CN103403922A - Surface-mediated lithium ion-exchanging energy storage device - Google Patents

Surface-mediated lithium ion-exchanging energy storage device Download PDF

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CN103403922A
CN103403922A CN2011800678669A CN201180067866A CN103403922A CN 103403922 A CN103403922 A CN 103403922A CN 2011800678669 A CN2011800678669 A CN 2011800678669A CN 201180067866 A CN201180067866 A CN 201180067866A CN 103403922 A CN103403922 A CN 103403922A
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lithium
graphene
carbon
active material
energy storing
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CN103403922B (en
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A·扎木
刘辰光
D·内夫
B·Z·张
于振宁
王喜庆
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Nanotek Instruments Inc
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Priority claimed from US12/928,927 external-priority patent/US9166252B2/en
Priority claimed from US12/930,294 external-priority patent/US8859143B2/en
Priority claimed from US13/199,450 external-priority patent/US8889298B2/en
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

Provided is a surface-mediated, lithium ion-exchanging energy storage device comprising: (a) A positive electrode (cathode) comprising a cathode active material that is functional or not functionalized, but having a surface area to capture or store lithium thereon; (b) A negative electrode (anode) comprising an anode active material that is functionalized or not functionalized having a surface area to capture or store lithium thereon; (c) A porous separator disposed between the two electrodes; and (d) A lithium-containing electrolyte in physical contact with the two electrodes. In one embodiment, at least one of the two electrodes contains therein a lithium source prior to a first charge or a first discharge cycle of the energy storage device.

Description

The lithium ion exchanged energy storing device of surface mediation
The present invention is based on the achievement in research by the project of national science foundation of the US SBIR-STTR plan patronage.
The application requires the right of following U.S. Patent application:
(a) Aruna Zhamu, C.G.Liu, David Neff, with Bor Z.Jang, " Surface-Controlled Lithium Ion-Exchanging Energy Storage Device, " Application No. 12/928,927 (12/23/2010);
(b) Aruna Zhamu, C.G.Liu, David Neff, Z.Yu, and Bor Z.Jang, " Partially and Fully Surface-Enabled Metal Ion-Exchanging Battery Device; " Application No. 12/930,294 (01/03/2011); And
(c) Aruna Zhamu, C.G.Liu, Xiqing Wang, with Bor Z.Jang, " Surface-Mediated Lithium Ion-Exchanging Energy Storage Device, " Application No. 13/199,450 (08/30/2011).
Invention field
The present invention relates generally to the electrochemical energy storage device field, and more specifically relate to a kind of brand-new lithium ion exchanged energy storing device, its Anodic and negative electrode do not relate to the lithium diffusion (that is to say, do not need the slotting embedding of lithium or take off embedding) of turnover solid electrode active material body.Lithium memory mechanism in anode and negative electrode is all that surface is controlled, and eliminated the demand of the solid-state diffusion (insert embedding or take off embedding) to lithium, otherwise it is extremely low.This device has the high power density (usually even higher than the power density of ultracapacitor) of high-energy-density and the ultracapacitor of lithium ion battery.(mediated) lithium ion exchanged cell apparatus that in this article this device is called the surface mediation.
Background of invention
Ultracapacitor (ultra-capacitor or electrochemical capacitor):
Ultracapacitor is being considered for motor vehicle (EV), renewable stored energy and modern power network application.The high volume capacitance density of ultracapacitor comes from and uses porous electrode to produce Help the diffuse double layer electric charge to formHigh surface area.When applying voltage, form this electric charge electric double layer (EDL) near the electrolyte electrode surface.Near electrode the required ion of this EDL mechanism preexists in liquid electrolyte while making battery or is present in discharge condition, and comes from electrode hardly.In other words, remain the desired ion and the nonessential positive pole (negative electrode) that comes from that form in the EDL of negative pole (anode) active material (for example, active carbon granule) near surface; That is to say, not catch or be stored in the active material of cathode surface or inside.Similarly, remain the desired ion that forms in the EDL of active material of cathode near surface and nonessential come from active material of positive electrode the surface or inner.
, when ultracapacitor is charged again, be in ion (cation and anion) in liquid electrolyte and formed the typically ionic polarization by local molecule or electric charge of EDL(near their localizing electrodes separately).There do not is main ion-exchange between active material of positive electrode and active material of cathode.Can only by the concentration of cation available in electrolyte and anion, be determined by the stored quantity of electric charge (capacitance).These concentration typical case very low (being subjected to the solubility limit of salt in solvent), cause low energy density.In addition, lithium ion is not ultracapacitor electrolysis matter preferred or commonly used usually.
In some ultracapacitors, the energy of storage further increases by the pseudo-capacity effect that causes because of some electrochemical reactions (for example, redox reaction).In so pseudo-capacitor, the ion that relates to redox couple also is stored in electrolyte in advance.Equally, there is no main ion-exchange between active material of positive electrode and active material of cathode.
Because the formation of EDL does not relate to ion-exchange between chemical reaction or two comparative electrodes, the charging of EDL ultracapacitor or discharge process can be very quick, typically in seconds, cause very high power density (typically 5,000-10,000W/Kg).Compare with storage battery, ultracapacitor provides higher energy density, does not need to safeguard, much higher cycle life is provided, and needs very simple charging circuit, and usually safety many.Physics and non-chemically stored energy are the key reasons of their safety operation and especially high cycle life.
, although ultracapacitor has positive attribute, ultracapacitor is widely used in various commercial Application still has some technology barriers.For instance, when with storage battery, comparing, ultracapacitor has very low energy density (for example, the 5-8Wh/kg of business ultracapacitor is than the 10-30Wh/Kg of lead acid accumulator and the 50-100Wh/kg of NiMH storage battery).Lithium-ions battery has much higher energy density, typically in the 100-180Wh/kg scope, based on battery weight.
Lithium ion battery:
Although have much higher energy density, lithium ion battery provides very low power density (typically 100-500W/Kg), typically needs recharge in several hours.Conventional lithium ion battery also causes some safety problems.
The low power density of lithium ion battery or long recharge time are due to the mechanism of the lithium ion reciprocating motion between anode interior and negative electrode inside, it needs lithium ion to enter during recharging or inserts to be embedded in the body of active material of positive electrode particle, and at interdischarge interval, enters in the body of active material of cathode particle.For example, as shown in Fig. 1 (A), using during graphite granule makes the most frequently used lithium ion battery of active material of positive electrode as its characteristic, needing lithium ion to be diffused into during recharging between the face of graphite crystal at anode place in space.These lithium ions of great majority must leave cathode activity particle body, pass the hole (hole is filled with liquid electrolyte) of solid spacer body and enter in the graphite granule body of anode by diffusion from cathode side always.
At interdischarge interval, lithium ion diffuses out active material of positive electrode (for example take off embedding and leave graphite granule), the liquid electrolyte phase is passed in migration, and then diffuses in the body of composite cathode crystal (for example insert be embedded into graininess lithium and cobalt oxides, LiFePO4 or other lithium insert in compound).In other words, liquid electrolyte only arrives the outer surface (for example graphite granule of 10 μ m diameters) of solid particle, and the lithium ion that moves about in liquid electrolyte can only move (by liquid state diffusion fast) to graphite surface.Penetrating the solid graphite particles body will need the slow solid-state diffusion of lithium ion (being commonly called " inserting embedding ").Lithium diffusion coefficient in the solid particle of lithium metal oxide is typically 10 -16-10 -8cm 2/ sec(more is typically 10 -14-10 -10cm 2/ sec), and the lithium diffusion coefficient in liquid is approximately 10 -6cm 2/ sec.
In other words, the long time of these slotting embeddings or solid-state diffusion process need completes, because solid-state diffusion (the perhaps diffusion in solid) difficulty and slow.The present lithium ion battery why Here it is for example is used for plug-in hybrid-power automobile needs the recharge time of 2-7 hour, and completely contradict only several seconds of this and ultracapacitor.Above-mentioned discussion shows, can store with storage battery in the energy of as much and the energy storing device that still can recharge fully in one or two minute as ultracapacitor the revolutionary advancement in will being considered as energy storage technologies.
More new development:
In recent years, the people such as Lee use and comprise the cathode material of the multi-walled carbon nano-tubes (CNT) of carbonyl as lithium-ion capacitor (LIC), this lithium-ion capacitor comprises lithium titanate as anode material [S.W.Lee et al, " High Power Lithium Batteries from Functionalized Carbon Nanotubes; " Nature Nanotechnology, 5 (2010) 531-537].In half cell configuration, use the lithium paper tinsel as anode and use functionalized CNT as negative electrode, it provides relatively high power density.Yet the CNT base electrode of (LBL) method preparation also meets with some technical problems except expensive by successively.Some in these problems are:
(1) known CNT comprises a large amount of impurity, in particular as those transition metal or the noble metal granule of the required catalyst of chemical vapor deposition method.Cause and electrolytical adverse reaction because these catalysis materials have high tendency, so they are out of favour very much in battery electrode.
(2) CNT tends to form the entanglement group as ball top, and this entanglement group is difficult to process (for example, in being difficult to be dispersed in liquid flux or resinous substrates) during electrode is made.
(3) so-called " successively " method (LBL) used of the people such as Lee is slow and expensive technique, the extensive manufacturing that it is not suitable for battery electrode, perhaps have a large amount of productions of the electrode (most of batteries have the thickness of electrode of 100-300 μ m) of suitable thickness.The thickness of the LBL electrode that the people such as Lee (famous MIT research group) make is limited in 3 μ m or less.
(4) people may wonder how the thickness of LBL CNT electrode affects their performance.The careful inspection of the data that the people such as Lee (such as the figure S-7 of the people's such as Lee support material) provide shows: when LBL CNT thickness of electrode was increased to 3.0 μ m from 0.3 μ m, power density reduced an order of magnitude.If thickness of electrode is increased to useful battery or the thickness of electrode of super capacitor (for example 100-300 μ m), performance may further reduce.
(5) although ultra-thin LBL CNT electrode provides high power density (the extremely short distance because the Li ion only need to be advanced), but there is no the CNT base electrode endure of digital proof actual (real) thickness, because there is bad CNT to disperse and the unapproachable problem of electrolyte.The people such as Lee represent not use the CNT based combined electrode of LBL method preparation not show good performance.
(6) CNT has very limited amount appropriate site and accepts functional group and do not damage the basal plane structure.It is functionalized that CNT only has an end to be easy to, and this end is the minimum ratio on whole CNT surface.By making outside basal plane chemical functionalization, the electron conduction of balance CNT significantly.
Recently, our research group has reported the development of the high conduction active material of cathode of two kinds of newtypes in two pieces of patent applications, and described material has can be fast and reversibly with lithium ion, form the functional group of redox reaction.These materials are that (single-layer graphene and multi-layer graphene sheet are called as nano-graphene plate (platelet) or NGP) and disordered carbon (comprising soft carbon, hard carbon, carbon black, activated carbon, amorphous carbon etc.) to nano-graphene jointly.These two pieces of patent applications are: the people such as C.G.Liu " Lithium Super-battery with a Functionalized Nano Graphene Cathode; " U.S. Patent application 12/806,679 (08/19/2010) and the people such as C.G.Liu " Lithium Super-battery with a Functionalized Disordered Carbon Cathode; " U.S. Patent application 12/924,211 (09/23/2010).
These novel active material of cathode (being used for alleged " lithium superbattery ") comprise the nano-graphene plate (NGP) of chemical functionalization or functionalized disordered carbon material, it has some specific functional group, and described functional group is can be in charging and discharging cycle period of secondary battery unit reversible and form redox couple with lithium ion rapidly.In these two pieces of patent applications, functionalized disordered carbon or functionalized NGP are used for the negative electrode (but not anode) of lithium superbattery.In this negative electrode, the lithium ion in liquid electrolyte only must move to the edge of graphene film or the edge/surface of the aromatic ring structure (little graphene film) in surface (in the situation that functionalized NGP negative electrode) or disordered carbon matrix.Do not need solid-state diffusion at this negative electrode place.Exist functionalized Graphene with functional group or carbon to make it possible on cathode material surface (comprising edge) on it but not realize reversible lithium storage on body.Such cathode material provides a kind of lithium storage or has caught the lithium surface.
In the lithium ion battery of routine, lithium ion must diffuse into and leave the body of active material of cathode, for example lithium and cobalt oxides (LiCoO 2) and LiFePO4 (LiFePO 4).In these conventional lithium ion batteries, lithium ion also must diffuse into and leave space between face in the graphite crystal of taking on active material of positive electrode.The lithium at negative electrode and anode place inserts and to shift out process all very slow.Diffuse into and leave the slow process (being commonly called solid-state diffusion or slotting embedding process) of these intercalation compounds due to lithium, conventional lithium ion battery does not represent high power density, and these batteries recharge times that need to grow.These conventional equipments all do not rely on the selected functional group (for example being connected to edge or the basal plane of graphene film) that is easy to and reversibly with the lithium ion that carrys out self-contained lithium electrolyte, forms redox reaction.
In contrast, at two pieces of patent application (U. S. applications 12/806 early, 679 and 12/924,211) in the superbattery of report depend between lithium ion in functional group's (connecting or be bonded to the graphene-structured at negative electrode place) and electrolyte fast and the operation of reversible reaction.Only must spread to reach the surface/edge on Graphene plane at the liquid electrolyte that is arranged in negative electrode by the lithium ion of spacer body from anode-side.These lithium ions do not need to diffuse into or leave the volume of solid particle.Owing to not relating to the slotting embedding of diffusion-restricted at the negative electrode place, this process fast and can occur in seconds.Therefore, this is a kind of hybrid super capacitor-storage battery of brand-new type, and it shows unrivaled and unprecedented associating performance: excellent power density, high energy density, length and stable cycle life and wide operating temperature range.This device has the best part in storage battery and ultracapacitor field.
In the lithium superbattery of describing in these two pieces of patent applications, anode or the particle that comprises lithium titanate type active material of positive electrode (still needs solid-state diffusion, signal shows in Fig. 1 (B)), only comprise lithium paper tinsel (there is no nano structural material to support or to catch lithium ion/atom, signal shows in Fig. 1 (C)).In a rear situation, when to battery recharge, lithium is inevitable only be deposited on the front surface of anode collector (for example Copper Foil).Due to the specific area of collector very low (typically＜＜1m 2/ gram), overall lithium deposition rate relatively low (this problem is overcome in the present invention) again.
Summary of the invention
One embodiment of the invention are disclosed in following application: Aruna Zhamu, C.G.Liu, David Neff and Bor Z.Jang, " Surface-Controlled Lithium Ion-Exchanging Energy Storage Device; " U.S. Patent application 12/928,927 (12/23/2010).In this device, at least one in negative electrode and anode (just negative electrode) have that lithium is caught or lithium memory function surface (typically having the functional group with the lithium reversible reaction) and two electrodes all (just negative electrode) got rid of carrying out the needs of solid-state diffusion.Fig. 1 (D) and Fig. 2 are illustrated this.Anode and negative electrode all have the surface area of large quantity to allow lithium ion simultaneously deposited thereon, make it possible to realize significantly higher charging and discharging speed and higher power density.These surfaces of the nano structural material in electrode (for example Graphene, CNT, disordered carbon, nano wire and nanofiber) dispersed also provides more uniform electric field in electrode, lithium can be deposited on more equably in this electricity level and not form dendrite (dendrite).Such nanostructure has been eliminated the potential formation of dendrite, and described dendrite is the problem (being generally used for the 1980's and generation nineteen ninety early stage before by lithium ion battery, being replaced) in conventional lithium metal battery.In this article such device is called surface is controlled, lithium ion exchanged battery.
