CN106298250B - 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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CN106298250B
CN106298250B CN201610927180.7A CN201610927180A CN106298250B CN 106298250 B CN106298250 B CN 106298250B CN 201610927180 A CN201610927180 A CN 201610927180A CN 106298250 B CN106298250 B CN 106298250B
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lithium
carbon material
lithium ion
solid electrolyte
ion battery
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CN106298250A (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, LIGHT-SENSITIVE OR TEMPERATURE-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

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  • Microelectronics & Electronic Packaging (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of solid lithium ion battery-super capacitor hybrid batteries comprising lithium ion cell positive, electrolyte, lithium/carbon material composite negative pole and shell；The electrolyte is made of electrolytic solution for super capacitor and lithium salts solid electrolyte film layer；The electrolytic solution for super capacitor is arranged between lithium ion cell positive and lithium salts solid electrolyte film layer；Alternatively, the lithium salts solid electrolyte film layer that the electrolyte separately includes different radii anion lithium salts by least two layers is constituted；Each lithium salts solid electrolyte film layer according to lithium salts anion radius it is ascending from lithium ion cell positive one end to lithium/carbon material composite negative pole one end gradient be arranged, close to lithium/carbon material composite negative pole one end the above lithium salts solid electrolyte film layer of one or two layers in include carbon material；The hybrid battery has the excellent properties such as height ratio capacity, high-energy density, high power density, fast charging and discharging.

Description

Solid-state lithium ion-super capacitor hybrid battery
Technical Field
The invention relates to a solid lithium ion-super capacitor hybrid battery, in particular to a battery with high energy density, high power density and rapid charge and discharge energy storage; belongs to the technical field of electrochemical energy.
Background
Along with the increasing demand of electronic devices, portable communication tools, power cars and the like in daily life of people, the development of new generation clean energy is accelerated in various countries, and thus the demand of people for secondary batteries represented by lithium ion batteries is also increasing. Although lithium ion batteries have advantages of small size, large capacitance, high voltage, etc., and are widely used in electronic products such as mobile phones and portable computers, and in increasingly expanded fields such as electric vehicles, how to obtain batteries with higher energy density, higher power density, and more excellent high-rate charging performance has received great attention from researchers in recent years.
The traditional lithium ion battery, such as the lithium ion battery taking ternary materials as the anode, the lithium sulfur battery and the like, has stable specific capacity, power density and energy density. For example, the theoretical specific capacity of the battery taking lithium cobaltate, lithium manganate and lithium iron phosphate as the positive electrode is 170mAh g-1And is already commercially produced. However, due to poor conductivity of such battery materials, some conductive carbon materials with high electron conductivity (such as super P carbon nanotubes, graphene, graphite, etc.) need to be added to the positive electrode material to improve the comprehensive electrochemical performance of the positive electrode material. Just as in a lithium-sulfur battery, carbon materials with different carbon sources and different shapes are synthesized to serve as sulfur carriers, and the carbon carriers are compounded with carbon to remarkably improve the conductivity of a sulfur positive electrode and inhibit the dissolution of polysulfide, so that the performance of the lithium-sulfur battery can be improved. For example, Hou et al ([ J ]]2016,6 (12)) takes agar as a carbon source, prepares a three-dimensional vertically-arranged porous carbon-based material through carbonization treatment, and is used as a sulfur carrier of a lithium-sulfur battery, and the battery shows excellent electrochemical performance (at 837mA g)-1At a current density of (1), after circulating for 300 cycles, the capacity was maintained at 844mAh g-1Capacity retention reached 80.3%).
Although the problem of poor conductivity of the lithium ion battery can be well solved by adding the carbon material, the carbon material is not an active material in the lithium ion battery and does not contribute to the capacity of the lithium ion battery, so that the actual specific capacity and the energy density of the lithium ion battery are far lower than theoretical values, and the requirements of light weight, high energy density, high power density, quick charge and quick discharge of an energy storage device are difficult to meet.
Disclosure of Invention
Aiming at the defects of the existing lithium ion battery, the invention aims to provide a lithium ion battery-super capacitor hybrid battery with excellent performances such as high specific capacity, high energy density, high power density, rapid charge and discharge and the like; the defect that the addition of a carbon source in the traditional lithium ion battery does not contribute to the capacity of the lithium sulfur battery is overcome, and therefore the electrochemical performance of the traditional lithium sulfur battery is improved.
