CN103403922B - The lithium ion exchanged energy storing device of surface mediation - Google Patents

The lithium ion exchanged energy storing device of surface mediation Download PDF

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CN103403922B
CN103403922B CN201180067866.9A CN201180067866A CN103403922B CN 103403922 B CN103403922 B CN 103403922B CN 201180067866 A CN201180067866 A CN 201180067866A CN 103403922 B CN103403922 B CN 103403922B
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lithium
carbon
graphene
active material
energy storing
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CN103403922A (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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Priority to CN201610819520.4A priority Critical patent/CN106252581B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • 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
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • 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
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • 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

The lithium ion exchanged energy storing device of a kind of surface mediation, described device includes: (a) positive pole (negative electrode), and it comprises sense or nonfunctionalized active material of cathode, but described active material of cathode has capture or the surface area of storage lithium thereon；B () negative pole (anode), it comprises functionalization or nonfunctionalized anode pole active material, and described active material of positive electrode has the surface area capturing or storing lithium thereon；C () is arranged at the porous separator between two electrodes；And (d) and the electrolyte containing lithium of two electrode physical contacts.In one embodiment, before the first time charging or first time discharge cycles of this energy storing device, at least one in two electrodes wherein comprises lithium source.

Description

The lithium ion exchanged energy storing device of surface mediation
The present invention is achievement in research based on the project by national science foundation of the US SBIR-STTR plan patronage.
This application claims the right of following U.S. Patent application:
(a) Aruna Zhamu, C.G.Liu, David Neff, and Bor Z.Jang, " Surface-Controlled Lithium Ion-Exchanging Energy Storage Device, " U.S. Patent 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, " U.S. Patent Application No. 12/ 930,294(01/03/2011);And
(c) Aruna Zhamu, C.G.Liu, Xiqing Wang, and Bor Z.Jang, " Surface-Mediated Lithium Ion-Exchanging Energy Storage Device, " U.S. Patent Application No. 13/199,450 (08/30/ 2011)。
Invention field
The present invention relates generally to electrochemical energy storage device field, and is more particularly to a kind of brand-new lithium ion friendship Changing energy storing device, its Anodic and negative electrode are all not related to pass in and out the lithium of solid electrode active material body and spread (namely Say, it is not necessary to the slotting embedding or deintercalation of lithium).Lithium memory mechanism in anode and negative electrode is all granule surface contral, eliminates lithium The demand of solid-state diffusion (inserting embedding or deintercalation), otherwise it is extremely low.This device have lithium ion battery high-energy-density and The high power density (the usually even higher than power density of ultracapacitor) of ultracapacitor.In this article this device is referred to as (mediated) lithium ion exchanged cell apparatus of surface mediation.
Background of invention
Ultracapacitor (ultra-capacitor or electrochemical capacitor):
Ultracapacitor is being considered for electric vehicle (EV), the storage of renewable energy and modern power network application.Super The high volumetric capacitance density of level capacitor comes from use porous electrode to produceContribute to spreading double-deck electric charge to be formedBig surface Long-pending.Upon application of a voltage, the electrolyte near electrode surface forms this electric charge electric double layer (EDL).This near electrode Ion needed for planting EDL mechanism preexists in liquid electrolyte when manufacturing battery or is present in discharge condition, and And come from hardly electrode.In other words, negative pole (anode) active material (such as, the carbon granule of activity) surface is stayed in The desired ion formed in neighbouring EDL not necessarily comes from positive pole (negative electrode)；It is to say, not capture or be stored in In cathode active material surface or inside.Similarly, have in the EDL stayed near cathode active material surface formed required from Son not necessarily comes from surface or the inside of active material of positive electrode.
When ultracapacitor is recharged, the ion (cation and anion) being in liquid electrolyte is at them Respective localizing electrode is formed about as EDL(typically via local molecular or the ionic polarization of electric charge).At anode activity material Main ion exchange is there is not between material and active material of cathode.Can the stored quantity of electric charge (capacitance) only by electrolyte Available cation and the concentration of anion determine.These concentration typical case the lowest (being limited by the dissolubility of salt in solvent), leads Cause low energy density.Additionally, lithium ion is frequently not preferred or conventional ultracapacitor electrolysis matter.
In some ultracapacitors, the energy of storage is by because of some electrochemical reactions (such as, redox reaction) And the pseudo-capacitance effect caused and increase further.In such pseudo-capacitance device, the ion relating to redox couple is deposited the most in advance In electrolyte.Equally, main ion is not had to exchange between active material of positive electrode and active material of cathode.
The ion exchange being not related between chemical reaction or two comparative electrodes due to the formation of EDL, EDL super capacitor The charge or discharge process of device can be very quick, the most in seconds, cause the highest power density (typically 5, 000-10,000W/Kg).Compared with accumulator, ultracapacitor provides higher energy density, it is not necessary to safeguard, it is provided that Gao get Many cycle life, needs very simple charging circuit, and the most much more secure.Physics and energy storage non-chemically are Their safety operation and the key reason of the highest cycle life.
Although ultracapacitor has positive attribute, but ultracapacitor is widely used in various commercial Application and yet suffers from Some technology barriers.For example, when comparing with accumulator, ultracapacitor has the lowest energy density (such as, business The 5-8Wh/kg of ultracapacitor is compared to the 50-100Wh/kg of 10-30Wh/Kg and the NiMH accumulator of lead-acid accumulator).Lithium Ion accumulator has much higher energy density, typically in the range of 100-180Wh/kg, based on battery weight.
Lithium ion battery:
Although having much higher energy density, lithium ion battery provides the lowest power density (typically 100-500W/ Kg), typically need within several hours, recharge.Conventional lithium ion battery also results in some safety problems.
The low power density of lithium ion battery or long recharge time are due between anode interior and cathode internal Lithium ion move back and forth mechanism, its need lithium ion recharge period enter or insert be embedded into anode active material particles In body, and enter during discharging in the body of active material of cathode granule.Such as, as shown in Fig. 1 (A), with graphite Granule makees active material of positive electrode as in the most frequently used lithium ion battery of its characteristic, needs lithium ion recharging period diffusion Between the face of the graphite crystal at anode in space.Great majority these lithium ions must always from cathode side by diffusing out the moon Pole active particle body, through the hole (hole is filled with liquid electrolyte) of solid spacer body and enter the stone at anode In ink particle bulk.
During discharging, lithium ion diffuses out active material of positive electrode (graphite granule is left in such as deintercalation), migrates across liquid Body electrolyte phase, and then diffuse in the body of composite cathode crystal and (such as to insert and to be embedded into graininess lithium and cobalt oxides, phosphoric acid In ferrum lithium or other lithium Insertion compound).In other words, liquid electrolyte only reaches to outer surface (such as 10 μm of solid particle The graphite granule of diameter), and lithium ion travelling in liquid electrolyte can only migrate (by quick liquid state diffusion) and arrive Graphite surface.Solid graphite particles body to be penetrated will need the slow solid-state diffusion (being commonly called " inserting embedding ") of lithium ion. Lithium diffusion coefficient in the solid particle of lithium metal oxide is typically 10-16-10-8cm2/ sec(is more typically 10-14-10- 10cm2/ sec), and the lithium diffusion coefficient in liquid is about 10-6cm2/sec。
In other words, these insert embedding or solid state diffusion process needs the long time to complete, because solid-state diffusion (or Diffusion in solid) difficult and slow.Here it is the most such as the current lithium ion battery of plug-in hybrid-power automobile Needing the recharge time of 2-7 hour, this completely contradicts with ultracapacitor for the most several seconds.Discussed above show, it is possible to deposit Storage and energy as much in accumulator and still being able to recharged as ultracapacitor in one or two minute completely Energy storing device will be considered as the revolutionary advancement in energy storage technologies.
More new development:
In recent years, Lee et al. uses and comprises the multi-walled carbon nano-tubes (CNT) of carbonyl as lithium-ion capacitor (LIC) Cathode material, 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, lithium paper tinsel is used as anode and to use functionalization CNT as negative electrode, it provides relatively high power density.But, the CNT base electrode that by successively prepared by (LBL) method removes Some technical problems are also met with outside high cost.Some in these problems are:
(1) known CNT comprises a large amount of impurity, in particular as those transition of catalyst needed for chemical vapor deposition method Metal or noble metal granule.Cause the adverse reaction with electrolyte owing to these catalysis materials have high tendency, therefore it Be out of favour very much in battery electrode.
(2) CNT tends to be formed as the entanglement group of ball top, and this entanglement group is difficult to during electrode manufactures process (such as, difficulty To be dispersed in liquid flux or resinous substrates).
(3) so-called " successively " method (LBL) that Lee et al. uses is slow and expensive technique, and it is not suitable for electricity The extensive manufacture of pond electrode, or there is the electrode thickness of electrode of 100-300 μm (most of batteries have) of suitable thickness A large amount of productions.The thickness of the LBL electrode that Lee et al. (famous MIT research group) manufactures is limited in 3 μm or less.
(4) people may wonder how the thickness of LBL CNT electrode affects their performance.Lee et al. (such as Lee Et al. the figure S-7 of support material) the going through of data that provide show: when LBL CNT thickness of electrode increases to from 0.3 μm During 3.0 μm, power density reduces an order of magnitude.If thickness of electrode increases to useful battery or electrode of super capacitor Thickness (such as 100-300 μm), performance may reduce further.
(5) although ultra-thin LBL CNT electrode provides high power density (because Li ion has only to extremely short distance of advancing), But the CNT base electrode of actual (real) thickness remains to work not to have data to prove, because having bad CNT dispersion and electrolyte to be difficult to reach The problem arrived.Lee et al. represents that the CNT based combined electrode not using LBL method to prepare lies in less than good performance.
(6) CNT has the appropriate site of very limited amount and does not damage basal plane structure to accept functional group.CNT only has one End is prone to functionalization, and this end is the minimum ratio of whole CNT surface.By making outside basal plane chemical functionalization, it is possible to aobvious Write the electron conduction of ground balance CNT.
Recently, our research group has reported the high conduction negative electrode work of two kinds of new types in two patent applications Property material development, described material has and quickly and reversibly can form the functional group of redox reaction with lithium ion.These Material is that (single-layer graphene and multi-layer graphene sheet are collectively referred to as nano-graphene plate (platelet) to nano-graphene Or NGP) with disordered carbon (including soft carbon, hard carbon, carbon black, activated carbon, amorphous carbon etc.).This two patents application is: " the Lithium Super-battery with a Functionalized Nano Graphene of C.G.Liu et al. Cathode, " U.S. Patent application 12/806,679 (08/19/2010) and C.G.Liu et al. " 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 (" lithium superbattery " for alleged) include the nanometer stone of chemical functionalization Ink alkene plate (NGP) or the disordered carbon material of functionalization, it has some specific functional group, and described functional group can store Battery unit charging and discharging circulation during reversible and rapidly with lithium ion formed redox couple.In this two patents Shen In please, the disordered carbon of functionalization or the NGP of functionalization be used for the negative electrode (rather than anode) of lithium superbattery.At this negative electrode In, the lithium ion in liquid electrolyte only must move to edge or the surface (situation at the NGP negative electrode of functionalization of graphene film Under) or disordered carbon substrate in the edge/surface of aromatic ring structure (little graphene film).Solid-state is need not at this negative electrode Diffusion.Exist on it and there is functionalized graphite's alkene of functional group or carbon makes it possible on cathode material surface (including edge) Reversible lithium storage is realized on non-body.Such cathode material provides a kind of lithium storage or catches lithium surface.
In conventional lithium ion battery, lithium ion must diffuse into and leave the body of active material of cathode, such as Lithium and cobalt oxides (LiCoO2) and LiFePO4 (LiFePO4).In the lithium ion battery of these routines, lithium ion must also expand Dissipate and enter and leave space between the face in the graphite crystal taking on active material of positive electrode.Lithium at negative electrode and anode is inserted and removed from Process is the most slowly.The slow process diffusing into and leaving these intercalation compounds due to lithium (is commonly called solid-state to expand Dissipate or insert embedding process), conventional lithium ion battery does not represent high power density, and these batteries need long recharging Time.These conventional equipments are all independent of being prone to and reversibly forming redox reaction with the lithium ion carrying out self-contained lithium electrolyte Selected functional group (being such as connected to edge or the basal plane of graphene film).
In contrast, report in two patent applications earlier (U. S. application 12/806,679 and 12/924,211) Superbattery depends between the lithium ion in functional group's (connect or be bonded to the graphene-structured at negative electrode) and electrolyte Quickly and the operation of reversible reaction.Only must be at the liquid electrolytic in being positioned at negative electrode from the lithium ion of anode-side by spacer body Matter spreads to reach the surface/edge of graphene planes.These lithium ions need not diffuse into or leave solid particle Volume.Owing to being not related to the slotting embedding of diffusion-restricted at negative electrode, this process quickly and can occur in seconds.Therefore, this is Hybrid super capacitor-the accumulator of a kind of brand new class, 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 electric power storage Pond and the optimal part in ultracapacitor field.
In the lithium superbattery described in this two patents application, anode or comprise lithium titanate type active material of positive electrode Granule (need nonetheless remain for solid-state diffusion, schematically show in Fig. 1 (B)), or only comprise lithium paper tinsel (do not have nano structural material with Support or capture lithium ion/atom, schematically show in Fig. 1 (C)).In later case, when battery is recharged, lithium Necessarily only deposit to (such as Copper Foil) on the front surface of anode collector.Due to the specific surface area of collector the lowest (typically < < 1m2/ gram), overall lithium redeposition speed is relatively low (this problem is overcome in the present invention).
Summary of the invention
One embodiment of the invention is 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 the apparatus, at least one in negative electrode and anode is (more than cloudy Pole) there is lithium capture or lithium storage function surface (typically having and the functional group of lithium reversible reaction) and two electrodes are all (more than negative electrode) eliminates the needs carrying out solid-state diffusion.This is illustrated by Fig. 1 (D) and Fig. 2.Anode and negative electrode are all There is the surface area of big quantity to allow lithium ion the most deposited thereon, enabling realize significantly higher charging and discharging Speed and higher power density.Nano structural material in electrode (such as Graphene, CNT, disordered carbon, nano wire and receive Rice fiber) the dispersed electric field provided the most in the electrodes evenly on these surfaces, lithium can more uniformly be deposited on This electricity level does not constitute dendrite (dendrite).Such nanostructured eliminates the potential formation of dendrite, and described dendrite is Problem (being generally used for the 1980's and early stage generation nineteen ninety before being replaced by lithium ion battery) in conventional lithium metal battery. In this article such device is referred to as granule surface contral, lithium ion exchanged battery.
