CN109004280A - A kind of preparation method and full solid state polymer battery of full solid state polymer electrolyte - Google Patents

A kind of preparation method and full solid state polymer battery of full solid state polymer electrolyte Download PDF

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CN109004280A
CN109004280A CN201810754004.7A CN201810754004A CN109004280A CN 109004280 A CN109004280 A CN 109004280A CN 201810754004 A CN201810754004 A CN 201810754004A CN 109004280 A CN109004280 A CN 109004280A
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mass parts
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CN109004280B (en
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唐伟超
李素丽
李俊义
徐延铭
赵伟
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Zhuhai Coslight Battery Co Ltd
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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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • H01M10/0564—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
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    • 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

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Abstract

A kind of preparation method and full solid state polymer battery of full solid state polymer electrolyte, the preparation step of electrolyte are as follows: polycarbonate monomer and carboxyl or isophorone diamine monomer being carried out polymerization reaction, obtain polymer A；Polyether monomer, polyethylene glycol acrylmonomers and functional polymer are added in solvent, and lithium salts, initiator is added, selectively adds auxiliary agent and functional stuffing, initiation reaction is carried out, obtains polymer B；Polymer A and polymer B are added in solvent, and selectively adds carboxyl crosslinking agent and is uniformly mixed, obtains mixed with polymers system；Hydroxyl crosslinking agent is added in mixed with polymers system and is uniformly mixed, obtained mixed liquor is uniformly coated on mold, carries out cross-linking reaction under atmosphere of inert gases in vacuum oven；After reaction, vacuum drying obtains full solid state polymer electrolyte film under atmosphere of inert gases.The compatibility and mechanical strength of solid polymer electrolyte of the invention are good and conductivity at room temperature is high.

Description

A kind of preparation method and full solid state polymer battery of full solid state polymer electrolyte
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of preparation methods of full solid state polymer electrolyte And lithium ion full solid state polymer battery.
Background technique
Lithium ion battery is since energy density is high, good reliability, in the development advanced by leaps and bounds in the late three decades.It passes The lithium ion battery of system mostly uses liquid electrolyte, such as ethylene carbonate, propene carbonate organic solvent.Due to liquid electrolyte Matter will lead to lithium ion battery, and there are the safety issues such as leakage, kindling, explosion, limit the further hair of lithium ion battery Exhibition.
Full solid state polymer electrolyte can overcome the disadvantage mentioned above of liquid electrolyte, improve the safety of lithium ion battery Energy.Ideal full solid state polymer electrolyte should possess following characteristic: 1. high ionic conductivities；2. having between electrode good Good compatibility；3. excellent mechanical performance；4. wide electrochemical window.But existing full solid state polymer electrolyte is difficult to together When have the above characteristic.If traditional polyether-based lithium ion battery solid electrolyte is in conductivity at room temperature and mechanical strength side Face Shortcomings, a kind of method for improving the conductivity at room temperature of polyether-based solid electrolyte are to introduce carbonyldioxy solid state electrolysis Matter, but the method for introducing carbonyldioxy solid electrolyte is generally copolymerized or mixing, and copolymerization method is easy to change molecule chain flexibility, The locomitivity of strand is reduced to weaken ionic conductivity, and there are consistency problems for mixing method, are easily reduced electrolyte Mechanical strength and energy density.Therefore poly- carbonic acid-polyethers knot that a kind of compatibility is good and conductivity at room temperature is high is needed The preparation method of all solid state electrolyte of structure.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of full solid state polymer electrolyte and lithium ion are all solid state Polymer battery, prepared poly- carbonic acid-polyethers Soild Polymer Electrolytes For Lithium Ion Batteries have compatibility is good, room temperature from The feature that electron conductivity is high, electrochemical window is high and mechanical strength is good.
