CN106298250A - A kind of solid lithium ion super capacitor hybrid battery - Google Patents

A kind of solid lithium ion super capacitor hybrid battery Download PDF

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Publication number
CN106298250A
CN106298250A CN201610927180.7A CN201610927180A CN106298250A CN 106298250 A CN106298250 A CN 106298250A CN 201610927180 A CN201610927180 A CN 201610927180A CN 106298250 A CN106298250 A CN 106298250A
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lithium
super capacitor
lithium ion
solid electrolyte
carbon
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CN106298250B (en
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刘晋
李劼
张智
林月
程昀
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Central South University
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    • 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
    • H01G11/08—Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of solid lithium ion battery super capacitor hybrid battery, it includes lithium ion cell positive, electrolyte, lithium/material with carbon element composite negative pole and shell；Described electrolyte is made up of with lithium salts solid electrolyte membrane layer electrolytic solution for super capacitor；Described electrolytic solution for super capacitor is arranged between lithium ion cell positive and lithium salts solid electrolyte membrane layer；Or, described electrolyte is comprised the lithium salts solid electrolyte membrane layer of different radii anion lithium salts respectively and constitutes by least two-layer；Each lithium salts solid electrolyte membrane layer is arranged to lithium/material with carbon element composite negative pole one end gradient from lithium ion cell positive one end according to lithium salts anion radius is ascending, comprises material with carbon element in one layer of lithium/material with carbon element composite negative pole one end or two-layer above lithium salts solid electrolyte membrane layer；This hybrid battery has the excellent properties such as height ratio capacity, high-energy-density, high power density, fast charging and discharging.

Description

A kind of solid lithium ion-super capacitor hybrid battery
Technical field
The present invention relates to a kind of solid lithium ion-super capacitor hybrid battery, be specifically related to one have high-energy-density, High power density and the battery of fast charging and discharging energy storage；Belong to electrochemical energy technical field.
Background technology
Constantly add along with the demand in people's daily life such as electronic equipment, portable communicating tool and power vehicle Greatly, the step of Speeding up development a new generation of various countries clean energy resource, therefore the secondary cell with lithium ion battery as representative is needed by people Ask and the most constantly promote.Although lithium ion battery has, volume is little, capacitance big, voltage advantages of higher, is widely used in mobile electricity The electronic products such as words, laptop computer, the field such as electric automobile of expanding day, but how to obtain higher energy density, more Gao Gong Rate density, the battery of more excellent big multiplying power charging performance receives greatly paying close attention to of researchers in recent years.
Traditional lithium ion battery such as ternary material is that lithium ion battery and the lithium-sulfur cell etc. of positive pole have stable ratio Capacity, power density and energy density.Such as cobalt acid lithium, LiMn2O4, LiFePO4 as the battery theoretical specific capacity of positive pole is 170mAh g-1, commercially produced.But this type of battery material is the best due to electric conductivity so that in positive electrode The conductive carbon material (such as super P CNT, Graphene, graphite etc.) adding some high electron conductions is needed just to improve The comprehensive electrochemical of pole material.As, in lithium-sulfur cell, the material with carbon element using different carbon source synthesis patterns different is made For sulfur-donor, suppressed the dissolution of polysulfide, Jin Erneng by the electric conductivity that can be obviously improved sulfur positive pole with carbon after compound simultaneously Enough promote lithium-sulfur cell performance.Such as, Hou et al. ([J] Advanced Energy Materials, 2016,6 (12)) is with fine jade Fat is carbon source, has prepared three-dimensional perpendicular arrangement porous carbon sill by carbonization treatment, and as the sulfur-donor of lithium-sulfur cell Using, the chemical property of battery performance excellence is (at 837mA g-1Electric current density under, circulation 300 circle after, capacity maintains 844mAh g-1, capacity reservation reaches 80.3%).