Another embodiment is disclosed in the U.S. Patent application 13/199,450 of submitting on August 30th, 2011, and wherein anode surface and cathode surface are not born with and can form with lithium the material of any functional group of redox couple.On the contrary, observe, during without any functional group, lithium atom be caught or be captured in some Graphene surfaces can in the situation that need not solid-state diffusion.No matter whether these surfaces contain functional group, if these surfaces can approach the electrolyte that contains lithium ion and with described electrolyte, directly contact, lithium atom can be stored with stable and reversible mode in the Graphene surface.Lithium memory capacity is directly proportional to directly being exposed to the electrolytical total surface area that contains lithium ion, as shown in figure 13.For example, the data point that has height ratio capacity in Figure 13 is about containing the battery (〉 98%C of Graphene electrodes), described Graphene electrodes only consists of carbon atom basically fully, do not have Zhu such as – OH or-functional group of COOH.Therefore, in this embodiment, Li functional group redox reaction mechanism is not the lithium memory mechanism of dominating.In order to define the scope of the application's claim, term " surface mediation battery " (SMC) do not comprise any lithium air (lithium-oxygen) battery, lithium-sulfur cell or wherein the operation of energy storing device relate to from installing and outsidely introduce oxygen or relate to any battery that forms metal oxide, metal sulfide, metal selenide, metal telluride, metal hydroxides or metal-halogen compounds at negative electrode.
The invention provides the lithium ion exchanged energy storing device (SMC) of surface mediation, it comprises: (a) anodal (negative electrode), this positive pole comprises functionalized or non-functionalized active material of cathode, and described active material of cathode has the surface area of catching or store lithium thereon; (b) negative pole (anode), described negative pole comprise functionalized or non-functionalized anode utmost point active material, and described active material of positive electrode has the surface area of catching or store lithium thereon; (c) be arranged at two porous spacer bodies between electrode; And (d) and two electrode physical contacts contain lithium electrolyte.In one embodiment, described active material of positive electrode and/or active material of cathode have the 100m of being not less than 2The specific area of/g, it contacts with the electrolyte direct physical, in order to receive thus lithium ion or to this, provide lithium ion.
In one embodiment, in the charging for the first time of energy storing device or for the first time before discharge cycles, at least one of two electrode kinds wherein comprises the lithium source, and at least active material of cathode be not functionalised materials (that is to say this material do not have can with the functional group of Li redox reaction).This lithium source can be preferably the form of the lithium particle of solid lithium paper tinsel, lithium bits, lithium powder or surface-stable.The lithium source can be to be pre-loaded into the lip-deep one deck lithium of active material of positive electrode film.
In another embodiment, the SMC electrode material (for example, comprise basically〉the primary Graphene of 99% carbon) surface, there is no bonding functional group thereon, can directly from liquid electrolyte, catch mutually lithium ion and in reversible and stable mode, lithium atom is stored on described surface, even this individual layer of lithium atom keeps being dipped in electrolyte.
In one embodiment, electrolyte comprises liquid electrolyte (for example organic liquid or ionic liquid) or gel electrolyte, and wherein lithium ion has high diffusion coefficient.Solid electrolyte is normally unacceptable, if but can use solid electrolyte some thin layers its show relatively high diffusivity.
For the operation principle of this battery or storage device (Fig. 2 (A)) is described, can consider following situation: wherein lithium source (for example lithium paper tinsel of small pieces) is applied between the anode (for example comprising non-functionalized graphene film) and porous polymer spacer body of nanostructure when making cell apparatus, and wherein the negative electrode of nanostructure comprise by interconnected pores around non-functionalized graphene film, described hole is preferably meso-scale (2nm-50nm), but can be less than 2nm.With reference to Fig. 2 (A)-(C), in discharge cycles for the first time, with the ionization of lithium paper tinsel to produce lithium ion in liquid electrolyte.Lithium ion moves rapidly the hole of passing the polymer spacer body and enters cathode side.Due to negative electrode be also be situated between to see porous have interconnected pores so that receiving fluids electrolyte therein, so in fact lithium ion need only pass liquid and arrive avtive spot on negative electrode.In one embodiment, this avtive spot is functional group, and in another embodiment, it can be edge or the surface of graphene film.In last situation, the functional group of on lithium ion and surface, carrying subsequently (for example carbonyl 〉=surface oxidation reduction reaction between O) is quick and reversible; In a rear situation, the Graphene surface directly contacts with electrolyte and is easy to and receives lithium ion from electrolyte.Two kinds of embodiments can realize repid discharge and the high power density of SMC.This and conventional lithium ion battery form sharp contrast, require lithium ion to diffuse in the body of solid state cathode particle (for example lithium and cobalt oxides of micron-scale) at interdischarge interval in conventional lithium ion battery, and this is process very slowly.
In above-mentioned example, discharge process continue until or the avtive spot on the complete ionization of lithium paper tinsel or active material of cathode occupied by lithium atom.During recharging, lithium ion discharges from the large surface of active material of cathode in one embodiment, diffuse through liquid electrolyte, and caught by the surface functional group of carrying or in without functional group's embodiment by the surface trapping of active material of positive electrode (for example only being electrochemically-deposited on the surface of anode material of nanostructure).Equally, do not need solid-state diffusion, and therefore whole process is very quick, needs of short duration recharge time.This is with enter the required solid-state diffusion of graphite granule at conventional lithium ion battery anode place lithium ion opposite.
Obviously, battery or energy storing device provide the platform of very unique exchange lithium ion between the large surface of the large surface of anode and negative electrode, the solid-state diffusion that they need to be in two electrodes.This process mainly is subjected to the surface of lithium to catch decision, additional liquid phase diffusion (these are all very fast).Therefore, this device is called as the lithium ion exchanged battery of surface mediation in this article.This compares from conventional lithium ion battery is the energy storing device of fully different and the type of obviously having any different, and all needs the solid-state diffusion (insert embedding and take off embedding) of lithium in described conventional lithium ion battery at charging and discharging cycle period anode and negative electrode.
The lithium ion exchanged cell apparatus of this surface mediation also is different from based on the conventional ultracapacitor of electric double layer (EDL) mechanism or pseudo-electric capacity mechanism same significantly.In two kinds of mechanism, between two electrodes not the exchange lithium ion (because lithium is not to be stored in the body or surface of electrode; On the contrary, they are stored near the electric double layer of electrode surface).When ultracapacitor is recharged, all form electric double layer near the activated carbon surface of anode-side and cathode side.Each and each EDL form (except the lip-deep electric charge of electrode material (such as activated carbon)) by the layer of the negatively charged species in electrolyte and the layer of positively charged species.When ultracapacitor is discharged, the randomization (electrode material surface further away from each other) that becomes in electrolyte of negatively charged species and positively charged species.In contrast, when SMC was recharged, all lithium ions were hunted down or are electroplated onto the active material of positive electrode surface basically, and the essentially no lithium of cathode side.When SMC was discharged, all lithium ions were caught (be stored in defect or be bonded to the phenyl ring center or and functional group reactions) by the active material of cathode surface basically.Few lithium retains in electrolyte.
Notably, in previous ultracapacitor, the charge storage capacity of ultracapacitor (even when use contains the Li electrolyte) is subject to the cation of participation EDL electric charge formation and the quantity of anion.This tittle is by the Li from lithium salts +The original concentration of ion and their counter ion counterionsl gegenions (anion) determines, this so that the solubility utmost point in electrolyte solvent determines by these ions.For this point is described, the let us hypothesis only has the Li of 1 mole at the most +Ion can be dissolved in the 1mL solvent and always have the 5mL solvent and add in specific ultracapacitor cell.At this moment, the Li of maximum 5 moles is arranged +Ion may reside in whole unit, and this quantity has determined to be stored in the maximum quantity of the electric charge in this ultracapacitor.
The chemolysis degree of the lithium salts during the lithium ion quantity that by contrast, can shuttle back and forth round between the anode surface of SMC and cathode surface is not subjected to this same solvent limits.Suppose to use identical 5mL solvent (to contain 5 moles of Li in SMC +Ion, as above described about ultracapacitor).Because this solvent is fully saturated by lithium salts, thus people can expect this solvent can't be from extra lithium source (5 moles is maximum) accept any more Li +Ion.Therefore, people can expect these 5 moles of Li +Ion is our maximum lithium quantity that can be used for storing electric charge (that is maximum Li that, at interdischarge interval, can be caught by negative electrode +Amount of ions, or the maximum Li that can be caught by anode during recharging +Amount of ions).Opposite with ordinary person in electrochemical field or even outstanding technical staff's this expection, we find beyond expectationly, the Li that can be caught by the surface of arbitrary electrode in SMC +(quantity of ion perhaps can be shuttled back and forth round Li between two electrodes +The quantity of ion) typically considerably beyond this solubility limit 1 or 2 orders of magnitude.As if thereby the realization in lithium source, anode place is by providing the lithium ion that significantly more than solvent, can dissolve therein to violate this expectation.
Unexpectedly in SMC, can help the lithium quantity of charge storage to be subjected to catch from electrolyte the quantity control (restriction) of the cathode surface avtive spot of lithium ion in addition.Even as the quantity in the surface activity site solvent Li that can once hold head and shoulders above +During the quantity of ion, (for example these in question 5 moles) are also so, and condition is the lithium ion that the lithium source of implementing can provide extra quantity.As mentioned above, these avtive spots can be functional groups in one embodiment, and perhaps they can be the blemish of Graphene, or the phenyl ring center on the Graphene plane (Fig. 3 (D) and (E)).Quite beyond expectationly in addition be, find that lithium atom can be strongly and reversibly be attached to each center of the phenyl ring (hexagon of carbon atom) that forms graphene film, perhaps can reversibly be captured by Graphene blemish position.
The lithium ion exchanged cell apparatus of this surface mediation also obviously is different from our two pieces of application (U. S. applications 12/806 early, 679 and 12/924,211) disclosed superbattery in, this superbattery do not have active material of positive electrode (anode-side only contains the anode collector) at the anode place.
In energy storing device of the present invention, not only negative electrode but also anode all have a large amount of surface areas to allow lithium ion to be deposited thereon simultaneously, make it possible to realize significantly higher charging and discharging speed and higher power density.In other words, in the high current density situation (during recharging fast), a large amount of lithium ions pours in anode-side fast, and each lithium ion is found site with deposition or is reacted on it.Anode collector (for example Cu paper tinsel) once only has alone a small amount of useable surface area, can't hold high like this lithium ion flux.By contrast, the bigger serface of nanostructure anode and optionally functionalised material (for example Graphene or CNT or their functionalized form) can hold a large amount of lithium ions simultaneously.In addition, these surfaces of nano material in electrode (as Graphene or CNT) dispersed also provides more uniform electric field in electrode, and wherein lithium can deposit more equably and not form dendrite.More surface area also means more saltation point, and each point only has a small amount of lithium, is not enough to form dangerous dendrite.Such nanostructure has been eliminated potential dendrite and has been formed, and it is the most serious problem that described dendrite is formed in conventional lithium metal battery.
In an embodiment of this SMC device, the negative electrode at least in two electrodes has the active material for non-functionalised materials (that is, not being attached to the functional group on its electrolytical surface of contact).Term " functionalized material " refers to have the material (for example carbonyl) of functional group, and this functional group can be with lithium atom or ionic reaction and forms redox couple.Active material of cathode has high specific area (〉 100m 2/ g), described specific area directly contact with electrolyte (for example directly being immersed in electrolyte) and can with from the reaction of electrolytical lithium ion with by electrolyte, catch lithium ion, and lithium atom is stored in surface activity site (for example blemish and phenyl ring center).
Preferably, two electrodes all have high-specific surface area (〉 100m 2/ g), it directly contacts with electrolyte, and can be with their surface activity site of lithium atom/ion trap/be stored in.Preferably, at least one in two electrodes has the non-sense material of nanostructure, and it has the 500m of being not less than 2/ gram (preferred〉1,000m 2/ gram, more preferably〉1,500m 2/ gram, and most preferably 2,000m 2/ gram) high-specific surface area is so that storage thereon or support lithium ion or atom.
Preferably, the lithium source comprises lithium bits, lithium paper tinsel, lithium powder, surface passivation or stable lithium particle, perhaps their combination.Before can the discharge process for the first time on this cell apparatus carrying out, the lithium source is implemented in anode-side.As an alternative, can carry out before charging process, the lithium source being implemented in cathode side for the first time to this cell apparatus.Select as another kind, can be during the battery manufacture process negative electrode and anode are all manufactured and comprise some lithium sources.Being noted that importantly that this solid lithium source provides awaits the most of lithium ion that exchanges between anode surface and cathode surface during charge-discharge cycles.Naturally provide some required lithium ions although contain lithium electrolyte, this quantity is too little so that can not make cell apparatus that high-energy-density is provided.This just why any symmetrical ultracapacitor (even contain based on lithium electrolyte) do not show high-energy-density.
In a kind of embodiment of this SMC device, at least a (preferably both) in active material of positive electrode and active material of cathode is selected from following:
(a) the disordered carbon material of porous, be selected from soft carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonization pitch, carbon black, activated carbon or part graphitized carbon;
(b) grapheme material, be selected from single-layer sheet or the multilayer plate of the graphene oxide of Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitrogenize Graphene, boron doped graphene, nitrogen-doped graphene or chemistry or thermal reduction;
(c) expanded graphite;
(d) mesoporous carbon (for example auxiliary synthetic the or chemical activation of the template by mesocarbon obtains);
(e) carbon nano-tube, be selected from Single Walled Carbon Nanotube or multi-walled carbon nano-tubes;
(f) carbon nano-fiber, metal nanometer line, metal oxide nano-wire or fiber or conductive polymer nanometer fiber; Perhaps
(g) their combination.
Although CNT is due to expensive and other technical problem rather than preferred nano structural material, CNT (separately or with other nano structural material, be combined) still can be used for the lithium ion exchanged battery of surface of the present invention control.
Comprise the embodiment of functional group for one of its Anodic and negative electrode or both, representational material can be selected from as follows: poly-(2,5-dihydroxy-Isosorbide-5-Nitrae-benzoquinones-3,6-methylene), Li xC 6O 6(x=1-3), Li 2(C 6H 2O 4), Li 2C 8H 4O 4(terephthalate of Li), Li 2C 6H 4O 4(Li trans-trans-muconate), 3,4,9,10-perylene tetracarboxylic acid-dianhydride (PTCDA) disulfide polymer, PTCDA, 1,4,5,8-naphthalene-tetrabasic carboxylic acid-dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5,8-tetra hydroxyanthraquinone, tetrahydroxy 1,4-benzoquinone and their combination.In one embodiment, at least a in the sense material have be selected from-COOH ,=O ,-NH 2,-OR and-functional group of COOR, wherein R is alkyl (for example 1 to 6 carbon atom).These organic or polymeric materials (molecule or salt) have and can carry out functional group reversible and redox reaction fast (as carbonyl) with lithium.These sense materials often have relatively low electron conduction, the sense material that therefore preferably will be selected from this group and (chemical bonding or be attached to nano structural material for example,, as nano-graphene, carbon nano-tube, disordered carbon, nano-graphite, be selected from the material of nano-graphene, carbon nano-tube, disordered carbon, nano-graphite, metal nanometer line, conducting nanowires, carbon nano-fiber and polymer nanofiber) combination.For example, the component aromatic ring of Graphene and disordered carbon (soft carbon, hard carbon, activated carbon, carbon black etc.) can they edge or surface on have functional group, described functional group can with above-mentioned sense material on place mat (matting) functional group (for example hydroxyl on the tetrahydroxy 1,4-benzoquinone) reaction.