To achieve the goals above, the present invention takes following technical solution:
A kind of preparation method of full solid state polymer electrolyte, comprising the following steps:
The polycarbonate monomer of 5~70 mass parts and the carboxyl or isophorone diamine monomer of 0.5~6 mass parts are added Polymerization reaction is carried out in reactor, obtains polymer A；
By the polyether monomer of 10~80 mass parts, the polyethylene glycol acrylmonomers of 0~5 mass parts and 0~10 mass parts Functional polymer be added in 100~300 parts of solvents, persistently lead to and inert gas and stir, 5~40 mass parts lithiums are then added Salt, 0.05~1 mass parts initiator, 0~50 mass parts auxiliary agent, 0~5 mass parts functional stuffing carry out initiation reaction, are gathered Close object B；
0~20 mass parts polymer A and 30~80 mass parts polymer Bs are added in 100~300 mass parts solvents, held Continuous logical inert gas simultaneously stirs, and 0~0.5 mass parts carboxyl crosslinking agent is then added and is uniformly mixed, obtains mixed with polymers system；
0.1~1 mass parts hydroxyl crosslinking agent is added in 1 mass parts solvent and is uniformly mixed, is added to obtained in the previous step It in mixed with polymers system and is uniformly mixed, obtained mixed liquor is uniformly coated on mold, the inertia in vacuum oven Cross-linking reaction is being carried out under atmosphere；
After reaction, it is dried in vacuo under atmosphere of inert gases, obtains full solid state polymer electrolyte film.
More specifically, in the step of preparing polymer A, the polycarbonate monomer is diphenol propane, trimethylene carbon One or more of acid esters.
More specifically, in the step of preparing polymer A, the carboxyl or isophorone diamine monomer are bis- (the 4- hydroxyls of 2,2- Base phenyl) propionic acid, 5- methyl -2- oxo -1,3- dioxanes -5- carboxylic acid, 5- hydroxyl -1,3- dioxanes -2- ketone, 5- ethyl -5- One or more of (hydroxymethyl) -1,3- dioxanes -2- ketone.
More specifically, polymer A is prepared using thermocatalytic method, inert gas is persistently led into reactor, and with 200~ The revolving speed of 900r/min stirs, and 30~60 mass parts solvents and 0.01~0.9 mass parts of catalyst is then added, 100~135 20~80min is reacted at DEG C.
A kind of preparation method of full solid state polymer electrolyte, comprising the following steps:
By the polyether monomer of 10~80 mass parts, the polyethylene glycol acrylmonomers of 0~5 mass parts and 0~10 mass parts Functional polymer be added in 100~300 parts of solvents, persistently lead to and inert gas and stir, 5~40 mass parts lithiums are then added Salt, 0.05~1 mass parts initiator, 0~50 mass parts auxiliary agent, 0~5 mass parts filler carry out initiation reaction, obtain polymer B；
30~80 mass parts polymer Bs are added in 100~300 mass parts solvents, inert gas is persistently led to and are stirred, so 0~0.5 mass parts carboxyl crosslinking agent is added afterwards to be uniformly mixed, obtains mixed with polymers system；
0.1~1 mass parts hydroxyl crosslinking agent is added in 1 mass parts solvent and is uniformly mixed, is added to obtained in the previous step It in mixed with polymers system and is uniformly mixed, obtained mixed liquor is uniformly coated on mold, the inertia in vacuum oven Cross-linking reaction is carried out under atmosphere；
After reaction, it is dried in vacuo under atmosphere of inert gases, obtains full solid state polymer electrolyte film.
More specifically, in the step of preparing polymer B, the polyether monomer is the polyethylene glycol of molecular weight 300~20000 One or more of methyl ether methacrylate or the methoxypolyethylene glycol acrylate of molecular weight 480~5000.
More specifically, in the step of preparing polymer B, the polyethylene glycol acrylmonomers are molecular weight 300~2500 Polyethylene glycol methyl methacrylate or one or more of the polyethylene glycol mono allyl ether of molecular weight 100~2400.
More specifically, prepare polymer B the step of in, the functional polymer be poly- (vinylidene fluoride-hexafluoropropene), One or more of high molecular polythene, polypropylene, polystyrene, Kynoar, polyethylene glycol oxide, polycarbonate.
More specifically, in the step of preparing polymer B, the initiator is azodiisobutyronitrile, azobisisoheptonitrile, idol Two isobutyl dimethyl phthalate of nitrogen, benzoyl peroxide, benzoyl peroxide, Benzophenone, benzophenone, 2- hydroxyl -2- first Base-1- phenyl ketone, 1- hydroxy-cyciohexyl-1- phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- third Ketone, benzoin dimethylether, 4- (N, N- dimethylamino) ethyl benzoate, isopropyl thioxanthone, 4- chlorobenzophenone, adjacent benzene first One or more of acyl methyl benzoate, 4- methyl benzophenone, 4- phenyl benzophenone, 4- methyl dimethoxy acetone.
