CN109065944A - Preparation method of solid electrolyte membrane - Google Patents
Preparation method of solid electrolyte membrane Download PDFInfo
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- CN109065944A CN109065944A CN201810886418.5A CN201810886418A CN109065944A CN 109065944 A CN109065944 A CN 109065944A CN 201810886418 A CN201810886418 A CN 201810886418A CN 109065944 A CN109065944 A CN 109065944A
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- Prior art keywords
- solid electrolyte
- reaction
- reaction chamber
- electrolyte membrane
- reactant
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 81
- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 165
- 239000000376 reactant Substances 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011261 inert gas Substances 0.000 claims abstract description 26
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 11
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000002203 sulfidic glass Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 8
- 238000000038 ultrahigh vacuum chemical vapour deposition Methods 0.000 claims description 8
- 229910001080 W alloy Inorganic materials 0.000 claims description 7
- 229910012305 LiPON Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 238000007086 side reaction Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910020343 SiS2 Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000005518 polymer electrolyte Substances 0.000 claims description 3
- 239000003870 refractory metal Substances 0.000 claims description 3
- 229910021332 silicide Inorganic materials 0.000 claims description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims 2
- 239000000956 alloy Substances 0.000 claims 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 229910052786 argon Inorganic materials 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 229910001069 Ti alloy Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- -1 rare earth metal Nitride Chemical class 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910011671 Li4-xGe1-xPxS4 Inorganic materials 0.000 description 1
- 229910011572 Li4−xGe1−xPxS4 Inorganic materials 0.000 description 1
- 229910012312 LiPOx Inorganic materials 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000001195 anabolic effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- IIBYAHWJQTYFKB-UHFFFAOYSA-N bezafibrate Chemical compound C1=CC(OC(C)(C)C(O)=O)=CC=C1CCNC(=O)C1=CC=C(Cl)C=C1 IIBYAHWJQTYFKB-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
- H01M2300/0082—Organic polymers
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Disclosed herein are a solid electrolyte membrane and a method of preparing the same, the method including: disposing a substrate in a reaction chamber; after the reaction chamber is purged by inert gas, setting the temperature and the pressure of the reaction chamber to reach specified values; when the temperature and the pressure of the reaction chamber reach specified values, introducing pretreated reactants into the reaction chamber, wherein the reactants at least comprise two reactants including a reactant A and a reactant B; and setting reaction conditions after the reactants are introduced into the reaction chamber, and generating a solid electrolyte membrane on the substrate through chemical vapor deposition reaction. The required and different solid electrolyte membranes can be obtained, the process is simple, and the cost is low.
Description
Technical field
This application involves but be not limited to electrochemistry and new energy materials field, and in particular to the preparation side of solid electrolyte membrane
Method.The application is related to a kind of solid electrolyte membrane simultaneously.
Background technique
Practical application of the battery in we live plays increasingly important role, including consumer electronics, electronic vapour
Vehicle, large, medium and small energy-storage system etc., power supply are all various types battery, wherein the lithium-ion electric to quickly grow again
Based on pond.However, commercialized lithium ion battery has not been able to satisfy the demand under product fast development gradually at present, such as require
Higher energy density, longer cycle life, and it is safer more cheap.Between more than 30 years of past, most lithium-ion electrics
The correlative study concern in pond is all liquid electrolyte systems, that is, makes it have high conductivity and outstanding electrode surface wetting
Property, but its chemical property and thermal stability are bad, and ion selectivity is low, and safety is poor.And liquid is substituted with solid electrolyte
Electrolyte not only overcomes the lasting problem of liquid electrolyte, also provides possibility to develop new battery system, is based on this
The research of a little advantages, solid-state electricity battery or all-solid-state battery uses and has already appeared the trend increased rapidly.
Solid state battery or all-solid-state battery are known as lithium by domestic and international most of scientific research institution, battery manufacturers etc.
The next-generation anchor man of ion battery, is all one after another laid out this.But solid state battery generally acknowledges that link the most difficult is solid-state
The preparation of electrolyte layer, electrolyte layer requirement is the excellence conductor of ion but electronic body, while having excellent solid-solid
Interfacial conductivities, this proposes very high requirement to the preparation of electrolyte layer.Currently, mostly using traditional mechanical coating, magnetic
The problems such as the methods of control sputtering, that there are intensity is inadequate for the solid-state electrolyte layer being prepared, conductibility is poor, conductive, partially thick.