Although the addition of material with carbon element can solve the problems such as above-mentioned lithium ion battery poorly conductive very well, but due to material with carbon element Lithium ion battery is not active material, lithium ion battery is not had capacity contribution, cause the actual ratio of lithium ion battery Capacity and energy density are well below theoretical value, it is difficult to meet energy storage device lightweight, high-energy-density, high power density, soon Fill the requirement put soon.
Summary of the invention
The defect existed for existing lithium ion battery, it is an object of the invention to be to provide one to have Fabrication of High Specific Capacitance Lithium ion battery-super capacitor the hybrid battery of the excellent properties such as amount, high-energy-density, high power density, fast charging and discharging；With Solve that conventional lithium ion battery adds carbon source and lithium-sulfur cell capacity is not had contributive shortcoming, thus promote tradition lithium-sulfur cell Chemical property.
In order to realize above-mentioned technical purpose, the invention provides a kind of solid lithium ion-super capacitor hybrid battery, this electricity Pond includes lithium ion cell positive, electrolyte, lithium/material with carbon element composite negative pole and shell；
Described electrolyte is made up of with lithium salts solid electrolyte membrane layer electrolytic solution for super capacitor；Described super capacitor electrode Solve liquid to be arranged between lithium ion cell positive and lithium salts solid electrolyte membrane layer；
Or,
Described electrolyte is comprised the lithium salts solid electrolyte membrane layer structure of different radii anion lithium salts respectively by least two-layer Become；Each lithium salts solid electrolyte membrane layer according to lithium salts anion radius ascending from lithium ion cell positive one end to lithium/carbon Material cladding negative pole one end gradient is arranged, near one layer or the two-layer above lithium salts solid-state electricity of lithium/material with carbon element composite negative pole one end Solve in plasma membrane layer and comprise material with carbon element.
Technical scheme, hybrid battery it is critical only that and have employed special electrolyte, and the electrolyte of employing is by surpassing Level capacitor electrolyte is constituted with lithium salts solid electrolyte membrane layer, and electrolyte is placed in around positive pole, or by least two-layer respectively The solid electrolyte membrane layer comprising different radii anion lithium salts is constituted, and the solid electrolyte containing radius less anion lithium salts Film is arranged near positive pole, arranges near negative pole with carbonaceous material and containing radius compared with the solid electrolyte membrane of macroanion lithium salts. In the hybrid battery of the present invention, near hybrid battery positive pole, add electrolytic solution for super capacitor or anion radius is set relatively The solid electrolyte membrane layer of little lithium salts, beneficially zwitterion migrate, and carry out electrochemistry for material with carbon element double in charge and discharge process Electric layer energy storage provides the ion that can move freely, and promotes the formation of both positive and negative polarity electrochemical double-layer energy storage.Super capacitor simultaneously Device electrolyte improves the easy fast transferring of anion that electrode is less with the wettability of solid electrolyte membrane or lithium salts, thus has Ionic mobility under the raising room temperature of effect, promotes the ability of battery repid discharge.Material with carbon element can pass through the anti-of absorption-De contamination Should, specific capacity and the ion mobility of battery be can effectively improve, thus energy density and the merit of this battery substantially increased Rate density.Therefore, hybrid battery positive pole, special electrolyte assemble with cathode of lithium, have excellent energy storage capacity, make battery have double Electric layer energy storage and the double grading of electrochemical energy storage, hybrid battery has height ratio capacity, high-energy-density, high power density, fast The excellent properties such as speed discharge and recharge.
Preferably scheme, near one layer or the two-layer above lithium salts solid electrolyte membrane of lithium/material with carbon element composite negative pole one end 1wt%～90wt% material with carbon element is comprised in Ceng.
More preferably scheme, material with carbon element include activated carbon, CNT, Graphene, graphene oxide, porous carbon materials, In Heteroatom doping material with carbon element, carbon aerosol at least one.
Preferably scheme, lithium salts solid electrolyte membrane is made up of solid polyelectrolyte or inorganic solid electrolyte.