More specifically, in the step of preparing polymer B, the auxiliary agent is methoxy poly (ethylene glycol) borate, methoxyl group is poly- Ethylene glycol Aluminate, succinonitrile, vinylethylene carbonate, vinylene carbonate, fluorinated ethylene carbonate, tetraethyleneglycol dimethyl ether One or more of.
More specifically, prepare polymer B the step of in, the functional stuffing be nano silica, nano-titanium dioxide, Nano-aluminium oxide, nano zircite, diatomite, bentonite, kaolin, attapulgite, lithium phosphate, lithium titanate, titanium phosphate Lithium, titanium phosphate aluminium lithium, lanthanium titanate lithium, tantalic acid lanthanum lithium, phosphoric acid germanium aluminium lithium, lithium aluminosilicate, silicon phosphate lithium, lanthanium titanate lithium, three oxidations One or more of two boron doping lithium phosphates, lanthanum platinum lithium, lanthanum lithium platinum alumina.
More specifically, the carboxyl crosslinking agent is trifunctional aziridine crosslinker, two functional group's aziridine crosslinkers, three Hydroxymethyl-propane three (3- aziridinyl propionic ester), pentaerythrite three [3- (1- aziridinyl) propionic acid], aliphatic poly carbonization two One or more of imines, aromatic polycarbodi-imide.
More specifically, the hydroxyl crosslinking agent is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane Diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hexandial, The one or more of glutaraldehyde, Adipoyl Chloride, aliphatic polycarbodiimide, aromatic polycarbodi-imide, Geniposide.
Full solid state polymer battery, including solid polymer electrolyte, the solid polymer electrolyte is using aforementioned complete The preparation method of solid polymer electrolyte is made.
From the above technical scheme, the present invention uses polyethers and polyethylene glycol acrylic for monomer, in centainly reaction item Under part formed have hydroxyl comb-like polyether polymer, while by the carbonate polymer with hydroxyl or carboxyl, The materials such as auxiliary agent are effectively mixed, and carboxyl crosslinking agent is first added and is crosslinked to mixed polymerization objects system, forms Controllable cross-linking Structure, carboxyl crosslinking agent and hydroxyl, the polyether structure of selection do not crosslink, and hydroxyl crosslinking agent are added, in carboxyl crosslinking agent Formed part reticular structure on the basis of, hydroxyl crosslinking agent to the hydroxyl in polycarbonate, the hydroxyl in polyether polymer into Row effectively crosslinking.The crosslinking agent that can also be selected while react with hydroxycarboxyl group carries out cross-linking reaction.This structure enables to Polyethers based high molecular is effectively connect with polycarbonate macromolecule in molecular level, and compatibility is good, while remaining poly- carbonic acid again Ester molecule chain flexibility achievees the effect that raising conductivity at room temperature is high；By the additional amount and reaction interval that control crosslinking agent The crosslinking degree of degree control cross-linked polymer makes crosslinking degree polymer in a certain range have linear polymer good Interfacial contact and good mechanical properties with cross-linked polymer have good answer in full solid state polymer lithium ion battery Use potentiality.In a preferred approach, by the way that nano silica is added, there is silica certain hydroxyl can carry out with crosslinking agent Interaction has the function of promoting mechanical property and stablizes battery system.
Detailed description of the invention
Fig. 1 is the electrochemical window curve graph of full solid state polymer electrolyte made from the embodiment of the present invention 1；
Fig. 2 is the electrochemical window curve graph of full solid state polymer electrolyte made from the embodiment of the present invention 5.
A specific embodiment of the invention is described in more detail below in conjunction with attached drawing.
Specific embodiment
In order to above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention is cited below particularly, It is described below in detail.