Another embodiment is disclosed in the U.S. Patent application 13/199,450 submitted on August 30th, 2011, its middle-jiao yang, function of the spleen and stomach Surface, pole and cathode surface do not carry the material with any functional group that can form redox couple with lithium.On the contrary, seen Observing, when not having any functional group, some graphenic surface can capture in the case of without solid-state diffusion or capture lithium Atom.No matter whether these surfaces contain functional group, if these surfaces can be close to the electrolyte containing lithium ion and with described Electrolyte directly contacts, and graphenic surface can store lithium atom in the way of stablizing and be reversible.Lithium memory capacity is with the most sudden and the most violent The total surface area being exposed to the electrolyte containing lithium ion is directly proportional, as shown in figure 13.Such as, Figure 13 has the number of height ratio capacity Strong point is about the battery (> 98%C containing Graphene electrodes), described Graphene electrodes is substantially only made up of carbon atom completely, There is no the functional group of such as OH or-COOH.Therefore, in this embodiment, Li functional group redox reaction mechanism is not Leading lithium memory mechanism.In order to define the scope of the application claim, term " surface mediation battery " (SMC) does not include appointing The operation of what lithium air (lithium-oxygen) battery, lithium-sulfur cell or wherein energy storing device relates to introducing oxygen from device is outside Gas or relate at negative electrode formed metal-oxide, metal sulfide, metal selenide, metal telluride, metallic hydrogen oxidation Thing or any battery of metal-halogen compound.
The invention provides the lithium ion exchanged energy storing device (SMC) of surface mediation, it comprises: (a) positive pole is (cloudy Pole), this positive pole comprises functionalization or nonfunctionalized active material of cathode, and described active material of cathode has and captures thereon Or the surface area of storage lithium；B () negative pole (anode), described negative pole comprises functionalization or nonfunctionalized anode extremely activity material Material, described active material of positive electrode has the surface area capturing or storing lithium thereon；C () is arranged between two electrodes Porous separator；And (d) and two electrode physical contacts containing lithium electrolyte.In one embodiment, described anode is lived Property material and/or active material of cathode have not less than 100m2The specific surface area of/g, it contacts with electrolyte direct physical, with The most thus receive lithium ion or provide lithium ion to this.
In one embodiment, charge or before first time discharge cycles in the first time of energy storing device, two At least one of individual electrode kind wherein comprises lithium source, and at least active material of cathode is not that functionalised materials (that is should Material does not have can be with the functional group of Li redox reaction).This lithium source be preferably solid lithium paper tinsel, lithium bits, lithium powder or The form of the lithium granule of surface-stable.Lithium source can be the one layer of lithium thin film being pre-loaded on active material of positive electrode surface.
In another embodiment, the table of the SMC electrode material raw graphite alkene of 99% carbon (such as, comprise substantially >) Face, is not bonded in functional group thereon, it is possible to directly capture lithium ion mutually from liquid electrolyte and with reversible and stable Lithium atom is stored on said surface by mode, even if this monolayer of lithium atom keeps being dipped in electrolyte.
In one embodiment, electrolyte comprises liquid electrolyte (such as organic liquid or ionic liquid) or coagulates Glue electrolyte, wherein lithium ion has high diffusivity coefficient.Solid electrolyte is the most unacceptable, but can use solid electricity If solve matter some thin layers its show relatively high diffusibility.
In order to this battery or the operation principle of storage device (Fig. 2 (A)) are described, it may be considered that following situation: wherein in system The anode that lithium source (the lithium paper tinsels of such as small pieces) are applied to when making cell apparatus nanostructured (such as includes the graphite of nonfunctionalized Alkene sheet) and porous polymer spacer body between, and the negative electrode of wherein nanostructured comprise be interconnected hole around non-functional The graphene film changed, described hole is preferably meso-scale (2nm-50nm), but can be less than 2nm.Reference Fig. 2 (A)-(C), For the first time in discharge cycles, by lithium paper tinsel ionizing to produce lithium ion in liquid electrolyte.Lithium ion migrates across rapidly poly- The hole of compound spacer body enters cathode side.Due to negative electrode also be situated between see porous there is interconnected pores to accommodate liquid wherein Electrolyte, therefore lithium ion actually need only arrive the avtive spot on negative electrode through liquid.In one embodiment, this is lived Property site is functional group, and in another embodiment, it can be edge or the surface of graphene film.At latter situation In, the surface oxidation reduction reaction between functional group that lithium ion and surface carry (such as carbonyl >=O) subsequently is quick And it is reversible；In later case, graphenic surface directly contacts with electrolyte and is prone to receive lithium ion from electrolyte.Two Plant embodiment and can realize repid discharge and the high power density of SMC.This forms sharp contrast with traditional lithium-ion battery, In traditional lithium-ion battery, require that lithium ion diffuses into solid state cathode granule (the lithium cobalt of such as micron-scale during discharging Oxide) body in, this is slowly process.
In the above-described example, discharge process continues until or work on the complete ionizing of lithium paper tinsel or active material of cathode Property site is occupied by lithium atom.Recharging period, lithium ion is from the big surface of active material of cathode in one embodiment Release, diffuses through liquid electrolyte, and the functional group carried by surface captures or quilt in without functional group's embodiment The surface trapping (on the surface of the anode material being the most only electrochemically-deposited in nanostructured) of active material of positive electrode.Equally, no Need solid-state diffusion, and the most whole process is very quick, needs of short duration recharge time.This is electric with at conventional lithium ion Solid-state diffusion needed for lithium ion enters graphite granule at the anode of pond is contrary.
Obviously, battery or energy storing device provide the most only between the big surface and the big surface of negative electrode of anode The platform of special exchange lithium ion, it need not the solid-state diffusion in two electrodes.This process is mainly captured by the surface of lithium Determine, additional liquid phase diffusion (these are the fastest).Therefore, this device is referred to herein as the lithium ion exchanged of surface mediation Battery.This is entirely different and the energy storing device of type of substantially having any different compared with traditional lithium-ion battery, described In traditional lithium-ion battery, during charging and discharging circulates, anode and negative electrode are required for the solid-state diffusion (inserting embedding and deintercalation) of lithium.
This surface mediation lithium ion exchanged cell apparatus be also clearly distinguished from based on electric double layer (EDL) mechanism or The typical ultracapacitor of pseudo-capacitance mechanism is same.In two kinds of mechanism, between two electrodes, exchange lithium ion (is not deposited because of lithium It is stored in body or the surface of electrode；On the contrary, they are stored in the electric double layer near electrode surface).When to super electricity When container recharges, near the activated carbon surface of anode-side and cathode side, all form electric double layer.Each and each EDL is by electricity The layer of the negatively charged species of Xie Zhizhong and the layer of positively charged species are constituted (except on electrode material (such as activated carbon) surface Outside electric charge).When being discharged by ultracapacitor, negatively charged species and positively charged species become randomization in the electrolyte (electrode material surface further away from each other).In contrast, when SMC is recharged, essentially all of lithium ion captured or Person is electroplated onto active material of positive electrode surface, and cathode side is substantially free of lithium.When SMC is discharged, essentially all of lithium from Son is captured (being stored in defect or be bonded to phenyl ring center or and functional group reactions) by cathode active material surface.Seldom Lithium retain in electrolyte.
It is interesting to note that in ultracapacitor previously, the charge storage capacity of ultracapacitor is (even if when use contains During Li electrolyte) it is limited to participate in cation and the quantity of anion that EDL electric charge is formed.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 by these ions in electrolyte solvent Dissolubility pole determines.In order to this point is described, let it is assumed that the Li of the most at most 1 mole+Ion is soluble in 1mL solvent In and a total of 5mL solvent add in specific ultracapacitor cell.At this moment, there is the Li of maximum 5 moles+Ion is permissible It is present in whole unit, and this quantity determines the maximum quantity of the electric charge can being stored in this ultracapacitor.
By contrast, the lithium ion quantity that can shuttle back and forth round between the anode surface of SMC and cathode surface is by being somebody's turn to do The chemical solubility of the lithium salts in same solvent limits.Assume to use identical 5mL solvent (containing 5 moles of Li in SMC+Ion, As described above for described in ultracapacitor).Because this solvent is the most saturated by lithium salts, therefore people can expect that this solvent can not be also Any more Li will not be accepted from extra lithium source (5 moles is maximum)+Ion.Therefore, people can expect these 5 moles of Li+ Ion is that we can be used to store maximum lithium quantity (that is, the maximum Li that can be captured by negative electrode during discharging of electric charge+From Quantum count, or the maximum Li can being more readily captured by the anode during recharging+Amount of ions).Common with in electrochemical field This expection of personnel or the most outstanding technical staff is contrary, we surprisingly, it is found that, can be by electrode arbitrary in SMC The Li of surface capture+The quantity of ion (or the round Li that can shuttle back and forth between two electrodes+The quantity of ion) the most remote Exceed well over this solubility limit 1 or 2 orders of magnitude.At anode the realization in lithium source seem by provide be significantly more than solvent can be at it The lithium ion of middle dissolving thus violate this expectation.
The most unexpectedly, in SMC, it is possible to contribute to the lithium quantity of electric charge storage by capturing from electrolyte The quantity of the cathode surface avtive spot of lithium ion controls (restriction).Even when the quantity in surface activity site is far beyond solvent The Li that can once accommodate+During the quantity of ion, (5 moles in such as this discussion) are also such, and condition is that the lithium source implemented can To provide the lithium ion of extra quantity.As it has been described above, these avtive spots can be functional group in one embodiment, or They can be the surface defect of Graphene, or the phenyl ring center (Fig. 3 (D) and (E)) on graphene planes.The most suitable Unexpectedly, find lithium atom can strongly and be reversibly bound to composition graphene film phenyl ring (six limits of carbon atom Shape) each center, or reversibly can be captured by graphenic surface rejected region.
The lithium ion exchanged cell apparatus of this surface mediation is also significantly different from our two relatively application morning (U. S. applications 12/806,679 and 12/924,211) superbattery disclosed in, this superbattery does not has active material of positive electrode at anode (anode-side is containing only anode collector).
In the energy storing device of the present invention, not only negative electrode but also anode all have substantial amounts of surface area with allow lithium from Son is concurrently deposited on it so that be capable of significantly higher charging and discharging speed and higher power density.Change and Yan Zhi, (quickly recharging period) in high current density situation, substantial amounts of lithium ion quickly pours in anode-side, and each lithium Ion is found site and with deposition or is reacted on it.Anode collector (such as Cu paper tinsel) the most only has a small amount of free list Area, cannot accommodate the highest lithium ion flux.By contrast, nanostructured anode and optionally functionalised material are (such as Graphene or CNT or their functionalized form) bigger serface can accommodate substantial amounts of lithium ion simultaneously.In addition, electrode The dispersed electric field provided the most in the electrodes evenly on these surfaces of middle nano material (such as Graphene or CNT), its Middle lithium can more uniformly deposit and be formed without dendrite.More surface area also implies that more saltation point, and each point The most a small amount of lithium, is not enough to form dangerous dendrite.Such nanostructured eliminates potential dendrite and is formed, described dendrite Being formed in the lithium metal battery of routine is the most serious problem.
In an embodiment of this SMC device, at least negative electrode in two electrodes has for nonfunctionalized material The active material of (that is, being not adhered to the functional group on the surface of its contact electrolyte).Term " material of functionalization " refers to tool Having the material (such as carbonyl) of functional group, this functional group can form redox couple with lithium atom or ionic reaction.Negative electrode Active material has high specific surface area (> 100m2/ g), described specific surface area directly contacts with electrolyte and (is the most directly immersed in In electrolyte) and can react and be captured by electrolyte lithium ion with the lithium ion from electrolyte, and lithium atom is stored up There is surface activity site (such as surface defect and phenyl ring center).
Preferably, two electrodes all have high-specific surface area (> 100m2/ g), it directly contacts with electrolyte, and can be by Their surface activity site of lithium atom/ion trap/be stored in.Preferably, at least one in two electrodes has nano junction The non-functional material of structure, it has not less than 500m2/ gram (preferably > 1,000m2/ gram, more preferably > 1,500m2/ gram, and most preferably >2,000m2/ gram) high-specific surface area to store or support lithium ion or atom thereon.
Preferably, lithium source includes lithium bits, lithium paper tinsel, lithium powder, surface passivation or stable lithium granule, or combinations thereof. Can the first time discharge process on this cell apparatus carry out before lithium source is implemented in anode-side.As an alternative, can be right Lithium source is implemented in cathode side before carrying out first time charging process by this cell apparatus.Alternatively, can be at battery During manufacture process, negative electrode and anode both of which are manufactured into and comprise some lithium sources.It is important to note that this solid lithium source carries The most of lithium ion exchanged between anode surface and cathode surface during having supplied to await charge-discharge cycles.Although containing Lithium electrolyte provides some required lithium ions naturally, but this quantity is too small to make cell apparatus provide high-energy close Degree.It is close that this most any symmetrical ultracapacitor (even if containing electrolyte based on lithium) does not show high-energy Degree.
In a kind of embodiment of this SMC device, at least one in active material of positive electrode and active material of cathode is (excellent Both choosings) selected from following:
A the disordered carbon material of () porous, selected from soft carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonization Colophonium, carbon black, activated carbon or part graphitized carbon；
B () grapheme material, selected from Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitridation stone The single-layer sheet of the graphene oxide of ink alkene, boron doped graphene, nitrogen-doped graphene or chemistry or thermal reduction or multi-layer sheet Sheet；
(c) expanded graphite；
D () mesoporous carbon (such as assists synthesis or chemical activation to obtain by the template of mesocarbon)；
E () CNT, selected from SWCN or multi-walled carbon nano-tubes；
F () carbon nano-fiber, metal nanometer line, metal oxide nano-wire or fiber or conductive polymer nanometer are fine Dimension；Or
(g) combinations thereof.
Although CNT is due to high cost and other technical problem rather than preferred nano structural material, but CNT is (individually Or be combined with other nano structural material) still can be used for the lithium ion exchanged battery of the granule surface contral of the present invention.
Its one or both of Anodic and negative electrode are included to the embodiment of functional group, representational material can be selected from As follows: poly-(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene), LixC6O6(x=1-3)、Li2(C6H2O4)、Li2C8H4O4(Li's Terephthalate), Li2C6H4O4(trans-trans-muconate of Li), 3,4,9,10-tetrabasic carboxylic acid-dianhydride (PTCDA) sulfur Ether polymer, PTCDA, 1,4,5,8-naphthalene-tetrabasic carboxylic acid-dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8-tetra- Hydroxyanthraquinone, tetrahydroxy 1,4-benzoquinone and combinations thereof.In one embodiment, the tool of at least one in functional material Have selected from-COOH ,=O ,-NH2, the functional group of-OR and-COOR, wherein R is alkyl (such as 1 to 6 carbon atom).These have Machine or polymeric material (molecule or salt) have and can carry out the functional group of reversible and quick redox reaction (such as carbonyl with lithium Base).These functional material often have a relatively low electron conduction, the most preferably by selected from the functional material of this group and (example Such as chemical bonding or be attached to nano structural material, such as nano-graphene, CNT, disordered carbon, nano-graphite, selected from nanometer Graphene, CNT, disordered carbon, nano-graphite, metal nanometer line, conducting nanowires, carbon nano-fiber and polymer nanocomposite The material of fiber) combine.Such as, the component aromatic ring of Graphene and disordered carbon (soft carbon, hard carbon, activated carbon, carbon black etc.) all may be used To have functional group on their edge or surface, described functional group can be with the place mat on above-mentioned functional material (matting) functional group's (such as hydroxyl on tetrahydroxy 1,4-benzoquinone) reaction.
