CN102623676A - Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same - Google Patents
Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same Download PDFInfo
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- CN102623676A CN102623676A CN2012100882582A CN201210088258A CN102623676A CN 102623676 A CN102623676 A CN 102623676A CN 2012100882582 A CN2012100882582 A CN 2012100882582A CN 201210088258 A CN201210088258 A CN 201210088258A CN 102623676 A CN102623676 A CN 102623676A
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Abstract
The invention relates to a composite material for a positive pole of a lithium-sulfur battery, and a positive pole and a battery both made of the material. The composite material is the mixture of polynaphthylene or polynaphthylene derivative with the mass percentage of 20-34 percent, and sulfur. The preparation method for the composite material comprises the steps that firstly, the polynaphthylene or the polynaphthylene derivative is uniformly mixed with the sulfur; secondly, the mixture is placed in an electric tube furnace at the temperature of 150 DEG C for 5-8 hours, and then at the temperature of 300 DEG C for 2-3 hours; and lastly, the material is reduced to room temperature through natural cooling, so as to obtain the composite material. The invention also provides the positive pole for the lithium-sulfur battery and the battery which are made of the composite material. The lithium-sulfur battery provide by the invention has high discharge specific capacity, meanwhile, the utilization ratio of active substance is effectively improved, the cycling stability of the battery is also improved to a certain extent, and the cost of the battery is reduced.
Description
Technical field
The present invention relates to a kind of anode composite material of lithium sulfur battery and, belong to the energy and material technical field by the Anode and battery that it is processed.
Background technology
From the development of current battery, the production technology of lithium ion battery (comprising lithium-sulfur cell) reaches its maturity, and progressively is applied to the various aspects of the modern life.In recent years, the negative material of lithium ion battery has obtained important breakthrough, but no matter the positive electrode slower development of lithium ion is the ternary material from assembling structure, the LiFePO of polyanion type
4, or the LiMn of spinel structure
2O
4, theoretical specific capacity is all less than 200mAhg
-1Therefore, new high-energy-density, long circulation life, low cost and the exploitation of eco-friendly novel anode material are particularly important.And be the secondary cell of the composite material of negative pole, elemental sulfur or sulphur as positive pole with the lithium metal, its theoretical energy density is 2600Whkg
-1, be considered to one of secondary cell system of current tool research attraction.
Yao Zhendong etc. (Yao Zhendong, Wei Wei, Wang Jiulin etc. the lithium-sulfur rechargeable battery anode progress. Acta PhySico-Chimica Sinica; 2011,27 (5): 1005-1016.) point out that also there is Several Key Problems in present lithium-sulfur rechargeable battery: (1) elemental sulfur at room temperature is insulator; (2) elemental sulfur can be reduced into the polysulfide that be prone to dissolve in discharge process, causes active material to run off, and after polysulfide is dissolved in electrolyte, can worsen the ionic conductivity of electrolyte; (3) be dissolved in the direct contacting metal cathode of lithium of polysulfide of electrolyte, the self discharge reaction takes place; (4) corresponding pucker & bloat can take place in sulfur electrode in the charge and discharge process, destroys the physical structure of electrode to a certain extent.
Wu Feng etc. (Wu Feng, Wu Shengxian, Chen outstanding personality etc. multi-walled carbon nano-tubes is to the modification of elemental sulfur positive electrode chemical property. new carbon; 2010; 6 (25): 421-425.) record: to the existing problem of sulfur electrode; The researcher is through adding conducting polymer such as polyaniline, polypyrrole or carbon class adsorbent formation sulphur composite material in elemental sulfur; Examples of such additives can effectively stop the dissolving of polysulfide when improving the sulfur electrode electric conductivity, improved the chemical property of battery to a certain extent.
Lithium-sulfur cell generally by the composite material of sulphur or sulphur as positive pole, form with corresponding negative pole, electrolyte, diaphragm and shell.Conventional positive pole is mixed into slurry by composite material, conductive agent, adhesive and the related solvents of sulphur or sulphur, is coated on the collector, and oven dry, roll compacting become positive plate.CNT has unique mechanical, characteristic electron and chemical characteristic, can be widely used in the chemical property that improves electrode material.