All solid state electrolyte of the invention the preparation method is as follows:
S1, by the carboxyl or isophorone diamine monomer of the polycarbonate monomer of 5~70 mass parts and 0.5~6 mass parts Reactor is added and carries out polymerization reaction, polymer A is obtained after purification；
Polycarbonate monomer can be one or more of diphenol propane, trimethylene carbonate, and carboxyl or hydroxyl are poly- Carbonate monomer can be bis- (4- hydroxy phenyl) propionic acid of 2,2-, 5- methyl -2- oxo -1,3- dioxanes -5- carboxylic acid, 5- hydroxyl - One or more of 1,3- dioxanes -2- ketone, 5- ethyl -5- (hydroxymethyl) -1,3- dioxanes -2- ketone；Polycarbonate list Body and polycarbonate monomer containing carboxyl or hydroxyl can carry out polymerization reaction by phosgenation, ester-interchange method or thermocatalytic method, Obtained polymer A is a kind of poly- carbonic acid polymer containing carboxyl or carboxyl, has poly- carbon on the main chain of one of polymer Sour structure, side chain contain carboxyl or hydroxyl, can carry out the cross-linking reaction of carboxyl or hydroxyl；R1, R2 depend on poly- in polymer A Close monomer structure, wherein R1 CxHyOz, R2 CaHbOc, x, y, z, a, b, c ∈ positive integer and x >=1, y >=0, z >=0, a >=1, b≥0,c≥0；
S2, by the polyether monomer of 10~80 mass parts, the polyethylene glycol acrylmonomers of 0~5 mass parts and 0~10 mass The functional polymer of part is added in 100~300 parts of solvents, maintaining nitrogen purge, is stirred with the revolving speed of 100~800r/min, then 5~40 mass parts lithium salts, 0.05~1 mass parts initiator, 0~50 mass parts auxiliary agent, 0~5 mass parts filler are added, are drawn Hair reaction, obtains polymer B；
Polyether monomer is methoxypolyethylene glycol methacrylate (molecular weight 300~20000) and methoxypolyethylene glycol third One or more of olefin(e) acid ester (molecular weight 480~5000)；Polyethylene glycol acrylmonomers are polyethylene glycol methacrylic acid One or more of methyl esters (molecular weight 300~2500), polyethylene glycol mono allyl ether (molecular weight 100~2400)；Function Polymer is the good and stable polymer of mechanical property, such as poly- (vinylidene fluoride-hexafluoropropene), high molecular polythene, poly- third One or more of alkene, polystyrene, Kynoar, or for the polymer for leading lithium function, such as polyethylene glycol oxide (molecular weight 1000~10,000,000), polycarbonate (types such as aliphatic, aromatic series, aliphatic-aromatic)；
S3,0~20 mass parts polymer A and 30~80 mass parts polymer Bs are added in 100~300 mass parts solvents, Maintaining nitrogen purge is stirred with the revolving speed of 100~800r/min, and 0~0.5 mass parts carboxyl crosslinking agent is then added and stirs 1~6h, Obtain mixed with polymers system；
S4, it will be uniformly mixed in 0.1~1 mass parts hydroxyl crosslinking agent, 1 mass parts solvent of addition, be added to the above polymer It is uniformly mixed, obtained mixed liquor is uniformly coated on mold, the atmosphere of inert gases in vacuum oven in mixed system Under 60~100 DEG C react 6~for 24 hours；
S5, after reaction, 90~98 DEG C of 30~60h of vacuum drying, obtain all solid state polymerization under atmosphere of inert gases Object dielectric film.
Solvent used in abovementioned steps can be toluene, acetonitrile, tetrahydrofuran, benzene, acetone, dimethyl sulfoxide, N, N- bis- One or more of methylformamide, N-Methyl pyrrolidone.
Below by specific embodiment, the present invention is further illustrated.Reagent, the material arrived used in following the description Material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available, institute The reagent being related to can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
S1, by 5 mass parts trimethylene carbonates and 0.5 mass parts 5- methyl -2- oxo -1,3- dioxanes -5- carboxylic acid Be added reactor in, using thermocatalytic polymerization carry out polymerization reaction, into reactor maintaining nitrogen purge and continue with 200r/ The revolving speed of min stirs, and 30 mass parts toluene (solvent), 0.01 mass parts stannous iso caprylate (catalyst) is then added, at 100 DEG C Lower reaction 60min, obtains polymer A；Catalyst used in this step can also be tributyl other than it can be stannous iso caprylate Tin oxide or tin acetate or rare earth or biological enzyme；
S2, by 80 mass parts methoxypolyethylene glycol methacrylates (molecular weight 300) and 0.5 mass parts polyethylene glycol first Base methyl acrylate (molecular weight 2500) is added in 300 mass parts toluene, maintaining nitrogen purge, is stirred with the revolving speed of 500r/min, Then the double trifluoromethanesulfonimide lithiums (LiTFSI) of 30 mass parts are added, 0.5 mass parts azodiisobutyronitrile carries out hot initiation Reaction, the temperature that heat causes are 60~100 DEG C, reaction 2~for 24 hours, and temperature is risen to 80 DEG C of progress thermal booster reactions by the present embodiment 3h obtains polymer B；Can also be used it is ultraviolet light-initiated, using the ultraviolet lamp of certain power, the initiation time be 2min~ 200min；
