CN108899579A - A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute - Google Patents

A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute Download PDF

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CN108899579A
CN108899579A CN201810615609.8A CN201810615609A CN108899579A CN 108899579 A CN108899579 A CN 108899579A CN 201810615609 A CN201810615609 A CN 201810615609A CN 108899579 A CN108899579 A CN 108899579A
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lithium
self
acid
solid electrolyte
mass fraction
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CN108899579B (en
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尉海军
林志远
郭现伟
申旭阳
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Beijing University of Technology
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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic 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
    • H01M10/05—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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
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    • 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
    • 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
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Abstract

A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute, is related to the field of lithium ion battery electrolyte.It specially uses end silane-terminated polyether (MS) for performed polymer, is uniformly mixed with having acid, the inorganic nanoparticles of alkalinity or organic polymer material, electric conducting lithium salt and organic solvent；Composite solid electrolyte is prepared with having acid, the inorganic nanoparticles of alkalinity or organic polymer material generation self-crosslinking solidification by MS.MS and the crystallinity that there is acid, the inorganic nanoparticles of alkalinity or organic polymer material self-crosslinking composite curing can reduce composite solid electrolyte; ionic conductivity, transference number of ions, mechanical property, electrochemical stability window and the battery rate charge-discharge performance of composite solid electrolyte are improved, solving the problems, such as solid lithium ion battery, there are interfacial contacts.Ionic conductivity is up to 10‑4Scm‑1, electrochemical window is greater than 5V, and contractibility is small, electrochemical stability is strong.

Description

A kind of all solid state lithium ion of self-crosslinking composite solid electrolyte prepared and its constitute Battery
Technical field
The present invention relates to the field of lithium ion battery electrolyte, especially a kind of self-crosslinking composite solid electrolyte and its The all-solid lithium-ion battery of composition.
Background technique
Lithium ion polymer electrolyte can effectively prevent the generation of metal Li dendrite, make to have that energy is high, specific power is big Lithium metal is possibly realized as cathode, and the electrochemistry capacitance of lithium ion battery is greatly improved.Lithium ion polymer electrolyte can appoint Meaning shape, may also be fabricated which multiple field superthin structure and miniaturization, is easier to and battery assembles.
1973, Wright etc., which reports polyethylene glycol oxide (PEO) and the mixture of electrolytic salt, had ionic conduction Property.Lithium ion polymer battery is mainly reflected in high-energy density and good times of forthright, easy processing, can quantify to produce.But with PEO polymer dielectric class is that low (PEO room-temperature conductivity is about 10 for the solid electrolyte ionic conductivity of representative-7S cm-1)、 With lithium ion positive and negative anodes active material there is biggish interface problem, lithium ion battery is caused to can not work normally.Therefore permitted More scholars destroy the crystallinity of PEO, mention to by adding a certain amount of inorganic particulate or plasticizer in PEO polymeric matrix (room temperature is up to 10 for high ionic conductivity-5~10-4S cm-1)。
Patent No. CN 102394313A provides a kind of organic/inorganic composite polymer electrolyte.By by two bromos As matrix, fluoric acid lithium class lithium salts, inorganic nanoparticles and organic solvent prepare compound for toluene glycidol ether and ethylene oxide Polymer dielectric, but the composite electrolyte poor mechanical property, preparation method are complicated, cannot industrialize.The patent No. CN106785032A uses end silane-terminated polyether oligomer for performed polymer, is the preparation of catalyst crosslinking curing by tin class salt Polymer dielectric.The polymer dielectric has good ionic conductivity, high-low temperature resistant stability and flexibility.But it should Electrolyte mechanical property deviation, needing to add tin class salt is catalyst, influences electrolyte electrochemical performance, and preparation process It is complicated.
