CN105870449A - All-solid-state lithium-air battery composite positive electrode material and all-solid-state lithium-air battery - Google Patents

All-solid-state lithium-air battery composite positive electrode material and all-solid-state lithium-air battery Download PDF

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CN105870449A
CN105870449A CN201610244847.3A CN201610244847A CN105870449A CN 105870449 A CN105870449 A CN 105870449A CN 201610244847 A CN201610244847 A CN 201610244847A CN 105870449 A CN105870449 A CN 105870449A
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air battery
zif
lithium
state lithium
solid state
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CN105870449B (en
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刘晋
李劼
黄辰翔
林月
刘业翔
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Central South University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses an all-solid-state lithium-air battery composite positive electrode material and an all-solid-state lithium-air battery. The composite positive electrode material comprises a conductive carbon material, a micro-nano frame structure, a lithium-conducting polymer and a redox mediator, wherein the composite positive electrode material has the characteristics of good conductivity and high oxygen permeability; a discharge product can be oxidized in a positive electrode region; and the all-solid-state lithium-air battery with high circulation capability and high safety performance can be obtained on the basis of a positive plate prepared from the composite positive electrode material.

Description

A kind of all solid state lithium-air battery composite positive pole and all solid state lithium-air battery
Technical field
The present invention relates to a kind of all solid state lithium-air battery composite positive pole and all solid state lithium-air battery, belong to Lithium-air technique field in new forms of energy.
Background technology
Fossil fuel decay and environmental problem cause increasing concern, and people are devoted to seek can replacementization The new energy technology of stone fuel.Lithium ion battery as the most dependable a kind of energy storage system the most for many years, But the factors such as relatively low energy density, safety and price, limit traditional lithium-ion battery the most extensive Application.
Lithium-air battery energy density in theory can reach 11680Wh kg-1, it is possible to the energy provided with gasoline Metric density (13000Wh kg-1) compare favourably, therefore, lithium-air battery is as a kind of new-type green secondary The energy, has the ability to replace conventional lithium ion battery and be used in electric automobile.
Still there are some problems, such as in lithium-air battery at present: electrolyte volatilization and leakage, inflammable, oxygen Gas dissolubility and diffusivity are poor etc..
Summary of the invention
Have for lithium-air battery of the prior art that cycle performance is poor, battery polarization is big, security performance is low Etc. problem, first purpose of the present invention is to provide one to conduct electricity very well, and OTR oxygen transmission rate is high, can make to put Electricity product is at the composite positive pole for all solid state lithium-air battery of positive pole zone internal oxidition.
Another object of the present invention be to provide a kind of circulation ability is strong, security performance is high all solid lithium- Air cell.
To achieve these goals, the invention provides a kind of all solid state lithium-air battery composite positive pole, This composite positive pole includes conductive carbon material, micro-nano frame structure, leads lighium polymer and oxidoreduction mediator.
Technical scheme mainly utilizes oxidoreduction mediator and discharging product (Li2O2) there is chemistry Reaction, promotes Li2O2Decompose, can effectively solve discharging product (Li in cyclic process2O2) poorly conductive and make The problem that polarization phenomenon is serious, improves the cycle performance of lithium-air battery further.
Preferably scheme, oxidoreduction mediator mass percentage content in described composite positive pole is 5%～25%.
More preferably scheme, oxidoreduction mediator is lithium iodide, TEMPO, LiNO3In at least one.
Preferably scheme, composite positive pole is made up of following mass percent component: conductive carbon material 5%～25%；Micro-nano frame structure 5%～25%；Lead lighium polymer 25%～85%；Oxidoreduction mediator 5%～25%.
More preferably scheme, conductive carbon material is conductive carbon, activated carbon, Graphene, CNT, carbon nanometer At least one in fiber.
More preferably scheme, lead lighium polymer be poly(ethylene oxide), polymethyl methacrylate, polyacrylonitrile, Polyacrylic acid, poly(propylene oxide), Kynoar, polyvinylidene fluoride vinyl copolymer, polyvinyl alcohol, poly-four Fluorothene, sodium carboxymethyl cellulose, polyethylene, polyethylene kind copolymer, Viton, polyurethane, poly-silicon At least one in oxygen alkane.