Lithium salts used in this step can also be lithium perchlorate other than available double trifluoromethanesulfonimide lithiums (LiClO4), lithium hexafluoro phosphate (LiPF6), di-oxalate lithium borate (LiBOB), LiODFB (LiDFBD), trifluoromethyl Sulfonic Lithium (LiCF3SO3), LiBF4 (LiBF4), dimalonic acid boric acid (LiBMB), malonato lithium borate (LiMOB) One or more of；Initiator can also be azobisisoheptonitrile, two isobutyric acid two of azo other than available azodiisobutyronitrile Methyl esters, benzoyl peroxide, benzoyl peroxide, Benzophenone, benzophenone, 2- hydroxy-2-methyl -1- phenyl first Ketone, 1- hydroxy-cyciohexyl-1- phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone, styrax are double Methyl ether, 4- (N, N- dimethylamino) ethyl benzoate, isopropyl thioxanthone, 4- chlorobenzophenone, o-benzoylbenzoic acid first One or more of ester, 4- methyl benzophenone, 4- phenyl benzophenone, 4- methyl dimethoxy acetone etc.；
S3,20 mass parts polymer A and 30 mass parts polymer Bs are added in 100 mass parts toluene, maintaining nitrogen purge, It is stirred with the revolving speed of 800r/min, 0.5 mass parts trifunctional aziridine crosslinker (HD100, HD105, HD110) is then added 1h is stirred, mixed with polymers system is obtained；
In this step other than available trifunctional aziridine crosslinker is as carboxyl crosslinking agent, carboxyl crosslinking agent can also be Two functional group's aziridine crosslinkers, trimethylolpropane tris (3- aziridinyl propionic ester), [3- (the 1- ethylene imine of pentaerythrite three Base) propionic acid], aliphatic polycarbodiimide, one or more of aromatic polycarbodi-imide, or use metal ion class Crosslinking agent, epoxy silane class crosslinking agent etc.；
S4, it will be uniformly mixed in 0.1 mass parts toluene di-isocyanate(TDI) (TDI), 1 mass parts solvent of addition, be added to step It is uniformly mixed in the mixed with polymers system that S3 is obtained, obtained mixed liquor is uniformly coated on Teflon mould, The lower 60 DEG C of reactions of vacuum oven nitrogen atmosphere are for 24 hours；
Isophorone diisocyanate (IPDI), methyl diphenylene diisocyanate (MDI), two rings also can be used in this step Hexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), oneself two One or more of conducts of aldehyde, glutaraldehyde, Adipoyl Chloride, aliphatic polycarbodiimide, aromatic polycarbodi-imide, Geniposide Hydroxyl crosslinking agent substitutes toluene di-isocyanate(TDI)；
S5, after reaction, 98 DEG C of vacuum drying 30h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.It include poly- carbonic acid-polyethers lithium ion battery solid polymer in the lithium ion full solid state polymer battery Electrolyte.
Embodiment 2
S1, reactor is added in 70 mass parts trimethylene carbonates and 6 mass parts 5- hydroxyl -1,3- dioxanes -2- ketone Middle progress thermocatalytic polymerization reaction, into reactor, maintaining nitrogen purge and the lasting revolving speed stirring with 800r/min, are then added 60 mass parts toluene and 0.9 mass parts tributyltin oxide, react 80min at 100 DEG C, obtain polymer A；
S2, by 10 mass parts methoxypolyethylene glycol methacrylates (molecular weight 20000), 5 mass parts polyethylene glycol first 200 mass parts tetrahydrofurans are added in base methyl acrylate (molecular weight 300), 10 mass parts polyethylene glycol oxides (molecular weight 10,000,000) In, maintaining nitrogen purge is stirred with the revolving speed of 800r/min, 5 mass parts di-oxalate lithium borates (LiBOB), 0.05 matter is then added Part benzoyl peroxide is measured, adds and is mixed with 5 mass parts methoxy poly (ethylene glycol) borates and 5 mass parts nanometers two The toluene of silica (partial size 700nm) is uniformly mixed, temperature is risen to 100 DEG C of progress thermal booster reaction 2h, obtains polymer B；
The present embodiment has used methoxy poly (ethylene glycol) borate (B-PEG) as auxiliary agent and nanometer in initiation reaction Silica (7~700nm) is used as functional stuffing.In addition, auxiliary agent can also be methoxy poly (ethylene glycol) Aluminate (Al-PEG), fourth Dintrile, vinylethylene carbonate, vinylene carbonate, fluorinated ethylene carbonate, one kind in tetraethyleneglycol dimethyl ether or several Kind；Functional stuffing can also for nano-titanium dioxide, nano-aluminium oxide, nano zircite, diatomite, bentonite, kaolin, Attapulgite, lithium phosphate, lithium titanate, titanium phosphate lithium, titanium phosphate aluminium lithium, lanthanium titanate lithium, tantalic acid lanthanum lithium, phosphoric acid germanium aluminium lithium, sial One or more of sour lithium, silicon phosphate lithium, lanthanium titanate lithium, diboron trioxide doping phosphoric acid lithium, lanthanum platinum lithium, lanthanum lithium platinum alumina；