In view of the above problems, we have developed a kind of novel self-crosslinking lithium ion batteries is electrolysed with composite solid Matter and preparation method thereof.By using have acid, alkalinity inorganic nanoparticles or organic polymer material, electric conducting lithium salt and Organic solvent and end silane-terminated polyether prepare composite solid electrolyte by self-crosslinking.MS receives with having acid, the inorganic of alkalinity Rice grain or organic polymer material self-crosslinking composite curing in addition to can be improved composite solid electrolyte ionic conductivity, from Sub- transport number, electrochemical stability window and mechanical property can also optimize preparation process, reduce cost.By changing MS and tool There are acid, the inorganic nanoparticles of alkalinity or organic polymer material ratio to adjust the curing time of composite solid electrolyte, changes Become the mechanical property and chemical property (ionic conductivity, transference number of ions, electrochemical window etc.) of solid electrolyte, is applicable in Range is wide, and experimental technique is simplified.
Summary of the invention
The object of the present invention is to provide a kind of self-crosslinking composite solid electrolyte and its all solid state lithium ion of composition electricity Pond.
The technical scheme is that：
Use end silane-terminated polyether MS for performed polymer, with the inorganic nanoparticles or organic polymer with acid or alkalinity Object material, electric conducting lithium salt and organic solvent are uniformly mixed；By MS with have acid or alkalinity inorganic nanoparticles or have Organic polymeric material occurs self-crosslinking solidification and prepares composite solid electrolyte；Wherein the end silane-terminated polyether accounts for mixing The mass fraction of object is 10-80%, and there are the inorganic nanoparticles of acid or alkalinity or organic polymer material to account for the matter of mixture Amount score is 5-60%, and the mass fraction that electric conducting lithium salt accounts for mixture is 5-60%, and organic solvent accounts for the mass fraction of mixture For 10-80%.
It is preferred that the end silane-terminated polyether viscosity is in 5000-20000 centipoise.Molecular formula is general formula 1.
Wherein, a value is 0-500, and b value is 0-500, and a and b are not 0 simultaneously.
R2For-H ,-CH3,-OCH3,-OCH2CH3In it is one or more.
The organic polymer is one or more of following：Polyethylene glycol oxide (PEO), succinonitrile (SN), poly- third Alkene nitrile (PAN), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), thermoplastic polyurethane (TPU), polyethylene glycol (PEG), polyvinyl acetate (PVAC), Kynoar-hexafluoropropylene copolymer (PVDF-HFP), polyvinyl formal (PVFM), polybutylcyanoacrylate (PCA), poly- ethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbon Acid esters (PTMC), polyetherimide (PEI), polyimides (PI), by acid or oxygenation pretreatment with acid or alkalinity.
The inorganic electrolyte particle is one or more of following：Li7La3ZrO12、Li10GeP2S12、 Li3OCl0.5Br0.5、Li3xLa(2/3)-xTiO3(0.04<x0.14)、Li5La3M2O3(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX(X=Cl, Br, I), Li14Zn(GeO4)4、LiZr2(PO4)3：Montmorillonite, nanometer two Silica, nano zirconium dioxide, nanometer calcium carbonate, nano zine oxide, nano-titanium dioxide, nanometer silicon carbide, without acid, alkali Property by acid or oxygenation pretreatment with acid, alkalinity.
The electric conducting lithium salt is one or more of following：Lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), double trifluoromethanesulfonimide lithiums (LiTFSI), double fluorine sulfimide lithiums (LiFSI).
The organic solvent is one or more of following：Ethylene carbonate, propene carbonate, tetrahydrofuran, 2- Methyltetrahydrofuran, acetonitrile, gamma-butyrolacton, tetraethyleneglycol dimethyl ether, triethylene glycol dimethyl ether, -2 pyrrolidones of 1- methyl, N,N-dimethylformamide.
A kind of self-crosslinking composite solid electrolyte, includes the following steps：After end silane-terminated polyether, processing Inorganic nanoparticles or organic polymer material, organic solvent with acid or alkalinity are stirred；Electric conducting lithium salt stirring is added Uniformly；The mixed solution stirred evenly is coated in Teflon mould, is heating and curing at 30-80 DEG C 2-12 hours Film forming.