Summary of the invention
The application provides a kind of preparation method of solid electrolyte membrane, to solve the intensity of existing solid-state electrolyte layer not
It reaches, conductibility is poor, partially thick problem.A kind of method that the application is additionally provided with flexible, wearable solid electrolyte membrane.
A kind of preparation method of solid electrolyte membrane of the application comprising:
Substrate is set in reaction chamber；
After the reaction chamber inert gas purge, the reaction chamber temperature and pressure is set and reaches specified numerical value；
Reach specified numerical value to the reaction chamber temperature and pressure, pretreated reactant is passed through the reaction chamber
In room, wherein the reactant includes at least two kinds, including reactant A and reactant B；
After the reactant is passed through the reaction chamber, reaction condition is set, by chemical vapour deposition reaction in institute
It states and generates solid electrolyte membrane on substrate.
Optionally, the chemical vapour deposition reaction is aumospheric pressure cvd or ultra-high vacuum CVD.
Optionally, the reactant A include at least one inorganic oxide perhaps sulfide solid electrolyte or including
At least one solid polyelectrolyte；
The reactant B, ingredient comprise at least one of the following active gas: N2、Cl2、O2、CO2、CO、 NO、SO2；Or
Person comprises at least one of the following non-metal simple-substance: S, P, C, Si, or including following at least one active metal simple substance: Li, Na,
K。
Optionally, described to comprise at least one of the following refractory metal to substrate: tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium；Or
Person includes the compound of following at least one rare earth metal: the boride of rare earth metal, the carbide of rare earth metal, rare earth metal
Nitride, the silicide of rare earth metal, the phosphide of rare earth metal, rare earth metal sulfide.
Optionally,
It is described that pretreated reactant is passed through in the reaction chamber specially one kind of following steps: first will reaction
The mixed gas of object B and inert gas is passed through the reaction chamber, then will pass through the reaction after pre-processing with inert gas
Object A preheating, and it is sent into the reaction chamber；Or
First the nanosizing reactant A after pretreatment is preheated with inert gas, is sent into the reaction chamber, then
The mixed gas of reactant B and inert gas is passed through the reaction chamber.
Optionally, the chemical vapour deposition reaction is specially ultra-high vacuum CVD reaction；
Solid electrolyte membrane is generated by chemical vapour deposition reaction on the substrate include: correspondingly, described
It is 350 DEG C~530 DEG C that the reaction chamber temperature, which is arranged, and pressure is not less than 10-2Pa；
Under the temperature and pressure environment of setting, the mixed gas of inert gas and the nitrogen as reactant B is passed through
The reaction chamber,
The nitrogen and inert gas will be passed through by the pretreated lithium phosphate feeding as reactant A of preheating
Reaction chamber, adjust the temperature and pressure of reaction chamber, react lithium phosphate and nitrogen and carry out, export is secondary anti-in reaction process
Answer product；Being passed through for the inert gas is kept during the reaction；
After reaction carries out setting time, reaction temperature is reduced；And the discharge of by-product and the complete substance of unreacted is carried out,
Solid electrolyte membrane is formed on titanium alloy or tungsten alloy substrate.
Optionally, the setting reaction chamber temperature is 350 DEG C~530 DEG C, and pressure is not less than 10-2In Pa, specifically
For
It is 350 DEG C, 450 DEG C or 520 DEG C that the reaction chamber temperature, which is arranged,；
It is 10 that the reaction chamber pressure, which is arranged,-5Pa、10-5Pa or 10-2Pa。
Optionally, the reactant B and the molar ratio of reactant A are 1.5:1~4:1.
Optionally, the chemical vapour deposition reaction is aumospheric pressure cvd reaction；
Solid electrolyte membrane is generated by chemical vapour deposition reaction on the substrate include: correspondingly, described
It is 200 DEG C~350 DEG C that the reaction chamber temperature, which is arranged, and pressure is not less than 30kPa；
Under the temperature and pressure environment of setting, the polymer after melting will be passed through the reaction chamber as reactant A
Room increases the reaction chamber temperature to after being higher than 300 DEG C, and control inert gas flow quickly recycles, and polymer is presented
Fine droplet boiling-like；
The lithium metal of melting is sent into the reaction chamber for being passed through polymer as reactant B, adjusts the temperature of reaction chamber
Degree and pressure are reacted the polymer and lithium metal and are carried out, exports side reaction product in reaction process；It protects during the reaction
Hold being passed through for the inert gas；
After reaction carries out setting time, reaction temperature is reduced；And the discharge of by-product and the complete substance of unreacted is carried out,
Solid electrolyte membrane is formed on titanium alloy or tungsten alloy substrate.