As an alternative, nanostructured material with carbon element (as the nano-graphene of nonfunctionalized, CNT, disordered carbon or Nano-graphite) may be provided solely for the surface that lithium atom can be deposited thereon, such as, being captured or in phenyl ring by defective bit The heart captures.Only existing nano structural material, even if there is no reactive functional groups, remaining able to provide substantial amounts of lithium storage surface.
In one embodiment, disordered carbon material can be by two phase compositions, and the first phase is graphite crystal or Graphene In the stacked body of plane and the second phase are amorphous carbon, and wherein the first phase is dispersed in the second phase or combined by second. This disordered carbon material can comprise by the graphite crystal less than 90 volume % and the amorphous carbon of at least 10 volume %.
The active material of positive electrode of SMC or active material of cathode can comprise selected from single-layer graphene film or multi-layer graphene The nonfunctionalized nano-graphene of plate.As an alternative, active material can comprise single wall or multi-walled carbon nano-tubes.
In one embodiment of the invention, therefore, the active material of positive electrode of SMC and/or active material of cathode right and wrong The grapheme material of functionalization, its selected from selected from graphene oxide, Graphene fluoride, hydrogenation Graphene, nitridation Graphene, The graphene oxide of boron doped graphene, nitrogen-doped graphene, doped graphene, chemistry or thermal reduction or Graphene Single-layer sheet or multilamellar plate.As an alternative, active material of positive electrode and/or active material of cathode are the single wall of nonfunctionalized or many walls CNT (CNT), oxidation CNT, fluorination CNT, hydrogenation CNT, nitridation CNT, boron doping CNT, N doping CNT or doping CNT。
Lithium source can be selected from lithium metal (for example, thin foil or powder morphology, the most stable or surface passivation), lithium gold Belong to alloy, lithium metal or lithium alloy and the mixture of lithium intercalation compound, the compound of lithiumation, the titanium dioxide of lithiumation, metatitanic acid Lithium, LiMn2O4, lithium transition-metal oxide, Li4Ti5O12, or combinations thereof.Specifically, lithium intercalation compound or lithiumation Compound can be selected from llowing group of materials group:
The silicon (Si) of (a) lithiumation, germanium (Ge), stannum (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd) and their mixture；
The lithiumation alloy of (b) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd and their mixture or Intermetallic compound；
(c) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd and their mixture or complex The oxide of lithiumation, carbide, nitride, sulfide, phosphide, selenides, tellurides or antimonide, and
The lithiumation salt of (d) Sn or hydroxide.
Electrolyte can be selected from any electrolyte used in traditional lithium-ion battery or lithium metal battery.Electrolyte is preferred It is liquid electrolyte or gel electrolyte.Electrolyte can comprise the ionic liquid of doping lithium salts.In cell apparatus, positive pole is excellent Choosing has the thickness more than 5 μm, preferably greater than 50 μm, and more preferably greater than 100 μm.
In one embodiment, in SMC, when this device is in charged state, the lithium of at least 90% is stored in anode On the surface of active material (lithium contacts with anode surface direct physical), maybe when this device is in discharge condition at least 90% Lithium is stored on the surface of active material of cathode (lithium contacts) with cathode surface direct physical.
This SMC is typically operating in the voltage range of 1.0 volts to 4.5 volts, but can specify that it is in this scope Subset in (such as from 1.5 volts to 4.0 volts or from 2.0 volts to 3.9 volts, etc.) operation.Can also be at 4.5 volts Above or slightly below 1.0 volts (the most preferred) operation.It may be mentioned that the symmetrical super capacitor being characterized with organic bath Device can only operate under 0 to 2.7 volts at most 3.0 volt operation and typical case.By contrast, use identical organic The SMC typical case of electrolyte operates under 1.5 volts to 4.5 volts.This is SMC and ultracapacitor is two kinds of fundamental difference kinds Another part evidence of energy storing device, based on different mechanism and principle during their operation.
Preferably, charging and/or the discharge operation of SMC is not related to lithium and inserts embedding or solid-state diffusion.It is generally all this situation, Even if multi-layer graphene plate is used in male or female.The lithium in clearance space between two graphene planes is inserted embedding Typically occur in less than 1.5 volts (relative to Li/Li+) voltage, mostly less than 0.3 volt.The lithium ion exchanged of the present invention Battery its relate to the reciprocal lithium ion that shuttles back and forth between anode surface and cathode surface, it is in the scope of 1.5 accompanying drawings to 4.5 volt Carry out.
The most surprisingly, this SMC device provides the typical energy density being not less than 150Wh/kg and is not less than The power density of 25Kw/kg, is based on total electrode weight.More typically, this cell apparatus provides the energy more than 300Wh/kg Metric density and the power density more than 20Kw/kg.In many cases, this cell apparatus provides the energy more than 400Wh/kg close Degree and the power density more than 10Kw/kg.Most typical, this cell apparatus provides the energy density more than 300Wh/kg and is more than The power density of 100Kw/kg.In some cases, power density is significantly higher than 200Wh/kg, or even above 400Wh/ Kg, this 1-3 order of magnitude higher than the power density of typical ultracapacitor (1-10Kw/kg).
In this SMC, positive pole preferably has greater than the thickness of 5 μm, more preferably greater than 50 μm, most preferably greater than 100 μm.
Present invention also offers the method operating described energy storing device (SMC).The method is included at anode to be implemented Lithium source described in lithium source and ionizing is to discharge lithium ion during the first time discharge cycles of this device in electrolyte.The method Farther including electrochemistry drives the lithium ion that discharged to negative electrode, and the lithium ion discharged is here by active material of cathode Surface captures, such as by interacting with functional group or interacting with Graphene.The method may further include step Rapid: described device recharge circulation during from described cathode surface discharge lithium ion, use external cell charging device will The described lithium-ion electric being released drives to described active material of positive electrode surface.
As an alternative, the method can be included at negative electrode and implement lithium source and operate described lithium source to come at the first of this device Discharge lithium ion during secondary charging cycle and enter electrolyte.
The method that invention further provides the energy storing device of operation surface mediation, the method includes: (a) provides The battery of surface mediation, it comprises anode, lithium source, porous separator, liquid or gel electrolyte and negative electrode, wherein one In individual embodiment, anode and/or negative electrode are functionalizations and anode and/or negative electrode are to have to catch in this second embodiment The nonfunctionalized material on lithium surface；B () discharges lithium ion during the first time of this device discharges from lithium source；And (c) with After charge or discharge operation during anode catch lithium surface and negative electrode catch exchange lithium ion between lithium surface.Preferably, The charging and discharging of this device is all not related to lithium and inserts embedding or solid-state diffusion.
The method that this application discloses another kind of operation surface mediation energy storing device.The method includes: (a) provides table Face mediation battery, it comprises anode, lithium source, porous separator, electrolyte (having the lithium ion of initial number) and negative electrode, wherein Anode and negative electrode have the material catching lithium surface with electrolyte contact；(b) this device first time discharge during from lithium source Release lithium ion enters in electrolyte；C () operation negative electrode is to capture lithium ion and the lithium of capture is stored in the moon from electrolyte Pole (preferably has greater than 100m on surface2The specific surface area of/g, more preferably greater than 1,000m2The specific surface area of/g, the most greatly In 2,000m2The specific surface area of/g)；And (d) subsequently charge or discharge operate during anode catch lithium surface and Catching of negative electrode exchanges a number of lithium ion (more than initial number) between lithium surface, wherein charging operations be not related to lithium insert Embedding.
Accompanying drawing is sketched
The lithium ionic cell unit of Fig. 1 (A) prior art, it uses 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, its with Lithium titanate is made (nano-graphene, CNT or the disordered carbon such as functionalization as active material of positive electrode and negative electrode by functional material Powder)；(C) the lithium superbattery unit of prior art, it has lithium paper tinsel anode (but not having the functional material of nanostructured) and official The negative electrode that energy functionalized graphene, CNT or disordered carbon are made；(D) surface mediation lithium ion according to an embodiment of the invention is handed over Changing an example of cell apparatus, it comprises: nano structural material at anode is (with or without can be with lithium ion or former The functional group of son reaction), lithium source (the lithium powder of such as lithium paper tinsel or surface passivation), porous separator, liquid or gel electrolyte (liquid is preferred), nanostructured functional material at negative electrode.
The structure of the lithium ion exchanged cell apparatus of Fig. 2 (A) surface mediation, (discharges for the first time or fills when fabricated Before electricity circulation) it is included in the nano structural material at anode, lithium source (the lithium powder of such as lithium paper tinsel or surface-stable), porous Spacer body, liquid electrolyte, nanostructured nonfunctionalized material at negative electrode；(B) this electricity after first time discharge operation (lithium is ionized and lithium ion diffuses through liquid electrolyte thus arrives (functionalization or nonfunctionalized) for the structure of pool device The surface of nanostructured negative electrode is also quickly captured by these surfaces);(C) after recharging this cell apparatus structure (lithium from Son discharges from cathode surface, is arrived the surface of (functionalization or nonfunctionalized) nanostructured anode by liquid electrolyte diffusion And quickly it is plated on these surfaces).Huge surface area can serve as support substrate, and substantial amounts of lithium ion can be simultaneously It is electrodeposited on this substrate.The anode collector with low specific surface area can not be used individually to complete so a large amount of, simultaneously heavy Long-pending.
The schematic diagram of Fig. 3 (A) lithium memory mechanism, is wherein attached to aromatic ring or the edge of graphene film or the functional group on surface It is readily able to react formation redox couple with lithium ion；(B) theoretical informatics of electric double layer, as secondary or insignificant electric charge Memory mechanism;(C) lithium in the capture of phenyl ring center of graphene planes；(D) lithium in graphenic surface defect it is captured on Atom.
Fig. 4 can be used as have the disordered carbon of the nano structural material of high surface (with electrolysis at anode and/or negative electrode Upright contact) example: the schematic diagram of (A) soft carbon, wherein the neighbouring stacked body of graphene film or little aromatic ring each other with Low-angle preferred orientation, this is of value to growth or merges (graphitizable);(B) hard carbon (the most non-graphitized);(C) carbon black, has Substantial amounts of arrangement forms the little aromatics ring region territory of nano-level sphere granule.Preferably, individual carbon black granules is activated to and opens Wicket, described wicket makes the functional group that liquid electrolytic mass-energy arrival edge within granule or surface are carried, as shown in (D).
The SEM image of the nano-graphene sheet that Fig. 5 (A) bends；(B) SEM image of another kind of Graphene pattern.These stones Ink alkene pattern can provide the highest specific surface area (typically from 300 to 2,000m2/g)。
The Ragone figure of Fig. 6 (A) five class battery: (class is at two kinds for the lithium ion exchanged battery unit of two class surface mediations Electrode active material all has functional group and the another kind of active material with nonfunctionalized), the super electricity of lithium of prior art Pond (is formed by the disordered carbon negative electrode of Li metal anode and functionalization), the prior art being made up of two kinds of functionalization disordered carbon electrodes Symmetrical ultracapacitor (not using lithium paper tinsel as lithium source), and symmetrical ultracapacitor (the super electricity of CNT base based on LBL-CNT The digital independent of container is in the figure of Lee et al.).(B) for functionalized surfaces battery and nonfunctionalized SMC, as charge/discharge The energy density values that the function of period is drawn.
The NGP base lithium superbattery of Fig. 7 (A) functionalization and two kinds of corresponding surface mediation lithium ion exchanged cell apparatus The Ragone figure of (one has functional group and one does not has functional group).These data prove the property of surface mediation device further Superbattery can be better than, particularly under higher density (higher power density region).(B) according to one embodiment party of the application The long-term cyclical stability of the SMC of case, the long-term circulation compared to the SMC (having functional group in its electrode) of previously application is steady Qualitative.
(M=is from graphite for the charge/discharge curve of the battery of three kinds of surface activations (surface-enabled) of Fig. 8 (A) NGP, C=are from the NGP of carbon fiber, G=expanded graphite, EG).Discharge current density is 1A/g, and (B) is with sweep speed 25mV/s The CV figure of same battery, (C) has the Ragone figure of these batteries of thick negative electrode (200 μm), (D) NGP, CB (carbon black), t-CB (chemically treated CB) and have thick negative electrode surface based on AC mediation battery Ragone figure.All of energy density and Power density values is all based on the LITHIUM BATTERY numerical value that total battery weight calculates.
Fig. 9 symmetrical ultracapacitor (leftmost curve) based on Graphene and there is lithium source accordingly that be implemented at anode Surface of the present invention mediation battery (right side graph) cyclic voltammetric (CV) figure.
The Ragone of the graphenic surface activation Li ion communicating battery that Figure 10 has Different electrodes thickness schemes: energy density It is based on total battery weight (A) and to be based only upon cathode weight (B) calculating with power density values.
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 battery of Figure 12 is drawn.Described electrode is from different stone Prepared by ink alkene associated materials.
Preferred embodiment describes
The detailed description of the Invention carried out by referring to following combination accompanying drawing (it constitutes a part of this disclosure), can more hold Change places and understand the present invention.It should be understood that the invention is not restricted to described herein and/or display specific device, method, condition or Parameter, and terms used herein is only used to describe specific embodiment by way of example, and it is not intended to limit Make invention required for protection.
The invention provides a kind of electrochemical energy accumulating device, the referred to herein as lithium ion of surface mediation to hand over Change battery (or referred to as surface mediation battery, SMC).In many embodiments, the power density that this SMC device can provide Apparently higher than typical ultracapacitor power density, and it is significantly higher than the power density of the lithium ion battery of routine.This device The energy density suitable with accumulator can be shown, and apparently higher than conventional ultracapacitor.
The ion communicating battery of this surface mediation is made up of following: positive pole, and it comprises and has storage lithium or catch the official on lithium surface (this functionalization or nonfunctionalized material are preferably nanostructured, have nanoscale or the sight chi that is situated between for energyization or nonfunctionalized material Degree hole and substantial amounts of surface area)；Negative pole, it comprises and has storage lithium or catch high surface area material (the preferably nanometer on lithium surface Structure, there is nanoscale or meso-scale hole)；It is arranged at the porous separator between two electrodes；With two electrode things Reason contact containing lithium electrolyte；And it is implemented in the lithium ion source at male or female.It is direct with electrolyte that these catch lithium surface Contact is thus to capture lithium ion or discharging lithium ion to this.Preferred electrolyte type includes liquid organic electrolyte, coagulates Glue electrolyte and il electrolyte (preferably comprising lithium ion), or combinations thereof, however can select use aqueous or Solid electrolyte.
Lithium ion source can be selected from lithium bits, the lithium granule of lithium paper tinsel, lithium powder, surface-stable, be coated on active material of positive electrode or Lithium film on cathode active material surface, or combinations thereof.In a preferred embodiment, active material of positive electrode is Lithiumation in advance, or coat in advance with lithium or plating in advance.In addition to relatively pure lithium metal, lithium source can be selected from lithium gold Belong to alloy, lithium metal or lithium alloy and insert the mixture of embedding compound, lithiated compound, lithiumation titanium dioxide, lithium titanate, manganese with lithium Acid lithium, lithium transition-metal oxide, Li4Ti5O12, or combinations thereof.Lithium inserts embedding compound or lithiated compound is permissible Selected from materials described below group: the silicon (Si) of (a) lithiumation, germanium (Ge), stannum (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd) and their mixture；(b) Si, Ge, Sn, Pb, Sb, Bi, The lithiumation alloy of Zn, Al, Ti, Co, Ni, Mn, Cd and their mixture or intermetallic compound；(c) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd and their mixture or the lithiated oxide of complex, carbide, nitridation Thing, sulfide, phosphide, selenides, tellurides or antimonide；Or (d) the lithiumation salt of Sn or hydroxide.