Preferably scheme, solid polyelectrolyte include polyoxyethylene, polypropylene nitrile, polyvinylidene difluoride, Polycarbonate-based, polymethyl methacrylate, Vingon, boroxane class polysiloxane-based, poly-, poly-nitrogen oxygen alkanes, poly-phosphorus Oxygen alkanes, polymer single ion conductor apoplexy due to endogenous wind at least one.More preferably scheme, solid polyelectrolyte includes leading lithium polymerization Thing, filler and lithium salts, wherein, the general ratio leading lighium polymer, filler and lithium salts is 25～35:2～4:10～15.
More preferably scheme, leads lighium polymer and includes polyoxyethylene (PEO), polypropylene nitrile (PAN), poly-inclined difluoro second Alkenes (PVDF), polycarbonate-based (such as PEC, PTMC, PPCEC etc.), poly-silicon (phosphorus, boron) oxygen alkanes (as KF50, KF615A, PMHS etc.), polymethyl methacrylate, Vingon, polymer single ion conductor apoplexy due to endogenous wind at least one.
More preferably scheme, filler includes Al2O3、TiO2、SiO2、ZrO2、BaTiO3, in MOF-5, MOF-53 (Al) at least A kind of.
More preferably scheme, lithium salts includes LiClO4、LiTFSI、LiFSI、LiFNFSI、LiN(SO2CF3)2、LiCF3SO3、 LiC(SO2CF3)3、LiBC2O4F2、LiC4BO8、LiBF4、LiPF6、LiBOB、LiX、LiNO3In at least one；Wherein, X=F, Cl, Br or I.
Preferably scheme, inorganic solid electrolyte include Ca-Ti ore type, NASICON type, LISICON type, carbuncle type, In LiPON, sulfide type at least one.The common Ca-Ti ore type in this area is (such as CaTiO3、Li3xLa2/3-xTiO3, wherein 0.04 < X < 0.17), NASICON type is (such as LiTi2(PO4)3, wherein replace Ti with Al, Ga, Sc, In, Y portion4+), LISICON type, Punica granatum L. Stone-type, LiPON, sulfide type is (such as Li2S-GeS2-P2S5、P2S5、SiS2、B2S3).
Preferably scheme, electrolytic solution for super capacitor includes organic bath and organic solvent.
Preferably scheme, in electrolytic solution for super capacitor, the mass percent concentration of organic bath is 10～90%.
More preferably scheme, organic bath by Me4N+、Et4N+、Bu4N+、Me3EtN+、TEA+、TEMA+、MeEt3N+、 Li+、R4P+In at least one cation, with ClO4 -、BF4 -、PF6 -、AsF6 -In at least one anion combine.
Preferably scheme, organic solvent is ethylene carbonate (EC), Allyl carbonate (PC), acetonitrile (AN), carbonic acid diformazan Ester (DMC), Ethyl methyl carbonate (EMC), diethyl carbonate (DEC), γ-2 butyrolactone, Allyl carbonate, N, N-dimethyl formyl In amine at least one.
Preferably scheme, electrolytic solution for super capacitor is 10:1～1:10 with the mass ratio of lithium salts solid electrolyte membrane.
Preferably scheme, lithium ion cell positive is constituted by anode material for lithium-ion batteries and material with carbon element are compound.
Preferably scheme, anode material for lithium-ion batteries includes LiFePO4, cobalt acid lithium, LiMn2O4, lithium nickelate or NMC tri- Unit's material system (such as NMC(811), NMC(111), NMC(631), NMC(532)), elemental sulfur or sulfenyl complex.
Preferably scheme, material with carbon element includes activated carbon, CNT, Graphene, graphene oxide, porous carbon materials, miscellaneous In atom doped material with carbon element (doping nitrogen, phosphorus, the element such as oxygen), carbon aerosol at least one.
Preferably scheme, lithium/material with carbon element composite negative pole is coated on lithium metal or lithium alloy sheet by material with carbon element and constitutes.