In order to achieve the technical objects, the present invention provides a solid-state lithium ion-supercapacitor hybrid battery comprising a lithium ion battery positive electrode, an electrolyte, a lithium/carbon material composite negative electrode, and a case;
the electrolyte consists of a super capacitor electrolyte and a lithium salt solid electrolyte membrane layer; the electrolyte of the super capacitor is arranged between the anode of the lithium ion battery and the lithium salt solid electrolyte film layer;
or,
the electrolyte is composed of at least two lithium salt solid electrolyte membrane layers respectively containing anion lithium salts with different radiuses; the lithium salt solid electrolyte membrane layers are arranged in a gradient manner from one end of the positive electrode of the lithium ion battery to one end of the lithium/carbon material composite negative electrode according to the radius of lithium salt anions from small to large, and one or more than two lithium salt solid electrolyte membrane layers close to one end of the lithium/carbon material composite negative electrode contain carbon materials.
According to the technical scheme, the hybrid battery is characterized in that a special electrolyte is adopted, the adopted electrolyte is composed of a super capacitor electrolyte and a lithium salt solid electrolyte membrane layer, the electrolyte is arranged around a positive electrode, or the electrolyte is composed of at least two solid electrolyte membrane layers respectively containing anion lithium salts with different radiuses, the solid electrolyte membrane containing the anion lithium salt with the smaller radius is arranged close to the positive electrode, and a carbon-containing material and the solid electrolyte membrane containing the anion lithium salt with the larger radius are arranged close to a negative electrode. In the hybrid battery, the supercapacitor electrolyte or the solid electrolyte film layer with the lithium salt with the smaller anion radius is added near the anode of the hybrid battery, so that the migration of anions and cations is facilitated, ions capable of moving freely are provided for the carbon material to perform electrochemical double-layer energy storage in the charging and discharging processes, and the formation of the electrochemical double-layer energy storage of the anode and the cathode is promoted. Meanwhile, the electrolyte of the super capacitor improves the wettability of the electrode and a solid electrolyte membrane or small anions in lithium salt are easy to rapidly migrate, so that the ion mobility at room temperature is effectively improved, and the rapid discharging capability of the battery is improved. The carbon material can effectively improve the specific capacity and the ion migration rate of the battery through the adsorption-desorption reaction, thereby greatly improving the energy density and the power density of the battery. Therefore, the hybrid battery anode, the special electrolyte and the lithium cathode are assembled, so that the hybrid battery has excellent energy storage capacity, the battery has double characteristics of double-electric-layer energy storage and electrochemical energy storage, and the hybrid battery has excellent performances such as high specific capacity, high energy density, high power density, rapid charge and discharge and the like.
Preferably, one or more than two lithium salt solid electrolyte membrane layers close to one end of the lithium/carbon material composite negative electrode contain 1-90 wt% of carbon material.
In a more preferred embodiment, the carbon material includes at least one of activated carbon, carbon nanotubes, graphene oxide, porous carbon material, heteroatom-doped carbon material, and carbon aerosol.
Preferably, the lithium salt solid electrolyte membrane is composed of a polymer solid electrolyte or an inorganic solid electrolyte.
Preferably, the polymer solid electrolyte includes at least one of polyoxyethylene, polyacrylonitrile, polyvinylidene fluoride, polycarbonate, polymethyl methacrylate, polyvinylidene chloride, polysiloxane, polyboroxane, polyoxoane, polyphosphazene, and polymer single ion conductor. In a more preferable scheme, the polymer solid electrolyte comprises a lithium conducting polymer, a filler and a lithium salt, wherein the general ratio of the lithium conducting polymer, the filler and the lithium salt is 25-35: 2-4: 10-15.
More preferably, the lithium-conducting polymer comprises at least one of Polyoxyethylene (PEO), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polycarbonate (such as PEC, PTMC, PPCEC, etc.), polysiloxane (phosphorus, boron), such as KF50, KF615A, PMHS, etc., polymethyl methacrylate, polyvinylidene chloride, and polymeric single ion conductor.