Optionally, the setting reaction chamber temperature is 200 DEG C~350 DEG C, and pressure is not less than 30kPa specifically:
It is 250 DEG C, 300 DEG C or 350 DEG C that the reaction chamber temperature, which is arranged,；
It is 30kPa, 50kPa or 100kPa that the reaction chamber temperature, pressure, which is arranged,.
Optionally, react formation solid electrolyte membrane include oxide solid electrolyte, sulfide solid electrolyte or
Organic composite solid dielectric film；Wherein,
Oxide solid electrolyte includes at least following a kind of: Ca-Ti ore type, NaSiCON type, LiSiCON type or LiPON
Type；
Sulfide solid electrolyte includes at least following a kind of: P2S5、SiS2、B2S3；
Organic composite solid dielectric film includes at least following one kind: polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride
Alkene, polymethyl methacrylate, polypropylene oxide, Vingon, single-ion polymer electrolyte；
Or
A kind of solid electrolyte membrane that reaction is formed is Li4-xA1-xBxS4, wherein at least one of x < 1, A Ge, Si, B
For at least one of P, A1, Zn.
In addition, the application also provides a kind of solid electrolyte membrane, aforementioned any method is used to prepare.
The one aspect of the preparation method of the solid electrolyte membrane of the application at least has the advantage that can be by changing
Condition, the method for selection, chemical deposition of reactant etc. for becoming reaction obtain required, different solid electrolyte membranes；It can be fast
Speed prepares different types of solid electrolyte membrane；The solid electrolyte membrane being prepared has frivolous soft and high toughness spy
Point, for can significantly reduce solid state battery volume and weight in solid state battery preparation；It can be used for preparing ultrathin flexible solid-state electricity
Pond.
Detailed description of the invention
Fig. 1 is the deposition reactor structural schematic diagram of the embodiment of the present application 1,2.
Fig. 2 is a kind of flow diagram of solid electrolyte membrane preparation method provided by the embodiments of the present application.
Specific embodiment
It is with reference to the accompanying drawing and specific real in order to be more clearly understood that the above objects, features, and advantages of the application
Mode is applied the application is further described in detail.It should be noted that in the absence of conflict, the implementation of the application
Feature in example and embodiment can be combined with each other.
Many details are explained in the following description in order to fully understand the application.But the application can be with
Much it is different from other way described herein to implement, those skilled in the art can be without prejudice to present specification intension
In the case of do similar popularization, therefore the application is not limited by following public specific implementation.Below by way of specific embodiment
The preparation method of ultrathin flexible solid electrolyte membrane provided by the present application is described in detail and is illustrated.
The embodiment of the present application is described in further detail below in conjunction with attached drawing.
This application provides a kind of method of solid electrolyte membrane that can be used for solid state battery or all-solid-state battery, use
Chemical vapour deposition reaction method, the chemical vapour deposition reaction method include but is not limited to aumospheric pressure cvd,
Low-pressure chemical vapor deposition, ultra-high vacuum CVD, laser chemical vapor deposition, metal-organic chemical vapor are heavy
Product, plasma enhanced chemical vapor deposition reaction.The present embodiment is using the preparation oxidation of ultra-high vacuum CVD method
It is illustrated for object solid electrolyte.
Embodiment 1: oxide solid electrolyte is prepared using ultra-high vacuum CVD method
Fig. 1 is the deposition reactor structural schematic diagram of the embodiment of the present application 1,2.Wherein, 1 is multi-stage vacuum generator, and 2 are
Flow controller, 3 be mster-control centre, and 4 be temperature, pressure acquisition mouth, and 5 are open for reactor, and 6 be exhaust outlet, and 7 is solid for row
Mouthful, 8 be film forming substrate.1,6,7 is the gas purge system of reactor；2, the gasmetry of 3,4 anabolic reaction devices and control unit
Point；5 positions of reactor opening are in reaction chamber top center position, and film forming 8 position of substrate is in reaction chamber bottom center
Position.