The composite solid electrolyte with a thickness of 20-200 μm.
A kind of compound all-solid lithium-ion battery of self-crosslinking, including positive electrode, negative electrode material and the present invention above-mentioned have both The self-crosslinking composite solid electrolyte of diaphragm and electrolyte function；
The preparation of all-solid lithium-ion battery positive electrode includes the following steps：The anode that mass fraction is 50-90% will be accounted for Active material accounts for the conductive agent acetylene black ground and mixed that mass fraction is 5-30%；Being added and accounting for mass fraction is the poly- of 1-15% (electrolyte mixed liquor group is divided into end silane-terminated polyether and accounts for mixture for vinylidene (PVDF), 1-15% electrolyte mixed liquor Mass fraction is 10-80%, and there are the inorganic nanoparticles of acid or alkalinity or organic polymer material to account for the quality point of mixture Number is 5-60%, and the mass fraction that electric conducting lithium salt accounts for mixture is 5-60%, and the mass fraction that organic solvent accounts for mixture is 10-80%, identical as above-mentioned self-crosslinking composite solid electrolyte raw material), it is ground using -2 pyrrolidones of 1- methyl (NMP) Mill mixing；Coated in aluminium foil surface, drying；Lithium metal, lithium metal alloy can directly as corresponding negative electrode active material, The preparation of other negative electrode active materials includes the following steps：The negative electrode active material that mass fraction is 30-80% will be accounted for, accounts for quality Score is the conductive agent acetylene black ground and mixed of 5-30%；Addition account for mass fraction be 5-25% Kynoar (PVDF), It is 10- that 1-15% electrolyte mixed liquor electrolyte mixed liquor group, which is divided into end silane-terminated polyether to account for the mass fraction of mixture, 80%, it is 5-60% that there are the inorganic nanoparticles of acid or alkalinity or organic polymer material, which to account for the mass fraction of mixture, is led The mass fraction that electric lithium salts accounts for mixture is 5-60%, and the mass fraction that organic solvent accounts for mixture is 10-80%, and above-mentioned Self-crosslinking composite solid electrolyte raw material it is identical), using -2 pyrrolidones of 1- methyl (NMP) ground and mixed；Coated in copper Foil surface, drying.
Anode active material of lithium ion battery is cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), lithium ion lithium fluophosphate, Lithium manganese oxide, LiMn2O4, nickel ion doped, lithium-rich manganese-based, iron manganese phosphate for lithium, nickel cobalt lithium aluminate (NCA), nickle cobalt lithium manganate, phosphorus Sour iron lithium (LiFeO4), phosphoric acid vanadium lithium (Li3V2(PO4)3) in it is one or more of；Negative electrode active material is lithium metal, and lithium metal closes Gold, graphite, hard carbon, metal lithium nitride, antimony oxide, carbon germanium composite material, carbon-silicon composite material, lithium titanate, Li-Ti oxide Middle one or more.
A kind of preparation of self-crosslinking composite solid electrolyte and its all-solid lithium-ion battery constituted, Quan Gu State lithium ion battery is assembled into following form：Anode cover-spring leaf-stainless steel gasket-positive electrode active materials-polymer electrolytic Matter-negative electrode active material-negative electrode casing.
Innovation and practicality of the invention is：
1, using the siloxanes of MS acid, under alkaline condition can dehydration condensation, received with having acid, the inorganic of alkalinity Rice grain or organic polymer material pass through the cured composite solid electrolyte of self-crosslinking.
2, MS and the inorganic nanoparticles or organic polymer material self-crosslinking composite curing with acid, alkalinity, can reduce The crystallinity of composite solid electrolyte improves ionic conductivity, transference number of ions, the mechanical property, electricity of composite solid electrolyte Chemical stabilization window and battery rate charge-discharge performance, solving the problems, such as solid lithium ion battery, there are interfacial contacts.