As an alternative, the material with carbon element of nanostructure (as non-functionalized nano-graphene, carbon nano-tube, disordered carbon or nano-graphite) may only provide the surface that lithium atom can be deposited thereon, for example by defective bit, catches or catch at the phenyl ring center.Only there is nano structural material,, even without reactive functional groups, still can provide a large amount of lithium storage surfaces.
In one embodiment, the disordered carbon material can be by two phase compositions, and first-phase is that stacked body and the second-phase on graphite crystal or Graphene plane is amorphous carbon, and wherein first-phase is dispersed in second-phase or by the second-phase combination.This disordered carbon material can comprise the amorphous carbon by the graphite crystal that is less than 90 volume % and at least 10 volume %.
The active material of positive electrode of SMC or active material of cathode can comprise the non-functionalized nano-graphene that is selected from single-layer graphene film or multi-layer graphene plate.As an alternative, active material can comprise single wall or multi-walled carbon nano-tubes.
Therefore, in one embodiment of the invention, the active material of positive electrode of SMC and/or the functionalized grapheme material of active material of cathode right and wrong, it is selected from the graphene oxide of graphene oxide, Graphene fluoride, hydrogenation Graphene, nitrogenize Graphene, boron doped graphene, nitrogen-doped graphene, doped graphene, chemistry or thermal reduction or single-layer sheet or the multilayer plate of Graphene.As an alternative, functionalized single wall or multi-walled carbon nano-tubes (CNT), the oxidation CNT of active material of positive electrode and/or active material of cathode right and wrong, fluoridize the CNT of CNT, hydrogenation CNT, nitrogenize CNT, boron doping CNT, nitrogen doping CNT or doping.
The lithium source can be selected from mixture, the compound of lithiumation, the titanium dioxide of lithiumation, lithium titanate, LiMn2O4, lithium transition-metal oxide, the Li of lithium metal (for example for thin foil or powder morphology, preferred stable or surface passivation), lithium metal alloy, lithium metal or lithium alloy and lithium intercalation compound 4Ti 5O 12, or their combination.Particularly, lithium intercalation compound or lithiated compound can be selected from following material group:
(a) silicon of lithiumation (Si), germanium (Ge), tin (Sn), plumbous (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminium (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd) and their mixture;
(b) lithiumation alloy or the intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd and their mixture;
(c) oxide, carbide, nitride, sulfide, phosphide, selenides, tellurides or the antimonide of the lithiumation of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd and their mixture or compound, and
(d) lithiumation salt or the hydroxide of Sn.
Electrolyte can be selected from any electrolyte used in conventional lithium ion battery or lithium metal battery.Electrolyte is liquid electrolyte or gel electrolyte preferably.Electrolyte can comprise the ionic liquid of the lithium salts that adulterates.In cell apparatus, the anodal thickness that preferably has greater than 5 μ m, be preferably greater than 50 μ m, and more preferably greater than 100 μ m.
In one embodiment, in SMC, at least 90% lithium is stored on the surface of active material of positive electrode (lithium contacts with the anode surface direct physical) when this device is in charged state, and maybe at least 90% lithium is stored on the surface of active material of cathode (lithium contacts with the cathode surface direct physical) when this device is in discharge condition.
This SMC typically operates in the voltage range from 1.0 volts to 4.5 volts, but can stipulate its (for example from 1.5 volts to 4.0 volts or from 2.0 volts to 3.9 volts, etc.) operation in the subset of this scope.Also can operate more than 4.5 volts or a little less than 1.0 volts (not preferred).What can mention is that the symmetrical ultracapacitor take organic bath as feature can only be in 3.0 volts of operations and typical operation under 0 to 2.7 volt at the most.By contrast, use the SMC typical case of identical organic bath to operate under 1.5 volts to 4.5 volts.This is that SMC and ultracapacitor are another part evidences of two kinds of not congener energy storing devices, during their operation based on different mechanism and principle.
Preferably, the charging of SMC and/or discharge operation do not relate to the slotting embedding of lithium or solid-state diffusion.Usually be all this situation, even the multi-layer graphene plate is used for male or female.The slotting embedding typical case of lithium in the clearance space between two Graphene planes occurs in lower than 1.5 volts (with respect to Li/Li +) voltage, mostly lower than 0.3 volt.It relates to the reciprocal lithium ion that shuttles back and forth between anode surface and cathode surface lithium ion exchanged battery of the present invention, and its scope at 1.5 accompanying drawings to 4.5 volt is carried out.
Very surprisingly, this SMC device provides the typical case energy density that is not less than 150Wh/kg and the power density that is not less than 25Kw/kg, all based on total electrode weight.More typically, this cell apparatus provides greater than the energy density of 300Wh/kg with greater than the power density of 20Kw/kg.In many cases, this cell apparatus provides greater than the energy density of 400Wh/kg with greater than the power density of 10Kw/kg.Most typical, this cell apparatus provides greater than the energy density of 300Wh/kg with greater than the power density of 100Kw/kg.In some cases, power density is significantly higher than 200Wh/kg, and perhaps even higher than 400Wh/kg, this is than the high 1-3 of the power density of conventional ultracapacitor (1-10Kw/kg) order of magnitude.
In this SMC, the anodal thickness that preferably has greater than 5 μ m, more preferably greater than 50 μ m, most preferably greater than 100 μ m.
The present invention also provides the method for the described energy storing device of operation (SMC).The method is included in the anode place and implements lithium source and the described lithium of ionization source to discharge lithium ion in electrolyte during the discharge cycles for the first time of this device.The method comprises that further electrochemistry drives the lithium ion discharge to negative electrode, and the lithium ion that discharges is here caught by the active material of cathode surface, for example by with functional group, interacting or with Graphene, interact.The method may further include step: the cycle period that recharges at described device discharges lithium ion from described cathode surface, uses the external cell charging device that described d/d lithium-ion electric is urged to described active material of positive electrode surface.
As an alternative, the method can be included in the negative electrode place and implements lithium source and operation described lithium source and discharge lithium ion enter electrolyte during the charging cycle for the first time of this device.
The present invention further provides the method for the energy storing device of operating surface mediation, the method comprises: the battery that the surface mediation (a) is provided, it comprises anode, lithium source, porous spacer body, liquid or gel electrolyte and negative electrode, wherein in one embodiment, anode and/or negative electrode are functionalized and at the second embodiment Anodic and/or negative electrode, are to have the non-functionalised materials of catching the lithium surface; (b) interdischarge interval for the first time at this device discharges lithium ion from the lithium source; And (c) the exchange lithium ion between the lithium surface of catching of catching lithium surface and negative electrode at anode in subsequently charge or discharge operating period.Preferably, the charging and discharging of this device does not relate to the slotting embedding of lithium or solid-state diffusion.
The application discloses the method for another kind of operating surface mediation energy storing device.The method comprises: mediation battery in surface (a) is provided, and it comprises anode, lithium source, porous spacer body, electrolyte (lithium ion with initial number) and negative electrode, and its Anodic has with negative electrode the material of catching the lithium surface that contacts with electrolyte; (b) discharge from the lithium source at the interdischarge interval for the first time of this device lithium ion enters electrolyte; (c) the operation negative electrode is stored on cathode surface and (preferably has greater than 100m with the lithium of catching lithium ion and will catch from electrolyte 2The specific area of/g, more preferably greater than 1,000m 2The specific area of/g, most preferably greater than 2,000m 2The specific area of/g); And (d) during subsequently charging or discharge operation at the lithium ion (greater than initial number) of catching exchange some between the lithium surface of catching lithium surface and negative electrode of anode, wherein charging operations does not relate to lithium and inserts embedding.
The accompanying drawing summary
The lithium ionic cell unit of Fig. 1 (A) prior art, its use graphite, Si or lithium titanate as active material of positive electrode and LiFePO4 (or lithium and cobalt oxides etc.) as active material of cathode; (B) the lithium superbattery unit of prior art, it is used lithium titanate and makes (as functionalized nano-graphene, CNT or unordered carbon dust) as active material of positive electrode and negative electrode by the sense material; (C) the lithium superbattery unit of prior art, it has the negative electrode that the lithium paper tinsel anode sense material of nanostructure (but do not have) and functionalized Graphene, CNT or disordered carbon are made; (D) according to an embodiment of the invention an example of surface mediation lithium ion exchanged cell apparatus, it comprises: the nano structural material at anode place (have or do not have can with the functional group of lithium ion or atomic reaction), lithium source (for example lithium powder of lithium paper tinsel or surface passivation), porous spacer body, liquid or gel electrolyte (liquid is for preferred), can material the nanostructure official at negative electrode place.
The structure of the lithium ion exchanged cell apparatus of Fig. 2 (A) surface mediation, when making (before discharge or charging cycle for the first time) its be included in the nano structural material, lithium source (for example lithium powder of lithium paper tinsel or surface-stable), porous spacer body, liquid electrolyte at anode place, at the non-functionalised materials of the nanostructure at negative electrode place; (B) structure of this cell apparatus (thereby lithium is ionized and lithium ion diffuses through liquid electrolyte and arrives the surface of (functionalized or non-functionalized) nanostructure negative electrode and being caught by these surfaces fast) after discharge operation for the first time; (C) structure of this cell apparatus (lithium ion discharges from cathode surface, by liquid electrolyte, spreads the surface of arrival (functionalized or non-functionalized) nanostructure anode and is plated to fast on these surfaces) after recharging.Huge surface area can serve as support substrates, a large amount of lithium ions can Simultaneous Electrodeposition to this substrate.Can not use the anode collector with low specific surface area to complete separately so a large amount of, deposition simultaneously.
The schematic diagram of Fig. 3 (A) lithium memory mechanism, wherein be attached to the edge of aromatic ring or graphene film or the functional group on surface and can be easy to form redox couple with the lithium ion reaction; (B) theory of electric double layer forms, as less important or insignificant charge-storage mechanism; (C) lithium of in the phenyl ring center, catching on Graphene plane; (D) be captured on lithium atom in the Graphene blemish.
Fig. 4 can be at anode and/or negative electrode place as the example of the disordered carbon (with electrolyte, directly contacting) of the nano structural material with high surface: (A) schematic diagram of soft carbon, wherein the contiguous stacked body of graphene film or little aromatic ring is each other with the low-angle preferred orientation, and this is of value to growth or merges (but graphitization); (B) hard carbon (not non-graphitized); (C) carbon black, have a large amount of arrangements and form the little aromatic ring zone of nano-level sphere particle.Preferably, individual carbon black granules is activated with and opens wicket, and described wicket makes liquid electrolytic mass-energy arrive the edge of granule interior or the functional group that carry on surface, as shown in (D).
The SEM image of the nano-graphene sheet that Fig. 5 (A) is crooked; (B) the SEM image of another kind of Graphene pattern.These Graphene patterns can provide very high specific area (typically from 300 to 2,000m 2/ g).
The Ragone of Fig. 6 (A) five class batteries figure: the lithium ion exchanged battery unit of two classes surface mediations (class all have functional group in two kinds of electrode active materials and another kind of have a non-functionalized active material), the lithium superbattery of prior art (by Li metal anode and functionalized disordered carbon negative electrode, being formed), the symmetrical ultracapacitor (not using the lithium paper tinsel as the lithium source) of the prior art that is formed by two kinds of functionalized disordered carbon electrodes, and based on the symmetrical ultracapacitor (data of CNT based super capacitor read in the people's such as Lee figure) of LBL-CNT.(B) for functionalized surfaces battery and non-functionalized SMC, the energy density values of drawing as the function of charge/discharge cycle number.
The Ragone figure of the functionalized NGP of Fig. 7 (A) base lithium superbattery and two kinds of corresponding surface mediation lithium ion exchanged cell apparatus (a kind of have functional group and a kind ofly there is no a functional group).These data prove that further the performance of surface mediation device is better than superbattery, particularly under higher density (higher power density zone).(B) according to the long-term cyclical stability of the SMC of an embodiment of the application, than the long-term cyclical stability of the SMC (having functional group in its electrode) of previous application.
The charge/discharge curve of the battery of three kinds of surface activations of Fig. 8 (A) (surface-enabled) (M=is from the NGP of graphite, and C=is from the NGP of carbon fiber, the G=expanded graphite, EG).Discharge current density is 1A/g, (B) with the CV figure of the same battery of sweep speed 25mV/s, (C) has the Ragone figure of these batteries of thick negative electrode (200 μ m), (D) NGP, CB (carbon black), t-CB (chemically treated CB) and have the Ragone figure of the mediation of the surface based on the AC battery of thick negative electrode.All energy densities and power density values all are based on the LITHIUM BATTERY numerical value that total battery weight is calculated.
Fig. 9 is based on the symmetrical ultracapacitor (left side curve) of Graphene and have accordingly cyclic voltammetric (CV) figure of the present invention's surface mediation battery (right side graph) in the lithium source that is implemented in the anode place.
Figure 10 has the Ragone figure of the Graphene surface activation Li ion-exchange battery of Different electrodes thickness: energy density and power density values are based on total battery weight (A) and only based on cathode weight (B), calculate.
The cycle performance of several SMC of Figure 11: battery N (electronation graphene-based), battery AC (activated carbon) and battery M (from the expanded graphite of Delanium).
The specific capacity that the function as electrode specific surface area of several batteries of Figure 12 is drawn.Described electrode is from different Graphene associated materials preparations.
Preferred embodiment is described
, by the detailed description of the Invention that carries out with reference to following (it forms a part of this disclosure) by reference to the accompanying drawings, can more easily understand the present invention.Should understand the specific device, method, condition or the parameter that the invention is not restricted to that this paper describes and/or show, and term used herein is only to describe specific embodiment for mode by way of example, and do not plan to limit invention required for protection.
The invention provides a kind of electrochemical energy accumulating device, be referred to as in this article the lithium ion exchanged battery of surface mediation (or referred to as surface mediation battery, SMC).In many embodiments, the power density that this SMC device can provide is apparently higher than conventional ultracapacitor power density, and is significantly higher than the power density of conventional lithium ion battery.This device can show the energy density suitable with storage battery, and apparently higher than the ultracapacitor of routine.
The ion-exchange battery of this surface mediation consists of following: positive pole, it comprises the functionalized or non-functionalised materials (this functionalized or non-functionalised materials is preferably nanostructure, has nanoscale or meso-scale hole and a large amount of surface areas) that has the storage lithium or catch the lithium surface; Negative pole, it comprises the high surface area material (be preferably nanostructure, have nanoscale or meso-scale hole) that has the storage lithium or catch the lithium surface; Be arranged at two porous spacer bodies between electrode; The lithium electrolyte that contains with two electrode physical contacts; And the lithium ion source that is implemented in the male or female place.These are caught the lithium surface and directly contact with electrolyte in order to catch thus lithium ion or to this, discharge lithium ion.The preferred electrolyte type comprises liquid organic electrolyte, gel electrolyte and il electrolyte (preferably containing lithium ion), or their combination, yet can choice for use water-based or solid electrolyte.