Although not limiting thickness of electrode, but the thickness of positive pole is preferably greater than 5 μm, more preferably greater than 50 μm, and Preferably greater than 100 μm.Fig. 1 (D) and Fig. 2 gives the example of the ion communicating battery device of such surface mediation.
While not wishing to retrained by any theory, but following Theory Thinking may is that helpful.
The internal structure of conventional lithium ion battery can be schematically shown in Fig. 1 (A).In the case of battery discharge, lithium Ion must be from anode active material particles (such as graphite, silicon and lithium titanate) bulk diffusion (deintercalation) out (particle diameter=daWith And averagely solid-state diffusion distance=da/ 2), and then migrate across in liquid electrolyte anode thickness (anode layer thickness=La with And average diffusion distance=La/2).Subsequently, lithium ion must move (in liquid electrolyte) through porous separator (thickness= Ls), diffusing through part cathode thickness (thickness=Lc) in liquid electrolyte, to arrive specific active material of cathode granule (flat All diffusion length=Lc/2), and then diffusion (inserting embedding) is to (diameter=d in the body of granulecAnd the average solid-state diffusion needed Distance=dc/2).In the case of recharging, lithium ion moves in a reverse direction, but approximately the same distance of must advancing.
In other words, the operation of traditional lithium-ion battery relates to the electricity from an electrode (such as anode, during discharging) The lithium ion deintercalation of pole active material particle body (not being surface), and in comparative electrode (such as negative electrode) in electrode activity Lithium ion in material granule body is inserted embedding.It is said that in general, be quick by the diffusion of liquid electrolyte, but by solid Diffusion notable relatively slow (the about 3-8 order of magnitude).The operation on surface mediation battery (SMC) of the present invention is fundamentally based on porous electrode Surface between the exchange (rather than in the body of electrode, as in lithium ion battery) of a large amount of lithium ions.This strategy Completely removes the needs of the time-consuming process that lithium is inserted embedding and deintercalation.SMC is substantially embedding without inserting, and most of lithiums are stored in electricity In the huge surface area of pole active material.The lithium atom of typically > 90% is trapped on graphenic surface, and the least Lithium in 1% may enter the inside of multi-layer graphene structure by accident.The charge/discharge time of SMC is only passed through liquid electrolytic The lithium ion mobility of matter (organic or ionic liquid) limits, and this migration is very fast and cause even ultracapacitor (it is with height Power density and well-known) the ultra high power density that also cannot be equal to.Hereinafter this is explained further:
Assume that lithium ion diffusion coefficient in particular medium is D and required travel distance is x, then according to known Diffusion time needed for kinetics equation can be approximately t～x2/D.As first approximation, lithium ion completes charge or discharge process Required total time yardstick can be estimated as:
tAlways=(La/2)2/DElectrolyte+(da/2)2/Da+(Ls)2/Ds+(Lc/2)2/DElectrolyte+(dc/2)2/Dc (1)
Wherein DElectrolyteLi ionic diffusion coefficient in=electrolyte, DaLi ion diffusion in=anode active material particles is Number, Ds=by the Li ionic diffusion coefficient of porous separator, and DcLi ion diffusion in=active material of cathode granule is Number.
Li is given below+In various liquid mediums or solid film or granule or by their typical diffusion coefficient (based on open source literature data): liquid electrolyte (2 × 10-6cm2/s)；Spacer body (7.5 × 10-7cm2/s)；LiFePO4Negative electrode (10-13cm2/s)；Li3V2(PO4)3Negative electrode (10-13To 10-9cm2/s)；Nano Si anode (10-12cm2/s)；Graphite anode (1-4 ×10-10cm2/s);And Li4Ti5O12Anode (1.3 × 10-11cm2/s).It means that for wherein using LiFePO4Granule is made For the traditional lithium-ion battery unit of active material of cathode, the last item in equation (1), (dc/2)2/DcDue to the diffusion that it is extremely low Coefficient thus determine required total diffusion time.Actually, the value of diffusion coefficient is 10-10With 10-16cm2Change between/s, This depends at solid solution LiXFePO4And Li1-XFePO4Lithium content in (X < 0.02) or LiFePO4/FePO4The ratio of phase.
By contrast, mesopore negative electrode and the lithium of functionalization nano-carbon material (such as Graphene, CNT or disordered carbon) are being comprised Metal forming is as in the superbattery (battery of part surface mediation) of anode (schematically showing in Fig. 1 (C)), and Li ion is not required to Solid state cathode granule to be diffused through, and therefore without undergoing restriction (the such as LiFePO of the low solid-state diffusion coefficient at negative electrode4? In Li 10-13cm2/s).On the contrary, active material of cathode is highly porous, it is allowed to liquid electrolyte arrives pore interior, official Can group be present in herein, thus be prone to and reversibly with by liquid medium (and non-solid medium) with high diffusivity coefficient (such as 2 × 10-6cm2/ s) lithium ion that diffuses into these holes reacts.Last item in such superbattery, in equation (1) (dc/2)2/DcThe most non-existent.Required total diffusion time is determined by the thickness of electrode and spacer body now.Above Discussion is based on following premise: the reversible reaction between lithium ion in functional group and electrolyte is quick, and whole fills Electricity-discharge process is not to control reaction.
In the lithium-ion capacitor (LIC) of prior art, negative electrode is the nano-carbon material (such as activated carbon) of central hole structure, But lithium titanate or graphite granule constitute anode (being schematically shown in Fig. 1 (B)).In the case of battery discharge, lithium ion must Lithium titanate particle or graphite granule (deintercalation step slowly) must be diffused out, in liquid electrolyte, then migrate across anode thick Degree.Subsequently, lithium ion (in liquid electrolyte) must move through porous separator, diffuses through one in liquid electrolyte Part cathode thickness arrives the position of the surface area close to nanostructured active material of cathode.Expand without solid-state at cathode side Dissipate.Whole process is substantially determined by the solid-state diffusion of anode.Therefore, with superbattery (part surface mediation) and this paper institute Disclosed surface mediation battery (SMC) completely is compared, and this LIC should show slower dynamic process (therefore, relatively low power Density).
By using the representative value of parameters in equation (1), we obtain several traditional lithium-ion battery type and Total lithium migration time needed for the lithium superbattery unit of several prior aries and the battery charge or discharge process of LIC. First group is to have graphite granule anode and lithiated-iron-phosphate cathode (Gr/LiFePO4) traditional lithium-ion battery.Second and the 3rd Group is all conventional Li ion battery, has LiFePO4Negative electrode and based on Si granule or anode based on lithium titanate, is respectively (nanometer-Si/LiFePO4And Li4Ti5O12/LiFePO4).4th group is LIC (Li4Ti5O12/ f-CNM), its Anodic by Li4Ti5O12Granule composition and negative electrode are the carbon nanomaterials (f-CNM) of functionalization, such as CNT or activated carbon (AC).5th Group is the battery (lithium paper tinsel/f-CNM) of part surface mediation, and its Anodic is lithium paper tinsel and negative electrode is carbon nanomaterial.These numbers According to following display in table 1 below (a) and (b):
Table 1 (a): (CNM=carbon nanomaterial, including CNT (CNT), nano-graphene plate for this parameter calculated Sheet (NGP), disordered carbon etc.;Gr=graphite).
Table 1 (b): arrive (t diffusion time needed for the granule in anodeLa), the diffusion (ta) in anode pellets, pass through The diffusion time (ts) of spacer body, arrive (t diffusion time of cathode particlesLc), and the diffusion time in cathode particles (tc)。
Several important observed result can be drawn from the data of table 1 (a) He (b):
(1) (graphite is straight for the graphite granule anode that feature is micron-scale of conventional lithium ion battery (above-mentioned first group) Footpath=20 μm) and the LiFePO of micron-scale4Negative electrode (particle diameter=1 μm), it needs some hours (such as 8.4h) to complete Required lithium ion diffusion process.This is with regard to why traditional lithium-ion battery shows low-down power density (typically The reason of recharge time 100-500W/Kg) and very grown.
(2) problem of this long diffusion time can be alleviated, such as above-mentioned second by using nano-scale particle to be able to part With the 3rd group (if such as anode and active material of cathode granule all have the diameter of 100 nanometers, be 8 minutes).
By contrast, (3) for being characterised by carbon cathode (such as f-CNT) and Li4Ti5O12The LIC of nano-particle anode, 235 seconds (< 4 minutes) when 200 μm cathode thickness required diffusion time and ultra thin cathode (such as pass through MIT research group 0.3 μm LBL prepared by the successively method of [S.W.Lee, et al., Nature Nanotechnology, 5 (2010) 531-537] F-CNT) between 1.96 seconds.Regrettably, such ultrathin electrodes (0.3-3 μm) has extremely limited practical value.
(4) for lithium superbattery (part surface mediation), thickness of electrode is leading factor.Such as, lithium metal is being used In the case of paper tinsel is as anode (first kind), short can reach that < 0.6 second (when cathode thickness is 0.3 μm or 3 μm total diffusion time Time), when cathode thickness is 200 μm, increase to 103 seconds (still less than 2 minutes) total diffusion time.
(5) above-mentioned observed result means that lithium superbattery should have outstanding power density, particularly surpasses when electrode Bao Shi.Here it is why the Lee et al. of MIT can have the super lithium of the LBL f-CNT negative electrode of 0.3 μ m thick about them The power density of the 100Kw/Kg that battery unit is reported.But, useful electrode size is that thickness is at least 50 μm (typically Between 100 and 300 μm), furthermore and, these batteries with 0.3-3.0 μm cathode thickness have very limited amount of reality Value.The highest viewed merit of the lithium superbattery with LBL f-CNT negative electrode that Lee et al. is reported Rate density is due to ultra-thin cathode thickness (0.3 μm).
As Figure 11 shows, our surface based on Graphene mediation battery (typically has the electrode of 100-300 μm Thickness) performance more preferable than LBL f-CNT battery (part surface mediation) based on thin electrodes.
It may be noted that it is above-mentioned about the surface being also applied for the present invention containing lithium paper tinsel as the calculating of the superbattery of anode Mediation energy storing device, except lithium paper tinsel thickness can be replaced with the thickness of nanostructured anode.Lithium source (lithium granule or lithium paper tinsel Sheet) extra anode thickness value will not be increased in Time Calculation, because the anode of nanostructured is " elastic " or compressible. Lithium paper tinsel can be pressed against the anode of nanostructured, or when manufacturing cell apparatus, lithium granule can be brought into nano junction In the anode of structure.During first time discharge cycles, once lithium granule or lithium paper tinsel are ionized, and the anode of nanostructured is (such as The pad of NGP or CNT base) contact spacer body by reverting to rapidly.
It is noted that be the lithium superbattery (Li paper tinsel/f-CNM) of lithium paper tinsel for its Anodic, there is no anode pellets, and Therefore there is no particle diameter (in above-mentioned calculating daIt is designated as zero).During for the first time electric discharge, by Li paper tinsel by electrochemistry from Sonization is to discharge ion.In above-mentioned calculating, the reaction of this granule surface contral is assumed to be it is that quick and non-multiplying power limits.Actual On, when needing high-discharge-rate (when external circuit or the high electric current density of load request), the reaction of this surface can become Limit for multiplying power.This restriction self may not be controlled by surface ionization speed, but by lithium during first time discharge cycles The surface area of the limited quantity of paper tinsel controls.In other words, the given time during electric discharge for the first time, only exist much more so The surface area of lithium ion can be discharged from it simultaneously.
During recharging circulation, lithium ion returns to anode-side from movable cathode, attempts to redeposit on anode collector Surface (such as Copper Foil) on, this surface is available at the anode of superbattery to only have surface (part surface mediation electricity Pond).Recharging period, receiving for being used alone collector (such as Copper Foil) flux of a large amount of lithium ion to have two and ask Topic:
(1) high (having high electric current density) if recharging multiplying power, fast transferring returns to a large amount of lithium ions of anode-side All trying concurrently to deposit to the surface of collector, this surface typically has the lowest surface area and (compares table for Cu paper tinsel Area typically < < 1m2/g).This limited surface area becomes deposition velocity and limits.
(2) if recharging multiplying power low (having low electric current density), the lithium ion of return can find a way out with inequality Even mode deposits on collection liquid surface.First some Advantageous sites will receive more lithium deposition atom, and these positions Point can continue deposition with higher speed.Such uneven lithium deposition can cause dendrite to be formed at anode, and this dendrite can Increase along with cycle-index and become the longest, and finally penetrate spacer body arrival cathode side, thus cause internal short-circuit.This Planting probability and can cause the problem similar to the problem perplexing lithium metal battery industry in late period in the 1980's, this problem is finally led Cause the essentially all of lithium metal battery product termination in early stage generation nineteen ninety.
The two problem can solve by implementing nanostructured anode between anode collector and porous separator. The anode of this nanostructured is preferably by having high-specific surface area (preferably greater than 100m2/ g) nano-carbon material composition, such as nanometer Graphene plate (NGP, unified representation monolayer and the Graphene of multilayer form, graphene oxide, Graphene fluoride, doping Graphene etc.), CNT (single wall or many wall), carbon nano-fiber (vapor phase growth, electric spinning polymer is derivative, Etc.), disordered carbon, metal nanometer line, conducting nanowires, etc..The specific surface area of the anode of this nanostructured is preferably greater than 100m2/ g, more preferably greater than 500m2/ g, further preferably greater than 1,000m2/ g, even more preferably greater than 1,500m2/ g, and Most preferably greater than 2,000m2/g.These surfaces preferably directly contact so that thus with electrolyte (preferably liquid organic electrolyte) Direct Acquisition lithium ion or directly discharge lithium ion to this.
The enforcement of this nanostructured anode not only dramatically increases the merit of this surface mediation lithium ion exchanged energy accumulating device Rate density (Kw/Kg), and increase its energy density (Wh/Kg).It is not intended to bound by theory, it is believed that receiving of this new enforcement Rice structure anode plays at least following three kinds of effects:
(1) during recharging circulation, the huge surface area of this nanostructured anode enables a large amount of lithium ion at height (charge rate) fast deposition simultaneously in electric current density situation.This makes this energy storing device likely in several seconds or a few minutes One of recharge in the second.
(2) coming of new the present invention surface mediation energy storing device first time discharge operation during, lithium paper tinsel or Lithium granule is ionized, and discharges lithium ion at anode, and described lithium ion moves into cathode side and by the Graphene table of negative electrode Face captures.When recharging, these lithium ions return anode and uniform deposition to the huge surface of nanostructured anode, Ultra-thin lithium coating is formed on it.The while that the hugest surface area on decorations lithium surface allowing during discharge cycles subsequently Discharge substantial amounts of lithium ion.It is typically well below 1m only having specific surface area2In the battery of the anode collector of/g, this same Time, substantial amounts of lithium ion release be infeasible.(> of the high-specific surface area of nanostructured anode > 100m2/ g) making can be fast Speed charging again can repid discharge, it is achieved that high power density.