3, composite solid electrolyte excellent in mechanical performance, ionic conductivity is good, and electrochemical stability window is wide, is suitable for High and low temperature environment, preparation process is simple, can quantify to produce.
4, it is made by MS with having acid, the inorganic nanoparticles of alkalinity or organic polymer material generation self-crosslinking solidification Standby composite solid electrolyte.MS and the inorganic nanoparticles or organic polymer material self-crosslinking composite curing with acid, alkalinity The crystallinity that composite solid electrolyte can be reduced improves ionic conductivity, the transference number of ions, mechanics of composite solid electrolyte Performance, electrochemical stability window and battery rate charge-discharge performance, solving the problems, such as solid lithium ion battery, there are interfacial contacts. The composite solid electrolyte with a thickness of 20-200 μm；Ionic conductivity is up to 10-4Scm-1(25 DEG C), electrochemical window is big In 5V, contractibility is small, electrochemical stability is strong, securely and reliably, is suitable for lithium ion solid state battery.
Detailed description of the invention
Fig. 1 is the charge-discharge performance that all-solid lithium-ion battery prepares lithium ion solid state battery in embodiment 8.
Specific embodiment
Illustrate the present invention below by way of specific embodiment, improving embodiment is for a better understanding of the present invention, never It is to limit the scope of the invention.
The preparation of composite solid electrolyte：
Embodiment 1
By the polypropylene oxide (number-average molecular weight=12000) of the end 3g silane-terminated polyether, 3g Li7La3ZrO12、 4ml Acetonitrile and 4ml tetraethyleneglycol dimethyl ether uniformly mix；3g lithium hexafluoro phosphate (LiPF is added6) be uniformly mixed；By what is stirred evenly On mixed solution blade coating to Teflon mould, heats 8 hours for 60 DEG C, be transferred in 80 DEG C of vacuum under air dry oven Drying box, which solidifies 4 hours, to form a film.
Embodiment 2
By the polypropylene oxide (number-average molecular weight=12000) of the end 1.5g silane-terminated polyether, 1g acid treated PEO, 2ml propene carbonate and 30ml tetrahydrofuran uniformly mix；0.8g lithium hexafluoro phosphate (LiPF is added6) be uniformly mixed；It will stirring Uniform mixed solution blade coating is heated 8 hours for 60 DEG C under air dry oven, is transferred to 80 on Teflon mould DEG C vacuum oven, which solidifies 4 hours, to form a film.
Embodiment 3
By the SiO after the polypropylene oxide (number-average molecular weight=12000) of 2.2g end capped polyether, 2.8g basic treatment2With 4ml triethylene glycol dimethyl ether uniformly mixes；The bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1.4g are added to be uniformly mixed；It will stir Uniform mixed solution blade coating is mixed on Teflon mould, heats 8 hours for 60 DEG C, is transferred under air dry oven 80 DEG C of vacuum ovens, which solidify 4 hours, to form a film.
Embodiment 4
By the polypropylene oxide (number-average molecular weight=30000) of 1.8g end capped polyether, 2.5g Li5La3Nb2O3, 0.5g acid Treated PEO, 3m propene carbonate and 20ml acetonitrile uniformly mix；The bis- trifluoromethanesulfonimide lithiums of 1.8g are added (LiTFSI) it is uniformly mixed；By the mixed solution stirred evenly blade coating on Teflon mould, 60 under air dry oven It DEG C heating 8 hours, is transferred to solidify 4 hours in 80 DEG C of vacuum ovens and forms a film.
Embodiment 5
By the polypropylene oxide (number-average molecular weight=30000) of 4.5g end capped polyether, 3g Li5La3Nb2O3, 1g acid processing PAN, 4m propene carbonate and 40ml acetonitrile afterwards uniformly mixes；5g lithium perchlorate (LiClO is added4) be uniformly mixed；It will stirring Uniform mixed solution blade coating is heated 8 hours for 60 DEG C under air dry oven, is transferred to 80 on Teflon mould DEG C vacuum oven, which solidifies 4 hours, to form a film.