Lithium ion source can be selected from lithium bits, lithium paper tinsel, lithium powder, surface-stable the lithium particle, be coated on active material of positive electrode or the lip-deep lithium film of active material of cathode, perhaps their combination.In a preferred embodiment, active material of positive electrode is lithiumation in advance, perhaps with lithium, applies in advance or plating in advance.Except relatively pure lithium metal, the lithium source can be selected from mixture, lithiated compound, lithiumation titanium dioxide, lithium titanate, LiMn2O4, lithium transition-metal oxide, the Li of lithium metal alloy, lithium metal or lithium alloy and the slotting embedding compound of lithium 4Ti 5O 12, perhaps their combination.Lithium is inserted the embedding compound or lithiated compound can be selected from following material group: (a) silicon of lithiumation (Si), germanium (Ge), tin (Sn), plumbous (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminium (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd) and their mixture; (b) lithiumation alloy or the intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd and their mixture; (c) lithiumation oxide, carbide, nitride, sulfide, phosphide, selenides, tellurides or the antimonide of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd and their mixture or compound; Perhaps lithiumation salt or the hydroxide of (d) Sn.
Although to not restriction of thickness of electrode, anodal thickness is preferably greater than 5 μ m, more preferably greater than 50 μ m, and most preferably greater than 100 μ m.Provided the example of the ion-exchange cell apparatus of such surface mediation in Fig. 1 (D) and Fig. 2.
Although do not wish to be subjected to any theory constraint, perhaps following Theory Thinking is helpful.
The internal structure of conventional lithium ion battery can be illustrated to be presented in Fig. 1 (A).In the battery discharge situation, lithium ion must be from active material of positive electrode particle (as graphite, silicon and lithium titanate) bulk diffusion (taking off embedding) (particle diameter=d out aAnd average solid-state diffusion distance=d a, and then/2) anode thickness (anode layer thickness=La and average diffusion distance=La/2) are passed in migration in liquid electrolyte.Subsequently, lithium ion must move (in liquid electrolyte) and pass porous spacer body (thickness=Ls), (thickness=Lc) arrives specific active material of cathode particle (average diffusion distance=Lc/2), and then diffusion (inserting embedding) is to (diameter=d in the body of particle to diffuse through the part cathode thickness in liquid electrolyte cAnd the average solid-state diffusion distance=d that needs c/ 2).Recharging in situation, lithium ion moves with opposite direction, but the roughly the same distance of must advancing.
In other words, the operation of conventional lithium ion battery relates to from an electrode (as anode, at interdischarge interval) in the lithium ion of electrode active material particles body (be not surface) take off embedding, and the lithium ion in the electrode active material particles body in (as negative electrode) is inserted embedding in comparative electrode.Generally speaking, the diffusion by liquid electrolyte is fast, but the diffusion by solid significantly slow (the approximately 3-8 order of magnitude).The operation of mediation battery in surface of the present invention (SMC) is based on the exchange (rather than in body of electrode, as in lithium ion battery) of a large amount of lithium ions between the surface of porous electrode in essence.This strategy has been removed fully lithium is inserted embedding and taken off the needs of the time-consuming process of embedding.SMC is that most of lithiums are stored on the huge surface area of electrode active material without inserting embedding basically.Typically〉90% lithium atom is trapped on the Graphene surface, and more typically less than 1% lithium, may enter by accident the inside of multi-layer graphene structure.The charge/discharge time of SMC only is subjected to the lithium ion migration restriction by liquid electrolyte (organic or ionic liquid), and this migration very soon and the ultra high power density that causes ultracapacitor (it is well-known with high power density) even also can't be equal to.Hereinafter to this further explanation:
Suppose that the diffusion coefficient of lithium ion in particular medium is that D and required travel distance are x, can be approximately t～x the diffusion time required according to known kinetics equation 2/ D.As first approximation, lithium ion is completed the required total time yardstick of charge or discharge process and can be estimated as:
t Always=(La/2) 2/ D Electrolyte+ (d a/ 2) 2/ D a+ (Ls) 2/ D s+ (Lc/2) 2/ D Electrolyte+ (d c/ 2) 2/ D c(1)
D wherein ElectrolyteLi ionic diffusion coefficient in=electrolyte, D aLi ionic diffusion coefficient in=active material of positive electrode particle, D s=pass through the Li ionic diffusion coefficient of porous spacer body, and D cLi ionic diffusion coefficient in=active material of cathode particle.
Below provide Li +In various liquid mediums or solid film or particle or by their typical diffusion coefficient (based on the open source literature data): liquid electrolyte (2 * 10 -6cm 2/ s); Spacer body (7.5 * 10 -7cm 2/ s); LiFePO 4Negative electrode (10 -13cm 2/ s); Li 3V 2(PO 4) 3Negative electrode (10 -13To 10 -9cm 2/ s); Nanometer Si anode (10 -12cm 2/ s); Graphite anode (1-4 * 10 -10cm 2/ s); And Li 4Ti 5O 12Anode (1.3 * 10 -11cm 2/ s).This means, for wherein using LiFePO 4Particle is as the conventional lithium ionic cell unit of active material of cathode, the last item in equation (1), (d c/ 2) 2/ D cBecause thereby its extremely low diffusion coefficient has determined required total diffusion time.In fact, the value of diffusion coefficient is 10 -10With 10 -16cm 2Change between/s, this depends at solid solution Li XFePO 4And Li 1-XFePO 4Lithium content or LiFePO in (X＜0.02) 4/ FePO 4The ratio of phase.
By contrast, the mesopore negative electrode that comprises functionalized nano-carbon material (as Graphene, CNT or disordered carbon) and lithium metal foil as the anode superbattery of (signal shows in Fig. 1 (C)) (battery of part surface mediation) in, therefore the Li ion does not need to diffuse through the solid state cathode particle, and without undergoing the restriction of the low solid-state diffusion coefficient at negative electrode place (LiFePO for example 4In particle 10 -13cm 2/ s).On the contrary, active material of cathode is highly porous, allows liquid electrolyte to arrive hole inner, and functional group is present in herein, thus be easy to and reversibly with by liquid medium (but not solid dielectric) with high diffusion coefficient (as 2 * 10 -6cm 2/ the lithium ion that s) diffuses into these holes reacts.In such superbattery, the last item (d in equation (1) c/ 2) 2/ D cBe actually non-existent.By the thickness of electrode and spacer body, determined now required total diffusion time.Top discussion is based on following prerequisite: the reversible reaction between the lithium ion in functional group and electrolyte is fast, and whole charging-discharge process is not to control reaction.
In the lithium-ion capacitor (LIC) of prior art, negative electrode is the nano-carbon material (as activated carbon) of central hole structure, but lithium titanate or graphite granule form anode (signal is presented in Fig. 1 (B)).In the situation that battery discharge, lithium ion must diffuse out lithium titanate particle or graphite granule (taking off slowly the embedding step), and then anode thickness is passed in migration in liquid electrolyte.Subsequently, lithium ion must (in liquid electrolyte) move through the porous spacer body, diffuses through the position of a part of cathode thickness arrival near the surface area of nanostructure active material of cathode in liquid electrolyte.Need not solid-state diffusion at cathode side.Whole process is determined by the solid-state diffusion at anode place basically.Therefore, with superbattery (part surface mediation), with complete surface mediation battery disclosed herein (SMC), compare, this LIC should show slower dynamic process (therefore, lower power density).
By using the typical value of parameters in equation (1), we have obtained the lithium superbattery unit of several conventional lithium ion battery types and several prior aries and the required total lithium transit time of battery charge or discharge process of LIC.First group is to have graphite granule anode and LiFePO4 negative electrode (Gr/LiFePO 4) conventional lithium ion battery.Second and the 3rd group is all conventional Li ion battery, has LiFePO 4Negative electrode and based on the Si particle or based on the anode of lithium titanate, be respectively (nanometer-Si/LiFePO 4And Li 4Ti 5O 12/ LiFePO 4).The 4th group is LIC (Li 4Ti 5O 12/ f-CNM), its Anodic is by Li 4Ti 5O 12Particle forms and negative electrode is functionalized carbon nanomaterial (f-CNM), for example CNT or active carbon (AC).The 5th group is that (the lithium paper tinsel/f-CNM), its Anodic is that lithium paper tinsel and negative electrode are carbon nanomaterials for the battery of part surface mediation.These data are following be presented at following table 1 (a) and (b) in:
Table 1 (a): (the CNM=carbon nanomaterial, comprise carbon nano-tube (CNT), nano-graphene plate (NGP), disordered carbon etc. to be used for the parameter of this calculating; Gr=graphite).
Figure BDA0000368256590000241
Table 1 (b): arrive required (t diffusion time of particle in anode La), the diffusion in the anode particle (ta),, by the diffusion time (ts) of spacer body, arrive (t diffusion time of cathode particles Lc), and the diffusion time in cathode particles (tc).
Figure BDA0000368256590000242
Can draw several important observed results from table 1 (a) and data (b):
(1) the graphite granule anode that is characterized as micron-scale (graphite diameter=20 μ m) of conventional lithium ion battery (above-mentioned first group) and the LiFePO of micron-scale 4Negative electrode (particle diameter=1 μ m), it needs some hours (as 8.4h) to complete required lithium ion diffusion process.With regard to why, conventional lithium ion battery shows low-down power density (typically 100-500W/Kg) and the unusual reason of long recharge time for this.
(2) problem of this long diffusion time can be able to partial rcsponse by using nano-scale particle, as above-mentioned second and the 3rd group (if for example anode and active material of cathode particle all have the diameter of 100 nanometers be 8 minutes).
(3) by contrast, for being characterised in that carbon cathode (for example f-CNT) and Li 4Ti 5O 12The LIC of nano particle anode, required diffusion time, 235 seconds (＜4 minutes) and the ultra-thin negative electrode when 200 μ m cathode thickness was (for example by the [S.W.Lee of MIT research group, Deng the people, Nature Nanotechnology, 5 (2010) 531-537] 0.3 μ m LBL f-CNT of successively method preparation) 1.96 seconds between.Regrettably, such ultrathin electrodes (0.3-3 μ m) has extremely limited practical value.
(4) for lithium superbattery (part surface mediation), thickness of electrode is leading factor.For example, in the situation that use lithium metal foil as anode (first kind), can shortly reach＜0.6 second (when cathode thickness is 0.3 μ m or 3 μ m) total diffusion time, and when cathode thickness was 200 μ m, be increased to 103 seconds (still less than 2 minutes) total diffusion time.
(5) above-mentioned observed result means that the lithium superbattery should have outstanding power density, particularly when electrode is ultra-thin.Here it is why the people such as Lee of MIT can have about them the power density of the 100Kw/Kg that the super lithium cells of the LBL f-CNT negative electrode of 0.3 μ m thickness reports.Yet useful electrode size is that thickness is at least 50 μ m (typically between 100 and 300 μ m), and moreover, these batteries with 0.3-3.0 μ m cathode thickness have very limited actual value.The viewed especially high power density of the lithium superbattery with LBL f-CNT negative electrode of reporting for people such as Lee is due to ultra-thin cathode thickness (0.3 μ m).
Show as Figure 11, the Performance Ratio of our mediation battery of the surface based on Graphene (thickness of electrode that typically has 100-300 μ m) is better based on the LBL f-CNT battery (part surface mediation) of thin electrodes.
Can notice, above-mentionedly about containing the lithium paper tinsel, as the calculating of the superbattery of anode, also be applicable to mediation energy storing device in surface of the present invention, except lithium paper tinsel thickness can be replaced with the thickness of nanostructure anode.Lithium source (lithium particle or lithium paillon foil) can not increase extra anode thickness value in Time Calculation, because the anode of nanostructure is " elasticity " or compressible.The lithium paper tinsel can be pressed against the anode of nanostructure, perhaps when making cell apparatus, the lithium particle can be brought in the anode of nanostructure.In case lithium particle or lithium paper tinsel are ionized during discharge cycles for the first time, the anode of nanostructure (for example pad of NGP or CNT base) will revert to rapidly the contact spacer body.
Can notice, be lithium superbattery (the Li paper tinsel/f-CNM), there is no the anode particle, and therefore there is no particle diameter (d in above-mentioned calculating of lithium paper tinsel for its Anodic aBe designated as zero).At interdischarge interval for the first time, with the Li paper tinsel by electrochemical ion to discharge ion.In above-mentioned calculating, the reaction that this surface is controlled is assumed to be it is to limit with non-multiplying power fast.In fact, when needing high-discharge-rate (when external circuit or the high current density of load request), this surface reaction can become the multiplying power restriction.This restriction self is not controlled by surface ionization speed may, but by the surface area of the limited quantity of lithium paper tinsel during discharge cycles for the first time, is controlled.In other words,, at the given time of interdischarge interval for the first time, only exist so many can discharge simultaneously from it surface area of lithium ion.
Recharging cycle period, lithium ion is got back to anode-side from movable cathode, attempts redepositedly on the surface (for example Copper Foil) of anode collector, and this surface is available at the anode place of superbattery surface (part surface mediation battery) only to be arranged.During recharging, for independent use collector (for example Copper Foil), admit the flux of a large amount of lithium ions to have two problems:
(1) if recharge multiplying power high (having high current density), fast transferring is got back to the surface that a large amount of lithium ions of anode-side all attempt to deposit to simultaneously collector, this surface typically have very low surface area (for the Cu paper tinsel specific area typically＜＜1m 2/ g).This limited surface area becomes the deposition velocity restriction.
(2) if recharge multiplying power low (having low current density), the lithium ion that returns can find a way out and deposit on collection liquid surface in inhomogeneous mode.At first some favourable site will receive more lithium deposition atom, and deposition can be continued with higher speed in these sites.Inhomogeneous lithium deposition like this can cause at the anode place dendrite to form, and this dendrite can increase and become more and more longer along with cycle-index, and finally penetrates spacer body arrival cathode side, thereby causes internal short-circuit.This possibility can cause the problem similar to the problem that perplexs the lithium metal battery industry in late period in the 1980's, and this problem finally causes basically all lithium metal battery products in early stage termination of generation nineteen ninety.
These two problems can solve by implement the nanostructure anode between anode collector and porous spacer body.The anode of this nanostructure preferably (is preferably greater than 100m by having high-specific surface area 2/ g) nano-carbon material forms, as nano-graphene plate (NGP, the Graphene of unified representation individual layer and multilayer form, graphene oxide, Graphene fluoride, doped graphene etc.), carbon nano-tube (single wall or many walls), carbon nano-fiber (vapor phase growth, electric spinning polymer is derivative, etc.), disordered carbon, metal nanometer line, conducting nanowires, etc.The specific area of the anode of this nanostructure is preferably greater than 100m 2/ g, more preferably greater than 500m 2/ g, further be preferably greater than 1,000m 2/ g, even more preferably greater than 1,500m 2/ g, and most preferably greater than 2,000m 2/ g.These surfaces are preferred directly contact with electrolyte (preferred liquid organic electrolyte) so that Direct Acquisition lithium ion or to this direct release lithium ion thus.