(3) anode of nanostructured, it is electronically connected to collector, also provides uniform electric field in anode compartment, from And allow the lithium ion returned more uniformly to deposit to the surface (such as Graphene) of nano material.Because big surface area can be used In this purpose, the most minimal amount of lithium deposits to any single point, is not enough to form dendritic growth.These reasons mean The energy storing device of the granule surface contral of the present invention is a kind of safer energy storing device.
This surface mediation lithium ion exchanged cell apparatus be clearly distinguishable from the most in the following areas routine ultracapacitor:
(1) conventional or prior art ultracapacitor does not have the lithium ion implemented at anode when manufacturing a battery Source.
(2) electrolyte in these prior art ultracapacitors is mainly without lithium or non-lithio.Even When using lithium salts in ultracapacitor electrolysis matter when, lithium salts dissolubility in a solvent substantially sets and can participate in Be internally formed mutually at electrolyte the amount of lithium ions of electric charge electric double layer the upper limit (close to but not in electrode material surface, such as Fig. 3 (B) shown in).Therefore, the ratio electric capacity of gained ultracapacitor and energy density are relatively low (the most typically < 6Wh/kg, bases In total battery weight), this is formed with the 160Wh/kg (based on total battery weight) of the surface of such as present invention mediation battery and compares.
(3) ultracapacitor of prior art is to store them based on electric double layer (EDL) mechanism or pseudo-capacitance mechanism Electric charge.In both mechanism, substantial amounts of lithium ion is not had to be exchanged (even if when electrolyte uses between two electrodes The when of lithium salts).In EDL mechanism, such as, the cation in electrolyte and anion are matched on the surface of electrode active material Neighbouring (but not being from the teeth outwards) forms electric charge electric double layer.Cation is at large to be obtained or is stored among electrode active material or it On.By contrast, use Graphene as the example of the electrode active material in the surface of present invention mediation battery, lithium atom Can be captured or be trapped in the sense on defective bit, graphene edge, the phenyl ring center of graphene planes or graphenic surface Group.
(4) in EDL, when ultracapacitor is in charged state, cation and anion coexist in anode and the moon In extremely.Such as, in one of two electrodes of symmetrical ultracapacitor, negative charge is present on the surface of activated carbon granule, its Attract the species of positively charged thus form one layer of positive charge at these near surfaces.But, in turn, exist by these positive charges Attract electronegative species thus nearby formed one layer of negative charge.Ultracapacitor electrode is had similar arrangement, But electric charge is contrary in polarity.This is the concept of well-known Helmholtz diffusion charge layer in electrochemistry.When super During capacitor discharge, the electric charge on activated carbon particle surface is used or is disappeared, and therefore the electronegative species of salt and band be just Electricity species become randomization and stay electrolyte mutually in (rather than on surface of active carbon particle).In contrast, fill when SMC is in During electricity condition, most of lithium ions are attracted thus adhere to or electroplate on the graphenic surface of anode and cathode side does not has substantially There is any lithium.After discharge, essentially all of lithium atom is captured by cathode active material surface, does not has or almost without lithium Stay in electrolyte.
(5) only the prior art symmetry ultracapacitor (EDL ultracapacitor) of organic bath based on lithium salts is used Operate in the range of 0-3 volt.They can not operate more than 3 volts；Extra charge storage capacity is not had during beyond 3 volts And actually organic bath generally starts to decompose at 2.7 volts.By contrast, the operation of the surface mediation battery of the present invention Typical case, in the range of 1.0-4.5 volt, (such as refers to Fig. 9) to most typically in the range of 1.5-4.5 volt, but preferably In the range of 1.5-4.0 volt.The two scope of operation voltage reflects diverse charge-storage mechanism.Although, Seem between the two voltage range to have on written 1.5-3.0 volt overlap (scope of 1-3 volt and 1.5-4.5 volt Scope), but this overlap is artificial, accidental rather than scientific meaning, because charge-storage mechanism is fundamentally different , as two distinct cyclic voltammetric (CV) figures in Fig. 9 confirm.
(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 most commonly > 1.0 volts (some > 1.2 volts or even > 1.5 volts, this depends on the type of active material of positive electrode and relative to the quantity of negative electrode, and lithium source Quantity).
(7) the Ragone figure of Figure 10 (A) and (B) confirms that the surface mediation battery self of the present invention is one the most well Class energy storage batteries, be both different from super capacitor its also different from lithium ion battery.
(8) Figure 11 shows 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 continuing to increase (at some with charge/discharge cycle number After less initial decay), this observed result further demonstrate that SMC is different from the only of ultracapacitor or lithium ion battery Characteristic.
Charge-storage mechanism and energy density Consideration
Being reluctant to be limited to theory, in surface mediation battery (SMC) of Li ion exchange, the specific capacity of electrode seems to depend on The number of the avtive spot on the graphenic surface of nanostructured carbon material, described graphenic surface can be caught in or on which Obtain lithium ion.Just as previously disclosed, this carbon nano-structured material can be selected from activated carbon (AC), carbon black (CB), hard carbon, soft Carbon, expanded graphite (EG) and from native graphite or the separation of Delanium graphene film (nano-graphene plate or NGP).These material with carbon elements have common building block Graphene or the aromatic ring structure of class Graphene.It is considered that there are four kinds Possible lithium memory mechanism, as described below:
Mechanism 1: in graphene planes, the geometric center of phenyl ring is the avtive spot that lithium atom is adsorbed onto;
Mechanism 2: the defective bit on graphene film can capture lithium ion;
Mechanism 3: the cation (Li in liquid electrolyte+) and anion (from lithium salts) can be attached in electrode material surface The nearly electric double layer forming electric charge;
Mechanism 4: the functional group on graphenic surface/edge can form redox couple with lithium ion.
Surface bond mechanism (mechanism 1): when there is not electrolyte contention lithium when, lithium atom can be with graphene planes On C atom form stable interaction.The Li-C key (not having functional group) in such layer is not result in the sp of carbon track2 To sp3Transformation.Energy balane has shown that the graphene layer of such absorption lithium atom (has the benzene being bonded to graphene planes The lithium atom at ring center) in the case of there is not electrolyte can stabilizability.We the most surprisingly observe the graphite of absorption Li Alkene layer (Fig. 3 (D)) can spontaneously form in the presence of electrolyte.This is beyond expectation, because lithium ion and electrolysis In matter, other composition has good chemical compatibility (here it is they are naturally occurring in the reason in electrolyte), and these Composition (such as solvent) can be competed with graphenic surface to attempt to be maintained in solvent phase by lithium ion rather than by Graphene table Face " is kidnapped ".Bonding between lithium atom and graphenic surface is the strongest.
Lithium ion in defective bit is captured (mechanism 2): the such as edge of the active defects in carbonaceous material and room (such as Fig. 3 (D)) can have the ability to receive extra lithium.NGP exists and is inevitably produced conventional oxidation and reduction by Graphene These defects a large amount of that process causes or unordered site.
Electric double layer (EDL) (mechanism 3): SMC electrolyte is typically made up of the lithium ion salt dissolved in a solvent.Electrolytic salt Lithium perchlorate (LiClO can be selected from4), lithium hexafluoro phosphate (LiPF6), lithium fluoroborate (LiBF4), hexafluoroarsenate lithium (LiAsF6)、 And trifluoromethanesulfonic acid lithium (LiCF3SO3) etc..In principle, as shown in Fig. 3 (B), some electric double layers (EDL) can conceptually by Cation (such as Li+) and their gegenion (such as PF6 -And BF4 -Anion) formed, and the SMC energy content of battery is deposited This EDL contribution of storage capacity is controlled by the electrolytic salt concentration in solvent.
Give sufficient amount of electrode surface areas, mechanism 3 to the maximum contribution of overall charge memory capacity by cation Or the concentration of anion determines.EDL mechanism typically contributes less than about 10%, and total lithium ion of SMC of (more typical < 5%) stores holds Amount, is explained as follows: we have prepared and have tested several symmetrical ultracapacitor, and every kind by two identical Graphenes Structure or other nano structure electrodes constitute (anode and negative electrode have same composition), but anode does not has lithium metal foil/powder As lithium source and there is no prelithiation.Such as, shown in Fig. 9 it is the CV coordinate of ultracapacitor based on Graphene and corresponding SMC Figure.In two kinds of unit, electrolyte is 1M LiPF6/ EC+DMC and sweep speed are 25mV/s.Interestingly note Meaning arrives, and this organic bath can only operate in 0 to < 2.7 volts, but can in SMC constructs in symmetrical ultracapacitor structure To operate in 1.5 to 4.5 volts.This is the most unexpected because not having organic bath in ultracapacitor (based on having Machine solvent) can operate under up to 4.0 volts (typically < 3.5 volts and more typically < < 3.0 volts).Organic bath It is defined as being not based on those electrolyte of water or ionic liquid, but containing organic solvent.Represent from 1.5 volts to 2.7 volts The capacity of special overlapping voltage scope account for SMC total capacity less than 5%.It practice, the operation of SMC, even if at 1.5-2.7 volt Voltage range within, also mainly captured rather than the formation of electric double layer by surface.
The formation of redox couple (mechanism 4): the redox reaction on surface can occur lithium ion and functional group it Between (if any), such as carbonyl (> C=O) or carboxyl (-COOH), as shown in Fig. 3 (A).The existence of functional group, such as- COOH and > C=O, have good grounds in the graphene oxide of chemical preparation.The formation of these functional groups is that graphite passes through sulfur Naturally the knot of the oxidation reaction of acid and strong oxidizer (such as be commonly used for nitric acid and potassium permanganate prepared by graphene oxide) Really.Unsegregated graphite worm (expanded graphite) and graphene film (NGP) both of which separated can have surface or edge and take The functional group of band.In one embodiment, in the application, SMC is based primarily upon mechanism 1 and 2.
Generally, layer mechanism contribution is less than the SMC charge storage capacity of 10% (mostly less than 5%).Work as male or female When comprising some multi-layer graphene plates, if SMC operation voltage drops below 1.5 volts, some lithiums may be had to insert and to be embedded into In the body of active material.Even if in this case, when this device is in charged state, the lithium of not more than 20% is stored In the body of active material of positive electrode, or when this device is in discharge condition, the lithium less than 20% is stored in negative electrode and lives In the body of property material.Typically, when this device is in charged state, the lithium less than 10% is stored in anode activity material In the body of material, or when this device is in discharge condition, the lithium less than 10% is stored in the body of active material of cathode In.
The nano structural material used in the male or female of the present invention can preferably comprise nano-graphene plate (NGP), CNT (CNT) or disordered carbon.These nanostructured carbon material can serve as having useful functional group (such as carbonyl Base) but other organic or support substrates of polymer functional material nonconducting.CNT is the material known in nanometer material industry Material, and therefore, the most no longer it is discussed.The description of the disordered carbon of NGP and nanostructured be presented herein below:
Nano-graphene plate (NGP)
The application of the research group of applicant active development single-layer graphene always [B.Z.Jang and W.C.Huang, " Nano-scaled Graphene Plates, " U.S. Patent Application No. 10/274,473 (10/21/2002);It is the U.S. now Patent US7,071,258 (07/04/2006)], including Graphene use in ultracapacitor [L.Song, A.Zhamu, J.Guo, and B.Z.Jang " Nano-scaled Graphene Plate Nanocomposites for Supercapacitor Electrodes " U.S. Patent Application No. 11/499,861 (08/07/2006) is United States Patent (USP) US7,623,340 (11/ now 24/2009) application [A.Zhamu and B.Z.Jang, " Nano Graphene Platelet-], and in lithium ion battery Based Composite Anode Compositions for Lithium Ion Batteries, " U.S. Patent Application No. 11/982,672 (11/05/2007), be United States Patent (USP) US7,745,047 (06/29/2010) now].
Single-layer graphene or graphene planes (forming hexagon or one layer of carbon atom of alveolate texture) are a large amount of stones The common building block of ink material, including native graphite, Delanium, soft carbon, hard carbon, coke, activated carbon, carbon black etc..At these In graphite material, usual multiple graphene films are along Graphene thickness direction stacking thus form the domain of order of graphene planes or micro- Brilliant.Then multiple crystallites in farmland link with unordered or amorphous carbon species.In this application, we can extract or separate this Crystalline substance or farmland are to obtain multi-layer graphene plate from disordered carbon kind apoplexy due to endogenous wind slightly.In some cases, we peel off and separate this A little multiple Graphene plates become isolated single-layer graphene film.In other cases (such as at activated carbon, hard carbon and soft carbon In), our chemistry removes some disordered carbon species to open wicket, thus it is internal (by Graphene to allow liquid electrolyte to enter Surface is exposed to electrolyte).
In this application, nano-graphene plate (NGP) or " grapheme material " unified representation monolayer and multilayer form Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitridation Graphene, the Graphene of doping, etc..
In order to limit the geometry of NGP, NGP is described as has 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, no more than 10nm is (preferably no greater than 5nm).NGP can be single-layer graphene.When plate is approximately circle in shape, length and width is referred to as diameter.At mesh In the NGP of front restriction, length and width is not limited, but they are preferably smaller than 10 μm and more preferably less than 1 μm.I Have been able to produce length less than 100nm or more than the NGP of 10 μm.This NGP can be that raw graphite alkene (has substantially The oxygen content of 0%, typically < 2% oxygen) or graphene oxide (typically from 10 weight % to the oxygen of about 45 weight %).Graphite Olefinic oxide can be become the graphene oxide of reduction by heat or electronation, and (typically oxygen content is 1-20%, most of low In 5 weight %).For the lithium superbattery disclosed in we relatively early apply for and granule surface contral battery based on functional material Anode and/or negative electrode, oxygen content is the most preferably in the range of 5% to 30%, and the most more preferably 10% to 30% In the range of.But, in this application, SMC electrode typically has the oxygen (therefore, substantially free of functional group) less than 5%, and And in many cases less than 2%.Liquid electrolyte can and specific surface area be to determine the energy density of SMC and power density One most important parameter.
Although individual graphene film has a highest specific surface area, but the flat pattern prepared by regular course Graphene film has big tendency and stacks or overlap each other, thereby dramatically reduce electrolyte can and specific surface area. Fig. 5 (A) shows referred to herein as bending Graphene plate or the Graphene of sheet.When bending NGP be stacked thus When forming electrode, they can form the central hole structure with desired pore-size scope (the most slightly > 2nm).This chi It is close containing lithium electrolyte that very little scope seems to contribute to be commonly used.