Embodiment 6
Illiteracy after the polypropylene oxide (number-average molecular weight=30000) of 3.2g end capped polyether, 2.4g basic treatment is de- Soil, 5m propene carbonate；2.1g lithium perchlorate (LiClO is added4) be uniformly mixed；The mixed solution stirred evenly blade coating is existed On Teflon mould, is heated 8 hours for 60 DEG C under air dry oven, be transferred to and solidify 4 hours in 80 DEG C of vacuum ovens Film forming.
Embodiment 7
By the polypropylene oxide (number-average molecular weight=30000) of 2.4g end capped polyether, g Li10GeP2S12, 0.4g acid processing PMMA, 3m propene carbonate and 20ml acetonitrile afterwards uniformly mixes；The bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 2.2g are added It is uniformly mixed；By the mixed solution stirred evenly blade coating on Teflon mould, 60 DEG C of heating 8 under air dry oven Hour, it is transferred to and solidifies 4 hours film forming in 80 DEG C of vacuum ovens.
Electrolyte performance characterization：
Electrolyte thickness：Using the thickness of micrometer (0.01 millimeter of precision) measurement block polymer electrolyte, arbitrarily go The measurement of 3 points, averages on film, the thickness of embodiment 1-7 is respectively 112 μm, 103 μm, 106 μm, 121 μm, 107 μm, 114μm、107μm。
Ionic conductivity：Polymer dielectric is clamped using two stainless steel gaskets, assembles 2032 button cell measurement Impedance, according to formulaWherein, L is the thickness of polymer dielectric, and S is stainless steel gasket area, and R is that measurement obtains Impedance value.
Electrochemical window：Polymer dielectric is clamped using stainless steel and lithium piece, 2032 button cell is assembled, is carried out Linear voltammetric scan measurement, originates power grid 2.8V, maximum potential 5.5V, scanning speed 1mV/s.
The preparation of all-solid lithium-ion battery：
Embodiment 8
The conductive agent acetylene black of the nickel cobalt lithium aluminate of 180mg and 30mg is uniformly ground into 40min；15mg binder is added Kynoar, 3mg electrolyte mixed liquor and -2 pyrrolidones of 150 μ L 1- methyl uniformly grind 40min；Coated in aluminium foil table Face, under vacuum conditions 80 DEG C of drying 8h；Pole piece is cut into the disk of R=0.6mm, is prepared using above-mentioned solid electrolyte real Apply the solid electrolyte assembling lithium ion polymer half-cell in example 1.
Embodiment 9
The conductive agent acetylene black of the LiFePO4 of 100mg and 12mg are uniformly ground into 40min；It is poly- that 10mg binder is added Vinylidene, 2mg electrolyte mixed liquor and -2 pyrrolidones of 150 μ L 1- methyl uniformly grind 40min；Coated in aluminium foil table Face, under vacuum conditions 80 DEG C of drying 8h；Pole piece is cut into the disk of R=0.6mm, is prepared using above-mentioned solid electrolyte real Apply the solid electrolyte assembling lithium ion polymer half-cell in example 4.
Embodiment 10
The conductive agent acetylene black of the nickel cobalt lithium aluminate of 85mg and 15mg is uniformly ground into 40min；It is poly- that 10mg binder is added Vinylidene, 2.5mg electrolyte mixed liquor and -2 pyrrolidones of 150 μ L 1- methyl uniformly grind 40min；Coated in aluminium foil table Face, under vacuum conditions 80 DEG C of drying 8h；Pole piece is cut into the disk of R=0.6mm, is prepared using above-mentioned solid electrolyte real Apply the solid electrolyte assembling lithium ion polymer half-cell in example 7.