The enforcement of this nanostructure anode not only significantly increases the power density (Kw/Kg) of this surface mediation lithium ion exchanged energy accumulating device, and increases its energy density (Wh/Kg).Do not wish bound by theory, we think that the nanostructure anode of this new enforcement plays following at least three kinds of effects:
(1) recharging cycle period, the huge surface area of this nanostructure anode make a large amount of lithium ions can be in the high current density situation (high charge multiplying power) fast deposition simultaneously.This makes this energy storing device likely in several seconds or part, recharge in second.
(2) during the surface of the present invention of coming of new mediated the discharge operation for the first time of energy storing device, lithium paper tinsel or lithium particle were ionized, and discharged lithium ion at the anode place, and described lithium ion moves into cathode side and by the Graphene surface of negative electrode, caught.When recharging, these lithium ions return to anode and uniform deposition to the huge surface of nanostructure anode, form ultra-thin lithium coating thereon.The like this huge surface area on decorations lithium surface allows to discharge simultaneously a large amount of lithium ions during discharge cycles subsequently.Only has specific area usually far below 1m 2In the battery of the anode collector of/g, this while, a large amount of lithium ion release are infeasible.(〉 of the high-specific surface area of nanostructure anode〉100m 2/ g) make can quick charge again can repid discharge, realized high power density.
(3) anode of nanostructure, its electronics is connected to collector, and uniform electric field also is provided in anode compartment, thereby allows the lithium ion that returns to deposit to more equably the surface (as Graphene) of nano material.Because large surface area can be used for this purpose, therefore only have the lithium of minute quantity to deposit to any single point, be not enough to form dendritic growth.These reasons mean that the energy storing device that surface of the present invention is controlled is a kind of safer energy storing device.
The lithium ion exchanged cell apparatus of this surface mediation also obviously is different from conventional ultracapacitor in the following areas:
(1) conventional or ultracapacitor prior art does not have the lithium ion source of implementing at the anode place when making battery.
(2) electrolyte that is used for these prior art ultracapacitors is mainly without lithium base lithium or non-.Even when using lithium salts in ultracapacitor electrolysis matter when, the solubility of lithium salts in solvent has been set in fact and can have been participated in the electrolyte inner upper limit that forms the amount of lithium ions of electric charge electric double layer (approach but not on electrode material surface, as shown in Fig. 3 (B)) mutually.Therefore, ratio electric capacity and the energy density of gained ultracapacitor is relative low (for example typically＜6Wh/kg, based on total battery weight), and this forms contrast with for example 160Wh/kg (based on total battery weight) of mediation battery in surface of the present invention.
(3) ultracapacitor of prior art is based on electric double layer (EDL) mechanism or pseudo-electric capacity mechanism is stored their electric charge.In these two kinds of mechanism, there is no a large amount of lithium ion exchanged (even when using lithium salts in electrolyte) between two electrodes.In EDL mechanism, for example, the cation in electrolyte and anion pairing form the electric charge electric double layer at the near surface (but not being from the teeth outwards) of electrode active material.Cation is at large obtain or be stored among electrode active material or on.By contrast, use the example of Graphene as the electrode active material in mediation battery in surface of the present invention, lithium atom can be hunted down or be trapped in phenyl ring center or the lip-deep functional group of Graphene on defective bit, Graphene edge, Graphene plane.
(4) in EDL, cation and anion coexist in anode and negative electrode when ultracapacitor is in charged state.For example, in one of two electrodes of symmetrical ultracapacitor, negative electrical charge is present on the surface of activated carbon granule, thereby the thing class of its suction band positive electricity forms one deck positive charge at these near surfaces.Yet, in turn, thereby exist the electronegative thing class that is attracted by these positive charges to form one deck negative electrical charge nearby.Ultracapacitor electrode is had similarly and arranges, but electric charge is opposite on polarity.This is the concept of well-known Helmholtz diffusion charge layer in electrochemistry.When ultracapacitor discharged, the lip-deep electric charge of active carbon particle was used or disappears, and therefore the electronegative thing class of salt becomes randomization with positively charged thing class and stays electrolyte interior (but not on surface of active carbon particle) mutually.In contrast, when SMC is in charged state, thereby most of lithium ion be attracted adhere to or electroplate on the Graphene surface of anode and cathode side substantially without any lithium.After discharge, all lithium atoms are caught by the active material of cathode surface basically, do not have or almost do not have lithium to stay in electrolyte.
(5) use only operates based on the symmetrical ultracapacitor of prior art (EDL ultracapacitor) of the organic bath of lithium salts in the scope of 0-3 volt.They can not be in operation more than 3 volts; Do not have while exceeding 3 volts extra charge storage capacity and in fact organic bath usually at 2.7 volts, start to decompose.By contrast, the operate typical of mediation battery in surface of the present invention in the scope of 1.0-4.5 volt, the most typically (for example sees also Fig. 9) in the scope of 1.5-4.5 volt, but preferred in the scope of 1.5-4.0 volt.Two scopes of this of operating voltage have reflected diverse charge-storage mechanism.Although, overlapping (scope of 1-3 volt and the scope of 1.5-4.5 volt) that as if the 1.5-3.0 volt is arranged between these two voltage ranges on written, but this is overlapping is artificial, accidental, rather than scientific meaning, because charge-storage mechanism is fundamentally different, such as two the distinct cyclic voltammetrics (CV) in Fig. 9 figure confirmation.
(6) the EDL ultracapacitor of prior art typically has the open circuit voltage of 0-0.3 volt.By contrast, described SMC typically has〉open circuit voltage of 0.6 volt, more commonly〉0.8 volt, and the most common ground〉1.0 volts (some〉1.2 volts or even 1.5 volts, this depends on the type of active material of positive electrode and with respect to the quantity of negative electrode, and the quantity in lithium source).
(7) Figure 10 (A) and the figure of Ragone (B) have confirmed well that mediation battery self in surface of the present invention is a class energy storage batteries, and it also is different from lithium ion battery both to be different from super capacitor.
(8) Figure 11 has shown the cycle performance of several SMC: battery N (based on Graphene), battery AC (activated carbon) and battery M (from the expanded graphite of Delanium).Some SMC demonstrate capacity continue to increase (after some less initial decaies) with the charge/discharge cycle number, and this observed result has confirmed that further SMC is different from the uniqueness of ultracapacitor or lithium ion battery.
Charge-storage mechanism and energy density Consideration
Be reluctant to be subject to theory, as if in the surface mediation battery (SMC) of Li ion-exchange, the specific capacity of electrode depends on the number of the lip-deep avtive spot of Graphene of nanostructured carbon material, lithium ion can therein or be caught on described Graphene surface on it.Disclosed as front, this carbon nano-structured material can be selected from activated carbon (AC), carbon black (CB), hard carbon, soft carbon, expanded graphite (EG) and the graphene film that separates (nano-graphene plate or NGP) from native graphite or Delanium.These material with carbon elements have the aromatic ring structure of common building block-Graphene or class Graphene.We think and have four kinds of possible lithium memory mechanisms, and are as described below:
Mechanism 1: in the Graphene plane, the geometric center of phenyl ring is that lithium atom is adsorbed onto the avtive spot on it;
Mechanism 2: the defective bit on graphene film can be caught lithium ion;
Mechanism 3: the cation (Li in liquid electrolyte +) and anion (from lithium salts) can form the electric double layer of electric charge near electrode material surface;
Mechanism 4: the functional group on Graphene surface/edge can form redox couple with lithium ion.
Surface bond mechanism (mechanism 1): when not having electrolyte contention lithium, lithium atom can with the Graphene plane on the C atom form stable interaction.The Li-C key of (there is no functional group) can not cause the sp of carbon track in such layer 2To sp 3Transformation.Energy calculate the graphene layer (lithium atom with the phenyl ring center that is bonded to the Graphene plane) shown such absorption lithium atom but in the stabilizability that does not exist in the electrolyte situation.Our the unexpected graphene layer (Fig. 3 (D)) of observing absorption Li can be in the situation that there be spontaneous formation in electrolyte.This is beyond expectation, because in lithium ion and electrolyte, other composition has good chemical compatibility (Here it is, and they are present in reason in electrolyte naturally), and these compositions (for example solvent) can remain on lithium ion in solvent phase attempting with Graphene surface competition, rather than by Graphene surface " abduction ".Bonding between lithium atom and Graphene surface is strong very unexpectedly.
Lithium ion in defective bit is captured (mechanism 2): the active defect in carbonaceous material such as edge and room (for example Fig. 3 (D)) can have the ability to admit extra lithium.There are inevitably a large amount of these defects or the unordered site that are caused by Graphene production oxidation commonly used and reduction process in NGP.
Electric double layer (EDL) (mechanism 3): the SMC electrolyte typically consists of the lithium ion salt that is dissolved in solvent.Electrolytic salt can be selected from lithium perchlorate (LiClO 4), lithium hexafluoro phosphate (LiPF 6), lithium fluoroborate (LiBF 4), hexafluoroarsenate lithium (LiAsF 6) and trifluoromethanesulfonic acid lithium (LiCF 3SO 3) etc.In principle, as shown in Fig. 3 (B), some electric double layers (EDL) can be conceptive by cation (Li for example +) and their gegenion (PF for example 6 -And BF 4 -Anion) form, and for this EDL contribution of SMC energy content of battery memory capacity, controlled by the electrolytic salt concentration in solvent.
Give the electrode surface areas of sufficient amount, the maximum contribution of 3 pairs of overall charge memory capacity of mechanism is determined by the concentration of cation or anion.EDL mechanism is typically contributed less than about total lithium ion storage volume of the SMC of 10% (more typical＜5%), be explained as follows: we have prepared and have tested several symmetrical ultracapacitors, every kind forms (anode and negative electrode have same composition) by two identical graphene-structured or other nano structure electrodes, but anode does not have lithium metal foil/powder as the lithium source and there is no pre-lithiumation.For example, the CV coordinate diagram that is based on ultracapacitor and the corresponding SMC of Graphene shown in Figure 9.In two kinds of unit, electrolyte is 1M LiPF 6/ EC+DMC and sweep speed are 25mV/s.Interestingly notice, this organic bath can only operate in 0 to＜2.7 volts in symmetrical ultracapacitor structure, but can operate in 1.5 to 4.5 volts in the SMC structure.This is the most unexpected because do not have organic bath (based on organic solvent) to operate (typically＜3.5 volts and more typically＜＜3.0 volt) under up to 4.0 volts in ultracapacitor.Organic bath is defined as not being based on those electrolyte of water or ionic liquid, but contains organic solvent.Representative from the capacity of the overlapping voltage range of 1.5 volts to 2.7 volts account for the SMC total capacity less than 5%.In fact, the operation of SMC,, even in the voltage range of 1.5-2.7 volt, be mainly also to catch by surface, rather than the formation of electric double layer.
The formation of redox couple (mechanism 4): the redox reaction on surface can occur in (if any) between lithium ion and functional group, for example carbonyl (〉 C=O) or carboxyl (COOH), as shown in Fig. 3 (A).The existence of functional group, for example-COOH and C=O, have good grounds in the graphene oxide of chemical preparation.The formation of these functional groups is graphite natural results by the oxidation reaction of sulfuric acid and strong oxidizer (for example being generally used for nitric acid and the potassium permanganate of graphene oxide preparation).Both all can have the functional group that surface or edge carry unsegregated graphite worm (expanded graphite) and the graphene film that separates (NGP).In one embodiment, in the application SMC mainly based on mechanism 1 and 2.
Usually, the contribution of electric double layer mechanism is lower than the SMC charge storage capacity of 10% (mostly lower than 5%).When male or female comprises some multi-layer graphene plates,, if the SMC operating voltage drops to lower than 1.5 volts, may there be some lithiums to insert and be embedded in the body of active material.Even in this case, when this device was in charged state, no more than 20% lithium was stored in the body of active material of positive electrode, perhaps when this device is in discharge condition, was no more than 20% lithium and was stored in the body of active material of cathode.Typically, when this device is in charged state, is no more than 10% lithium and is stored in the body of active material of positive electrode, perhaps when this device is in discharge condition, is no more than 10% lithium and is stored in the body of active material of cathode.
The nano structural material that uses in male or female of the present invention can preferably contain nano-graphene plate (NGP), carbon nano-tube (CNT) or disordered carbon.These nanostructured carbon material can be used as has useful functional group (for example carbonyl) but nonconducting other support base organic or polymer official energy material.CNT is the material of knowing in nanometer material industry, and therefore, this paper no longer discusses to it.Below the description of the disordered carbon of NGP and nanostructure:
Nano-graphene plate (NGP)
the application of active development single-layer graphene always of applicant's research group [B.Z.Jang and W.C.Huang, " Nano-scaled Graphene Plates, " Application No. 10/274,473 (10/21/2002), be US Patent No. 7 now, 071, 258 (07/04/2006)], comprise the use [L.Song of Graphene in ultracapacitor, A.Zhamu, J.Guo, and B.Z.Jang " Nano-scaled Graphene Plate Nanocomposites for Supercapacitor Electrodes " Application No. 11/499, 861 (08/07/2006), be US Patent No. 7 now, 623, 340 (11/24/2009)], and the application in lithium ion battery [A.Zhamu and B.Z.Jang, " Nano Graphene Platelet-Based Composite Anode Compositions for Lithium Ion Batteries, " Application No. 11/982, 672 (11/05/2007), be US Patent No. 7 now, 745, 047 (06/29/2010)].
Single-layer graphene or Graphene plane (forming one deck carbon atom of hexagon or alveolate texture) are the common building blocks of a large amount of graphite materials, comprise native graphite, Delanium, soft carbon, hard carbon, coke, activated carbon, carbon black etc.In these graphite materials, thereby common a plurality of graphene film forms the domain of order or the crystallite on Graphene plane along Graphene thickness direction stacking.Then a plurality of crystallites in farmland link with unordered or amorphous carbon thing class.In this application, we can extract or separate these crystallites or farmland to obtain the multi-layer graphene plate from the disordered carbon kind.In some cases, we peel off and separate these multiple Graphene plates becomes isolated single-layer graphene film.(for example in activated carbon, hard carbon and soft carbon) in other cases, our chemistry is removed some disordered carbon thing classes to open wicket, thereby allows liquid electrolyte to enter inside (the Graphene surface is exposed to electrolyte).
In this application, the Graphene of the Graphene of nano-graphene plate (NGP) or " grapheme material " unified representation individual layer and multilayer form, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitrogenize Graphene, doping, etc.
In order to limit the geometry of NGP, NGP is described as have length (full-size), width (second largest size) and thickness.This thickness is minimum size, and it is not more than 100nm, and in this application, is not more than 10nm (preferably being not more than 5nm).NGP can be single-layer graphene.When plate was approximately circle in shape, length and width were called as diameter.In the NGP that limits at present, to length and not restriction of width, but they are preferably less than 10 μ m and be more preferably less than 1 μ m's.We can production length less than 100nm or greater than the NGP of 10 μ m.This NGP can be primary Graphene (having 0% oxygen content basically, typically＜2% oxygen) or graphene oxide (typically from 10 % by weight to the about oxygen of 45 % by weight).Graphene oxide can be become by heat or electronation the graphene oxide (typically oxygen content is 1-20%, and great majority are lower than 5 % by weight) of reduction.Anode and/or the negative electrode early applying for disclosed lithium superbattery and control battery based on the surface of sense material in order to be used for us, oxygen content are preferred in 5% to 30% scope by weight, and by weight more preferably in 10% to 30% scope.Yet in this application, the SMC electrode typically has the oxygen (therefore, essentially no functional group) less than 5%, and in many cases less than 2%.The specific area that liquid electrolyte can reach is to determine the energy density of SMC and a most important parameter of power density.