Preferably scheme, material with carbon element includes activated carbon, CNT, Graphene, graphene oxide, porous carbon materials, miscellaneous In atom doped material with carbon element (doping nitrogen, phosphorus, the element such as oxygen), carbon aerosol at least one.
In technical scheme, the operating voltage window of electrolytic solution for super capacitor is at about 0-2.8V, with lithium sulfur electricity The operating voltage window (1.2-2.8V) in pond overlaps.
Hinge structure, the Advantageous Effects that technical scheme is brought: the solid-state lithium sulfur of the present invention-super Electric capacity hybrid battery has the advantages such as height ratio capacity, high-energy-density, high power density, fast charging and discharging.
1, by the solid electrolyte of less to electrolytic solution for super capacitor or the radius Han anion lithium salts is set near positive pole Put, promote lithium salts anion energy fast transferring in charge and discharge process, and positive and negative interpolar has quick ion migration speed And have electrochemical double-layer energy storage characteristic, thus have higher than the fast charging and discharging capabilities of the theoretical capacity of lithium-sulfur cell and speed.And Electrolytic solution for super capacitor improves electrode/electrolyte interface wet ability, effectively reduces the solid-solid interface resistance of lithium-sulfur cell Anti-, and improve ion transfer efficiency.
2, by being arranged near cathode of lithium by lithium salts solid electrolyte membrane, lithium salts solid electrolyte membrane has excellent machinery And puncture resistance, it is possible to effectively stop the internal short-circuit of battery, serve the effect of barrier film；This is for promoting battery material Stability has the most excellent prospect.And lithium salts solid electrolyte membrane serves the transmission channel of lithium ion, and effectively every From both positive and negative polarity.
3, lithium salts solid electrolyte membrane use material with carbon element can effectively improve battery by the reaction of absorption-De contamination Specific capacity and ion mobility, thus substantially increase energy density and the power density of this battery.
Accompanying drawing explanation
[Fig. 1] is the solid lithium ion-super capacitor hybrid battery structural representation of embodiment 1 preparation.
[Fig. 2] is the first charge-discharge curve chart of the solid lithium ion-super capacitor hybrid battery of embodiment 1 preparation.
Detailed description of the invention
Following example are intended to further illustrate present invention rather than limit the model of the claims in the present invention protection Enclose.
Embodiment 1
With elemental sulfur load CNT as positive active material, using Super-P as conductive agent, acrylic resin (PAA) be binding agent, N-methyl-pyrrolidon (NMP) be solvent, after stirring into uniform slurry according to mass ratio 8:1:1, be coated with Cloth active substance on aluminium foil, with lithium metal as negative pole.With polyoxyethylene solid electrolyte membrane, specifically with containing LiI Solid electrolyte membrane with containing LiTFSI and porous active carbon mix (its preparation process: by MIL-53 (Al) 0.08g with LII 0.23g is dissolved in the acetonitrile of 9mL, stirs 2h, adds 0.4g PEO, stirs 24h, at ambient temperature solvent flashing 6h, then the 24h that volatilizees under the conditions of 80 DEG C, obtain polymer dielectric film, and same step is by many for 0.23g LiTFSI and 0.23g Hole activated carbon replaces LiI) as the composite solid electrolyte of battery, then it is assembled into battery, with 0.1C(1C=1672mAh g-1) Electric current is tested, and voltage window is 1.2-2.8V, and its first circle specific discharge capacity is 1621.4mAh g-1, charge specific capacity is 1070.1mAh g-1。
Embodiment 2
With elemental sulfur load Graphene as positive active material, using Super-P as conductive agent, acrylic resin (PAA) It is solvent for binding agent, N-methyl-pyrrolidon (NMP), after stirring into uniform slurry according to mass ratio 8:1:1, is coated on Active substance on aluminium foil, with lithium metal as negative pole.With polyoxyethylene as solid electrolyte membrane, specifically with containing LiCl's Solid electrolyte membrane with containing LiTFSI and Graphene mixture be used in combination (its preparation process: by MIL-53 (Al) 0.08g with LII 0.23g is dissolved in the acetonitrile of 9mL, stirs 2h, adds 0.4g PEO, stirs 24h, at ambient temperature solvent flashing 6h, then the 24h that volatilizees under the conditions of 80 DEG C, obtain polymer dielectric film, and same step is by 0.23g LiTFSI and 0.46g stone Ink alkene replaces LiCl) as the composite solid electrolyte of battery, then it is assembled into battery and tests, voltage window is 1.2- 2.8V。