(Juchen Guo such as Juchen Guo; Yunhua Xu; And Chunsheng Wang, Sulfur-ImpregatedDisordered Carbon Nanotubes Cathode for Lithium Sulfur Batteries.Nano Lett., 2011; 11:4288-4294.) reported a kind of composite material of CNT/sulphur, its first specific discharge capacity can reach 1000mAhg
-1More than.Though CNT/sulphur composite material is compared with other composite material, has remarkable advantages, it also has some to need badly to improve part, and for example: the total content of sulphur is little, and the utilance of sulphur is not high, and cyclical stability has much room for improvement etc.
Summary of the invention
For solving the problems of the technologies described above; The object of the present invention is to provide a kind of lithium-sulphur cell positive electrode to use composite material; Gather a kind of composite material that can be used in lithium-sulphur cell positive electrode that naphthalene obtains the package action and the good electrical conductivity of sulphur through mixing through gathering naphthalene and sulphur, utilizing.
The present invention also aims to provide the preparation method of above-mentioned lithium-sulphur cell positive electrode with composite material.
The present invention also aims to provide a kind of lithium-sulfur cell with anodal, it utilizes above-mentioned composite material to process.
The present invention also aims to provide a kind of lithium-sulfur cell, its just very above-mentioned lithium-sulfur cell is with anodal.
For achieving the above object, the present invention at first provides a kind of lithium-sulphur cell positive electrode to use composite material, and it is formed by gathering naphthalene or derivatives thereof and sulphur, wherein, gathers the naphthalene or derivatives thereof and uses the mass percent in the composite material to be 20-34% at this lithium-sulphur cell positive electrode.
In above-mentioned anode composite material of lithium sulfur battery, preferably, the structure of gathering naphthalene that adopts is shown below:
Wherein, n is >=100;
That is adopted gathers naphthalene derivatives through modifying and obtain gathering naphthalene, even gather naphthalene connection-NO
2,-NH
2Or-SO
3Obtain Deng functional group.
The present invention also provides the preparation method of above-mentioned lithium-sulphur cell positive electrode with composite material; It may further comprise the steps: will gather naphthalene or gather naphthalene derivatives and the sulphur mixing (wherein; The quality of gathering naphthalene or gathering naphthalene derivatives may be controlled to account for gathers naphthalene or gathers naphthalene derivatives and the 20-34% of the gross mass of sulphur), put into electric tube furnace, be warming up to 150 ℃ and keep 5h-8h; And then be warming up to 300 ℃ and keep 2h-3h, naturally cool to room temperature at last and obtain this lithium-sulphur cell positive electrode and use composite material.
In the preparation method of above-mentioned lithium-sulphur cell positive electrode with composite material, gathering naphthalene can prepare through following steps: with 3,4; 9,10-hexichol tetracarboxylic acid anhydride places electric tube furnace, after vacuumizing applying argon gas three times (wherein; Vacuum degree when vacuumizing will reach-and more than the 0.1MPa, during applying argon gas, make the pressure in the electric tube furnace reach 0-0.03MPa); Argon gas stream speed is adjusted into 20-30mL/min, is warming up to 530 ℃ and kept 6-10 hour, and then be warming up to 600 ℃-3500 ℃ and kept 5-10 hour; Naturally cooling obtains gathering naphthalene then.
In the preparation method of above-mentioned lithium-sulphur cell positive electrode with composite material, gathering naphthalene derivatives can prepare through following steps:
Concentration is that the sulfuric acid of 98wt% is as solvent; Is 20-30mL/g as the sulfuric acid of solvent with the ratio of gathering naphthalene, stir, and in reactor, to drip nitric acid that concentration is 65-68% and concentration through constant pressure funnel is 98% sulfuric acid; The mol ratio of gathering naphthalene and nitric acid is 1: 4-8, this nitric acid is with HNO
3Meter, the sulfuric acid of dropping and the volume ratio of nitric acid are 1-2: 1, in the process that drips nitric acid and sulfuric acid, temperature is controlled at 75-82 ℃, drips to finish, and stirs 1.5 hours again, obtains reactant liquor;
Then reactant liquor is poured in the frozen water, after fully stirring, is added an amount of alkali (for example NaOH) and be neutralized to pH value and reach 7, reduce to room temperature, filtration, the solid that obtains after the filtration is dried with high-purity washing 3 times, obtains gathering naphthalene derivatives.