Although individual graphene film has especially high specific area, it is stacking or overlap each other again together that the graphene film of the flat pattern by the preparation of conventional route has large tendency, significantly reduced thus electrolyte can and specific area.Fig. 5 (A) has shown the Graphene that is called crooked Graphene plate or sheet herein.When thereby the NGP of bending is stacked while forming electrode, they can form the central hole structure of pore-size scope with expectation (for example slightly〉2nm).As if this size range help the lithium electrolyte that contains of being commonly used to approach.
Can be by the crooked NGP of following production:
(a) lamellar graphite material (for example natural graphite powder) disperseed or immerse in the mixture of intercalator and oxidant (for example being respectively the concentrated sulfuric acid and nitric acid) to obtain compound between graphite layers (GIC) or graphite oxide (GO);
(b) gained GIC or GO are exposed to thermal shock, preferably in the lasting short period (being typically 15 to 60 seconds) of the temperature range of 600-1100 ℃, (, if allow intercalation/oxidation step to carry out the sufficiently long duration, in this stage, can form some oxidation NGP of thickness＜100nm to obtain expanded graphite or graphite worm; For example〉24 hours);
(c) expanded graphite is distributed to the optional functionalized reagent's's source of COOH group (such as oxidant such as sulfuric acid, nitric acid, hydrogen peroxide or optimization acid, formic acid etc., it be-) the liquid medium that comprises with formation suspension.Stirring, mechanical shearing or sonication method, thereby and/or temperature can be used to smash graphite worm form separate/isolated NGP and/or the functional group that helps expect be attached to oxidation NGP, cause the formation of functionalized NGP with acquisition Graphene-liquid suspension;
(d) described Graphene-liquid suspension is atomized into drop, the optional single or multiple NGP that contains chemical functionalization of described liquid, and remove simultaneously liquid to reclaim crooked NGP.There is no atomization steps, the Graphene plate that produces is flat shape often.
What can notice is that step (a) to (b) is the most frequently used step that obtains in the art expanded graphite (Fig. 5 B) and graphene oxide plate.Before chemical functionalization, during or afterwards, can use hydrazine as reducing agent with the NGP of oxidation or the electronation of GO plate to recover the conductivity characteristic.
In one embodiment, carboxylic acid (it is environmental protection) is desirable especially functionalized reagent for carbonyl or carboxyl being given NGP.Carboxylic acid can be selected from aromatic carboxylic acid, aliphat or alicyclic carboxylic acid, straight or branched carboxylic acid, have saturated and undersaturated monocarboxylic acid, dicarboxylic acids and the polybasic carboxylic acid of 1-10 carbon atom, their Arrcostab and their combination.Preferably, carboxylic acid is selected from the representative examples of saturated aliphatic carboxylic of formula H (CH2) nCOOH, and wherein n is from 0 to 5 numeral, comprises formic acid, acetic acid, propionic acid, butyric acid, valeric acid and caproic acid, their acid anhydrides, their reactive carboxylic acid derivatives, and their combination.Most preferred carboxylic acid is formic acid and acetic acid.
Before or after functionalized operation, NGP can stand following processing (alone or in combination):
(i) with different functional group's chemical functionalization.Other useful surface functional groups can comprise quinone, quinhydrones, quaternized aromatic amine or mercaptan;
(ii) with polymer-coated or scion grafting, this polymer contains functional group's (as carbonyl) of expectation;
(iii) standing activation processing (being similar to the activation of carbon black material) produces extra surface and the functionality chemical group may be given these surfaces.Can realize in the following way this activation processing: CO2 is physically activated, KOH chemical activation or contact nitric acid, fluorine or ammonia plasma treatment.
Above-mentioned process produces graphene oxide plate or oxidation NGP.The oxy radical that the heavy oxidation step that these processes relate to is introduced to edge surface and the basal plane surface (top and lower surface) of NGP in essence.That this can be or bad.On the one hand, we want to produce functional group as much as possible and catch the lithium capacity with maximization.But on the other hand, thus the functional group on basal plane or Graphene plane must cause and damage the monolithic conductive significantly reduce NGP this plane.Forming by this way functional group, there is no above step (c), is not the good process of controlling.
In more controlled mode, a kind of alternative method that functional group gives NGP is related in the situation that without conventional chemical intercalation/oxidizing process, produce primary NGP.Then the non-oxide Graphene (naturally having more chemically active edge surface) that produces carries out controlled oxidation or controlled functionalized.Before any a large amount of functional group started to be attached to basal plane, at first functional group was attached to edge surface and basically exhausts all avtive spots of edge surface.
In 2007, we have reported that the direct graphite granule from the suspension that is dispersed in surfactant-water produces the direct ultrasonic disintegration of the primary nano-graphene [people such as A.Zhamu, " Method of Producing Exfoliated Graphite; Flexible Graphite; and Nano-Scaled Graphene Plates; " Application No. 11/800,728 (05/08/2007)].The method need to be disperseed natural graphite particles in low surface tension liquid such as acetone or hexane.Then gained suspension stand the direct ultrasonic processing of 10-120 minute, and this operates to be equivalent to the every particle of per second and peels off the speed of graphene film for 20000 times and produce Graphene.Graphite is never by intercalation or oxidation, and therefore do not need follow-up electronation.The method be fast, environmental protection, and can be easy to amplify in proportion, thereby pave road for the large-scale production of primary nano-graphene material.Same method is afterwards by other people research and more generally be called as now " liquid phase production ".In case produce primary Graphene, then can make this material be exposed to oxidation or functionalized processing, for example, use gas phase or liquid acid or acid blend.Primary NGP can also be immersed in the NGP that continues for some time to obtain to have required functionalized level in the carboxylic acid of preferred temperature.
Specifically, oxidation processes comprises makes primary NGP material stand oxidant, and this oxidant preferably is selected from ozone, sulfonic acid (SO3) steam, oxygen-containing gas, hydrogen peroxide vapor, nitric acid vapor or their combination.Preferably, this processing comprises and makes primary NGP material stand oxidant in ambient containing hydrogen.Although can be by NGP being immersed liquid acid and/or the oxidant environment carries out oxidation processes, however the follow-up water washing of such process need and purifying step (but such washing process is not as required tediously long like that in conventional sulfuric acid intercalated graphite situation).Therefore, it is preferred not needing the gas treatment of reprocessing washing.
Can produce oxygen content and be not more than by weight 25% the functionalized NGP of conduction, preferably by weight between 5% to 25%.By inference, most of functional groups are positioned at the edge surface of NGP, because conductivity can not be significantly reduced.For the whole oxygen contents that surpass 25%, functional group starts to appear at the Graphene plane surface, interrupts electrical conductance path.Use analysis of chemical elements and x-ray photoelectron power spectrum (XPS) to measure oxygen content.
Can make partial oxidation NGP further functionalized by carrying out following other step: partial oxidation NGP to be contacted with reactant, in order to functional group is added to surface or the edge of nano-graphene plate.Described functional group can comprise alkyl silane or aryl-silane, alkyl or aralkyl, hydroxyl, amido, fluorocarbon, perhaps their combination.
After partial oxidation is processed, NGP will have reactive Graphene surface (RGS) or reactive Graphene edge (RGE).They can be described to occur following reaction:
(a) RGS/RGE+CH 2==CHCOX (at 1000 ℃) → Graphene-R ' COH (wherein X=-OH ,-Cl or-NH 2); For example, RGS/RGE+CH 2==CHCOOH → G-R ' CO-OH (wherein G=Graphene);
(b) RGS/RGE+ maleic anhydride → G-R ' (COOH) 2
(c) RGS/RGE+CH 2==CH-CH 2X → G-R ' CH 2X (wherein X=-OH ,-halogen or-NH 2);
(d)RGS/RGE+H 2O→G==O(Quinoidal);
(e)RGS/RGE+CH 2==CHCHO→G-R’CHO(Aldehydic);
List in the above in reaction, R ' is alkyl (alkyl, cycloalkyl etc.).The partial oxidation of primary NGP can be able to cause some functional groups to be attached on the surface on Graphene plane or edge, comprises carboxylic acid and hydroxyl.Can prepare a large amount of derivatives from carboxylic acid separately.For example, alcohol or amine can easily be connected to acid so that stable ester class or amide-type to be provided.Can be with carbonyl (〉 C=O) or amine (NH2) base any reaction of being attached to Graphene edge or basal plane surface all can be used for implementing the present invention.
The disordered carbon of nanostructure
The disordered carbon material can be selected from the carbonaceous material of broad range, as soft carbon, hard carbon, polymerization carbon (or carbide resin), mesocarbon, coke, carbonization pitch, carbon black, activated carbon or part graphitized carbon.Be schematically shown as Fig. 3 (A) with (B), the disordered carbon material is typically formed by two-phase, wherein first-phase be the little graphite crystal of graphite plane or little deposit (thereby typically at the most 10 graphite planes or aromatic ring structure be superimposed form the little domain of order) and second-phase be amorphous carbon, and wherein this first-phase is dispersed in second-phase or by the second-phase combination.Second-phase mainly consists of less molecule, less aromatic rings, defect and amorphous carbon.Optional expectation functional group (for example in Fig. 3 (B)-COOH and NH 2Group) be attached to edge or the plane surface of aromatic ring structure.Typically, therefore disordered carbon is highly porous (for example activated carbon) or be present in the superfines form (as carbon black) that has nanoscale features (have high specific area).
Soft carbon refers to the carbonaceous material that is comprised of little graphite crystal, and wherein the orientation of these graphite crystals or graphene film stacked body is conducive to the further merging of contiguous graphene film or utilizes the further growth (Fig. 4 (A)) of these graphite crystals of high-temperature heat treatment (graphitization) or graphene film stacked body.Therefore, claim that soft carbon is graphitisable.
Hard carbon (Fig. 4 (B)) refers to the carbonaceous material that is comprised of little graphite crystal, wherein therefore these graphite crystals or graphene film stacked body are not unfavorable for the further merging of contiguous Graphene plate or the further growth (that is not being, graphitisable) of these graphite crystals or graphene film stacked body with favourable direction orientation (for example almost orthogonal).
As shown in signal in Fig. 4 (C), carbon black (CB), acetylene black (AB) and activated carbon (AC) typically consist of the farmland of aromatic rings or little graphene film, and wherein the aromatic rings in adjacent domains or graphene film are connected in unordered phase (matrix) in some way by some chemical bonds.These material with carbon elements are usually available from the thermal decomposition (heat treatment, pyrolysis or burning) of hydrocarbon gas or liquid or natural prodcuts (timber, cocoanut shell etc.).
Simple pyrolysis by polymer or oil/coal tar pitch material prepared polymerization carbon known existing about 30 years.When polymer such as polyacrylonitrile (PAN), artificial silk (rayon), cellulose and P-F (phenol formaldehyde) were heated to more than 300 ℃ in inert gas, they lost its most non-carbon content gradually.Resulting structures is commonly called polymerization carbon.According to heat treated temperature (HTT) and time, polymerization carbon can be made into insulation, semiconductive or conduction, have and cover the approximately conductivity range of 12 orders of magnitude.The conductivity value of this wide region can be by further extending with electron donor or acceptor doping polymerization carbon.These features confirm uniquely polymerization carbon qualified as novelty, easily process the electroactive material of classification, can easily customize structure and the physical property of described material.
Polymerization carbon can present impalpable structure basically, perhaps has a plurality of graphite crystals or the Graphene stacked body that are dispersed in amorphous carbon matrix.According to the HTT that uses, the graphite crystal of various ratios and size and defects diffract are in [amorphous.The two dimension that can find different amounts in the microstructure of heat treated polymer such as PAN fiber condenses aromatic rings or hexagon (precursor on Graphene plane).Think under 300-1000 ℃ in the polymerization carbon of the PAN base processed the small size graphene film that has considerable amount.Utilize higher HTT or long heat treatment time (for example〉1500 ℃), these materials are fused into wider aromatic ring structure (larger sized graphene film) and thicker plate object (more graphene films are stacked).The stacked body of these Graphene plates or graphene film (basal plane) is dispersed in amorphous carbon matrix.Such two phase structure is the feature of some disordered carbon materials.
, for the disordered carbon material in present patent application, there is the precursor material of several types.For example, the first kind comprises the semi-crystalline state PAN of fibre morphology.Than phenolic resins, pyrolysis PAN fiber has higher tendency and forms the little crystallite that is dispersed in unordered matrix.Equations of The Second Kind,, take P-F as representative, be more isotropic, basically amorphous state and highly cross-linked polymer.The 3rd class comprises oil and the coal tar pitch material of bulk or fibers form.Three parameters that precursor material forms, heat treatment temperature (HTT) and heat treatment time (Htt) are the length, width, thickness (number on Graphene plane in graphite crystal) and the chemical composition that have determined gained disordered carbon material.
In this research, make under the tension force effect PAN fiber at 200-350 ℃ through oxidated, then 350-1500 ℃ partially or completely carbonization to obtain to have the polymerization carbon of various nanocrystal graphite-structures (graphite microcrystal).To the further heat treatment at the temperature of sample in 1500-2000 ℃ of scope of selecting of these polymerization carbon, so that this material part graphitization, but still the amorphous carbon (being not less than 10%) of reservation requirement.Phenol formaldehyde resin and oil and coal tar pitch material stand similar heat treatment in the temperature range of 500 to 1500 ℃.The disordered carbon material that obtains from PAN fiber or phenolic resins preferably stands activation, utilizes the technique (as processing 1-5 hour in the KOH melt at 900 ℃) of producing active carbon and commonly use.This activation processing purpose is to make the disordered carbon mesopore, makes liquid electrolytic mass-energy arrive edge or the surface of component aromatic rings SMC device.Such arrangement makes the lithium ion in liquid and is easy to deposit to the Graphene surface in the situation that needn't experience solid-state diffusion.
Can heat-treat (typically at 250-500 ℃) to obtain liquid crystalline type, optional anisotropic structure, phase in the middle of this structure is commonly called to petroleum asphalt or the coal tar pitch of some grade.Phase particle or spheroid in the middle of this interphase material can being extracted to produce from the liquid component of mixture.Randomly, phase particles or spheroid can stand further heat treatment so that graphitization in the middle of these.
Can carry out physics or chemical activation to obtain the disordered carbon of activation to various disordered carbons (for example soft carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonization pitch, carbon black, activated carbon or part graphitized carbon).For example, can be by oxidation, CO 2Physically activated, KOH or NaOH chemical activation or be exposed to nitric acid, fluorine or ammonia plasma treatment and realize this activation processing (for the enterable hole of the matter that produces electrolysis, rather than for functionalized).
The functionalized program of nanostructure disordered carbon is similar to those programs for NGP, therefore repeats no more here.Especially, can be with carbonyl (〉 C=O) or amine (NH 2) base is connected to the Graphene edge of disordered carbon material or any reaction on basal plane surface all can be used for implementing the present invention.