Embodiment 3
With elemental sulfur load CNT as positive active material, it is the active matter of negative pole by CNT and lithium metal Matter, with Super-P as conductive agent, acrylic resin (PAA) as binding agent, N-methyl-pyrrolidon (NMP) as solvent, press After stirring into uniform slurry according to mass ratio 8:1:1, it is respectively coated on aluminium foil and Copper Foil, makes anode pole piece and negative pole pole Sheet.With polyoxyethylene solid electrolyte membrane (its preparation process: MIL-53 (Al) 0.08g with LITFSI 0.23g is dissolved in In the acetonitrile of 9mL, stir 2h, add 0.4g PEO, stir 24h, at ambient temperature solvent flashing 6h, then under the conditions of 80 DEG C Volatilization 24h, obtains polymer dielectric film.) as the barrier film of hybrid battery and lead lithium ion material, then at positive electrode and Dielectric film surface drips 1-2 respectively and drips TEABF4The electrolyte (Ningbo Gauss new forms of energy) of/AN ultracapacitor, is assembled into mixed Closing battery to test, voltage window is 1.2-2.8V.
Embodiment 4
With elemental sulfur load Graphene as positive active material, it is the work of negative pole by Graphene (372mAh/g) and lithium metal Property material, with Super-P as conductive agent, acrylic resin (PAA) as binding agent, N-methyl-pyrrolidon (NMP) be molten Agent, after stirring into uniform slurry according to mass ratio 8:1:1, is respectively coated on aluminium foil and Copper Foil, makes anode pole piece and bears Pole pole piece.Using polymer single ion conductor class solid electrolyte membrane as the barrier film of hybrid battery and lead lithium ion material, then Drip 1-2 respectively at positive electrode and dielectric film surface and drip MeEt3NBF4(Ningbo is high for the electrolyte of/PC+AN ultracapacitor These new forms of energy), it is assembled into hybrid battery and tests, voltage window is 1.2-2.8V.
Embodiment 5
With elemental sulfur load Graphene as positive active material, by commercial activated carbon (specific surface area of superelevation) and lithium metal Powder is the active substance of negative pole, with Super-P as conductive agent, acrylic resin (PAA) as binding agent, N-methyi-pyrrofidinium Ketone (NMP) is solvent, after stirring into uniform slurry according to mass ratio 8:1:1, is respectively coated on aluminium foil and Copper Foil, just makes Pole pole piece and cathode pole piece.Using LiPON for inorganic solid electrolyte film as the barrier film of hybrid battery and lead lithium ion material, so After drip 1-2 respectively at positive electrode and dielectric film surface and drip MeEt3NBF4Electrolyte (the Ningbo of/PC+AN ultracapacitor Gauss new forms of energy), it is assembled into hybrid battery and tests, voltage window is 1.2-2.8V.

Claims (10)

1. solid lithium ion battery-super capacitor hybrid battery, it is characterised in that:
Including lithium ion cell positive, electrolyte, lithium/material with carbon element composite negative pole and shell；
Described electrolyte is made up of with lithium salts solid electrolyte membrane layer electrolytic solution for super capacitor；Described electrolytic solution for super capacitor It is arranged between lithium ion cell positive and lithium salts solid electrolyte membrane layer；
Or,
Described electrolyte is comprised the lithium salts solid electrolyte membrane layer of different radii anion lithium salts respectively and constitutes by least two-layer；Respectively Lithium salts solid electrolyte membrane layer is ascending multiple to lithium/material with carbon element from lithium ion cell positive one end according to lithium salts anion radius Close negative pole one end gradient to arrange, near one layer or the two-layer above lithium salts solid electrolyte membrane of lithium/material with carbon element composite negative pole one end Material with carbon element is comprised in Ceng.
