein the immobilized chalcogen forms a coordination bond. System or mass of immobilized chalcogen after Claim 1 wherein the immobilized chalcogen forms an electron donor acceptor bond. System or mass of immobilized chalcogen after Claim 1 wherein the carbon forms a carbon skeleton that contains a chemical deactivation function group that withdraws electrons from a delocalized Extremely Massive Aromatic Conjugated (EMAC) -π bonding system of the carbon skeleton. System or mass of immobilized chalcogen after Claim 5 , wherein the carbon framework includes a carbon cation center on the EMAC π bonding system. System or mass of immobilized chalcogen after Claim 5 , wherein the chemical deactivation function group includes an oxygen-containing group ≥ 0.1 millimole (mmol) O / g. System or mass of immobilized chalcogen after Claim 7 , wherein the chemical deactivation functional group including the oxygen group includes at least one of the following: -CHO (formyl group or aldehyde group), -COR (acyl group or ketone group), -COOH (carboxyl group or carboxylic acid group), -COOR (a carboxylate group or ester group), an anhydride group or a carbonyl group (-CO-). System or mass of immobilized chalcogen after Claim 5 , wherein the chemical deactivation function group contains a nitrogen-containing group ≥ 0.1 mmol N / g. System or mass of immobilized chalcogen after Claim 9 wherein the chemical deactivating functional group including the nitrogen-containing group includes at least one of the following: a nitro group, -NO ₂ ; a nitroso group, -NO; an ammonium group, -N ⁺ R ₃ , where R can be an alkyl group, an aryl group or an H; a cyano group (-CN); a thiocyano group (-SCN); and / or an isothiocyano group (-NCS). System or mass of immobilized chalcogen after Claim 5 , wherein the chemical deactivation function group includes a sulfur-containing group ≥ 0.1 mmol S / g. System or mass of immobilized chalcogen after Claim 9 wherein the chemical deactivation functional group including the sulfur-containing group includes at least one of the following: an SO ₃ H group (a sulfonic acid) group; an SCN group (a thiocyano group); an SO ₂ R group (a sulfonyl ester) group, where R can be an alkyl group, an aryl group, or halogen; an a SO ₂ CF ₃ group (a trifluoromethyl sulfonyl ester group); and / or an SO ₂ -OR- or a sulfonium group (-S ⁺ R ₂ ), where R can be an alkyl group, an aryl group or another organic functional group, and R can be different. System or mass of immobilized chalcogen after Claim 5 , wherein the chemical deactivation function group contains a phosphorus-containing group ≥ 0.1 mmol P / g. System or mass of immobilized chalcogen after Claim 12 wherein the chemical deactivating functional group including the phosphorus-containing group includes at least one of the following: a phosphonic acid group (-PO ₃ H ₂ ) or its salt (-PO ₃ H ^- , -PO ₃ ^2- ); a phosphonate (-PO ₃ R ₂ , -PO ₃ HR or -PO ₃ R ^- ); a phosphonyl group (-POR2), where R is an arkyl, aryl, organic functional group; and / or a phosphonium group (-P ⁺ R ₃ ). System or mass of immobilized chalcogen after Claim 5 , wherein the chemical deactivation functional group contains a halogen-containing group ≥ 0.1 mmol X / g, wherein the halogen (X) comprises one of the following: fluorine, chlorine, bromine and iodine. System or mass of immobilized chalcogen after Claim 14 wherein the chemical deactivating functional group that includes the halogen-containing group includes at least one of the following: F, Cl, Br, I, -CF ₃ , -CCl ₃ , -CBr ₃ , -Cl ₃ and / or a highly halogenated alkyl group with more than a carbon.

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