Containing the organic of lithium reactive functionality and polymerization official can material
Many organic group officials can materials or the Polymers official can contain the sense side group by material, described sense side group can be fast and reversibly with liquid electrolyte or gel electrolyte in the lithium ion reaction.Example comprises poly-(2,5-dihydroxy-Isosorbide-5-Nitrae-benzoquinones-3,6-methylene), Li xC 6O 6(x=1-3), Li 2(C 6H 2O 4), Li 2C 8H 4O 4(terephthalate of Li), Li 2C 6H 4O 4(Li trans-trans-muconate), 3,4,9,10-perylene tetracarboxylic acid-dianhydride (PTCDA) disulfide polymer, PTCDA, Isosorbide-5-Nitrae, 5,8-naphthalene-tetrabasic carboxylic acid-dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5, the 8-tetra hydroxyanthraquinone, tetrahydroxy 1,4-benzoquinone, and their combination.These functional molecules, polymer or salt have relatively low electron conduction usually, make and itself are not suitable for serving as electrode material.An exception is sulfur-crosslinked PTCDA (PTCDA disulfide polymer).
Any these nonconducting sense materials can preferably be combined with nano structural material (for example chemical bonding or connection), as NGP, CNT, disordered carbon, nano wire and nanofiber.For example, the formation aromatic ring of Graphene and disordered carbon (soft carbon, hard carbon, activated carbon, carbon black etc.) can have functional group on its edge or surface, described functional group can with the place mat functional group reactions (as the hydroxyl on the tetrahydroxy 1,4-benzoquinone) of above-mentioned sense material.As an alternative, these sense materials organic or polymerization can simply be supported on the surface of nano structural material (for example, Graphene or nanowire surface).This nano structural material (for example Graphene and disordered carbon) also can functionalised, make it not only provide to the support (giving conductivity) of organic or polymeric material and also provide can with the functional group of lithium reaction.
In a word, the active material of cathode of SMC of the present invention and/or active material of positive electrode can be selected from: (a) porous disordered carbon material, and it is selected from soft carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonization pitch, carbon black, activated carbon or part graphitized carbon; (b) grapheme material, it is selected from single-layer sheet or the multilayer plate of the graphene oxide of Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitrogenize Graphene, boron doped graphene, nitrogen-doped graphene, functionalized Graphene or reduction; (c) expanded graphite; (d) mesoporous carbon; (e) carbon nano-tube, it is selected from Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; (f) carbon nano-fiber, metal nanometer line, metal oxide nano-wire or fiber or conducting polymer nanofiber, perhaps (g) their combination.These materials can be functionalized or non-functionalized.
The following examples are used for illustrating the preferred embodiments of the invention and should be interpreted as limiting the scope of the invention:
Embodiment 1: functionalized and non-functionalized soft carbon (disordered carbon of a type), soft carbon back superbattery and surface mediation battery.
From the standby non-functionalized and functionalized soft material with carbon element of liquid crystal aromatic resin.The resin mortar is ground, and at 900 ℃ in N 2But calcine 2 hours in atmosphere with preparation graphitized carbon or soft carbon.The soft carbon that will produce in alumina crucible mixes with KOH small pieces (4 times of weight).Subsequently, at N 2The middle soft carbon of KOH that will contain was 750 ℃ of heating 2 hours.After cooling, with the residual carbon hot wash of rich alkali, until the pH value of draining reaches 7.Resulting materials is to activate but non-functionalized soft carbon.
Then individually, the soft carbon of part activation is immersed 45 ℃ at 90%H 2O 2-10%H 2O solution is in order to continue the oxidation processes of 2 hours.Then, the soft carbon of partial oxidation that generates is immersed formic acid under room temperature with functionalized 24 hours.The functionalized soft carbon that produces is by coming dry in 24 hours 60 ℃ of heating in vacuum furnace.
Manufactured and test following coin battery: use functionalized soft carbon as negative electrode and functionalized soft carbon as nanostructure anode (adding the paper tinsel of the lithium as the lithium source thin slice that is implemented between collector and spacer body layer, sample-1).Preparation does not have functionalized battery accordingly, and (sample-1b) also test is used for relatively.In all batteries, the spacer body of use is a slice microporous barrier (Celgard2500).In two electrodes, the collector of each is the aluminium foil that a slice carbon applies.The compound of electrode for by the soft carbon of 85 % by weight (+be coated in 5%Super-P and 10%PTFE binding agent on the Al paper tinsel), being formed.Electrolyte solution is that the volume ratio that is dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC) is the 1M LiPF in the mixture of 3:7 6With the moistening spacer body of minimum electrolyte to reduce background current.The cyclic voltammetry and the constant current that at room temperature (are being low to moderate in some cases ,-40 ℃ and high temperature to 60 ℃) and adopt Arbin32 passage ultracapacitor-battery condition tester to carry out lithium battery are measured.
As the reference sample (sample-1-CA), make and test class like coin battery, this battery contains a slice lithium paper tinsel at the anode place but there is no the carbon-coating of nanostructure.This is the lithium superbattery of prior art.In addition, (sample-1-CB), two electrode is all to consist of functionalized soft material with carbon element, but does not comprise other lithium source outside available in liquid electrolyte also to make and estimate symmetrical ultracapacitor.The data of the symmetrical ultracapacitor of the people's such as data and Lee prior art (f-LBL-CNT/f-LBL-CNT) are compared.
((constant current research of sample-1b) makes us can obtain to be summarised in significant data and cyclical stability data (Fig. 6 (B)) in the Ragone figure of Fig. 6 (A) for the battery unit (sample 1) that sample-1-CA) and corresponding surface are controlled and non-functionalized surfaces mediation battery as the superbattery of active material of cathode to have so functionalized soft carbon back block materials (thickness〉200 μ m).These figure let us are made following observed result:
(a) functionalized and non-functionalized surface control, lithium ion exchanged cell apparatus show than corresponding superbattery obvious higher energy density and power density, particularly under relatively high current density (the higher power density data point in this figure).This confirmed the existing of nanostructure anode (except the negative electrode of nanostructure) make recharge with discharge cycles during lithium ion can deposit to respectively with two-forty on the huge surface area of anode and by the huge surface area of anode, be discharged.The superbattery of prior art has the anode of collector and limited specific area, and it can not provide the surface area of q.s to deposit at one time limited surface area or from the lithium ion that limited surface area discharges, use for attempting.Whole charging or discharge process become surface-limited.
(b) the lithium ion exchanged cell apparatus ground controlled, surface shows than the corresponding symmetrical ultracapacitor (people's such as sample-1-CB) and Lee remarkable higher energy density and the power density of prior art ultracapacitor, the people's such as described Lee prior art ultracapacitor consists of functionalized LBL CNT anode and functionalized LBL-CNT negative electrode, and these two kinds of ultracapacitors all do not have the lithium paper tinsel as the lithium source.In fact, these two kinds of symmetrical ultracapacitors (without the lithium source) (based on disordered carbon or based on LBL-CNT) have represented almost identical Ragone figure, although two electrodes on thickness be significantly different (for the disordered carbon electrode for 100 μ m and be＜3.0 μ m for the LBN-CNT electrode).This may be the performance of local surfaces absorption or the electric double layer mechanism that interrelates with conventional ultracapacitor, and described electric double layer mechanism does not require the long-range transmission (especially, not need between anode and negative electrode exchange lithium ion) of electric charge.The quantity of lithium ion and their counter ion (anion) is subjected to the solubility limit of lithium salts in solvent.The middle lithium quantity that can be hunted down and be stored in the surface of active material of arbitrary electrode is significantly higher than this solubility limit.
(c) as previously mentioned, the power density typical case of known ultracapacitor is 5,000-10,000W/Kg, and still, the power density of lithium ion battery is 100-500W/kg.This means that this surface mediation lithium ion exchanged battery has the energy density suitable with modern batteries, its be conventional super capacitor energy density 5-16 doubly.This SMC also shows apparently higher than the power density of conventional electric chemical super capacitor power density (or charging-discharge-rate).
(d) SMC based on non-functionalized surfaces is all controlling battery significantly better than corresponding functionalized surfaces aspect energy density and power density two expressively.
(e) the most important thing is, non-functionalized surfaces mediation battery table reveals the cyclical stability more much better than the battery based on the sense material.Such as in Fig. 6 (B) confirmation, even non-functionalized surfaces battery still keeps high-energy-density after 2500 charge/discharge cycle.Yet functionalized surfaces is controlled battery and is suffered to decay faster along with charge/discharge repeatedly.
(f) show that from the further calculating of the data obtained the discharge time of this prior art superbattery under the current density of 10A/g is 19 seconds.By contrast, the discharge time of corresponding SMC under same current density was less than 5 seconds.
The battery of sample 1 and sample-1-CA affects the redox reaction of lithium ion and selected functional group, and described functional group is at cathode side (on sample-1-CA) and the surface/edge at the aromatic rings of negative electrode and anode (example 1).These are connected to the edge of aromatic rings (little graphene film) and the functional group of plane surface can react with lithium fast and reversibly.In many cases, the SMC based on non-functionalized surfaces shows better.The lithium ion exchanged battery of surface of the present invention mediation is a kind of revolutionary novel energy storage device, and it fundamentally is different from ultracapacitor and lithium ion battery.Aspect energy density and power density two, two kinds of conventional equipments are all incomparable.
Embodiment 2: from the sulfuric acid intercalation of MCMB and expanded NGP
MCMB2528 microballoon (Osaka Gas Chemical Company, Japan) has approximately 2.24g/cm 3Density, approximately median size and the about distance between the surface of 0.336nm of 22.5 microns.With acid solution (ratio is sulfuric acid, nitric acid and the potassium permanganate of 4:1:0.05) to MCMB2528 (10 gram) intercalation 24 hours.When completing reaction, this mixture is poured into deionized water and filtered.With the MCMB of intercalation in 5%HCl solution cyclic washing to remove most sulfate ion.Then use this sample of deionized water cyclic washing, until the pH value of filtrate is neutral.Make slurry drying and be stored in 60 ℃ of vacuum drying ovens 24 hours.The powder sample of drying is put into quartz ampoule and be inserted into and be preset in the temperature required i.e. horizontal pipe furnace of 600 ℃ and continue 30 seconds to obtain expanded graphite.In ultrasonic processing is bathed, make expanded MCMB sample carry out further functionalized 30 minutes to obtain functionalized Graphene (f-NGP) in 25 ℃ of formic acid.Also by the ultrasonic processing to expanded MCMB in the water without any the functionalized reagent, obtain non-functionalized NGP.
Battery for functionalized or non-functionalized surface is controlled, use NGP as cathode material and as anode material.Add the lithium paper tinsel between anode and spacer body.For the reference superbattery, anode is lithium paper tinsel (NGP that there is no nanostructure) and negative electrode is f-NGP.The Ragone figure of this three types battery is shown in Fig. 7.The lithium ion exchanged cell apparatus of two kinds of surfaces based on NGP mediation shows than remarkable higher energy density and the power density of corresponding superbattery, particularly under relatively high current density (in figure higher power density data point).This proving again the superior function of this SMC than superbattery.Non-functionalized surfaces mediation battery is better than in the performance aspect energy density and power density the battery that functionalized surfaces is controlled.Extremely important and surprisingly in addition, to compare with functionalized surfaces mediation battery, non-functionalized surfaces mediation battery is along with charge/discharge repeatedly continues to show much better long-time stability (Fig. 8).
Embodiment 3: organic 3,4,9, and the PTCDA that 10-perylene tetracarboxylic acid-dianhydride (PTCDA), PTCDA disulfide polymer and nanostructure NGP-support.
Enolization is the important two key reactions of carbonyl, and it can be stablized by conjugated structure.When carbonyl is reduced or during oxidation, enolization makes the Li ion reversibly to be caught or to discharge on the position of oxygen atom, this means that it can be used as a kind of organic energy storage system of novelty in the Li ion battery.
In the reduction process of PTCDA, thereby each carbonyl can receive an electronics and catch a Li ion formation lithium enolate, and can discharge the Li ion in opposite oxidizing process.
The electrode of the anode of the lithium ion exchanged cell apparatus that preparation is controlled as surface and/or the three types of negative electrode.The first kind is the simple mixtures of PTCDA and carbon black (approximately 20 % by weight), by PVDF combination (sample 3-A).
Second Type (sample 4-B) be the PTCDA disulfide polymer again with the similar mixtures of carbon black as conductive filler., by using PTCDA (shiny red) and sublimed sulfur to synthesize the PTCDA disulfide polymer as parent material, with the mass ratio of 1:1, by grinding, it is fully mixed.Described mixture is reacting 3 hours to obtain the kermesinus powder of PTCDA disulfide polymer in the argon atmospher that flows under 500 ℃.This synthetic route be by the people such as X.Y.Han [" Aromatic carbonyl derivative polymers as high-performance Li-ion storage materials; " Adv.Material, 19,1616 – 1621 (2007)] the initial proposition.
Embodiment 4: based on the grapheme material from native graphite, carbon fiber and Delanium (NGP) and based on carbon black (CB) with process the SMC of CB.
Use improved Hummers method to prepare oxidation NGP or graphene oxide (GO), the method relates to the mixture 72 hours that initial graphite material is exposed to sulfuric acid, sodium nitrate and potassium permanganate that ratio is 4:1:0.1.The GO water that then will produce fully washs to obtain GO suspension, is after this two kinds of different material syntheti c routes.A kind of route relates to suspends GO to stand ultrasonic processing (to be used for battery-N) to obtain to be suspended in separation graphene oxide sheet in water.Another route relates to spray drying GO suspension to obtain compound between graphite layers (GIC) or GO powder.Then with GIC or GO powder expanded 45 seconds of 1050 ℃ of heat to obtain expanded graphite or graphite worm (battery-G).Then expanded graphite worm from Delanium and carbon fiber carries out ultrasonic processing, to separate or from separating graphene oxide sheet (respectively for battery-M and battery-C).Carbon black (CB) thereby stand is similar to the chemical treatment of Hummers method and opens the nanometer door, makes electrolysis mass-energy enter inside (battery t-CB).
Apply every kind of electrode at the Al paper tinsel, described electrode is comprised of 85% Graphene, 5%Super-P (AB-base conductive additive) and 10%PTFE.The thickness typical case of electrode is about 150-200 μ m, but prepared thickness, is that the sample of the approximately extra series of 80,100,150 μ m is estimating the impact of electrode size on power density and the energy density of gained ultracapacitor-secondary battery unit.Also making the electrode that is as thin as 20 μ m is used for relatively.Before use in the vacuum furnace of 120 ℃ with pole drying 12 hours.Negative electrode is at the Li metal that is supported on one deck graphene film.The battery of assembling coin dimensions, use 1M LiPF in glove box 6/ EC+DMC is as electrolyte.
Embodiment 5: functionalized and non-functionalized activated carbon
Active carbon (AC, from Ashbury Carbon Co.) was processed (ratio is sulfuric acid, nitric acid and the potassium permanganate of 4:1:0.05) 24 hours with acid solution.When reaction is completed, this mixture is poured into deionized water and filtered.With the AC that processed in 5% HCl solution cyclic washing to remove most sulfate ion.Then use this sample of deionized water cyclic washing, until the pH value of filtrate is neutral.In ultrasonic processing is bathed, slurry was carried out further functionalized 30 minutes in 25 ℃ of formic acid.Subsequently, use dip-coating to obtain the film of chemical functionalization activated carbon (f-AC), the thickness of described film typically between 20 and 150 μ m, is coated on the surface as the carbon-coating of aluminizing of collector.Use such electrode as anode and the material that uses same type as negative electrode, implement the lithium paper tinsel as the lithium source between porous spacer body and an electrode.Also preparation does not have SMC battery and the test of functionalized processing accordingly.