The present embodiment prepares oxide solid electrolyte using ultra-high vacuum CVD method and is illustrated.Fig. 2 is
A kind of flow diagram of the ultrathin flexible solid electrolyte membrane preparation method of the embodiment of the present application.
Referring to FIG. 2, S1: substrate is set in the reaction chamber；
The substrate comprises at least one of the following, such as refractory metals tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium；Or rare earth gold
Boride, carbide, nitride, silicide, phosphide, the sulfide of category.The present embodiment is illustrated by taking titanium alloy as an example.
In a wherein specific example, the substrate can be area 80cm2Titanium alloy substrate.First by the base
Piece is in NH4OH-H2O2Certain time (such as 20 minutes) are impregnated in solution or chromic acid-sulfuric acid mixture liquid to remove substrate surface
Organic impurities or other impurity.Then the substrate is taken out, is rinsed well with deionized water, and be put in the peroxide of hydrogen chloride
Change in hydrogen solution and impregnates certain time (such as 5 minutes).Then it is rinsed well after taking out with deionized water.And it is soaked in third again
In ketone, it is cleaned by ultrasonic 10 minutes, is then rinsed well with deionized water and ethyl alcohol, then with being dried with nitrogen.It cleans up dried
Titanium alloy substrate be put into from 5 position as shown in figure 1, be placed on the film forming substrate pedestal of the 8 of the reaction chamber.
S2: setting reaction chamber temperature and pressure reaches specified numerical value；
It needs to clean reaction chamber before reaction, specifically, carrying out by the way of inert gas purge clear
It washes.In the present embodiment, the inert gas is chosen as argon gas, however, the present invention is not limited thereto.After being purged with argon gas, reaction chamber is set
Room temperature and pressure reach specified numerical value.
It is 350 DEG C~530 DEG C that the reaction chamber temperature, which can control in temperature, and pressure is higher than 10-2Pa~10-4 Pa。
Specifically, the settable reaction chamber temperature is 350 DEG C, 450 DEG C or 520 DEG C；It is 10 that the reaction chamber pressure, which is arranged,- 5Pa、10-5Pa or 10-2Pa。
The present embodiment specific steps: the valve 1 of reactor is opened, is vacuumized；Valve 1 is closed, flow controller valve is opened
Door, is passed through argon gas, is rinsed 3 times with the mode that argon gas is rushed-put to reaction chamber, is evacuated down to 10-4After Pa, valve 1 is closed
With 2.It is 530 DEG C ± 5 DEG C that reaction chamber temperature, which is arranged,.
S3: pretreated reactant is passed through reaction chamber.
In the present embodiment, the reactant includes at least two kinds, including reactant A and reactant B.The reactant A packet
Include at least one inorganic oxide perhaps sulfide solid electrolyte or including at least one solid polyelectrolyte.Its
Ingredient comprises at least one of the following inorganic oxide: perovskite, NaSiCOx、 LiSiCOx、LiPOx；Or including it is following at least
A kind of inorganic sulphide: P2S5、SiS2、B2S3；Or including following at least one inorganic phosphate: lithium phosphate, potassium phosphate, phosphoric acid
Sodium.The reactant B, ingredient comprise at least one of the following active gas: N2、Cl2、O2、CO2、CO、NO、SO2；Or including
Following at least one non-metal simple-substance: S, P, C, Si, or including following at least one active metal simple substance: Li, Na, K.This
Embodiment is illustrated so that lithium phosphate and nitrogen do reactant as an example.
Specifically: reactant A is first subjected to pretreatment operation, the reactant pretreatment include but is not limited to gasification,
The methods of nanosizing, granulating.The reactant pretreatment can be implemented with being much different from other way described herein,
Those skilled in the art can do similar popularization without prejudice to present specification intension.The present embodiment is pre- with nanosizing
It is illustrated for processing.