More preferably, the filler comprises Al2O3、TiO2、SiO2、ZrO2、BaTiO3At least one of MOF-5 and MOF-53 (Al).
More preferably, the lithium salt comprises LiClO4、LiTFSI、LiFSI、LiFNFSI、LiN(SO2CF3)2、LiCF3SO3、LiC(SO2CF3)3、LiBC2O4F2、LiC4BO8、LiBF4、LiPF6、LiBOB、LiX、LiNO3At least one of (1); wherein, X = F, Cl, Br or I.
Preferably, the inorganic solid electrolyte includes at least one of perovskite type, NASICON type, LISICON type, garnet type, LiPON, and sulfide type. Perovskite type (e.g. CaTiO) common in the art3、Li3xLa2/3-xTiO3Wherein 0.04<x<0.17), NASICON type (e.g., LiTi)2（PO4）3Wherein Ti is partially substituted by Al, Ga, Sc, In, Y4+) LISICON type, garnet type, LiPON, sulfide type (e.g. Li)2S-GeS2-P2S5、P2S5、SiS2、B2S3）。
In a preferred embodiment, the supercapacitor electrolyte comprises an organic electrolyte and an organic solvent.
In the preferable scheme, the mass percentage concentration of the organic electrolyte in the electrolyte of the super capacitor is 10-90%.
More preferably, the organic electrolyte consists of Me4N+、Et4N+、Bu4N+、Me3EtN+、TEA+、TEMA+、MeEt3N+、Li+、R4P+At least one cation with ClO4 -、BF4 -、PF6 -、AsF6 -At least one anion.
Preferably, the organic solvent is at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), Acetonitrile (AN), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), γ -2 butyrolactone, propylene carbonate, and N, N-dimethylformamide.
In the preferable scheme, the mass ratio of the electrolyte of the super capacitor to the lithium salt solid electrolyte membrane is 10: 1-1: 10.
Preferably, the lithium ion battery anode is formed by compounding a lithium ion battery anode material and a carbon material.
Preferably, the lithium ion battery positive electrode material comprises lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate or an NMC ternary material system (such as NMC (811), NMC (111), NMC (631) and NMC (532)), elemental sulfur or a sulfur-based compound.
In a preferred embodiment, the carbon material includes at least one of activated carbon, carbon nanotubes, graphene oxide, porous carbon material, heteroatom-doped carbon material (doped with elements such as nitrogen, phosphorus, and oxygen), and carbon aerosol.
Preferably, the lithium/carbon material composite negative electrode is formed by coating a carbon material on a lithium metal or lithium alloy sheet.
In a preferred embodiment, the carbon material includes at least one of activated carbon, carbon nanotubes, graphene oxide, porous carbon material, heteroatom-doped carbon material (doped with elements such as nitrogen, phosphorus, and oxygen), and carbon aerosol.
According to the technical scheme, the working voltage window of the electrolyte of the super capacitor is about 0-2.8V and is overlapped with the working voltage window (1.2-2.8V) of the lithium-sulfur battery.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that: the solid-state lithium-sulfur-super capacitor hybrid battery has the advantages of high specific capacity, high energy density, high power density, rapid charge and discharge and the like.
1. The super capacitor electrolyte or the solid electrolyte containing the lithium salt with smaller anion radius is arranged close to the positive electrode, so that the lithium salt anions can be promoted to rapidly migrate in the charging and discharging process, and the positive electrode and the negative electrode have rapid ion migration speed and the energy storage characteristic of an electrochemical double electric layer, so that the lithium-sulfur battery has higher theoretical capacity and rapid charging and discharging capacity than a lithium-sulfur battery. And the electrolyte of the super capacitor improves the wettability of an electrode/electrolyte interface, effectively reduces the solid-solid interface impedance of the lithium-sulfur battery, and improves the ion transfer efficiency.
2. The lithium salt solid electrolyte membrane is arranged close to the lithium cathode, so that the lithium salt solid electrolyte membrane has excellent mechanical and puncture-resistant properties, can effectively prevent the internal short circuit of the battery and plays a role of a diaphragm; the method has excellent prospect for improving the stability of the battery material. And the lithium salt solid electrolyte membrane plays a role of a lithium ion transmission channel and effectively isolates the anode and the cathode.