According to specific embodiments of the present invention, preferably, the above-mentioned naphthalene derivatives that gathers can prepare through following concrete steps:
Gather naphthalene to 2g and place the 250mL there-necked flask, adding 40mL-80mL concentration is the sulfuric acid of 98wt%, is heated to 80 ℃; Drip the mixed acid that sulfuric acid that nitric acid that 24mL-48mL concentration is 65-68wt% and 28mL-56mL concentration is 98wt% is formed then, in the process that drips mixed acid, temperature remains on 80 ℃; After being added dropwise to complete; Continuation was reacted 1.5 hours under this temperature, naturally cooled to room temperature then, obtained reactant liquor;
Then reactant liquor is poured in the 300mL frozen water, after fully stirring, is added an amount of alkali and be neutralized to pH value and reach 7, temperature is adjusted into room temperature, filtration, the solid that obtains after the filtration is dried with high-purity washing 3 times, obtains gathering naphthalene derivatives, promptly gathers the itrated compound of naphthalene.
The present invention also provides a kind of lithium-sulfur cell with anodal, and it uses Composite Preparation by lithium-sulphur cell positive electrode provided by the present invention.
According to specific embodiments of the present invention, this lithium-sulfur cell can prepare through following steps with anodal:
Said lithium-sulphur cell positive electrode is mixed with composite material, conductive agent and the adhesive mass ratio according to 7: 2: 1, be coated on the collector, at 60-70 ℃ of following vacuum drying, roll compacting obtains this lithium-sulfur cell with anodal then.
According to specific embodiments of the present invention; Above-mentioned lithium-sulfur cell with positive pole in; The conductive agent that is adopted can be the conductive agent arbitrarily of lithium-sulfur cell ability usefulness, and the adhesive that is adopted can be the adhesive arbitrarily of lithium-sulfur cell ability usefulness, preferably; Above-mentioned conductive agent comprises one or more the combination in carbon black, acetylene black and the graphite powder etc., and above-mentioned adhesive comprises one or more the combination in Kynoar (PVDF), cyclodextrin and the gel etc.
In above-mentioned lithium-sulfur cell, the collector that is adopted can be a conductive metal foil arbitrarily, and preferably, above-mentioned conductive metal foil is an aluminium foil.
The present invention also provides a kind of lithium-sulfur cell, and it comprises positive pole, negative pole, electrolyte, barrier film and shell, and wherein, above-mentioned lithium-sulfur cell just very provided by the present invention is with anodal.
In the lithium-sulfur cell provided by the invention, its negative pole, electrolyte, barrier film and shell can be to use always in the lithium-sulfur cell.According to specific embodiments of the present invention, preferably, above-mentioned negative pole is a lithium; Above-mentioned electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li (LiTFSI); 3-dioxolanes solution, wherein, the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L; As the glycol dimethyl ether (DME) and 1 of solvent, the volume ratio of 3-dioxolanes (DOL) is 2: 1.The diaphragm that is adopted in the above-mentioned lithium-sulfur cell can be this area lithium ion battery diaphragm commonly used (the for example lithium ion battery diaphragm Celgrad2300 of ZheJiang NanYang Science Co., Ltd's production); Through adopting these assemblies and the anodal lithium-sulfur cell of forming provided by the present invention can have more performance.
Lithium-sulphur cell positive electrode provided by the present invention gathers naphthalene with composite material by adopting and derivative comes place of carbon nanotubes, and gathering naphthalene not only has good electrical conductivity, also has preferably from the shape structure; Particularly outstanding is gathers naphthalene and derivative itself also has capacity, and to gather naphthalene and derivative replaces CNT, gathering naphthalene and derivative thereof can have certain package action to sulphur as CNT; Has good electrical conductivity; But also have the incomparable cooperative effect of CNT (sulphur has higher discharge capacity as positive active material, and as the load material gather that naphthalene not only has good electrical conductivity and to the covering property of sulphur; Itself also has discharge capacity; From this angle, the anode composite material that they are formed just comprises the discharge capacity sum of two aspects, has synergy.And be not have discharge capacity) as the material itself of CNT, these loads of Graphene.The specific discharge capacity of lithium-sulfur cell provided by the present invention is high, has obviously improved the utilance of active material, and has improved the cyclical stability of battery to a certain extent, has reduced battery cost.