In the present embodiment, with reactant A lithium phosphate, reactant B be nitrogen for illustrate.Using reinforced ball mill machine
Nanometer lithium phosphate particle, average grain diameter 10-100nm is made in tool comminuting method.After the preprocessed mistake of reactant, by nitrogen and argon
The mixed gas of gas (or other inert gases) is passed through reaction chamber, is then sent into the nanosizing lithium phosphate by preheating with argon gas
Reaction chamber.The molar ratio of nitrogen and lithium phosphate is 2:1~3:1 in reaction process.
Described pretreated reactant is passed through in reaction chamber can be for first by the gaseous mixture of reaction gas and argon gas
Body is passed through reaction chamber, then preheats the nanosizing reactant A after pretreatment with argon gas, is sent into reaction chamber；Or
Person is first preheated the nanosizing reactant A after pretreatment with argon gas, reaction chamber is sent into, then by reaction gas and argon
The mixed gas of gas is passed through reaction chamber.
S4: setting reaction condition generates solid electrolyte membrane by chemical vapour deposition reaction on substrate.
Reaction condition refers to the condition that temperature, pressure, humidity etc. influence or control reaction carries out, but unlimited parameter item above-mentioned
Part.
Chemical vapour deposition reaction is that the preparation process of chemical vapor deposition is to be exposed to substrate one or more easily to wave
In the presoma of hair, chemical reaction and/or chemical breakdown occurs in substrate surface to generate the film to be deposited.Therewith, also will
Some gaseous by-products are generated, these by-products can be taken away by the air-flow of reaction chamber.The present embodiment is with ultrahigh vacuum
It learns for vapour deposition process prepares oxide solid electrolyte and is illustrated.
Specifically: after reactant is passed through reaction chamber, keeping the temperature of reaction chamber is 530 DEG C ± 5 DEG C, and pressure is
10-4Pa reacts lithium phosphate and nitrogen and carries out, side reaction product phosphorous oxides, oxidate for lithium etc. are exported in reaction process；Anti-
Being passed through for argon gas (or other inert gases) should be kept in the process.After reaction proceeds to setting time, reaction temperature is reduced；And
The discharge for carrying out by-product and the complete substance of unreacted, obtains solid electrolyte membrane in substrate.Keep the temperature of reaction chamber
It is 530 DEG C ± 5 DEG C, pressure 10-4Pa reaches the specified reaction time (such as 1.5 to 2.5 hours), keeps the logical of argon gas
It crosses, reaction chamber room temperature is reduced to 100 DEG C with the cooling rate of 20 DEG C/min, valve 6 and valve 7 (Fig. 1) is opened, goes forward side by side
The discharge of row by-product and the complete substance of unreacted.It is lower than 30 DEG C to reaction chamber body temperature, turns off argon gas, opens reaction chamber
Top cover, as shown in fig. 15, take out substrate.
The temperature range, pressure are data in the present embodiment, but its application field is not limited thereto, for adopting
The guarantor of the application is also belonged to as long as temperature, pressure data rationally can be used for the technical program with the system of other reactants
Protect range.
It then, can be by the solid electrolyte membrane of generation by being removed on substrate.
It removes to obtain LiPON solid electrolyte membrane from substrate.Stripping process is referred to using including but not limited to absorption, vibration
The methods of dynamic, temperature shock.The present embodiment is illustrated by taking adsorption stripping as an example.
It is removed by the way of absorption from substrate, obtains LiPON solid electrolyte membrane, obtained solid electrolyte membrane saves
It is spare in low-temperature anhydrous environment.
9 μm of LiPON solid electrolyte thickness manufactured in the present embodiment, degree of drawing is more than 300%, with 1000V or more
Insulate voltage endurance capability.
The technical solution of the application is usually applied to above-mentioned aumospheric pressure cvd method and prepares Kynoar solid-state electricity
Plasma membrane is solved, but it is not limited thereto, and prepares oxide solid electrolyte membrane for other chemical vapour deposition techniques, can also be with
For the technical program, same beneficial effect is obtained.
Embodiment 2: Kynoar solid electrolyte membrane is prepared using aumospheric pressure cvd method.
S1: it is set in the reaction chamber to substrate
The substrate selection is the same as described in embodiment 1.The present embodiment is illustrated by taking tungsten alloy as an example.Take area 80cm2
Tungsten alloy, cleaning method is shown in embodiment 1.It is dried up after cleaning with inert gases such as nitrogen.It cleans up dried to be coated
Tungsten alloy substrate from reactor opening 5 position be put into, be placed in 8 position of the reaction chamber.