Can be by the following bending NGP that produces:
A lamellar graphite material (such as natural graphite powder) is disperseed or immerses in the mixture of intercalator and oxidant by () (being such as respectively concentrated sulphuric acid and nitric acid) is to obtain compound between graphite layers (GIC) or graphite oxide (GO);
B gained GIC or GO is exposed to thermal shock by (), the preferably temperature range at 600-1100 DEG C continues the short period (being typically 15 to 60 seconds), to obtain expanded graphite or graphite worm (if allowing intercalation/oxidation step to carry out sufficiently long holding The continuous time, then can form thickness < some oxidations NGP of 100nm in this stage;Such as > 24 hours);
C expanded graphite is distributed to optionally comprise functionalized reagent (such as: oxidant such as sulphuric acid, nitric acid, hydrogen peroxide by () Or optimization acid, formic acid etc., it is-source of COOH group) liquid medium to form suspension.Stirring, mechanical shearing Or sonication method, and/or temperature can be used to smash graphite worm thus form separation/isolated NGP and/or help the phase The functional group hoped is attached to aoxidize NGP, causes the formation of functionalization NGP to obtain Graphene-liquid suspension;
D described Graphene-liquid suspension is atomized into drop by (), described liquid optionally contains the single of chemical functionalization Or multiple NGP, and remove liquid to reclaim the NGP of bending simultaneously.Do not have atomization steps, then the Graphene plate produced is often Flat shape.
It might be noted that step (a) to (b) is to obtain expanded graphite (Fig. 5 B) and graphene oxide in the art The most frequently used step of plate.Before, during or after chemical functionalization, it is possible to use hydrazine is the reducing agent NGP by oxidation Or GO plate electronation is to recover conductive features.
In one embodiment, for giving NGP by carbonyl or carboxyl, carboxylic acid (it is environmental protection) is to close especially The functionalized reagent of meaning.Carboxylic acid can be selected from aromatic carboxylic acid, aliphatic or alicyclic carboxylic acid, straight or branched carboxylic acid, Have the saturated of 1-10 carbon atom and undersaturated monocarboxylic acid, dicarboxylic acids and polybasic carboxylic acid, they Arrcostab and Combinations thereof.Preferably, carboxylic acid is selected from the representative examples of saturated aliphatic carboxylic of formula H (CH2) nCOOH, and wherein n is the numeral from 0 to 5, Including formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid and caproic acid, their anhydride, their reactive carboxylic acid derivatives, and they Combination.Most preferably carboxylic acid is formic acid and acetic acid.
Before or after functionalization operates, NGP can stand following process (alone or in combination):
I () is by different chemical functional groups functionalizations.Other useful surface functional groups can include quinone, hydroquinone, quaternary ammonium Change aromatic amine or mercaptan;
(ii) with polymer-coated or scion grafting, this polymer (such as carbonyl) Han desired functional group;
(iii) stand activation processing (being similar to the activation of carbon black material) and produce extra surface and may be by official's energy Property chemical group gives these surfaces.This activation processing can be realized in the following way: 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 heavy oxidation step that these processes relate to The oxy radical substantially introduced to edge surface and the base surface (top and lower surface) of NGP.This can be good or It is bad.On the one hand, we want that producing functional group as much as possible catches lithium capacity to maximize.But on the other hand, at basal plane Or the functional group on graphene planes necessarily this plane is caused damage thus significantly reduce the monolithic conductive of NGP.With this Mode forms functional group, does not has above step (c), is not the good process controlled.
In more controlled manner functional group is given a kind of alternative method of NGP relate to without conventional chemical intercalation/ Primary NGP is produced in the case of oxidizing process.The non-oxidized graphite alkene produced (has more chemically active edge table naturally Face) then carry out controlled oxidation or controlled functionalization.Before any substantial amounts of functional group starts to be attached to basal plane, official The all avtive spots being first attach to edge surface and substantially used up edge surface can be rolled into a ball.
In 2007, the graphite granule that we report directly from the suspension being dispersed in surfactant-water produced Direct ultrasonic disintegration [A.Zhamu et al., " Method of Producing Exfoliated of primary nano-graphene Graphite, Flexible Graphite, and Nano-Scaled Graphene Plates, " U.S. Patent Application No. 11/ 800,728(05/08/2007)].The method needs to disperse native graphite in low surface tension liquid such as acetone or hexane Grain.Gained suspension is then subjected to the direct supersound process of 10-120 minute, and this operation is to be equivalent to every granule per second 20000 times The speed peeling off graphene film produces Graphene.Graphite is never by intercalation or oxidation, and therefore need not follow-up chemistry also Former.The method is quick, environmental protection, and is readily susceptible to scale up, thus is the big rule of primary nano-graphene material Mould produces and has paved road.Same method was studied by other people later and is more commonly referred to as now " liquid phase production ".One Denier produces raw graphite alkene, this material then can be made to be exposed to oxidation or functionalization processes, such as, use gas phase or liquid acid or Acid blend.Can also be immersed in primary NGP in the carboxylic acid of preferred temperature to continue for some time, to obtain, there is required sense The NGP of change level.
Specifically, oxidation processes comprises makes primary NGP material stand oxidant, this oxidant be preferably chosen from ozone, Sulfonic acid (SO3) steam, oxygen-containing gas, hydrogen peroxide vapor, nitric acid vapor or combinations thereof.Preferably, this process includes making Primary NGP material stands the oxidant in ambient containing hydrogen.Although can be by NGP being immersed liquid acid and/or oxidant ring Border carries out oxidation processes, but such process needs the washing of follow-up water and purifying step, and (but such washing process is not Needed in conventional sulfuric acid intercalated graphite situation tediously long).Therefore, it is not necessary to the gas treatment of post processing washing is preferred 's.
The NGP that oxygen content is not more than the conduction functionalization of 25% by weight can be produced, arrive 5% the most by weight Between 25%.It is assumed that most of functional groups are positioned at the edge surface of NGP, because electric conductivity will not be significantly reduced.For super Crossing whole oxygen contents of 25%, functional group begins to appear in graphene planes surface, interrupts electrical conductance path.Use chemistry unit Element is analyzed and x-ray photoelectron power spectrum (XPS) measures oxygen content.
The further functionalization of partial oxidation NGP can be made: by partial oxidation NGP with anti-by carrying out following other step Thing is answered to contact, in order to functional group adds 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, or combinations thereof.
After partial oxidation processes, NGP will have reactive graphenic surface (RGS) or reactive graphene edge (RGE).They can be described as occurring following reaction:
(a)RGS/RGE+CH2==CHCOX (at 1000 DEG C) → Graphene-R ' COH (wherein X=-OH ,-Cl or-NH2);Example As, RGS/RGE+CH2==CHCOOH → G-R ' CO-OH (wherein G=Graphene)；
(b) RGS/RGE+ maleic anhydride → G-R ' (COOH)2；
(c)RGS/RGE+CH2==CH-CH2X→G-R’CH2X (wherein X=-OH ,-halogen or-NH2);
(d)RGS/RGE+H2O→G==O(Quinoidal);
(e)RGS/RGE+CH2==CHCHO→G-R’CHO(Aldehydic);
In reaction listed above, R ' is alkyl (alkyl, cycloalkyl etc.).The partial oxidation of primary NGP can may result in Some functional groups are attached on the surface of graphene planes or edge, including carboxylic acid and hydroxyl.Can be individually big from carboxylic acid preparation The derivant of amount.Such as, alcohol or amine can easily connect to acid to provide stable esters or amide-type.Can be by carbonyl (> Or amine (-NH2) base is attached to any reaction of graphene edge or base surface and all can be used to implement the present invention C=O).
The disordered carbon of nanostructured
Disordered carbon material can selected from the carbonaceous material of broad range, as soft carbon, hard carbon, polymerization carbon (or carbide resin), Mesocarbon, coke, carbonized pitch, carbon black, activated carbon or part graphitized carbon.It is schematically shown in Fig. 3 (A) and (B), Disordered carbon material is typically formed by biphase, wherein the first phase be the little graphite crystal of graphite plane or little deposit (typically At most 10 graphite planes or aromatic ring structure are superimposed thus form the little domain of order) and the second phase be amorphous carbon, And wherein this first phase is dispersed in the second phase or is combined by second.Second phase is mainly by less molecule, less virtue Fragrant ring, defect and amorphous carbon are constituted.Optionally expect the functional group (-COOH in such as Fig. 3 (B) and NH2Group) it is attached to The edge of aromatic ring structure or plane surface.Typically, disordered carbon is highly porous (such as activated carbon) or be present in and gather around There is the superfines form (such as carbon black) of nanoscale features (therefore there is high specific surface area).
Soft carbon refers to the carbonaceous material being made up of little graphite crystal, wherein these graphite crystals or graphene film stacked body Orientation be conducive to neighbouring graphene film merge further or utilize high-temperature heat treatment (graphitization) these graphite crystals or The further growth (Fig. 4 (A)) of graphene film stacked body.Therefore, it is graphitisable for claiming soft carbon.
Hard carbon (Fig. 4 (B)) refers to the carbonaceous material being made up of little graphite crystal, wherein these graphite crystals or graphene film Therefore stacked body is not unfavorable for the further conjunction of neighbouring Graphene plate with favourable direction orientation (the most orthogonal) And or the further growth (that is, not being graphitisable) of these graphite crystals or graphene film stacked body.
As shown in signal in Fig. 4 (C), carbon black (CB), acetylene black (AB) and activated carbon (AC) are typically by aromatic rings or little The farmland of graphene film constitute, wherein the aromatic rings in adjacent domains or graphene film are connected in some way by some chemical bonds In unordered phase (substrate).These material with carbon elements are generally available from hydrocarbon gas or liquid or natural prodcuts (timber, Exocarpium cocois (Cocos nucifera L) etc.) Thermal decomposition (heat treatment, be pyrolyzed or burn).
By polymer or the simple pyrolysis preparation polymerization carbon known existing about three of oil/coal tar pitch material 10 years.As polymer such as polyacrylonitrile (PAN), artificial silk (rayon), cellulose and P-F (phenol When formaldehyde) being heated to more than 300 DEG C in noble gas, they gradually lose its most non-carbon content. Resulting structures is commonly called polymerization carbon.Temperature (HTT) according to heat treatment and time, polymerization carbon can be fabricated to insulation , semiconductive or conduction, have cover about 12 orders of magnitude conductivity range.The conductivity value of this wide scope can With by extending further with electron donor or acceptor doping polymerization carbon.These features confirm to be polymerized the qualified work of carbon uniquely For novel, to be easily worked classification electroactive material, it is possible to easily customize structure and the physical property of described material.
Polymerization carbon can present substantially free of amorphous configuration, or has the multiple graphite being dispersed in amorphous carbon substrate Crystal or Graphene stacked body.According to the HTT used, various ratios and the graphite crystal of size and defect are scattered in amorphous base In matter.Different amounts of two dimension condensed aromatic ring or six can be found in the polymer of heat treatment is such as the microstructure of PAN fiber Limit shape (precursor of graphene planes).Think that being polymerized in carbon of the PAN base processed at 300-1000 DEG C exists considerable amount Small size graphene film.Utilizing the heat treatment time (such as > 1500 DEG C) of higher HTT or longer, these materials are fused into Broader aromatic ring structure (larger sized graphene film) and thicker plate object (more graphene films are stacked).These The stacked body of Graphene plate or graphene film (basal plane) is dispersed in amorphous carbon substrate.Such two phase structure is some nothings The feature of sequence material with carbon element.
For the disordered carbon material in present patent application, there is the precursor material of several types.Such as, the first kind includes fibre The semi-crystalline state PAN of dimension form.Compared to phenolic resin, pyrolysis PAN fiber has higher tendency formation and is dispersed in unordered substrate In little crystallite.Equations of The Second Kind, with P-F as representative, is more isotropic, substantially amorphous state and highly cross-linked Polymer.3rd class includes bulk or the oil of fibers form and coal tar pitch material.Precursor material composition, heat treatment temperature And heat treatment time (Htt) is to determine the length of gained disordered carbon material, width, thickness (Graphene in graphite crystal (HTT) The number of plane) and three parameters of chemical composition.
In our current research, PAN fiber is made to stand oxidation at 200-350 DEG C, then at 350-1500 DEG C under tension Partially or completely carbonization is to obtain the polymerization carbon with various nanocrystal graphite-structure (graphite microcrystal).To these polymerization carbon Selected sample is further heat treatment at a temperature in the range of 1500-2000 DEG C, so that this material part graphitization, but still retain The amorphous carbon (being not less than 10%) of requirement.Phenol formaldehyde resin and oil and coal tar pitch material are at 500 to 1500 DEG C Within the temperature range of stand the heat treatment that is similar to.The disordered carbon material obtained from PAN fiber or phenolic resin preferably is subjected to activation, Utilize the technique (as processed 1-5 hour in the KOH melt of 900 DEG C) producing activated carbon and being commonly used.This activation processing purpose is Make disordered carbon mesopore, make liquid electrolytic mass-energy arrive edge or the surface of component aromatic rings SMC device.It is arranged such that Lithium ion in liquid is prone to deposit to graphenic surface in the case of need not experiencing solid-state diffusion.
The asphalt of some grade or coal tar pitch can be carried out heat treatment (typically at 250-500 DEG C) to obtain Obtaining liquid crystalline type, optional anisotropic structure, this structure is commonly called mesophase.Can be by this interphase material from mixed The liquid component of compound extracts produce mesophase granule or spheroid.Optionally, these mesophase granules or spheroid can To stand further heat treatment so that graphitization.
Can be to various disordered carbons (the softest carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonization drip Green grass or young crops, carbon black, activated carbon or part graphitized carbon) physically or chemically activate to obtain the disordered carbon of activation.Such as, Ke Yitong Peroxidating, CO2Physically activated, KOH or NaOH chemical activation or be exposed to nitric acid, fluorine or ammonia plasma treatment to realize this work Change processes (in order to produce the enterable hole of electrolyte rather than for functionalization).
The functionalization program of nanostructured disordered carbon is similar to those programs for NGP, repeats no more the most here.Special Not, can be by carbonyl (> C=O) or amine (-NH2) base be connected to the graphene edge of disordered carbon material or base surface any instead Should may be incorporated for implementing the present invention.
Containing the organic of lithium reactive functionality and polymerization functional material
Many organic group functional material or polymer base functional material can contain sense side base, and described sense side base can be fast Speed and reversibly react with the lithium ion in liquid electrolyte or gel electrolyte.Example includes poly-(2,5-dihydroxy-1,4-benzene Quinone-3,6-methylene), LixC6O6(x=1-3),Li2(C6H2O4),Li2C8H4O4(terephthalate of Li), Li2C6H4O4(Li's Trans-trans-muconate), 3,4,9,10-tetrabasic carboxylic acids-dianhydride (PTCDA) disulfide polymer, PTCDA, Isosorbide-5-Nitrae, 5,8-naphthalenes- Tetrabasic carboxylic acid-dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydrides, Isosorbide-5-Nitrae, 5,8-tetra hydroxyanthraquinones, tetrahydroxy 1,4-benzoquinone, and Combinations thereof.These functional molecules, polymer or salt are generally of relatively low electron conduction so that it is itself is not suitable for Serve as electrode material.One exception is sulfur-crosslinked PTCDA (PTCDA disulfide polymer).
These nonconducting functional material any are preferably combined with nano structural material (such as chemical bonding or connection), Such as NGP, CNT, disordered carbon, nano wire and nanofiber.Such as, Graphene and disordered carbon (soft carbon, hard carbon, activated carbon, carbon black Deng) composition aromatic ring can have functional group on its edge or surface, described functional group can be with the place mat of above-mentioned functional material Functional group reactions (hydroxyl as on tetrahydroxy 1,4-benzoquinone).As an alternative, these organic or polymerization functional material can be simple Singly it is supported on the surface of nano structural material (such as, Graphene or nanowire surface).This nano structural material (such as graphite Alkene and disordered carbon) also can functionalised so that it not only provide the organic or support (imparting electric conductivity) of polymeric material but also The functional group that offer can be reacted with lithium.