3. The lithium salt solid electrolyte membrane adopts carbon materials, and the specific capacity and the ion migration rate of the battery can be effectively improved through the adsorption-desorption reaction, so that the energy density and the power density of the battery are greatly improved.
Drawings
Fig. 1 is a schematic structural view of the solid-state lithium ion-supercapacitor hybrid battery prepared in example 1.
Fig. 2 is a first charge and discharge curve diagram of the solid-state lithium ion-supercapacitor hybrid battery prepared in example 1.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention as claimed.
Example 1
The method comprises the steps of taking elemental sulfur-loaded carbon nanotubes as a positive active substance, Super-P as a conductive agent, acrylic resin (PAA) as an adhesive and N-methyl-pyrrolidone (NMP) as a solvent, stirring the materials into uniform slurry according to a mass ratio of 8:1:1, coating the slurry on aluminum foil, and taking metal lithium as an active substance of a negative electrode. The preparation method comprises the steps of dissolving 0.08g of MIL-53(Al) and 0.23g of LII in 9mL of acetonitrile, stirring for 2h, adding 0.4g of PEO, stirring for 24h, volatilizing the solvent for 6h at room temperature, volatilizing for 24h at 80 ℃ to obtain a polymer electrolyte membrane, replacing LiI with 0.23g of LiTFSI and 0.23g of porous active carbon by using 0.23g of LiTFSI and 0.23g of porous active carbon as a composite solid electrolyte of the cell, assembling the cell, and using 0.1C (1C =1672mAh g of LiTFSI and a mixture of the LiTFSI and the porous active carbon to form the composite solid electrolyte of the cell-1) The current is tested, the voltage window is 1.2-2.8V, and the first-circle specific discharge capacity is 1621.4mAh g-1The charging specific capacity is 1070.1mAh g-1。
Example 2
Elemental sulfur-loaded graphene is used as a positive active material, Super-P is used as a conductive agent, acrylic resin (PAA) is used as an adhesive, N-methyl-pyrrolidone (NMP) is used as a solvent, the materials are stirred into uniform slurry according to the mass ratio of 8:1:1, and then the uniform slurry is coated on an aluminum foil, and metal lithium is used as an active material of a negative electrode. Polyoxyethylene is used as a solid electrolyte membrane, specifically, a solid electrolyte membrane containing LiCl is used in combination with a mixture containing LiTFSI and graphene (the preparation process comprises the steps of dissolving 0.08g of MIL-53(Al) and 0.23g of LII in 9mL of acetonitrile, stirring for 2h, adding 0.4g of PEO, stirring for 24h, volatilizing the solvent for 6h at room temperature, volatilizing for 24h at 80 ℃ to obtain a polymer electrolyte membrane, replacing LiCl with 0.23g of LiTFSI and 0.46g of graphene in the same step) to serve as a composite solid electrolyte of a battery, and then assembling the composite solid electrolyte into the battery for testing, wherein the voltage window is 1.2-2.8V.
Example 3
The method comprises the steps of taking elemental sulfur loaded carbon nanotubes as a positive active material, taking the carbon nanotubes and metal lithium as an active material of a negative electrode, taking Super-P as a conductive agent, acrylic resin (PAA) as an adhesive and N-methyl-pyrrolidone (NMP) as a solvent, stirring into uniform slurry according to the mass ratio of 8:1:1, and respectively coating the uniform slurry on aluminum foil and copper foil to prepare a positive electrode piece and a negative electrode piece. Dissolving 0.08g of MIL-53(Al) and 0.23g of LITFSI in 9mL of acetonitrile, stirring for 2h, adding 0.4g of PEO, stirring for 24h, volatilizing the solvent for 6h at room temperature, and volatilizing for 24h at 80 ℃ to obtain a polymer electrolyte membrane, and then respectively dropwise adding 1-2 drops of TEABF on the surfaces of the positive electrode material and the electrolyte membrane4The electrolyte (Ningbo Gauss new energy) of the/AN super capacitor is assembled into a hybrid battery for testing, and the voltage window is 1.2-2.8V.