S2: setting reaction chamber temperature and pressure reaches specified numerical value.
In the present embodiment, it is 200 DEG C~350 that aumospheric pressure cvd method reaction chamber temperature, which can control in temperature,
DEG C, pressure is higher than 30kPa.The present embodiment is illustrated by taking Kynoar and lithium metal reaction as an example.Reaction chamber room temperature is set
Degree is 260 DEG C ± 5 DEG C, pressure 100kPa.Further, it is also possible to which it is 250 DEG C, 300 DEG C or 350 that the reaction chamber temperature, which is arranged,
℃；It is 30kPa, 50kPa or 100kPa that the reaction chamber temperature, pressure, which is arranged,.
S3: pretreated reactant is passed through reaction chamber.
In the present embodiment, the reactant A includes at least one polyethylene oxide, polyacrylonitrile, Kynoar, poly- first
Base methyl acrylate, polypropylene oxide, Vingon, single-ion polymer.The reactant B, ingredient include such as down toward
Few a kind of active metal simple substance: Li, Na, K.
The present embodiment is illustrated so that A and B are respectively Kynoar and metal Li as an example.
Specifically: reactant A being first subjected to pretreatment operation, embodiment 1, the present embodiment are shown in the reactant pretreatment
It is illustrated by taking gasification pretreatment as an example.It is Piezoelectricity under Kynoar (PVDF) normality, crystallinity is about 50%.
First PVDF pellet is placed in baking oven or preheating furnace and is preheated, 210 DEG C of preheating temperature, Kynoar is heated to 235 DEG C, is made
It melts；
The argon atmosphere for keeping 100kPa in reaction chamber, the Kynoar after thawing is led to by 260 DEG C ± 5 DEG C of temperature
Enter reaction chamber；It increases reaction chamber temperature and quickly recycles to after 350 DEG C, increasing argon stream, Kynoar is presented
Fine droplet boiling-like；Make Kynoar that fine droplet boiling-like be presented, be passed through lithium metal solution, reaction starts to carry out.It is poly-
The molar ratio of vinylidene and lithium metal is 2:1~3:1.
S4: setting reaction condition generates solid electrolyte membrane by chemical vapour deposition reaction on substrate
The present embodiment is illustrated so that aumospheric pressure cvd method prepares Kynoar solid electrolyte membrane as an example.
After aforementioned pretreated reactant is passed through reaction chamber, keeping the temperature of reaction chamber is 350 DEG C ± 5 DEG C,
Pressure is 100kPa, reacts Kynoar and lithium metal and carries out, exports side reaction product in reaction process；In reaction process
It is middle to keep being passed through for argon gas.After reaction continues 1.5 to 2.5 hours, reaction is reduced with the cooling rate of 20 DEG C/min or so
Chamber room temperature opens valve 6 and valve 7 (Fig. 1) to 100 DEG C, and carries out the discharge of by-product and the complete substance of unreacted.To
Reaction chamber body temperature is lower than 30 DEG C, turns off argon gas, opens reaction chamber top cover, and as shown in fig. 15, take out substrate.
It then, can be by the solid electrolyte membrane of generation by being removed on substrate.
Substrate is removed to obtain Kynoar solid electrolyte membrane.Stripping process is referred to using including but not limited to suction
The methods of attached, vibration, temperature shock.The present embodiment using absorption the obtained solid electrolyte membrane of method, be stored in low temperature without
It is spare in water environment.
For Kynoar solid electrolyte membrane manufactured in the present embodiment with a thickness of 12 μm, degree of drawing is more than 220%, is had
The insulation voltage endurance capability of 1000V or more.
Above-described embodiment of the application is by taking aumospheric pressure cvd method prepares Kynoar solid electrolyte membrane as an example
It is illustrated, but it is not limited thereto, and prepares oxide solid electrolyte membrane for other chemical vapour deposition techniques, it can also
To be used for the technical program, same beneficial effect is obtained.