Description of drawings
Fig. 1 is the discharge curve first of the lithium-sulfur cell that provides of embodiment 1, Comparative Examples 1 and Comparative Examples 2;
Fig. 2 is the stable circulation linearity curve of the lithium-sulfur cell that provides of embodiment 1, Comparative Examples 1 and Comparative Examples 2;
The electrochemical impedance curve of the lithium-sulfur cell that Fig. 3 provides for embodiment 1 and Comparative Examples 1;
The electrochemical impedance curve of the lithium-sulfur cell that Fig. 4 provides for Comparative Examples 2;
Fig. 5 is the structural representation of lithium-sulfur cell;
The infrared spectrum that gathers naphthalene that Fig. 6 synthesizes for embodiment 1;
The infrared spectrum that gathers naphthalene that Fig. 7 synthesizes for embodiment 4.
Main drawing reference numeral explanation:
Embodiment
To understand in order technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification at present practical range of the present invention.
Present embodiment provides a kind of lithium-sulfur cell, and it prepares through following steps:
1, gather the synthetic of naphthalene:
4g dry good 3,4,9,10-hexichol tetracarboxylic acid anhydride (PTCDA) is positioned in the electric tube furnace; After vacuumizing applying argon gas three times, mix up argon gas flow velocity (25mL/min), install device for absorbing tail gas (absorption liquid is the calcium hydroxide saturated aqueous solution); Be that the speed with 5 ℃/min heats up under the condition of room temperature in initial temperature then, be warming up to 530 ℃, under this temperature, kept 8 hours; Then continue to heat up, be warming up to 1000 ℃, and under this temperature, kept 6 hours with the speed of 5 ℃/min; Naturally cooling obtains gathering naphthalene then, and its infrared spectrum is as shown in Figure 6.
2, the preparation of battery anode slice:
Mix synthetic gather naphthalene at 1: 3 by mass ratio with sulphur, in mortar, fully grind well, put into electric tube furnace calcining (be warming up to 150 ℃ earlier, keep 5h, continue to be warming up to 300 ℃ then, and under this temperature, keep 2h) then;
Calcined product is mixed thoroughly in mortar, mixed at 7: 2: 1 by mass ratio with conductive agent carbon black, PVDF then, grind, mix thoroughly, be coated on the aluminium foil,, be pressed into positive plate then at 60-70 ℃ of following vacuum drying.
3, the assembling of battery:
In glove box; It is (as shown in Figure 5 to be combined into button cell to the above-mentioned positive pole that makes 2 with negative pole 4, barrier film 3, electrolyte, shell (shell is made up of with lower casing 1 two parts last shell 5); Electrolyte is filled in button cell inside; Do not show among the figure), leave standstill more than 24 hours, test; Wherein, negative pole is a lithium; Electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li; 3-dioxolanes solution, the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, as the glycol dimethyl ether and 1 of solvent; The volume ratio of 3-dioxolanes is 2: 1, and diaphragm is Celgrad2300.
Present embodiment provides a kind of lithium-sulfur cell, and it prepares through following steps:
1, gathers the synthetic of naphthalene with embodiment 1.
2, the preparation of battery anode slice:
Mix synthetic gather naphthalene at 1: 4 by mass ratio with sulphur, in mortar, fully grind well, put into electric tube furnace calcining (be warming up to 150 ℃ earlier, keep 5h-8h, continue to be warming up to 300 ℃ then, and under this temperature, keep 2-3h) then;
Calcined product is mixed thoroughly in mortar, mixed at 7: 2: 1 by mass ratio with conductive agent carbon black, PVDF then, grind, mix thoroughly, be coated on the aluminium foil,, be pressed into positive plate then 60-70 ℃ of oven dry down.
3, the assembling of battery:
In glove box, be combined into button cell to the above-mentioned positive pole that makes with negative pole, barrier film, electrolyte, shell, left standstill 24 hours, test; Wherein, negative pole is a lithium; Electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li; 3-dioxolanes solution, the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, as the glycol dimethyl ether and 1 of solvent; The volume ratio of 3-dioxolanes is 2: 1, and diaphragm is Celgrad2300.