More preferably scheme, micro-nano frame structure be MOF-5, MIL-53 (Al), MIL-53 (Cr), Zn-MOF-74、HKUST-1、ZIF-1、ZIF-2、ZIF-3、ZIF-4、ZIF-5、ZIF-6、ZIF-7、 ZIF-8、ZIF-9、ZIF-10、ZIF-22、ZIF-69、ZIF-90、NAFS-1、MIL-47、CAU-1、 MIL-101(Cr)、CPO-27-Mg、CPO-27-Mn、CPO-27-Co、CPO-27-Ni、CPO-27-Zn、 Mn(HCOO)2、Co(HCOO)2、Ni(HCOO)2, at least one in G-MIL-53 (Al).The present invention relates to And micro-nano framework can directly buy or with reference to the simple synthesis of existing document report.
Present invention also offers a kind of all solid state lithium-air battery, including positive plate, solid electrolyte film and negative Pole piece, described positive plate is made up of described composite positive pole.
Preferably scheme, positive plate thickness is 0.1～50 μm.
Preferably scheme, solid electrolyte film thickness is 10～200 μm.
Preferably scheme, solid electrolyte film is made up of following mass percent component: lead lighium polymer 20%～70%, inorganic filler 5%～50%, lithium salts 10%～60%.The solid electrolyte film of the present invention can be kept away Exempt from cathode of lithium and O2、CO2And H2There is directly contact in O, greatly promotes the stability of lithium-air battery, Solid electrolyte film is it can be avoided that generate Li dendrite when circulating and cause short circuit phenomenon simultaneously so that lithium-air exists Safer during circulation for a long time.
Preferably scheme, lead lithium be polymerized to poly(ethylene oxide), polymethyl methacrylate, polyacrylonitrile, poly-third Olefin(e) acid, poly(propylene oxide), Kynoar, polyvinylidene fluoride vinyl copolymer, polyvinyl alcohol, politef, In sodium carboxymethyl cellulose, polyethylene, polyethylene kind copolymer, Viton, polyurethane, polysiloxanes At least one.
Preferably scheme, inorganic filler is aluminium oxide, silicon oxide, zirconium oxide, titanium oxide, Barium metatitanate., metal At least one in-organic frame.Metal-organic framework be preferably MOF-5, MIL-53 (Al), MIL-53(Cr)、Zn-MOF-74、HKUST-1、ZIF-1、ZIF-2、ZIF-3、ZIF-4、ZIF-5、 ZIF-6、ZIF-7、ZIF-8、ZIF-9、ZIF-10、ZIF-22、ZIF-69、ZIF-90、NAFS-1、MIL-47、 CAU-1、MIL-101(Cr)、CPO-27-Mg、CPO-27-Mn、CPO-27-Co、CPO-27-Ni、 CPO-27-Zn、Mn(HCOO)2、Co(HCOO)2、Ni(HCOO)2In at least one.
Preferably scheme, lithium salts is LiN (SO2CF3)2、LiCF3SO3、LiC(SO2CF3)3、LiBC2O4F2、 LiC4BO8, double oxalic acid borate lithiums, LiOCH (CH3)2In at least one.
The negative plate that the present invention relates to is metal lithium sheet.
The preparation method of the positive plate of the present invention is: by micro-nano frame structure, oxidoreduction mediator, leads lithium and gathers Compound and conductive carbon material are dissolved in solvent, after being sufficiently stirred for, evaporate solvent in 60 DEG C～80 DEG C, cut Slabbing, to obtain final product.
The solid electrolyte film of the present invention can use the solvent casting method of routine to prepare, it is also possible to passes through pressure sintering Preparation.
Hinge structure, the Advantageous Effects that technical scheme is brought:
1, all solid state lithium-air battery composite positive pole of the present invention is by adding oxidoreduction mediator, energy Effectively facilitate discharging product (Li2O2) occur chemical reaction to decompose, solve electric discharge in cyclic process and produce Thing (Li2O2) poorly conductive and cause the problem that polarization phenomena are serious, improve further following of lithium-air battery Ring performance.The micro-nano frame structure used in all solid state lithium-air battery composite positive pole of the present invention, shape State uniformly and contains unsatuated metal site, has again bigger specific surface area, therefore for O simultaneously2Have The strongest absorbability, and its uniform duct can be O2Transmission sufficient path is provided；On the other hand, The micro-nano frame structure of porous combines with conductive carbon material, and conductive carbon can make up used micro-nano framework not The shortcoming of conduction, also is able to the deposition into discharging product simultaneously and provides enough site.