The solid-state electrolyte layer of the formation of the above embodiments of the present application includes but is not limited to inorganic solid electrolyte, You Jifu
Close solid electrolyte etc.；
Further, inorganic solid electrolyte includes but is not limited to oxide and sulfide solid electrolyte, and oxide is solid
State electrolyte such as Ca-Ti ore type, NaSiCON type, LiSiCON type, LiPON type etc.；Sulfide solid electrolyte such as Li4-xGe1- xPxS4(A=Ge, Si etc., B=P, A1, Zn etc.) P2S5、SiS2、B2S3Deng；
Organic composite solid electrolyte includes but is not limited to solid polyelectrolyte film, as polyethylene oxide (PEO),
Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polypropylene oxide (PPO), gathers inclined chlorine at Kynoar (PVDF)
Ethylene (PVDC) and single-ion polymer electrolyte etc..
The thickness general control of the ultrathin flexible solid electrolyte membrane is maximum up to 15 microns within 10 microns, can
Select 8 microns or less；
Further, ultrathin flexible solid electrolyte membrane can bear the tensile strength and torsional strength of maximum 200-300%
Afterwards without will cause the change of overall performance, optional 200% intensity；
Further, ultrathin flexible solid electrolyte membrane has electronic isolation, the resistance to pressure energy of insulation with 1000V or more
Power, but the excellence conductor of ion.
The technical solution of the present embodiment is obtained by condition, the method for selection, chemical deposition of reactant etc. for changing reaction
To required, different solid electrolyte membranes；Have using solid electrolyte membrane made from chemical vapour deposition reaction main
Performance has: high ionic conductivity, low ion area specific resistance, high electronics area specific resistance, high ion selectivity, width
Electrochemical stability window, good chemical compatibility, excellent thermal stability, excellent mechanical performance, simple preparation process,
It is cheap, it is easy integration and it is environmental-friendly.
Although the application is disclosed as above with preferred embodiment, it is not for limiting the application, any this field skill
Art personnel are not departing from spirit and scope, can make possible variation and modification, therefore the guarantor of the application
Shield range should be subject to the range that the claims in the present invention are defined.
Claims (12)
1. a kind of preparation method of solid electrolyte membrane characterized by comprising
Substrate is set in reaction chamber；
After the reaction chamber inert gas purge, the reaction chamber temperature and pressure is set and reaches specified numerical value；
Reach specified numerical value to the reaction chamber temperature and pressure, pretreated reactant is passed through the reaction chamber
In, wherein the reactant includes at least two kinds, including reactant A and reactant B；
After the reactant is passed through the reaction chamber, reaction condition is set, by chemical vapour deposition reaction in the base
On piece generates solid electrolyte membrane.
2. a kind of preparation method of solid electrolyte membrane according to claim 1, which is characterized in that the chemical vapor deposition
Product reaction is aumospheric pressure cvd or ultra-high vacuum CVD.
3. a kind of preparation method of solid electrolyte membrane according to claim 1, which is characterized in that
The reactant A includes at least one inorganic oxide perhaps sulfide solid electrolyte or poly- including at least one
Close object solid electrolyte；
The reactant B, ingredient comprise at least one of the following active gas: N2、Cl2、O2、CO2、CO、NO、SO2；Or including
Following at least one non-metal simple-substance: S, P, C, Si, or including following at least one active metal simple substance: Li, Na, K.
4. a kind of preparation method of solid electrolyte membrane according to claim 1, which is characterized in that described to include to substrate
Following at least one refractory metal: tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium；Or the change including following at least one rare earth metal
Close object: the boride of rare earth metal, the carbide of rare earth metal, the nitride of rare earth metal, the silicide of rare earth metal, rare earth
The sulfide of the phosphide of metal, rare earth metal.
5. a kind of preparation method of solid electrolyte membrane according to claim 1 to 4, which is characterized in that
It is described that pretreated reactant is passed through in the reaction chamber specially one kind of following steps: first by reactant B
It is passed through the reaction chamber with the mixed gas of inert gas, then will pass through the reactant A after pre-processing with inert gas
Preheating, and it is sent into the reaction chamber；Or
First the nanosizing reactant A after pretreatment is preheated with inert gas, is sent into the reaction chamber, it then will be anti-
The mixed gas of object B and inert gas is answered to be passed through the reaction chamber.