Present embodiment provides a kind of lithium-sulfur cell, and it prepares through following steps:
1, itrated compound synthetic that gathers naphthalene:
Place the 250mL there-necked flask to the 2g embodiment 1 synthetic naphthalene that gathers, add 50mL sulfuric acid (concentration is 98wt%) again, stir, be heated to 80 ℃; And in there-necked flask, drip the nitric acid that concentration is 65-68wt% (24mL) and concentration is the mixed acid of the sulfuric acid (28mL) of 98wt% through constant pressure funnel, in the process that drips mixed acid, remain internal temperature at 80 ℃; Drip and finish, continue under this temperature, to react 1.5 hours, naturally cool to room temperature then; Then pour this reactant liquor in the 300mL frozen water into, after fully stirring, add an amount of alkali neutralization; Cause till the pH=7, filter, then the solid that obtains after filtering with high-purity washing 3 times; Oven dry obtains the 2.68g product at last, promptly gathers the itrated compound of naphthalene.
2, the preparation of battery anode slice:
Mix synthetic gather naphthalene itrated compound at 1: 3 by mass ratio with sulphur, in mortar, fully grind well, put into electric tube furnace calcining (be warming up to 150 ℃ earlier, keep 5h-8h, continue to be warming up to 300 ℃ then, and under this temperature, keep 2-3h) then;
Calcined product is mixed thoroughly in mortar, mixed at 7: 2: 1 by mass ratio with conductive agent carbon black, PVDF then, grind, mix thoroughly, be coated on the aluminium foil,, be pressed into positive plate then 60-70 ℃ of oven dry down.
3, the assembling of battery:
In glove box, be combined into button cell to the above-mentioned positive plate that makes with negative pole, barrier film, electrolyte, shell, leave standstill more than 24 hours, test; Wherein, negative pole is a lithium; Electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li; 3-dioxolanes solution; The concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L; As the glycol dimethyl ether and 1 of solvent, the volume ratio of 3-dioxolanes is 2: 1, and diaphragm is lithium ion battery separator Celgrad2300 (ZheJiang NanYang Science Co., Ltd's production).
Present embodiment provides a kind of lithium-sulfur cell, and it prepares through following steps:
1, gather the synthetic of naphthalene:
2g dry good 3,4,9,10-hexichol tetracarboxylic acid anhydride (PTCDA) is positioned in the electric tube furnace; After vacuumizing applying argon gas three times, mix up argon gas flow velocity (25mL/min), install device for absorbing tail gas (absorption liquid is the calcium hydroxide saturated aqueous solution); Be that the speed with 5 ℃/min heats up under the condition of room temperature in initial temperature then, be warming up to 530 ℃, under this temperature, kept 8 hours; Then continue to heat up, be warming up to 1100 ℃, and under this temperature, kept 6 hours with the speed of 5 ℃/min; Naturally cooling obtains gathering naphthalene then, and its infrared spectrum is as shown in Figure 7.
2, the preparation of battery anode slice:
Mix synthetic gather naphthalene at 1: 3 by mass ratio with sulphur, in mortar, fully grind well, put into electric tube furnace calcining (be warming up to 150 ℃ earlier, keep 5h, continue to be warming up to 300 ℃ then, and under this temperature, keep 2h) then;
Calcined product is mixed thoroughly in mortar, mixed at 7: 2: 1 by mass ratio with conductive agent carbon black, PVDF then, grind, mix thoroughly, be coated on the aluminium foil,, be pressed into positive plate then at 65 ℃ of following vacuum dryings.
3, the assembling of battery:
In glove box; It is (as shown in Figure 5 to be combined into button cell to the above-mentioned positive pole that makes 2 with negative pole 4, barrier film 3, electrolyte, shell (shell is made up of with lower casing 1 two parts last shell 5); Electrolyte is filled in button cell inside; Do not show among the figure), leave standstill more than 24 hours, test; Wherein, negative pole is a lithium; Electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li; 3-dioxolanes solution, the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, as the glycol dimethyl ether and 1 of solvent; The volume ratio of 3-dioxolanes is 2: 1, and diaphragm is Celgrad2300.
Comparative example 1
This comparative example provides a kind of lithium-sulfur cell, and it prepares through following steps:
1, the preparation of battery anode slice:
CNT is mixed by mass ratio with sulphur at 1: 3, in mortar, fully grind well, put into electric tube furnace calcining (be warming up to 150 ℃ earlier, keep 5h-8h, continue to be warming up to 300 ℃ then, and under this temperature, keep 2-3h) then;
Calcined product is mixed thoroughly in mortar, mixed at 7: 2: 1 by mass ratio with conductive agent carbon black, PVDF then, grind, mix thoroughly, be coated on the aluminium foil,, be pressed into positive plate then 60-70 ℃ of oven dry down.