Claims (10)

1. a kind of preparation method of self-crosslinking composite solid electrolyte, which is characterized in that it is pre- for using end silane-terminated polyether MS Aggressiveness is stirred with the inorganic nanoparticles or organic polymer material, electric conducting lithium salt and organic solvent with acid or alkalinity Uniformly；By MS with have acid or alkalinity inorganic nanoparticles or organic polymer material occur self-crosslinking solidification prepare it is compound Solid electrolyte.
2. a kind of preparation method of self-crosslinking composite solid electrolyte described in accordance with the claim 1, which is characterized in that described The mass fraction that end silane-terminated polyether accounts for mixture is 10-80%, has the inorganic nanoparticles or organic poly- of acid or alkalinity Closing object material and accounting for the mass fraction of mixture is 5-60%, and the mass fraction that electric conducting lithium salt accounts for mixture is 5-60%, You Jirong The mass fraction that agent accounts for mixture is 10-80%；The composite solid electrolyte with a thickness of 20-200 μm.
3. a kind of preparation method of self-crosslinking composite solid electrolyte described in accordance with the claim 1, which is characterized in that described Hold silane-terminated polyether viscosity in 5000-20000 centipoise；Molecular formula is general formula 1.
Wherein, a value is 0-500, and b value is 0-500, and a and b are not 0 simultaneously；
R2For-H ,-CH3,-OCH3,-OCH2CH3In it is one or more.
4. a kind of preparation method of self-crosslinking composite solid electrolyte described in accordance with the claim 1, which is characterized in that described Organic polymer is one or more of following：Polyethylene glycol oxide (PEO), succinonitrile (SN), polyacrylonitrile (PAN), poly- second Enol (PVA), polymethyl methacrylate (PMMA), thermoplastic polyurethane (TPU), polyethylene glycol (PEG), polyvinyl acetate (PVAC), Kynoar-hexafluoropropylene copolymer (PVDF-HFP), polyvinyl formal (PVFM), poly- alpha-cyanoacrylate Ester (PCA), poly- ethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polyetherimide (PEI), polyimides (PI), by acid or oxygenation pretreatment with acid or alkalinity；
The inorganic electrolyte particle is one or more of following：Li7La3ZrO12、Li10GeP2S12、 Li3OCl0.5Br0.5、Li3xLa(2/3)-xTiO3(0.04<x0.14)、Li5La3M2O3(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX(X=Cl, Br, I), Li14Zn(GeO4)4、LiZr2(PO4)3：Montmorillonite, nanometer two Silica, nano zirconium dioxide, nanometer calcium carbonate, nano zine oxide, nano-titanium dioxide, nanometer silicon carbide pass through acid or alkali Pretreatment is with acid, alkalinity.
5. a kind of preparation method of self-crosslinking composite solid electrolyte described in accordance with the claim 1, which is characterized in that described Electric conducting lithium salt is one or more of following：Lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), double fluoroform sulphonyl Imine lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI).
6. a kind of preparation method of self-crosslinking composite solid electrolyte described in accordance with the claim 1, which is characterized in that described Organic solvent is one or more of following：Ethylene carbonate, propene carbonate, tetrahydrofuran, 2- methyltetrahydrofuran, second Nitrile, gamma-butyrolacton, tetraethyleneglycol dimethyl ether, triethylene glycol dimethyl ether, -2 pyrrolidones of 1- methyl, N,N-dimethylformamide.
7. according to method described in any one of claims 1-6, which is characterized in that specifically include following steps：End silane is sealed After end polyethers, processing there are the inorganic nanoparticles of acid or alkalinity or organic polymer material, organic solvent to be stirred；It is added Electric conducting lithium salt stirs evenly；The mixed solution stirred evenly is coated in Teflon mould, is heated at 30-80 DEG C solid Change 2-12 hours and forms a film.
8. a kind of compound all-solid lithium-ion battery of self-crosslinking, which is characterized in that including positive electrode, negative electrode material and according to power Benefit requires the self-crosslinking composite solid electrolyte for having both diaphragm and electrolyte function of the described in any item method preparations of 1-6.