2, all solid state lithium-air battery of the present invention is to make based on composite positive pole, and composite positive pole is not It is only capable of the requirement meeting all solid state lithium-air battery to positive pole material conductivity, tradition can be solved all solid state simultaneously The problem that in lithium-air battery, catalytic site is few, makes all solid state lithium-air battery have relatively low, the cyclicity of polarization Can the stable and feature of higher-security energy.
3, all solid state lithium-air battery composite positive pole of the present invention and all solid state lithium-air battery preparation method Simple to operate, process conditions are gentle, low cost, beneficially industrialized production.
Accompanying drawing explanation
[Fig. 1] is 80 DEG C of embodiment 1,150mA/gcUnder the conditions of constant current charge-discharge, all solid state lithium-air battery follows Ring performance.
[Fig. 2] is 70 DEG C of embodiment 2,150mA/gcUnder the conditions of constant current charge-discharge, all solid state lithium-air battery follows Ring performance.
Detailed description of the invention
Following example are intended to further illustrate the present invention rather than the restriction to protection scope of the present invention.
Embodiment 1
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiI 0.03g, PEO 0.15g, CNT (CNT) 0.03g and MIL-53 (Al) 0.03g, is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, the most at ambient temperature Solvent flashing 6h, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, and quality is 0.005g, obtains anode composite sheet.
Prepare solid electrolyte film: MIL-53 (Al) 0.08g Yu LiTFSI 0.23g is dissolved in the second of 9mL In nitrile, stir 2h, add 0.4g PEO, stir 24h, at ambient temperature solvent flashing 6h, then 80 Volatilize under the conditions of DEG C 24h, obtains the polymer dielectric film of 150 μ m-thick.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First Circle discharge platform is 2.6V, and charging platform is 3.3V, and the voltage difference of circulation is 0.7V, discharges after circulation 7 circle Platform is 2.6V, and charging platform is 3.7V, and charging/discharging voltage difference is 1.2V.Concrete loop test data such as figure Shown in 1.
Embodiment 2
Prepare anode composite sheet in the same manner as in Example 1 and polymer dielectric, be assembled into all solid lithium- Air cell, at 70 DEG C, electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under test, The voltage difference of first circle circulation is 0.7V, and after circulation 5 circle, charging/discharging voltage difference is 1.3V.Concrete loop test number According to as shown in Figure 2.
Embodiment 3
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiTFSI 0.03g, PEO 0.15g, CNT (CNT) 0.06g And MIL-53 (Al) 0.03g, it is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, afterwards at room temperature bar Solvent flashing 6h under part, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, quality For 0.005g, obtain anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First The voltage difference of circle circulation is 0.6V, and after circulation 10 circle, charging/discharging voltage difference is 1.25V.
Embodiment 4
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiTFSI 0.03g, PEO 0.12g, CNT (CNT) 0.06g And MIL-53 (Al) 0.03g, it is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, afterwards at room temperature bar Solvent flashing 6h under part, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, quality For 0.005g, obtain anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First The voltage difference of circle circulation is 0.6V, and after circulation 10 circle, charging/discharging voltage difference is 1.25V.
Embodiment 5
Prepare anode composite sheet, and preparation G-MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of alkane sulfimide lithium (LiTFSI).
Preparation G-MIL-53 (Al): weigh MIL-53 (Al) 1g, glucose (Glucose) 1g, be fully ground it After, put into carbonization in the tube furnace of full argon, carburizing temperature is 480 DEG C, and programming rate is 10 DEG C/min, Being incubated 4 hours, gained khaki granule is G-MIL-53 (Al).
Prepare anode composite sheet: weigh LiTFSI0.03g, PEO 0.15g, CNT (CNT) 0.03g And G-MIL-53 (Al) 0.03g, it is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, afterwards in room Solvent flashing 6h under the conditions of temperature, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, Quality is 0.005g, obtains anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First The voltage difference of circle circulation is 0.7V, and after circulation 10 circle, charging/discharging voltage difference is 1.5V.
Embodiment 6
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiNO30.03g, PEO 0.15g, CNT (CNT) 0.03g And MIL-53 (Al) 0.03g, it is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, afterwards at room temperature bar Solvent flashing 6h under part, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, quality For 0.005g, obtain anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First Circle discharge platform is 2.45V, and charging platform is 3.4V, and the voltage difference of circulation is 0.95V, after circulation 10 circle Discharge platform is 2.4V, and charging platform is 3.7V, and charging/discharging voltage difference is 1.3V.