2, the assembling of battery:
In glove box, be combined into button cell to the above-mentioned positive plate that makes with negative pole, barrier film, electrolyte, shell, left standstill 24 hours, test; Wherein, negative pole is a lithium; Electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li, 3-dioxolanes solution, and the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, as the glycol dimethyl ether and 1 of solvent, the volume ratio of 3-dioxolanes is 2: 1; Diaphragm is lithium ion battery separator Celgrad2300.
Comparative example 2
This comparative example provides a kind of lithium-sulfur cell, and it prepares through following steps:
1, the preparation of battery anode slice:
Carbon black is mixed by mass ratio with sulphur at 1: 3, in mortar, fully grind well, put into electric tube furnace calcining (be warming up to 150 ℃ earlier, keep 5h-8h, continue to be warming up to 300 ℃ then, and under this temperature, keep 2-3h) then;
Calcined product is mixed thoroughly in mortar, mixed at 7: 2: 1 by mass ratio with conductive agent carbon black, PVDF then, grind, mix thoroughly, be coated on the aluminium foil,, be pressed into positive plate then 60-70 ℃ of oven dry down.
2, the assembling of battery:
In glove box, be combined into button cell to the above-mentioned positive plate that makes with negative pole, barrier film, electrolyte, shell, left standstill 24 hours, test; Wherein, negative pole is a lithium; Electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li, 3-dioxolanes solution, and the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, as the glycol dimethyl ether and 1 of solvent, the volume ratio of 3-dioxolanes is 2: 1; Diaphragm is Celgrad2300.
Performance test:
Adopt the Land test macro that the lithium-sulfur cell that embodiment 1-4 and Comparative Examples 1-2 are provided is carried out charge-discharge test; Wherein, Discharge and recharge the interval 1.0-3.0V that is; Charging and discharging currents density is 100mAh/g, and the specific discharge capacity of above-mentioned lithium-sulfur cell is as shown in table 1, and discharge curve and cyclical stability test result are as depicted in figs. 1 and 2 respectively first.
Adopt the CHI660d electrochemical workstation that the lithium-sulfur cell that embodiment 1-4 and Comparative Examples 1-2 are provided is carried out ac impedance measurement, wherein, the AC impedance frequency range is 10
-2-10
5Hz, amplitude are 5mv, electrochemical impedance test result Fig. 3 and shown in Figure 4.
In Fig. 1,3 and 4, the lithium-sulfur cell that on behalf of Comparative Examples 2, the lithium-sulfur cell that on behalf of Comparative Examples 1, the lithium-sulfur cell that on behalf of embodiment 1, A provide, B provide, C provide.In Fig. 2, the lithium-sulfur cell that on behalf of embodiment 1, curve 1 provide, the lithium-sulfur cell that on behalf of Comparative Examples 1, curve 2 provide, the lithium-sulfur cell that on behalf of Comparative Examples 2, curve 3 provide.
The specific discharge capacity of the lithium-sulfur cell that table 1 embodiment 1-4 and Comparative Examples 1-2 are provided
Can find out that from the content of table 1 and Fig. 1-4 employing that embodiment 1-4 is provided gathers naphthalene/sulphur composite material lithium-sulfur cell and obviously is being superior to the lithium-sulfur cell that Comparative Examples 1-2 is provided aspect discharge capacity, cyclical stability, the internal resistance of cell.
Claims (10)
1. a lithium-sulphur cell positive electrode is used composite material, and it is formed by gathering naphthalene or derivatives thereof and sulphur, and wherein, the said naphthalene or derivatives thereof that gathers uses the mass percent in the composite material to be 20-34% at this lithium-sulphur cell positive electrode.
2. lithium-sulphur cell positive electrode according to claim 1 is used composite material, and wherein, said structure of gathering naphthalene is shown below:
Wherein, n >=100;
The said naphthalene derivatives that gathers is to make to gather naphthalene connection-NO
2,-NH
2Or-SO
3Obtain.