9. the compound all-solid lithium-ion battery of a kind of self-crosslinking according to claim 8, which is characterized in that anode material Material preparation includes the following steps：The positive electrode active materials that mass fraction is 50-90% will be accounted for, accounting for mass fraction is leading for 5-30% Electric agent acetylene black ground and mixed；Being added and accounting for mass fraction is the Kynoar (PVDF) of 1-15%, the mixing of 1-15% electrolyte Liquid, using -2 pyrrolidones of 1- methyl (NMP) ground and mixed；Coated in aluminium foil surface, drying；Lithium metal, lithium metal alloy can With directly as corresponding negative electrode active material, the preparation of other negative electrode active materials includes the following steps：Mass fraction, which will be accounted for, is The negative electrode active material of 30-80% accounts for the conductive agent acetylene black ground and mixed that mass fraction is 5-30%；Addition accounts for mass fraction For 5-25% Kynoar (PVDF), 1-15% electrolyte mixed liquor, ground using -2 pyrrolidones of 1- methyl (NMP) mixed It closes；Coated in copper foil surface, drying；Electrolyte mixed liquor group is divided into the mass fraction for holding silane-terminated polyether to account for mixture 10-80%, it is 5-60% that there are the inorganic nanoparticles of acid or alkalinity or organic polymer material, which to account for the mass fraction of mixture, The mass fraction that electric conducting lithium salt accounts for mixture is 5-60%, and the mass fraction that organic solvent accounts for mixture is 10-80%.
Anode active material of lithium ion battery is cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), lithium ion lithium fluophosphate, lithium manganese Oxide, LiMn2O4, nickel ion doped, lithium-rich manganese-based, iron manganese phosphate for lithium, nickel cobalt lithium aluminate (NCA), nickle cobalt lithium manganate, ferric phosphate Lithium (LiFeO4), phosphoric acid vanadium lithium (Li3V2(PO4)3) in it is one or more of；Negative electrode active material is lithium metal, lithium metal alloy, stone It is ink, hard carbon, metal lithium nitride, antimony oxide, carbon germanium composite material, carbon-silicon composite material, lithium titanate, a kind of in Li-Ti oxide Or it is several.
10. according to the compound all-solid lithium-ion battery of self-crosslinking described in claim 8 or 9, which is characterized in that be assembled into following Form：Anode cover-spring leaf-stainless steel gasket-positive electrode active materials-polymer dielectric-negative electrode active material-negative electrode casing.
CN201810615609.8A 2018-06-14 2018-06-14 Preparation of self-crosslinking composite solid electrolyte and all-solid-state lithium ion battery formed by same Active CN108899579B (en)

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CN110224173A (en) * 2019-05-22 2019-09-10 浙江天能能源科技股份有限公司 A kind of lithium battery solid polymer electrolyte capable of self-healing and preparation method thereof
CN110400964A (en) * 2019-07-31 2019-11-01 苏州顺创新能源科技有限公司 A kind of lithium ion battery solid electrolyte membrane
CN111370760A (en) * 2020-03-19 2020-07-03 香港科技大学 Wide electrochemical window composite solid electrolyte and preparation method thereof
CN112397718A (en) * 2020-11-06 2021-02-23 开封大学 Self-healing silicon-based negative electrode material of lithium ion battery and preparation method thereof
CN112490495A (en) * 2020-11-23 2021-03-12 中国电子科技集团公司第十八研究所 Inorganic-organic composite solid electrolyte, preparation method and solid lithium battery
CN113140788A (en) * 2021-04-22 2021-07-20 昆山宝创新能源科技有限公司 Quasi-solid electrolyte and quasi-solid lithium ion battery