Embodiment 7
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh TEMPO 0.03g, PEO 0.15g, CNT (CNT) 0.03g And MIL-53 (Al) 0.03g, it is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, afterwards at room temperature bar Solvent flashing 6h under part, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, quality For 0.005g, obtain anode composite sheet.
Prepared anode composite sheet, polymer dielectric and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First Circle discharge platform is 2.5V, and charging platform is 3.5V, and the voltage difference of circulation is 1V, discharges after circulation 10 circle Platform is 2.4V, and charging platform is 3.7V, and charging/discharging voltage difference is 1.3V.
Embodiment 8
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiTFSI 0.03g, PEO 0.12g, conductive carbon 0.03g and MIL-53 (Al) 0.03g, is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, the most at ambient temperature Solvent flashing 6h, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, and quality is 0.005g, obtains anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First The voltage difference of circle circulation is 0.1.3V, and after circulation 10 circle, charging/discharging voltage difference is 1.7V.
Embodiment 9
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiTFSI 0.03g, PEO 0.12g, carbon nano-fiber 0.03g and MIL-53 (Al) 0.03g, is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, the most at ambient temperature Solvent flashing 6h, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, and quality is 0.005g, obtains anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First The voltage difference of circle circulation is 0.7V, and after circulation 5 circle, charging/discharging voltage difference is 1.45V.
Embodiment 10
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiTFSI 0.03g, PEO 0.12g, CNT (CNT) 0.03g And Zn-MOF-74 0.03g, it is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, afterwards in room temperature Under the conditions of solvent flashing 6h, then under conditions of 80 DEG C volatilize 24h, be cut into lamellar, thickness is 60 μm, matter Amount is 0.005g, obtains anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First The voltage difference of circle circulation is 0.8V, and after circulation 3 circle, charging/discharging voltage difference is 1V.
Embodiment 11
Prepare anode composite sheet, and preparation MIL-53 (Al), Pluronic F-127 (PEO), double fluoroform The polymer dielectric film (by embodiment 1 method) of sulfimide lithium (LiTFSI).
Prepare anode composite sheet: weigh LiTFSI 0.03g, Kynoar 0.12g, CNT (CNT) 0.03g and Zn-MOF-74 0.03g, is added thereto to acetonitrile 9g, is sufficiently stirred for making it uniform, exists afterwards Solvent flashing 6h under room temperature condition, then the 24h that volatilizees under conditions of 80 DEG C, be cut into lamellar, and thickness is 60 μm, Quality is 0.005g, obtains anode composite sheet.
Prepared anode composite sheet, polymer dielectric film and lithium sheet are assembled into button cell, at 80 DEG C, Electric current density is 150mA/gc, capacity cutoff is 1000mA/gcBar under carry out constant current charge-discharge test.First The voltage difference of circle circulation is 0.8V, and after circulation 5 circle, charging/discharging voltage difference is 1.05V.

Claims (10)

1. an all solid state lithium-air battery composite positive pole, it is characterised in that: include conductive carbon material, micro-nano Frame structure, lead lighium polymer and oxidoreduction mediator.
All solid state lithium-air battery composite positive pole the most according to claim 1, it is characterised in that: described Oxidoreduction mediator mass percentage content in described composite positive pole be 5%～25%.
All solid state lithium-air battery composite positive pole the most according to claim 2, it is characterised in that: described Oxidoreduction mediator be lithium iodide, TEMPO, LiNO3In at least one.
4., according to all solid state lithium-air battery composite positive pole described in any one of claims 1 to 3, its feature exists In: it is made up of following mass percent component:
Conductive carbon material 5%～25%；
Micro-nano frame structure 5%～25%；
Lead lighium polymer 25%～85%；
Oxidoreduction mediator 5%～25%.
All solid state lithium-air battery composite positive pole the most according to claim 4, it is characterised in that: described Conductive carbon material be at least one in conductive carbon, activated carbon, Graphene, CNT, carbon nano-fiber.
All solid state lithium-air battery composite positive pole the most according to claim 4, it is characterised in that: described Lighium polymer of leading be poly(ethylene oxide), polymethyl methacrylate, polyacrylonitrile, polyacrylic acid, polycyclic oxygen Propane, Kynoar, polyvinylidene fluoride vinyl copolymer, polyvinyl alcohol, politef, carboxymethyl cellulose At least one in element sodium, polyethylene, polyethylene kind copolymer, Viton, polyurethane, polysiloxanes.