In a word, active material of cathode and/or the active material of positive electrode of the SMC of the present invention can be selected from: (a) porous disordered carbon Material, it is selected from soft carbon, hard carbon, polymerization carbon or carbide resin, mesocarbon, coke, carbonized pitch, carbon black, activated carbon or portion Divide graphitized carbon;B () grapheme material, it is selected from Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitrogen The single-layer sheet of the graphene oxide of functionalized graphene, boron doped graphene, nitrogen-doped graphene, functionalized graphite's alkene or reduction Or multilamellar plate;(c) expanded graphite;(d) mesoporous carbon;E () CNT, it is selected from SWCN or multi-wall carbon nano-tube Pipe;(f) carbon nano-fiber, metal nanometer line, metal oxide nano-wire or fiber or conducting polymer nanofiber, or (g) combinations thereof.These materials can be functionalization or nonfunctionalized.
The following examples are used for the preferred embodiments of the invention being described and being not necessarily to be construed as limiting the present invention's Scope:
Embodiment 1: the soft carbon (a type of disordered carbon) of functionalization and nonfunctionalized, soft carbon back superbattery and surface Mediation battery.
From liquid crystal aromatic resin-made for nonfunctionalized and the soft material with carbon element of functionalization.By resin mortar grinder, and 900 DEG C in N2Atmosphere is calcined 2 hours to prepare graphitizable carbon or soft carbon.In alumina crucible by produce soft carbon with KOH small pieces (4 times of weight) mix.Subsequently, at N2Middle by the soft carbon containing KOH 750 DEG C heat 2 hours.After cooling, by rich alkali Residual carbon hot wash, until the pH value of draining reaches 7.Resulting materials is activation but the soft carbon of nonfunctionalized.
The most individually, by a part activate soft carbon-impregnated enter 45 DEG C at 90%H2O2-10%H2O solution is to hold The oxidation processes of continuous 2 hours.Then, soft for the partial oxidation of generation carbon-impregnated is entered formic acid under room temperature with functionalization 24 hours.Produce The raw soft carbon of functionalization by being dried 60 DEG C of heating in vacuum drying oven for 24 hours.
Manufactured and tested following coin battery: use the soft carbon of functionalization as the soft carbon of negative electrode and functionalization as nanometer Structure anode (plus the lithium paper tinsel thin slice as lithium source being implemented between collector and separator layer, sample-1).Preparation is corresponding The battery (sample-1b) not having functionalization and test be used for comparing.In all batteries, the spacer body of use is a piece of micropore Film (Celgard2500).In two electrodes, the collector of each is the aluminium foil of a piece of carbon coating.Electrode is by 85 weight % The complex that soft carbon (+be coated on Al paper tinsel 5%Super-P and 10%PTFE binding agent) is constituted.Electrolyte solution is dissolved in 1M LiPF in the mixture that volume ratio is 3:7 of ethylene carbonate (EC) and dimethyl carbonate (DMC)6.Use minimal amount of electricity Solve matter and moisten spacer body to reduce background current.In some cases, at room temperature (as little as-40 DEG C and the temperature of up to 60 DEG C Degree) use Arbin32 passage ultracapacitor-battery condition tester to carry out cyclic voltammetry and the constant current survey of lithium battery Amount.
As reference sample (sample-1-CA), manufacturing and coin battery as test class, this battery contains one at anode Sheet lithium paper tinsel but there is no the carbon-coating of nanostructured.This is the lithium superbattery of prior art.In addition, also manufacture and evaluate symmetrical super Capacitor (sample-1-CB), two electrode is all to be made up of the soft material with carbon element of functionalization, but available in liquid electrolyte Outside do not comprise other lithium source.Prior art symmetry ultracapacitor (f-LBL-CNT/f-by data with Lee et al. LBL-CNT) data compare.
There is the such functionalization soft carbon back block materials (thickness > 200 μm) superbattery as active material of cathode (sample-1-CA) and the battery unit (sample 1) of corresponding granule surface contral and nonfunctionalized surface mediate battery (sample- Constant current research 1b) enables us to acquisition and is summarised in the significant data in the Ragone figure of Fig. 6 (A) and cyclical stability Data (Fig. 6 (B)).These figure let us make following observation result:
A () functionalization and the granule surface contral of nonfunctionalized, lithium ion exchanged cell apparatus show than corresponding super electricity Energy density that pond is considerably higher and power density, particularly under relatively high electric current density, (higher-wattage in this figure is close Number of degrees strong point).The existence (in addition to the negative electrode of nanostructured) which demonstrating nanostructured anode makes recharging and discharging During circulation, lithium ion can deposit on the huge surface area of anode and by the face, huge surface of anode respectively with two-forty Long-pending release.The superbattery of prior art has collector and the anode of limited specific surface area, and it is not provided that q.s Surface area is for attempting to deposit to limited surface area or the lithium ion from limited surface area release in the same time Use.Whole charge or discharge process becomes surface and limits.
Show than corresponding symmetrical ultracapacitor (sample-1-the lithium ion exchanged cell apparatus of (b) granule surface contral CB) and the significantly higher energy density of the prior art ultracapacitor of Lee et al. and power density, described Lee et al. shows Technology ultracapacitor is had to be made up of the LBL CNT anode of functionalization and the LBL-CNT negative electrode of functionalization, both super capacitors Device does not all have lithium paper tinsel as lithium source.Actually, both symmetries ultracapacitor (without lithium source) is (based on disordered carbon or base In LBL-CNT) present almost identical Ragone figure, although two electrodes are dramatically different (for unordered on thickness Carbon electrode is>100 μm and for LBN-CNT electrode for<3.0 μm).This is probably local surfaces absorption or electric with conventional super The performance of the layer mechanism that container is associated, described layer mechanism do not require the long-range of electric charge transmit (especially, it is not necessary to Exchange lithium ion between the anode and cathode).The quantity of lithium ion and their counter ion (anion) by lithium salts at solvent In dissolubility limit.It is molten that the middle lithium quantity of the surface of active material that can be captured and stored in arbitrary electrode is significantly higher than this The solution degree limit.
C () is as previously mentioned, it is known that the power density typical case of ultracapacitor is 5,000-10,000W/Kg, but, The power density of lithium ion battery is 100-500W/kg.This means that this surface mediation lithium ion exchanged battery has with modern The energy density that battery is suitable, it is 5-16 times of typical ultracapacitor energy density.This SMC also shows apparently higher than often The power density (or recharge-discharge multiplying power) of rule electric chemical super capacitor power density.
D () SMC based on nonfunctionalized surface is significantly better than phase the most expressively in energy density and power density two aspect The functionalized surfaces answered controls battery.
E () the most important thing is, nonfunctionalized surface mediation battery table reveals more much better than battery based on functional material Cyclical stability.As demonstrated in Fig. 6 (B), though nonfunctionalized surface cell after 2500 charge/discharge cycle still Keep high-energy-density.But, functionalized surfaces controls battery and is decayed faster along with charge/discharge repeatedly.
F from calculating further of the data obtained, () shows that this prior art superbattery is under the electric current density of 10A/g Discharge time be 19 seconds.By contrast, corresponding SMC is less than 5 seconds the discharge time under same current density.
The battery of sample 1 and sample-1-CA affects the redox reaction of lithium ion and selected functional group, described functional group At cathode side (sample-1-CA) and on the surface/edge of negative electrode and the aromatic rings of anode (example 1).These connect Can quickly and reversibly with lithium react at the edge of aromatic rings (little graphene film) and the functional group of plane surface.In many In the case of, SMC based on nonfunctionalized surface shows more preferably.The lithium ion exchanged battery of the surface mediation of the present invention is a kind of Revolutionary novel energy storage device, it is fundamentally different from ultracapacitor and lithium ion battery.In energy density and Power density two aspect, two kinds of conventional equipments are the most incomparable.
Embodiment 2: from sulphuric acid intercalation and the expanded NGP of MCMB
MCMB2528 microsphere (Osaka Gas Chemical Company, Japan) has about 2.24g/cm3Density, about The median size of 22.5 microns and the distance between the surface of about 0.336nm.With acid solution (ratio be the sulphuric acid of 4:1:0.05, nitric acid and Potassium permanganate) to MCMB2528 (10 grams) intercalation 24 hours.When completing reaction, pour this mixture into deionized water mistake Filter.By the MCMB of intercalation in 5%HCl solution cyclic washing to remove most sulfate ion.Then anti-with deionized water This sample is washed in after backwashing, until the pH value of filtrate is neutral.Make slurry be dried and be stored in 60 DEG C of vacuum drying ovens 24 hours.Will be dry Dry powder sample put in quartz ampoule and be inserted in the horizontal pipe furnace being preset in temperature required i.e. 600 DEG C continue 30 seconds with Obtain expanded graphite.In supersound process is bathed, expanded MCMB sample is made to carry out further functionalization 30 points in 25 DEG C of formic acid Clock is to obtain functionalized graphite's alkene (f-NGP).Also by ultrasonic to expanded MCMB in the water not having any functionalized reagent Process and obtain nonfunctionalized NGP.
For functionalization or the battery of the granule surface contral of nonfunctionalized, use NGP as cathode material and as anode Material.Lithium paper tinsel is added between anode and spacer body.For with reference to superbattery, anode is that lithium paper tinsel (does not has nanostructured NGP) and negative electrode is f-NGP.The Ragone figure of these three type cell is shown in Fig. 7.Two kinds of surface based on NGP mediations Lithium ion exchanged cell apparatus shows the energy density more significantly higher than corresponding superbattery and power density, particularly in phase To (power intensity data point higher in figure) under high electric current density.This again demonstrate this SMC compared to superbattery Superior function.Nonfunctionalized surface mediation battery performance in terms of energy density and power density is better than functionalized surfaces control Battery.The most extremely important and surprisingly, compared with functionalized surfaces mediation battery, nonfunctionalized surface mediation electricity Pond continues to show much better long-time stability (Fig. 8) along with charge/discharge repeatedly.
Embodiment 3: organic 3,4,9,10-tetrabasic carboxylic acid-dianhydride (PTCDA), PTCDA disulfide polymer and nanostructured The PTCDA that NGP-supports.
Enolization is important carbonyl double bond reaction, and it can be stablized by conjugated structure.When carbonyl is reduced or oxygen During change, enolization makes Li ion can reversibly be captured on the position of oxygen atom or discharge, it means that it can be at Li Ion battery is used as the organic energy storage system of a kind of novelty.
In the reduction process of PTCDA, each carbonyl can receive an electronics and capture a Li ion thus formed Lithium enolate, and releasable Li ion in contrary oxidizing process.
Preparation is used as the anode of the lithium ion exchanged cell apparatus of granule surface contral and/or the electrode of the three types of negative electrode. The first kind is PTCDA and the simple mixtures of carbon black (about 20 weight %), combines (sample 3-A) by PVDF.
Second Type (sample 4-B) is that PTCDA disulfide polymer is similar with the carbon black as conductive filler mixed again Compound.By using PTCDA (shiny red) and Sublimed Sulfur to synthesize PTCDA disulfide polymer as parent material, with the quality of 1:1 Ratio is sufficiently mixed by grinding.Described mixture reacts 3 hours to obtain at 500 DEG C in the argon atmospher of flowing The dark red powder of PTCDA disulfide polymer.This synthetic route is by X.Y.Han et al. [" Aromatic carbonyl derivative polymers as high-performance Li-ion storage materials,” Adv.Material, 19,1616 1621 (2007)] initially propose.
Embodiment 4: based on the grapheme material (NGP) from native graphite, carbon fiber and Delanium and based on carbon Black (CB) and the SMC of process CB.
Using the Hummers method preparation oxidation NGP or graphene oxide (GO) improved, the method relates to initial stone Ink material is exposed to the mixture 72 hours that ratio is the sulphuric acid of 4:1:0.1, sodium nitrate and potassium permanganate.Then the GO that will produce Fully wash to obtain GO suspension with water, be hereafter two kinds of different material syntheti c routes.A kind of route relates to making GO suspend Stand the separation graphene oxide sheet (for battery-N) that supersound process is suspended in water with acquisition.Another route relates to It is spray-dried GO suspension to obtain compound between graphite layers (GIC) or GO powder.Then by GIC or GO powder 1050 DEG C of heat Expanded 45 seconds to obtain expanded graphite or graphite worm (battery-G).Right from the expanded graphite anthelmintic of Delanium and carbon fiber After carry out supersound process, with separate or dissociation graphene oxide sheet (respectively for battery-M and battery-C).Carbon black (CB) stands It is similar to the chemical treatment of Hummers method thus opens nanometer door, make electrolysis mass-energy enter internal (battery t-CB).
Coat every kind of electrode at Al paper tinsel, described electrode by 85% Graphene, 5%Super-P (AB-base conductive additive) and 10%PTFE forms.The thickness typical case of electrode is about 150-200 μm, but is prepared for thickness and is about the extra system of 80,100,150 μm The sample of row is to evaluate electrode size to the power density of gained ultracapacitor-secondary battery unit and the impact of energy density. Also make and be as thin as the electrode of 20 μm for comparing.Before use by pole drying 12 hours in the vacuum drying oven of 120 DEG C.Negative electrode It is to support the Li metal on a layer graphene sheet.In glove box, assemble the battery of coin dimensions, use 1M LiPF6/EC + DMC is as electrolyte.
Embodiment 5: functionalization and the activated carbon of nonfunctionalized
By activated carbon (AC, from Ashbury Carbon Co.) with acid solution process (ratio be 4:1:0.05 sulphuric acid, Nitric acid and potassium permanganate) 24 hours.When reaction completes, pour this mixture into deionized water and filter.The AC that will process In the HCl solution of 5%, cyclic washing is to remove most sulfate ion.Then with this sample of deionized water cyclic washing, Until the pH value of filtrate is neutral.In supersound process is bathed, slurry is made to carry out further functionalization in 25 DEG C of formic acid 30 minutes. Subsequently, using dip-coating to obtain the thin film of chemical functionalization activated carbon (f-AC), the thickness of described thin film typically ranges between 20 Hes Between 150 μm, it is coated in as on the surface of the carbon-coating of aluminizing of collector.Such electrode is used as anode and to use phase With the material of type as negative electrode, between porous separator and an electrode, it is implemented with lithium paper tinsel as lithium source.Also prepare corresponding There is no SMC battery that functionalization processes and test.
Arbin SCTS electrochemical test is used to utilize constant current experiment to measure capacity.At CHI660Instruments Cyclic voltammetry (CV) has been carried out on electrochemical workstation.Use scanning electron microscope (SEM, Hitachi S-4800), thoroughly Penetrate ultramicroscope (TEM, Hitachi H-7600), FTIR (PerkinElmer GX FT-IR), Raman spectrum (Renishaw InVia Reflex Micro-Raman) and atomic force microscope characterize NGP and the chemical composition of expanded graphite sample and micro- See structure.