3. claim 1 or 2 described lithium-sulphur cell positive electrodes are with the preparation method of composite material, and it may further comprise the steps:
To gather naphthalene or gather naphthalene derivatives and the sulphur mixing, put into electric tube furnace, and be warming up to 150 ℃ and keep 5h-8h, and then be warming up to 300 ℃ and keep 2h-3h, and naturally cool to room temperature at last and obtain said lithium-sulphur cell positive electrode and use composite material.
4. preparation method according to claim 3, wherein, the said naphthalene that gathers prepares through following steps:
With 3,4,9,10-hexichol tetracarboxylic acid anhydride places electric tube furnace; After vacuumizing applying argon gas three times, argon gas stream speed is adjusted into 20-30mL/min, be warming up to 530 ℃ and kept 6-10 hour; And then be warming up to 600 ℃-3500 ℃ and kept 5-10 hour, cooling obtains the said naphthalene that gathers naturally.
5. according to claim 3 or 4 described preparation methods, wherein, the said naphthalene derivatives that gathers prepares through following steps:
Place reactor gathering naphthalene; The sulfuric acid that adds concentration and be 98wt% is as solvent; Is 20-30mL/g as the sulfuric acid of solvent with the ratio of gathering naphthalene, stir, and in reactor, to drip nitric acid that concentration is 65-68% and concentration through constant pressure funnel is 98% sulfuric acid; Said mol ratio of gathering naphthalene and said nitric acid is 1: 4-8, said nitric acid is with HNO
3Meter, the sulfuric acid of dropping and the volume ratio of nitric acid are 1-2: 1, in the process that drips nitric acid and sulfuric acid, temperature is controlled at 75-82 ℃, drips to finish, and stirs 1.5 hours again, obtains reactant liquor;
Then reactant liquor is poured in the frozen water, after fully stirring, is added an amount of alkali and be neutralized to pH value and reach 7, temperature is adjusted into room temperature, filtration, the solid that obtains after the filtration is dried with high-purity washing 3 times, obtains the said naphthalene derivatives that gathers.
6. preparation method according to claim 5, wherein, the said naphthalene derivatives that gathers prepares through following steps:
Gather naphthalene to 2g and place the 250mL there-necked flask, adding 40mL-80mL concentration is the sulfuric acid of 98wt%, is heated to 80 ℃; Drip the mixed acid that sulfuric acid that nitric acid that 24mL-48mL concentration is 65-68wt% and 28mL-56mL concentration is 98wt% is formed then, in the process that drips mixed acid, temperature remains on 80 ℃; After being added dropwise to complete; Continuation was reacted 1.5 hours under this temperature, naturally cooled to room temperature then, obtained reactant liquor;
Then reactant liquor is poured in the 300mL frozen water, after fully stirring, is added an amount of alkali and be neutralized to pH value and reach 7, temperature is adjusted into room temperature, filtration, the solid that obtains after the filtration is dried with high-purity washing 3 times, obtains the said naphthalene derivatives that gathers.
7. a lithium-sulfur cell is with anodal, and it uses Composite Preparation by claim 1 or 2 described lithium-sulphur cell positive electrodes.
8. lithium-sulfur cell according to claim 7 is with anodal, and wherein, this lithium-sulfur cell prepares through following steps with anodal:
Said lithium-sulphur cell positive electrode is mixed with composite material, conductive agent and the adhesive mass ratio according to 7: 2: 1, be coated on the collector, at 60-70 ℃ of following vacuum drying, roll compacting obtains this lithium-sulfur cell with anodal then.
According to claim 7 or 8 described lithium-sulfur cells with anodal, wherein, said conductive agent comprises one or more the combination in carbon black, acetylene black and the graphite powder;
Said adhesive comprises one or more the combination in Kynoar, cyclodextrin and the gel;
Said collector is a conductive metal foil, and preferably, said conductive metal foil is an aluminium foil.
10. lithium-sulfur cell, it comprises positive pole, negative pole, electrolyte, barrier film and shell, wherein, each described lithium-sulfur cell of said just very claim 7-9 is with anodal; Preferably; Said negative pole is a lithium, and said electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li, 3-dioxolanes solution; Wherein, The concentration of said bis trifluoromethyl sulfonic acid imide li is 1mol/L, and as the glycol dimethyl ether and 1 of solvent, the volume ratio of 3-dioxolanes is 2: 1.
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