Use Arbin SCTS electrochemical test to utilize constant current experiment measuring capacity.Carried out cyclic voltammetry (CV) on the CHI660Instruments electrochemical workstation.Use scanning electron microscopy (SEM, Hitachi S-4800), transmission electron microscope (TEM, Hitachi H-7600), FTIR (PerkinElmer GX FT-IR), Raman spectrum (Renishaw inVia Reflex Micro-Raman) and atomic force microscope characterize chemical composition and the microstructure of NGP and expanded graphite sample.
The electrode of NGP mediation is the specific capacity that battery (for example battery M) provides 127mAh/g when current density is 1A/g, reach 85Wh/kg when current density is 0.1A/g BatteryThe LITHIUM BATTERY energy density of (Fig. 8 (C)), this is the representative value 5Wh/kg of the symmetrical ultracapacitor of business AC-base Battery17 times.
It is 160Wh/kg that another kind of Graphene surface mediation battery (battery N, Fig. 8 (D)) shows even higher energy density Battery, this is comparable to the energy density of lithium ion battery.Even the energy density of battery N is still kept over 51.2Wh/kg under the current density up to 10A/g BatteryValue, 4.55kW/kg is provided BatteryPower density.At 5Wh/kg BatteryEnergy density under, the power density typical case of the symmetrical ultracapacitor of business AC base is at 1-10kW/kg BatteryIn scope, this means, with the conventional ultracapacitor of equal-wattage density, compare, this surface mediation device can provide〉energy density of 10 times.
Power density when 50A/g is 25.6kW/kg Battery, and energy density is 24Wh/kg BatteryPower density is increased to 93.7kW/kg when 200A/g Battery, and energy density is 12Wh/kg Battery(Fig. 8 (D)).This power density is higher than with the well-known order of magnitude of conventional ultracapacitor of high power density, and than the power density of conventional lithium ion battery, (is typically 0.1-1.0kW/kg Battery) a high 2-3 order of magnitude.These data have proved that clearly this surface activation battery itself is a class energy storage batteries, are different from conventional ultracapacitor and lithium ion battery.
Fig. 8 (B) comprises the comparison of CV data, has shown that the derivative Graphene of carbon fiber is as the slightly better performance of the electrode active material Graphene more derivative than graphite.This may be due to the more macrobending of the derivative Graphene of fiber or the shape of fold, and this has been avoided the stacking face-to-face completely of during electrode preparation graphene film.Based on the battery of expanded graphite (battery-G) with respect to the NGP base battery (battery M and C) that separates fully than low energy densities and power density can owing to EG (measurement is typically 200-300m based on BET than low specific surface area 2/ g), the representative value 600-900m of the single-layer graphene film that separates than great majority 2/ g.
Fig. 8 (D) shows, the energy density of carbon black (CB) and power density values can significantly be increased by making CB stand activation/functionalized processing, and described activation/functionalized processing relates to the mixture 24 hours that contacts sulfuric acid, sodium nitrate and potassium permanganate.Find that the BET surface area is from about 60m 2/ g is increased to approximately 300m 2/ g, cause capacity to rise to 46.63mAh/g by 8.47mAh/g.Battery with carbon black electrode of processing demonstrates the power density suitable with active carbon electrode and energy density.
Figure 10 has shown the Ragone figure of the Li ion-exchange battery of the Graphene surface activation with Different electrodes thickness.Only based on cathode weight, come calculating energy density and power density values based on total battery weight and at Figure 10 (B) in Figure 10 (A).These tables of data prescribed electrode thickness play vital effect in the energy density that determines SMC and power density.Of paramount importancely be, these data clearly prove, the performance of our SMC with thick electrode can be very good, needn't use costliness and and slowly technique (, as by people such as Lee, being proposed successively, LBL) make the ultrathin electrodes for CNT base superbattery.Figure 10 has also clearly proved surface mediation battery self to be a class energy storage batteries, is different from ultracapacitor and lithium ion battery.
Figure 12 shows that the specific area of electrode is determining that on lithium memory capacity be most important parameter.The data point that has height ratio capacity in this figure is obtained by the electronation graphene oxide.Our chemical analysis data shows, the grapheme material of this height reduction has the oxygen content less than 2.0%, shows and there is no that functional group exists.Highly oxidized Graphene, when chemistry or thermal reduction, known have an a considerable amount of blemish position.This and other several data points have confirmed the importance of surface trapping mechanism.Four data points (with " x " expression) are about primary Graphene electrodes, and wherein grapheme material obtains from pure graphite (〉 99.9% carbon) direct ultrasonic processing.These data points have shown that pure Graphene surface (have the phenyl ring center, and there is no blemish or functional group) can catch lithium ion and store a considerable amount of lithiums on per unit surface area basis from electrolyte too.
The long-time stability of these SMC batteries are significant (Figure 11).The most surprisingly, those batteries of SMC based on non-functionalized surfaces (battery N and AC) show such capacity: this capacity after some slight declines of initial 300 cycle periods, increases with period thereafter.This is quite unique and beyond expectation.For the battery that ultracapacitor, lithium-ion capacitor, lithium ion battery, lithium superbattery or the functionalized surfaces of any routine are controlled, this never is observed.
In sum, the invention provides a kind of energy storing device, it has the characteristics of ultracapacitor and lithium ion battery.The battery of these complete surface activations, lithium ion exchanged can be stored 160Wh/kg at least BatteryEnergy density, this is significantly higher than conventional electric double layer (EDL) ultracapacitor.At least 100kW/kg BatteryPower density be significantly higher than conventional EDL ultracapacitor and far above the lithium ion battery of routine.The battery of these surface mediations can be recharged fast, in order to use as conventional lithium ion battery.
In detail and with reference to specific embodiments, described the present invention, obviously in the situation that do not deviate from the many variations of the spirit and scope of the present invention and modification is possible, scope of the present invention limits by following claims:

Claims (32)

1. the lithium ion exchanged energy storing device of a surface mediation, it comprises:
(a) comprise the negative electrode of active material of cathode, described active material of cathode has the surface area that can catch or store lithium thereon;
(b) comprise the anode of active material of positive electrode, described active material of positive electrode has the surface area that can catch or store lithium thereon;
(c) be arranged on two porous spacer bodies between electrode; With
(d) with the electrolyte that contains lithium of two electrode physical contacts, wherein said active material of positive electrode and/or described active material of cathode have the 100m of being not less than 2The specific area of/g, it contacts with described electrolyte direct physical, to receive thus lithium ion or to this, to provide lithium ion;
Wherein one or both in active material of positive electrode and active material of cathode can be functionalized, and in the charging for the first time of this energy storing device or for the first time before discharge cycles, and at least one in two electrodes wherein comprises the lithium source.
2. the energy storing device of claim 1, wherein active material of cathode is not functionalized material at least.
3. the energy storing device of claim 1, wherein said device has the open circuit voltage of at least 0.6 volt.
4. the energy storing device of claim 1, wherein when this device is in charged state, at least 80% lithium is stored on the surface of described active material of positive electrode, and described lithium contacts with described anode surface direct physical, perhaps when this device is in discharge condition, at least 80% lithium is stored on the surface of described active material of cathode, and described lithium contacts with described cathode surface direct physical.
5. the energy storing device of claim 1, wherein electrolyte is liquid electrolyte or the gel electrolyte that comprises the lithium ion of the first quantity.
6. the energy storing device of claim 1, wherein the active material at least one in two electrodes comprises the functional group with lithium atom or ion reversible reaction.
7. the energy storing device of claim 6, wherein with functional group, described active material of positive electrode and active material of cathode are carried out functionalized, described functional group and lithium atom or ion reversible reaction.
8. the energy storing device of claim 1, wherein when described device operation, described active material of positive electrode is not inserted embedding lithium or removal lithium embedded.
9. the energy storing device of claim 1, wherein said device operates in the voltage range from 1.0 volts to 4.5 volts.
10. the energy storing device of claim 1, wherein at least one in two electrodes has the 500m of being not less than 2The specific area of/g, described specific area directly contacts with described electrolyte.
11. the energy storing device of claim 1, wherein when this device is in charged state, be no more than 20% lithium and be stored in the body of described active material of positive electrode, perhaps when this device is in discharge condition, is no more than 20% lithium and is stored in the body of described active material of cathode.
12. the energy storing device of claim 1, wherein the operation of this device does not relate to the slotting embedding of lithium or takes off embedding.
13. the energy storing device of claim 1, wherein said active material of positive electrode prestrain has lithium.
14. the energy storing device of claim 1, wherein said active material of positive electrode is selected from:
(a) the disordered carbon material of porous, be selected from soft carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonization pitch, carbon black, activated carbon or part graphitized carbon;
(b) grapheme material, be selected from single-layer sheet or the multilayer plate of the graphene oxide of Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitrogenize Graphene, boron doped graphene, nitrogen-doped graphene or chemistry or thermal reduction;
(c) expanded graphite;
(d) mesoporous carbon;
(e) carbon nano-tube, be selected from Single Walled Carbon Nanotube or multi-walled carbon nano-tubes;
(f) carbon nano-fiber, metal nanometer line, metal oxide nano-wire or fiber or conductive polymer nanometer fiber;
(g) contain the molecule of the organic or polymerization of carbonyl;
(h) contain the functionalized grapheme material of carbonyl, carboxyl or amido; And
(i) their combination.
15. the energy storing device of claim 1, wherein said active material of cathode is selected from:
(a) the disordered carbon material of porous, be selected from soft carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonization pitch, carbon black, activated carbon or part graphitized carbon;
(b) grapheme material, be selected from single-layer sheet or the multilayer plate of the graphene oxide of Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitrogenize Graphene, boron doped graphene, nitrogen-doped graphene, functionalized Graphene or reduction;
(c) expanded graphite;
(d) mesoporous carbon;
(e) carbon nano-tube, be selected from Single Walled Carbon Nanotube or multi-walled carbon nano-tubes;
(f) carbon nano-fiber, metal nanometer line, metal oxide nano-wire or fiber or conductive polymer nanometer fiber; Perhaps
(g) their combination
(h) contain the molecule of the organic or polymerization of carbonyl;
(i) contain the functionalized Graphene of carbonyl, carboxyl or amido; And
(j) their combination.
16. the energy storing device of claim 15, wherein said active material of positive electrode or active material of cathode are the grapheme materials that does not contain functional group.
17. the energy storing device of claim 15, wherein the sense material is selected from poly-(2,5-dihydroxy-Isosorbide-5-Nitrae-benzoquinones-3,6-methylene), Li xC 6O 6(x=1-3), Li 2(C 6H 2O 4), Li 2C 8H 4O 4(terephthalate of Li), Li 2C 6H 4O 4(Li trans-trans-muconate), 3,4,9,10-perylene tetracarboxylic acid-dianhydride (PTCDA) disulfide polymer, PTCDA, Isosorbide-5-Nitrae, 5,8-naphthalene-tetrabasic carboxylic acid-dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5, the 8-tetra hydroxyanthraquinone, tetrahydroxy 1,4-benzoquinone, and their combination.
18. the energy storing device of claim 15, wherein the sense material is selected from poly-(2,5-dihydroxy-Isosorbide-5-Nitrae-benzoquinones-3,6-methylene), Li xC 6O 6(x=1-3), Li 2(C 6H 2O 4), Li 2C 8H 4O 4(terephthalate of Li), Li 2C 6H 4O 4(Li trans-trans-muconate), 3,4,9,10-perylene tetracarboxylic acid-dianhydride (PTCDA) disulfide polymer, PTCDA, 1,4,5,8-naphthalene tetracarboxylic acid-dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8-tetra hydroxyanthraquinone, the tetrahydroxy 1,4-benzoquinone, and their combination, and this sense material is combined with nano structural material or by its support, described nano structural material is selected from nano-graphene, carbon nano-tube, disordered carbon, nano-graphite, metal nanometer line, conducting nanowires, carbon nano-fiber, polymer nanofiber.
19. the energy storing device of claim 16, wherein said active material of positive electrode or active material of cathode are to be selected from following non-functionalized grapheme material: the single-layer sheet of the graphene oxide of primary Graphene, Graphene fluoride, hydrogenation Graphene, nitrogenize Graphene, boron doped graphene, nitrogen-doped graphene or chemistry or thermal reduction or multilayer plate.
20. the energy storing device of claim 1, at least a in wherein said active material is single wall or multi-walled carbon nano-tubes.
21. having, the energy storing device of claim 1, at least a in wherein said sense material be selected from following functional group :-COOH ,=O ,-NH 2,-OR, perhaps-COOR, wherein R is hydroxyl, perhaps their combination.
22. the energy storing device of claim 14, wherein said disordered carbon material is formed by two-phase, and first-phase is the stacked body on graphite crystal or Graphene plane, and second-phase is amorphous carbon, and wherein first-phase is scattered in second-phase or by the second-phase combination.
23. the energy storing device of claim 1, the single wall that wherein said active material of positive electrode or described active material of cathode right and wrong are functionalized or multi-walled carbon nano-tubes (CNT), oxidation CNT, the CNT that fluoridizes CNT, hydrogenation CNT, nitrogenize CNT, boron doping CNT, nitrogen doping CNT or adulterate.
24. the energy storing device of claim 1, wherein said electrolyte comprise the ionic liquid of the lithium salts that adulterates.
25. the energy storing device of claim 1, wherein said device provide the energy density that is not less than 300Wh/kg and the power density that is not less than 5Kw/kg, all based on total electrode weight.
26. the energy storing device of claim 2, wherein the electrode place catch or store comprise with surface of active material on the Graphene entity interact.
27. the energy storing device of claim 26, wherein said electrode is negative electrode.
28. the method for the energy storing device of an operational rights requirement 1, described method comprises: implement the lithium source at the anode place and make described lithium source ion to enter described electrolyte in order to discharge lithium ion during the discharge cycles for the first time at described device; Perhaps at the negative electrode place, implement the lithium source and operate described lithium source to enter described electrolyte in order to discharge lithium ion during the charging cycle for the first time at described device, the charging and discharging of wherein said device does not all relate to lithium and inserts embedding or solid-state diffusion.
29. the method for claim 28, wherein the method comprises:
(A) provide the battery of surface mediation, it comprises anode, lithium source, porous spacer body, the electrolyte with primary quantity lithium ion and negative electrode, its Anodic and the material that negative electrode has all have contact with described electrolyte catch the lithium surface;
(B) interdischarge interval for the first time at described device discharges lithium ion from described lithium source to described electrolyte;
(C) the described negative electrode of operation is to catch lithium ion and described lithium of catching is stored on cathode surface from described electrolyte; And
(D) during subsequently charging or discharge operation at a certain amount of lithium ion of exchange between the lithium surface of catching of catching lithium surface and described negative electrode of described anode, described amount is greater than described primary quantity, wherein said charging operations does not relate to lithium and inserts embedding.
30. the energy storing device of claim 1, wherein said device has the open circuit voltage of at least 1.5 volts.
31. the energy storing device of claim 1, wherein said anode comprises active material of positive electrode, and described active material of positive electrode has with described electrolyte directly contacts and is not less than 500m 2The specific area of/g.
32. the energy storing device of claim 1, wherein in two electrodes, at least one has with described electrolyte directly contacts and is not less than 1500m 2The specific area of/g.
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