6. a kind of preparation method of solid electrolyte membrane according to claim 1, which is characterized in that
The chemical vapour deposition reaction is specially ultra-high vacuum CVD reaction；
Solid electrolyte membrane is generated by chemical vapour deposition reaction on the substrate include: correspondingly, described
It is 350 DEG C~530 DEG C that the reaction chamber temperature, which is arranged, and pressure is not less than 10-2Pa；
Under the temperature and pressure environment of setting, the mixed gas of inert gas and the nitrogen as reactant B is passed through described
Reaction chamber,
The anti-of the nitrogen and inert gas has been passed through by being sent by the pretreated lithium phosphate as reactant A of preheating
Chamber is answered, the temperature and pressure of reaction chamber is adjusted, lithium phosphate and nitrogen is reacted and carries out, export side reaction produces in reaction process
Object；Being passed through for the inert gas is kept during the reaction；
After reaction carries out setting time, reaction temperature is reduced；And the discharge of by-product and the complete substance of unreacted is carried out, in titanium
Solid electrolyte membrane is formed in alloy or tungsten alloy substrate.
7. a kind of preparation method of solid electrolyte membrane according to claim 6, which is characterized in that the setting is described anti-
Answering chamber temp is 350 DEG C~530 DEG C, and pressure is not less than 10-2In Pa, specially
It is 350 DEG C, 450 DEG C or 520 DEG C that the reaction chamber temperature, which is arranged,；
It is 10 that the reaction chamber pressure, which is arranged,-5Pa、10-5Pa or 10-2Pa。
8. a kind of preparation method of solid electrolyte membrane according to claim 6, which is characterized in that the reactant B
Molar ratio with reactant A is 1.5:1~4:1.
9. a kind of preparation method of solid electrolyte membrane according to claim 1, which is characterized in that
The chemical vapour deposition reaction is aumospheric pressure cvd reaction；
Solid electrolyte membrane is generated by chemical vapour deposition reaction on the substrate include: correspondingly, described
It is 200 DEG C~350 DEG C that the reaction chamber temperature, which is arranged, and pressure is not less than 30kPa；
Under the temperature and pressure environment of setting, the polymer after melting will be passed through the reaction chamber as reactant A, risen
To after being higher than 300 DEG C, control inert gas flow quickly recycles the high reaction chamber temperature, makes polymer that small liquid be presented
Drip boiling-like；
The lithium metal of melting is sent into as reactant B and has been passed through the reaction chamber of polymer, adjust reaction chamber temperature and
Pressure is reacted the polymer and lithium metal and is carried out, exports side reaction product in reaction process；Institute is kept during the reaction
State being passed through for inert gas；
After reaction carries out setting time, reaction temperature is reduced；And the discharge of by-product and the complete substance of unreacted is carried out, in titanium
Solid electrolyte membrane is formed in alloy or tungsten alloy substrate.
10. a kind of preparation method of solid electrolyte membrane according to claim 9, which is characterized in that described in the setting
Reaction chamber temperature is 200 DEG C~350 DEG C, and pressure is not less than 30kPa specifically:
It is 250 DEG C, 300 DEG C or 350 DEG C that the reaction chamber temperature, which is arranged,；
It is 30kPa, 50kPa or 100kPa that the reaction chamber temperature, pressure, which is arranged,.
11. a kind of according to claim 1-4, preparation method of any solid electrolyte membrane of 6-10, which is characterized in that
The solid electrolyte membrane that reaction is formed includes oxide solid electrolyte, sulfide solid electrolyte or organic composite solid
Dielectric film；Wherein,
Oxide solid electrolyte includes at least following a kind of: Ca-Ti ore type, NaSiCON type, LiSiCON type or LiPON type；
Sulfide solid electrolyte includes at least following a kind of: P2S5、SiS2、B2S3；
Organic composite solid dielectric film includes at least following one kind: polyethylene oxide, Kynoar, is gathered polyacrylonitrile
Methyl methacrylate, polypropylene oxide, Vingon, single-ion polymer electrolyte；
Or
A kind of solid electrolyte membrane that reaction is formed is Li4-xA1-xBxS4, wherein at least one of x < 1, A Ge, Si, B P,
At least one of A1, Zn.
12. a kind of solid electrolyte membrane, which is characterized in that obtained using any method preparation of preceding claims 1 to 11
?.
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| CN115172865A (en) * | 2022-09-07 | 2022-10-11 | 溧阳天目先导电池材料科技有限公司 | Composite solid electrolyte membrane and preparation method and application thereof |
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