Solid lithium ion battery the most according to claim 1-super capacitor hybrid battery, it is characterised in that: near lithium/carbon One layer of Material cladding negative pole one end or two-layer above lithium salts solid electrolyte membrane layer comprise 1wt%～90wt% material with carbon element.
Solid lithium ion battery the most according to claim 1 and 2-super capacitor hybrid battery, it is characterised in that: described Material with carbon element includes activated carbon, CNT, Graphene, graphene oxide, porous carbon materials, Heteroatom doping material with carbon element, carbon gas In colloidal sol at least one.
Solid lithium ion battery the most according to claim 1-super capacitor hybrid battery, it is characterised in that: described lithium Salt solid electrolyte membrane is made up of solid polyelectrolyte or inorganic solid electrolyte.
Solid lithium ion battery the most according to claim 4-super capacitor hybrid battery, it is characterised in that: described is poly- Compound solid electrolyte includes polyoxyethylene, polypropylene nitrile, polyvinylidene difluoride, polycarbonate-based, polymethyl Acid methyl ester, Vingon, boroxane class polysiloxane-based, poly-, poly-nitrogen oxygen alkanes, poly-phosphorus oxygen alkanes, polymer list ion guide Body apoplexy due to endogenous wind at least one；
Described inorganic solid electrolyte includes Ca-Ti ore type, NASICON type, LISICON type, carbuncle type, LiPON, sulfuration In thing type at least one.
Solid lithium ion battery the most according to claim 1-super capacitor hybrid battery, it is characterised in that: described super Capacitor electrolyte includes organic bath and organic solvent；The quality hundred of organic bath in described electrolytic solution for super capacitor Proportion by subtraction concentration is 10～90%.
Solid lithium ion battery the most according to claim 6-super capacitor hybrid battery, it is characterised in that:
Described organic bath by Me4N+、Et4N+、Bu4N+、Me3EtN+、TEA+、TEMA+、MeEt3N+、Li+、R4P+In extremely Few a kind of cation, with ClO4 -、BF4 -、PF6 -、AsF6 -In at least one anion combine；
Described organic solvent is ethylene carbonate, Allyl carbonate, acetonitrile, dimethyl carbonate, Ethyl methyl carbonate, carbonic acid diethyl In ester, γ-2 butyrolactone, Allyl carbonate, N,N-dimethylformamide at least one.
8. according to the solid lithium ion battery-super capacitor hybrid battery described in any one of claim 1,2,4～7, its feature It is: described electrolytic solution for super capacitor is 10:1～1:10 with the mass ratio of lithium salts solid electrolyte membrane.
Solid lithium ion the most according to claim 1-super capacitor hybrid battery, it is characterised in that:
Described lithium ion cell positive is constituted by anode material for lithium-ion batteries and material with carbon element are compound；
Described anode material for lithium-ion batteries include LiFePO4, cobalt acid lithium, LiMn2O4, lithium nickelate or NMC ternary material system, Elemental sulfur or sulfenyl complex；
Described material with carbon element includes activated carbon, CNT, Graphene, graphene oxide, porous carbon materials, Heteroatom doping carbon material Material, in carbon aerosol at least one.
Solid lithium ion the most according to claim 1-super capacitor hybrid battery, it is characterised in that:
Described lithium/material with carbon element composite negative pole is coated on lithium metal or lithium alloy sheet by material with carbon element and constitutes；
Described material with carbon element includes activated carbon, CNT, Graphene, graphene oxide, porous carbon materials, Heteroatom doping carbon material Material, in carbon aerosol at least one.
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