S3,10 mass parts polymer A and 80 mass parts polymer Bs are added in 300 mass parts solvents, maintaining nitrogen purge, 6h is stirred with the revolving speed of 500r/min, obtains mixed with polymers system；
S4, it will be uniformly mixed in the appropriate solvent of 1 mass parts isophorone diisocyanate addition, be added to previous step and obtain Mixed with polymers system in be uniformly mixed, obtained mixed liquor is uniformly coated on Teflon mould, it is dry in vacuum It is reacted for 24 hours for 60 DEG C in dry case inert gas；
S5, after reaction, 90 DEG C of vacuum drying 40h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.
For the present embodiment in order to reduce influence of the crosslinking agent structure introducing to Chain Flexibility, selection nano silica is function Energy filler, nano-silica surface have certain hydroxyl, can adsorb hydroxyl crosslinking agent, so that the node majority distribution of crosslinking Nano silica surface or around, so that hydroxyl cross-linker molecules chain (contains phenyl ring segment part or other rigid chains Section) it is distributed in surface or the surrounding of nano silica, although the presence of nano silica can hinder the fortune of surrounding molecular chain It is dynamic, but nano silica is capable of providing another lithium ion transport approach to eliminate this adverse effect.Phenyl ring will be contained Segment part or rigid chain segment are distributed in surface or the surrounding of silica, using silica elimination phenyl ring segment part or just Property influence of the segment to conductivity, polyether-based can be improved by introducing phenyl ring segment part or rigid chain segment on polyethers based high molecular High molecular mechanical strength, and interpenetrating type network structure is conducive to improve the density of material to improve mechanical performance.
Functional stuffing is in addition to inert fillers such as available nano-titanium dioxide, nano-aluminium oxide, nano zircites；Or phosphorus Sour lithium, lithium titanate, titanium phosphate lithium, titanium phosphate aluminium lithium, lanthanium titanate lithium, tantalic acid lanthanum lithium, phosphoric acid germanium aluminium lithium, lithium aluminosilicate, silicon phosphate Lithium, lanthanium titanate lithium, diboron trioxide doping phosphoric acid lithium, lanthanum platinum lithium, lanthanum lithium platinum alumina etc. have that leads lithium function to lead lithium filler； Or diatomite, bentonite, kaolin, attapulgite etc. have some hydroxyls and other organo-functional groups by modified rear surface Filler plays the role of promoting mechanical property and stablizes battery system.
Embodiment 3
S1, by 22 mass parts trimethylene carbonates and 4 mass parts 5- ethyl -5- (hydroxymethyl) -1,3- dioxanes -2- Ketone is added in reactor, and into reactor, maintaining nitrogen purge and the lasting revolving speed stirring with 200r/min, are then added 40 mass Part toluene and 0.04 mass parts stannous octoate, react 20min at 135 DEG C, obtain polymer A；
S2, by 60 mass parts methoxypolyethylene glycol acrylate (molecular weight 5000), 2 mass parts polyethylene glycol monoallyls Ether (molecular weight 2400), 2 mass parts polyethylene glycol oxides (molecular weight 1000) are added in 100 mass parts benzene, maintaining nitrogen purge, with The revolving speed of 100r/min stirs, and is then added 20 mass parts lithium perchlorates (LiClO4), 1 mass parts azobisisoheptonitrile, then plus Enter the toluene for being mixed with 50 mass parts methoxy poly (ethylene glycol) Aluminates and 3 mass parts nano silicas (partial size 7nm), mixes Uniformly, temperature is risen into 70 DEG C of progress thermal booster reaction 6h, obtains polymer B；
S3,15 mass parts polymer A and 50 mass parts polymer Bs are added in 200 mass parts solvents, maintaining nitrogen purge, 5h is stirred with the revolving speed of 300r/min, obtains mixed with polymers system；
S4, it will be uniformly mixed, be added in 0.5 mass parts methyl diphenylene diisocyanate, 1 mass parts solvent of addition It is uniformly mixed in the mixed with polymers system that one step obtains, obtained mixed liquor is uniformly coated on Teflon mould, 70 DEG C of reaction 20h in vacuum oven inert gas；
S5, after reaction, 96 DEG C of vacuum drying 50h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.