The electrode of NGP mediation is the specific capacity that battery (such as battery M) provides 127mAh/g when electric current density is 1A/g, 85Wh/kg is reached when electric current density is 0.1A/gBatteryThe LITHIUM BATTERY energy density of (Fig. 8 (C)), this is that business AC-base symmetry surpasses The representative value 5Wh/kg of level capacitorBattery17 times.
Another kind of graphenic surface mediation battery (battery N, Fig. 8 (D)) shows the most higher energy density i.e. 160Wh/kgBattery, this is comparable to the energy density of lithium ion battery.Even if the energy density of battery N is at the electric current of up to 10A/g 51.2Wh/kg still it is maintained for more than under densityBatteryValue, it is provided that 4.55kW/kgBatteryPower density.At 5Wh/kgBatteryEnergy close Under degree, the power density typical case of business AC base symmetry ultracapacitor is at 1-10kW/kgBatteryIn the range of, it means that, with identical The typical ultracapacitor of power density is compared, and this surface mediation device is provided that > energy density of 10 times.
Power density when 50A/g is 25.6kW/kgBattery, and energy density is 24Wh/kgBattery.The merit when 200A/g Rate density increases to 93.7kW/kgBattery, and energy density is 12Wh/kgBattery(Fig. 8 (D)).This power density is higher than with Gao Gong Typical ultracapacitor an order of magnitude that rate density is well-known, and (be typically than the power density of conventional lithium ion battery 0.1-1.0kW/kgBattery) high 2-3 the order of magnitude.These data clearly demonstrate that this surface activation battery itself is a class energy Storage battery, is different from ultracapacitor and the lithium ion battery of routine.
Fig. 8 (B) comprises the comparison of CV data, it is shown that the Graphene that carbon fiber derives compares graphite as electrode active material Derivative Graphene slightly better performance.This more macrobending being likely due to the derivative Graphene of fiber or the shape of fold Shape, this avoids the stacking again face-to-face completely of graphene film during prepared by electrode.Battery based on expanded graphite (electricity Pond-G) can be owing to EG relative to relatively low energy densities and the power density of the NGP base battery (battery M and C) being kept completely separate Relatively low specific surface area (be typically 200-300m based on BET measurement2/ g), the single-layer graphene film separated compared to great majority Representative value 600-900m2/g。
Fig. 8 (D) shows, the energy density of carbon black (CB) and power density values can stand activation/functionalization by making CB Processing and be significantly increased, described activation/functionalization processes and relates to contacting sulphuric acid, sodium nitrate and the mixture 24 of potassium permanganate Hour.Find that BET surface area is from about 60m2/ g increases to about 300m2/ g, causes capacity to be risen to 46.63mAh/ by 8.47mAh/g g.The battery with the carbon black electrode processed demonstrates the power density suitable with active carbon electrode and energy density.
Figure 10 shows the Ragone figure of the Li ion communicating battery of the graphenic surface activation with Different electrodes thickness. Based on total battery weight and be based only upon cathode weight at Figure 10 (B) and calculate energy density and power density in Figure 10 (A) Value.These tables of data prescribed electrode thickness play vital effect in the energy density determining SMC and power density.The most It is important that, these data clearly demonstrate that, and the performance of our SMC with thick electrode can be the best, it is not necessary to use Expensive and and slowly technique (as proposed successively by Lee et al., LBL) manufacture in CNT base superbattery ultra-thin Electrode.Figure 10 also clearly demonstrate that this surface mediation battery self is a class energy storage batteries, is different from ultracapacitor With lithium ion battery.
Figure 12 shows that the specific surface area of electrode is determining that in lithium memory capacity be most important parameter.This figure have the highest The data point of specific capacity is obtained by electronation graphene oxide.Our chemical analysis data shows, this height The grapheme material of reduction has the oxygen content less than 2.0%, shows to there is no that functional group exists.Highly oxidized graphite Alkene, when chemistry or thermal reduction, it is known that have a considerable amount of surface defect position.This and other several data points confirm The importance of surface trapping mechanism.Four data points (representing with " x ") are about raw graphite alkene electrode, wherein grapheme material Be derived from pure graphite (> 99.9% carbon) direct supersound process.These data points show that pure graphenic surface (has in phenyl ring The heart, and there is no surface defect or functional group) too can be from electrolyte capture lithium ion and at per unit surface area On the basis of store a considerable amount of lithium.
The long-time stability of these SMC batteries are significantly (Figure 11).The most surprisingly, those are based on nonfunctionalized The SMC battery (battery N and AC) on surface shows such capacity: some during initial 300 circulations of this capacity slightly decline Step back, increase with period thereafter.This is unique and beyond expectation.Ultracapacitor, lithium for any routine The battery that ionistor, lithium ion battery, lithium superbattery or functionalized surfaces control, this is never observed.
In sum, the invention provides a kind of energy storing device, it has ultracapacitor and lithium ion battery two The feature of person.These complete surface activations, the battery of lithium ion exchanged have been able to store at least 160Wh/kgBatteryEnergy close Degree, this is significantly higher than electric double layer (EDL) ultracapacitor of routine.At least 100kW/kgBatteryPower density be significantly higher than routine EDL ultracapacitor and the lithium ion battery far above routine.The battery of these surfaces mediation can quickly be recharged, with Just use as traditional lithium-ion battery.
In detail and the present invention has been described with reference to specific embodiments, it is clear that without departing substantially from the spirit of the present invention and model In the case of enclosing, many changing and modifications is possible, and the scope of the present invention is limited by claims below:

Claims (34)

1. a lithium ion exchanged energy storing device for surface mediation, comprising:
A () comprises the negative electrode of active material of cathode, described active material of cathode has the table that can capture or store lithium thereon Face area；
B () comprises the anode of active material of positive electrode, described active material of positive electrode has the table that can capture or store lithium thereon Face area；
C () arranges porous separator between two electrodes；With
The electrolyte containing lithium of (d) and two electrode physical contacts, wherein said active material of positive electrode and/or described cathode activity Material has not less than 100m2The specific surface area of/g, it contacts with described electrolyte direct physical, with thus receive lithium ion or Person provides lithium ion to this, and wherein when this device is in charged state, the lithium of at least 80% is stored in described anode and lives On the surface of property material, or when this device is in discharge condition, the lithium of at least 80% is stored in described active material of cathode Surface on；
Wherein one or both in active material of positive electrode and active material of cathode are functionalizations or are not functionalizations, and And before the first time charging or first time discharge cycles of this energy storing device, at least one in two electrodes is wherein Comprise lithium source, and active material of cathode described at least a part of which constituted by selected from following material:
(A) the disordered carbon material of porous, selected from soft carbon or hard carbon；
(B) grapheme material, selected from raw graphite alkene, Graphene fluoride, hydrogenation Graphene, nitridation Graphene, boron doping stone The single-layer sheet of the graphene oxide of ink alkene, nitrogen-doped graphene or electronation or multilamellar plate；
(C) expanded graphite；
(D) mesoporous carbon；
(E) carbon nano-fiber, metal nanometer line, metal oxide nano-wire or conductive polymer nanometer fiber；
Or combinations thereof.
Energy storing device the most according to claim 1, the disordered carbon material of wherein said porous is selected from polymerization carbon, carbonization Resin, mesocarbon, coke, carbonized pitch, activated carbon or part graphitized carbon.
Energy storing device the most according to claim 1, at least a part of which active material of cathode is not the material of functionalization.
Energy storing device the most according to claim 1, wherein said device has the open-circuit voltage of at least 0.6 volt.
Energy storing device the most according to claim 1, wherein electrolyte is the liquid of the lithium ion comprising the first quantity Electrolyte or gel electrolyte.
Energy storing device the most according to claim 1, the active material bag at least one in two of which electrode Include and the functional group of lithium ion reversible reaction.
Energy storing device the most according to claim 6, wherein lives to described active material of positive electrode and negative electrode with functional group Property material be functionalized, described functional group and lithium ion reversible reaction.
Energy storing device the most according to claim 1, wherein when described device operates, described active material of positive electrode is not Insert embedding lithium or removal lithium embedded.
Energy storing device the most according to claim 1, wherein said device is from the voltage of 1.0 volts to 4.5 volts Range of operation.
Energy storing device the most according to claim 1, at least one in two of which electrode is upright with described electrolysis Contact and have not less than 500m2The specific surface area of/g.
11. energy storing devices according to claim 1, wherein when this device is in charged state, less than 20% Lithium be stored in the body of described active material of positive electrode, or when this device is in discharge condition, the lithium less than 20% It is stored in the body of described active material of cathode.
12. energy storing devices according to claim 1, wherein the operation of this device is not related to the slotting embedding or deintercalation of lithium.
13. energy storing devices according to claim 1, wherein said active material of positive electrode is preloaded with lithium.
14. energy storing devices according to claim 1, wherein said active material of positive electrode is selected from:
A the disordered carbon material of () porous, selected from soft carbon or hard carbon；
(b) grapheme material, selected from Graphene, graphene oxide, Graphene fluoride, hydrogenation Graphene, nitridation Graphene, The single-layer sheet of the graphene oxide of boron doped graphene, nitrogen-doped graphene or chemistry or thermal reduction or multilamellar plate；
(c) expanded graphite；
(d) mesoporous carbon；
E () CNT, selected from SWCN or multi-walled carbon nano-tubes；
(f) carbon nano-fiber, metal nanometer line, metal oxide nano-wire or conductive polymer nanometer fiber；
(g) organic molecule containing carbonyl；
H () is containing carbonyl, carboxyl or functionalized graphite's alkene material of amido；And
(i) combinations thereof.
15. energy storing devices according to claim 14, the disordered carbon material of wherein said porous selected from polymerization carbon or Carbide resin, mesocarbon, coke, carbonized pitch, activated carbon or part graphitized carbon.
16. energy storing devices according to claim 1, wherein said active material of positive electrode or active material of cathode are Grapheme material without functional group.
17. energy storing devices according to claim 1, wherein functional material is selected from poly-(2,5-dihydroxy-Isosorbide-5-Nitrae-benzene Quinone-3,6-methylene), LixC6O6,Li2(C6H2O4), the terephthalate Li of Li2C8H4O4, the trans-trans-muconate of Li Li2C6H4O4, 3,4,9,10-tetrabasic carboxylic acids-dianhydride disulfide polymer, 3,4,9,10-tetrabasic carboxylic acids-dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalenes- Tetrabasic carboxylic acid-dianhydride, benzene-1,2,4,5-tetracarboxylic dianhydrides, Isosorbide-5-Nitrae, 5,8-tetra hydroxyanthraquinones, tetrahydroxy 1,4-benzoquinone, and they Combination, wherein x=1-3.
18. energy storing devices according to claim 1, wherein functional material is selected from poly-(2,5-dihydroxy-Isosorbide-5-Nitrae-benzene Quinone-3,6-methylene), LixC6O6,Li2(C6H2O4), the terephthalate Li of Li2C8H4O4, the trans-trans-muconate of Li Li2C6H4O4, 3,4,9,10-tetrabasic carboxylic acids-dianhydride disulfide polymer, 3,4,9,10-tetrabasic carboxylic acids-dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalenes four Carboxylic acid-dianhydride, benzene-1,2,4,5-tetracarboxylic dianhydrides, Isosorbide-5-Nitrae, 5,8-tetra hydroxyanthraquinones, tetrahydroxy 1,4-benzoquinone, and their group Close, wherein x=1-3；And this functional material is combined with nano structural material or is supported by it, and described nano structural material is selected from Nano-graphene, CNT, disordered carbon, nano-graphite, conducting nanowires, carbon nano-fiber, polymer nanofiber.
19. energy storing devices according to claim 18, wherein said nano structural material is metal nanometer line.
20. energy storing devices according to claim 16, wherein said active material of positive electrode or active material of cathode are Nonfunctionalized grapheme material selected from following: raw graphite alkene, Graphene fluoride, hydrogenation Graphene, nitridation Graphene, boron The single-layer sheet of the graphene oxide of doped graphene, nitrogen-doped graphene or chemistry or thermal reduction or multilamellar plate.
21. energy storing devices according to claim 1, at least one in wherein said active material is single wall or many Wall carbon nano tube.
22. energy storing devices according to claim 1, at least one in wherein said functional material has selected from such as Under functional group :-COOH ,=O ,-NH2,-OR, or-COOR, or combinations thereof, wherein R is alkyl.
23. energy storing devices according to claim 14, wherein said disordered carbon material is formed by biphase, and the first phase is Graphite crystal or the stacked body of graphene planes, and the second phase is amorphous carbon, and wherein the first phase is scattered in the second phase In or combined by second.
24. energy storing devices according to claim 1, wherein said active material of positive electrode or described active material of cathode It is single wall or multi-walled carbon nano-tubes, the CNT of oxidation, the CNT of fluorination, hydrogenated carbon nanotube, the nitrogen of nonfunctionalized The CNT changed or the CNT of doping.
25. energy storing devices according to claim 24, the CNT of wherein said doping is that boron doped carbon is received Mitron or the CNT of N doping.
26. energy storing devices according to claim 1, wherein said electrolyte comprises the ionic liquid of doping lithium salts.
27. energy storing devices according to claim 1, wherein said device provides the energy being not less than 300Wh/kg close Spend and be not less than the power density of 5Kw/kg, be based on total electrode weight.
28. energy storing devices according to claim 2, wherein capture at electrode or storage includes and active material Graphene entity on surface interacts.
29. energy storing devices according to claim 28, wherein said electrode is negative electrode.
30. energy storing devices according to claim 1, wherein said device has the open-circuit voltage of at least 1.5 volts.
The energy storing device of 31. claim 1, wherein said anode comprises active material of positive electrode, described active material of positive electrode Directly contact with described electrolyte and have not less than 500m2The specific surface area of/g.
The energy storing device of 32. claim 1, in two of which electrode at least one directly contact with described electrolyte and Have not less than 1500m2The specific surface area of/g.
33. 1 kinds of operational rights require the method for the lithium ion exchanged energy storing device of the surface mediation described in 1, described method Including: at anode, implementing lithium source and making described lithium source ion to discharge during the first time discharge cycles of described device Lithium ion enters described electrolyte；Or at negative electrode, implement lithium source and operate described lithium source so that in first time of described device During charging cycle discharge lithium ion enter described electrolyte, the charging and discharging of wherein said device be all not related to lithium insert embedding or Solid-state diffusion.
34. 1 kinds of operational rights require the method for the lithium ion exchanged energy storing device of the surface mediation described in 1, wherein said Method includes:
(A) providing the battery of surface mediation, it comprises anode, lithium source, porous separator, has the electrolysis of primary quantity lithium ion Matter and negative electrode, the material that its Anodic and negative electrode have all have with described electrolyte contact catch lithium surface；
(B) during the first time electric discharge of described device, to described electrolyte, lithium ion is discharged from described lithium source；
(C) described negative electrode is operated to capture lithium ion from described electrolyte and the lithium of described capture is stored in cathode surface On；And
(D) during charge or discharge subsequently operates described anode catch lithium surface and described negative electrode catch lithium surface it Between exchange a certain amount of lithium ion, described amount be more than described primary quantity, wherein said charging operations is not related to lithium and inserts embedding.
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