CN113394447A (en) * 2021-05-26 2021-09-14 浙江南都电源动力股份有限公司 Electrolyte for preventing micro short circuit of solid-state battery, solid-state battery and preparation method
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CN113604159A (en) * 2021-09-14 2021-11-05 芜湖徽氏新材料科技有限公司 Degradable swelling adhesive tape for lithium ion battery and preparation method thereof
CN113871709A (en) * 2021-09-26 2021-12-31 珠海冠宇电池股份有限公司 Positive pole piece and solid-state battery comprising same
CN113937343A (en) * 2021-09-30 2022-01-14 蜂巢能源科技有限公司 Modified all-solid-state lithium ion battery and preparation method thereof
CN114464880A (en) * 2022-01-11 2022-05-10 电子科技大学 Self-repairing composite solid lithium ion battery electrolyte and preparation method thereof
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CN109786822A (en) * 2018-12-28 2019-05-21 南方科技大学 Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof
CN110224173A (en) * 2019-05-22 2019-09-10 浙江天能能源科技股份有限公司 A kind of lithium battery solid polymer electrolyte capable of self-healing and preparation method thereof
CN110400964A (en) * 2019-07-31 2019-11-01 苏州顺创新能源科技有限公司 A kind of lithium ion battery solid electrolyte membrane
CN111370760A (en) * 2020-03-19 2020-07-03 香港科技大学 Wide electrochemical window composite solid electrolyte and preparation method thereof
CN111370760B (en) * 2020-03-19 2023-06-23 香港科技大学 Composite solid electrolyte with wide electrochemical window and preparation method thereof
EP3993130A4 (en) * 2020-04-14 2022-12-14 LG Energy Solution, Ltd. Lithium-sulfur battery electrolyte and lithium-sulfur battery comprising same
CN112397718B (en) * 2020-11-06 2022-08-09 开封大学 Self-healing silicon-based negative electrode material of lithium ion battery and preparation method thereof
CN112397718A (en) * 2020-11-06 2021-02-23 开封大学 Self-healing silicon-based negative electrode material of lithium ion battery and preparation method thereof
CN112490495A (en) * 2020-11-23 2021-03-12 中国电子科技集团公司第十八研究所 Inorganic-organic composite solid electrolyte, preparation method and solid lithium battery
CN113140788A (en) * 2021-04-22 2021-07-20 昆山宝创新能源科技有限公司 Quasi-solid electrolyte and quasi-solid lithium ion battery
CN113394447B (en) * 2021-05-26 2022-09-23 浙江南都电源动力股份有限公司 Electrolyte for preventing micro short circuit of solid-state battery, solid-state battery and preparation method
CN113394447A (en) * 2021-05-26 2021-09-14 浙江南都电源动力股份有限公司 Electrolyte for preventing micro short circuit of solid-state battery, solid-state battery and preparation method
CN113410516A (en) * 2021-08-02 2021-09-17 清远萨菲安新材料有限公司 Organic silicon electrolyte and preparation method and application thereof
CN113604159B (en) * 2021-09-14 2022-05-17 芜湖徽氏新材料科技有限公司 Degradable swelling adhesive tape for lithium ion battery and preparation method thereof
CN113604159A (en) * 2021-09-14 2021-11-05 芜湖徽氏新材料科技有限公司 Degradable swelling adhesive tape for lithium ion battery and preparation method thereof
CN113871709A (en) * 2021-09-26 2021-12-31 珠海冠宇电池股份有限公司 Positive pole piece and solid-state battery comprising same
CN113937343A (en) * 2021-09-30 2022-01-14 蜂巢能源科技有限公司 Modified all-solid-state lithium ion battery and preparation method thereof
CN113937343B (en) * 2021-09-30 2023-01-24 蜂巢能源科技有限公司 Modified all-solid-state lithium ion battery and preparation method thereof
CN114464880A (en) * 2022-01-11 2022-05-10 电子科技大学 Self-repairing composite solid lithium ion battery electrolyte and preparation method thereof
CN116082776A (en) * 2023-01-13 2023-05-09 中国科学院宁波材料技术与工程研究所 Polymer solid electrolyte adhesive film for electrochromic device, and preparation method and application thereof

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