Composite air positive pole the most according to claim 4 and all solid state lithium-air battery thereof and preparation method, its Be characterised by: described micro-nano frame structure be MOF-5, MIL-53 (Al), MIL-53 (Cr), Zn-MOF-74, HKUST-1、ZIF-1、ZIF-2、ZIF-3、ZIF-4、ZIF-5、ZIF-6、ZIF-7、ZIF-8、ZIF-9、 ZIF-10、ZIF-22、ZIF-69、ZIF-90、NAFS-1、MIL-47、CAU-1、MIL-101(Cr)、 CPO-27-Mg、CPO-27-Mn、CPO-27-Co、CPO-27-Ni、CPO-27-Zn、Mn(HCOO)2、 Co(HCOO)2、Ni(HCOO)2, at least one in G-MIL-53 (Al).
8. an all solid state lithium-air battery, including positive plate, solid electrolyte film and negative plate, it is characterised in that: Described positive plate is made up of the composite positive pole described in any one of claims 1 to 3.
All solid state lithium-air battery the most according to claim 8, it is characterised in that: described positive plate thickness It is 0.1～50 μm.
All solid state lithium-air battery the most according to claim 8, it is characterised in that:
Described solid electrolyte film thickness is 10～200 μm；
Described solid electrolyte film is made up of following mass percent component: lead lighium polymer 20%～70%, inorganic Filler 5%～50%, lithium salts 10%～60%；
Described lithium of leading is polymerized to poly(ethylene oxide), polymethyl methacrylate, polyacrylonitrile, polyacrylic acid, polycyclic Ethylene Oxide, Kynoar, polyvinylidene fluoride vinyl copolymer, polyvinyl alcohol, politef, carboxymethyl are fine At least one in dimension element sodium, polyethylene, polyethylene kind copolymer, Viton, polyurethane, polysiloxanes；
Described inorganic filler is aluminium oxide, silicon oxide, zirconium oxide, titanium oxide, Barium metatitanate., metal-organic framework In at least one；
Described lithium salts is LiN (SO2CF3)2、LiCF3SO3、LiC(SO2CF3)3、LiBC2O4F2、LiC4BO8、 Double oxalic acid borate lithiums, LiOCH (CH3)2In at least one.
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CN108321395A (en) * 2018-01-22 2018-07-24 厦门大学 A kind of all-solid-state battery additive for electrode and its application
CN109509872A (en) * 2017-09-14 2019-03-22 中南大学 A kind of halide is as all solid lithium of electrode active material and catalyst sulphur/sodium-sulphur battery
CN111653798A (en) * 2020-06-22 2020-09-11 武汉瑞科美新能源有限责任公司 Metal-air battery cathode, preparation method and application thereof, and battery
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CN115064702A (en) * 2022-07-22 2022-09-16 哈尔滨工业大学 Sodium-philic 3D carbon current collector, preparation method and application thereof, and preparation method of non-negative solid sodium battery
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CN109509872A (en) * 2017-09-14 2019-03-22 中南大学 A kind of halide is as all solid lithium of electrode active material and catalyst sulphur/sodium-sulphur battery
CN109509872B (en) * 2017-09-14 2021-01-01 中南大学 All-solid-state lithium sulfur/sodium sulfur battery with halide serving as electrode active substance and catalyst
CN108321395A (en) * 2018-01-22 2018-07-24 厦门大学 A kind of all-solid-state battery additive for electrode and its application
CN112534528A (en) * 2018-05-17 2021-03-19 华盛顿州立大学 Positive electrode material of lithium-oxygen battery
CN111653798A (en) * 2020-06-22 2020-09-11 武汉瑞科美新能源有限责任公司 Metal-air battery cathode, preparation method and application thereof, and battery
CN112186203A (en) * 2020-09-25 2021-01-05 江苏大学 Preparation method of all-solid-state lithium-air battery anode
CN114552074A (en) * 2022-03-04 2022-05-27 哈尔滨工业大学 Polymer-based solid rechargeable metal-air battery capable of running at room temperature
CN115189076A (en) * 2022-05-16 2022-10-14 吉林大学 Wide-temperature-range solid-state metal-air battery and preparation method thereof
CN115064702A (en) * 2022-07-22 2022-09-16 哈尔滨工业大学 Sodium-philic 3D carbon current collector, preparation method and application thereof, and preparation method of non-negative solid sodium battery
WO2024087013A1 (en) * 2022-10-25 2024-05-02 宁德时代新能源科技股份有限公司 Electrode assembly, battery cell, battery and electric device

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