Example 4
Elemental sulfur loaded graphene is taken as a positive active material, graphene (372mAh/g) and metal lithium are taken as active materials of a negative electrode, Super-P is taken as a conductive agent, acrylic resin (PAA) is taken as an adhesive, and N-methyl-pyrrolidone (NMP) is taken as a solvent, the mixture is stirred into uniform slurry according to the mass ratio of 8:1:1, and then the uniform slurry is respectively coated on an aluminum foil and a copper foil to prepare a positive pole piece and a negative pole piece. Taking a polymer single-ion conductor solid electrolyte membrane as a diaphragm of a hybrid battery and a lithium ion conducting material, and then respectively dropwise adding 1-2 drops of MeEt on the surfaces of a positive electrode material and the electrolyte membrane3NBF4And the electrolyte (Ningbo Gauss new energy) of the/PC + AN super capacitor is assembled into a hybrid battery for testing, and the voltage window is 1.2-2.8V.
Example 5
Elemental sulfur loaded graphene is used as a positive electrode active substance, commercial activated carbon (with ultra-high specific surface area) and metal lithium powder are used as active substances of a negative electrode, Super-P is used as a conductive agent, acrylic resin (PAA) is used as an adhesive, and N-methyl-pyrrolidone (NMP) is used as a solvent, and the materials are stirred into uniform slurry according to the mass ratio of 8:1:1 and then respectively coated on an aluminum foil and a copper foil to prepare a positive electrode piece and a negative electrode piece. LiPON is used as an inorganic solid electrolyte membrane as a diaphragm of a hybrid battery and a lithium ion conducting material, and then 1-2 drops of MeEt are respectively dripped on the surfaces of a positive electrode material and the electrolyte membrane3NBF4And the electrolyte (Ningbo Gauss new energy) of the/PC + AN super capacitor is assembled into a hybrid battery for testing, and the voltage window is 1.2-2.8V.

Claims (6)

1. A solid state lithium ion battery-super capacitor hybrid battery is characterized in that:
the lithium ion battery comprises a lithium ion battery anode, an electrolyte, a lithium/carbon material composite cathode and a shell;
the electrolyte is composed of at least two lithium salt solid electrolyte membrane layers respectively containing anion lithium salts with different radiuses; each lithium salt solid electrolyte membrane layer is arranged in a gradient manner from one end of the anode of the lithium ion battery to one end of the lithium/carbon material composite cathode according to the radius of lithium salt anions from small to large, and one or more than two lithium salt solid electrolyte membrane layers close to one end of the lithium/carbon material composite cathode comprise carbon materials;
one or more than two lithium salt solid electrolyte membrane layers close to one end of the lithium/carbon material composite negative electrode contain 1-90 wt% of carbon material.
2. The solid state lithium ion battery-supercapacitor hybrid battery according to claim 1, wherein:
the carbon material comprises at least one of carbon nano tube, graphene oxide, porous carbon material, heteroatom doped carbon material and carbon aerosol.
3. The solid state lithium ion battery-supercapacitor hybrid battery according to claim 1, wherein:
the lithium salt solid electrolyte film layer is composed of polymer solid electrolyte or inorganic solid electrolyte.
4. The solid state lithium ion battery-supercapacitor hybrid battery according to claim 3, wherein:
the polymer solid electrolyte comprises at least one of polyoxyethylene, polyacrylonitrile, polyvinylidene fluoride, polycarbonate, polymethyl methacrylate, polyvinylidene chloride, polysiloxane, polyboroxine, poly-nitroxide, poly-phosphoxane and polymer single ion conductor;
the inorganic solid electrolyte comprises at least one of perovskite type, NASICON type, LISICON type, garnet type, LiPON and sulfide type.
5. The solid state lithium ion battery-supercapacitor hybrid battery according to claim 1, wherein:
the lithium ion battery anode is formed by compounding a lithium ion battery anode material and a carbon material;
the lithium ion battery anode material comprises a ternary material system of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate or NMC and elemental sulfur or a sulfur-based compound;
the carbon material comprises at least one of carbon nano tube, graphene oxide, porous carbon material, heteroatom doped carbon material and carbon aerosol.
6. The solid state lithium ion battery-supercapacitor hybrid battery according to claim 1, wherein:
the lithium/carbon material composite negative electrode is formed by coating a carbon material on a metal lithium or lithium alloy sheet;
the carbon material comprises at least one of carbon nano tube, graphene oxide, porous carbon material, heteroatom doped carbon material and carbon aerosol.
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