Embodiment 4
S1,50 mass parts trimethylene carbonates and 5 mass parts 2- methyl -2- carboxyls-trimethylene carbonate are added In reactor, into reactor, maintaining nitrogen purge and the lasting revolving speed stirring with 600r/min, are then added 50 mass parts toluene With 0.6 mass parts stannous octoate, 40min is reacted at 125 DEG C, obtains polymer A；
S2, by 45 mass parts methoxypolyethylene glycol acrylate (molecular weight 480), 4 mass parts polyethylene glycol monoallyls Ether (molecular weight 100), 3 mass parts poly- (vinylidene fluoride-hexafluoropropene) are added in 150 mass parts n,N-Dimethylformamide, Maintaining nitrogen purge is stirred with the revolving speed of 400r/min, 40 mass parts dimalonic acid boric acid (LiBMB), 0.3 mass parts is then added Benzoyl peroxide adds and is mixed with 5 mass parts succinonitrile and 8 mass parts vinylethylene carbonates and 1 mass parts nanometer The toluene of titanium dioxide is uniformly mixed, temperature is risen to 90 DEG C of progress thermal booster reaction 4h, obtains polymer B；
S3,5 mass parts polymer A and 60 mass parts polymer Bs are added in 150 mass parts solvents, maintaining nitrogen purge, with The revolving speed of 600r/min stirs, and 0.3 mass parts pentaerythrite three [3- (1- aziridinyl) propionic acid] stirring 2h is then added, obtains Mixed with polymers system；
S4, it will be uniformly mixed, be added extremely in 0.6 mass parts dicyclohexyl methyl hydride diisocyanate, 1 mass parts solvent of addition It is uniformly mixed in mixed with polymers system obtained in the previous step, obtained mixed liquor is uniformly coated on Teflon mould On, 90 DEG C of reaction 12h under vacuum oven nitrogen atmosphere；
S5, after reaction, 96 DEG C of vacuum drying 60h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.
Embodiment 5
S1,36 mass parts trimethylene carbonates and 2 mass parts 2- methyl -2- carboxyls-trimethylene carbonate are added In reactor, into reactor, maintaining nitrogen purge and the lasting revolving speed stirring with 500r/min, are then added 55 mass parts toluene With 0.5 mass parts tin acetate, 70min is reacted at 110 DEG C, obtains polymer A；
S2, by 35 mass parts methoxypolyethylene glycol methacrylates (molecular weight 950), 20 mass parts methoxypolyethylene glycols Acrylate (molecular weight 2000), 3 mass parts polyethylene glycol methyl methacrylates (molecular weight 1500), the poly- second two of 2 mass parts Alcohol mono allyl ether (molecular weight 1200), 2 mass parts polyethylene glycol oxides (molecular weight 7,000,000), 6 mass parts polypropylene carbonates (molecular weight 20,000) is added in 260 mass parts acetonitriles, maintaining nitrogen purge, is stirred with the revolving speed of 600r/min, 35 mass are then added Part trifluoromethyl sulfonic acid lithium (LiCF3SO3), 0.8 mass parts benzoyl peroxide, add and be mixed with 10 mass parts carbonic acid Asia second Enester, 20 mass parts methoxy poly (ethylene glycol) borates, 5 mass parts tetraethyleneglycol dimethyl ethers, 3.5 mass parts phosphoric acid germanium aluminium lithiums Toluene is uniformly mixed, temperature is risen to 85 DEG C of thermal booster reaction 5h, obtains polymer B；
S3,5 mass parts polymer A and 70 mass parts polymer Bs are added in 250 mass parts solvents, maintaining nitrogen purge, with The revolving speed of 400r/min stirs, and 0.2 mass parts aliphatic polycarbodiimide stirring 4h is then added, obtains polyblend System；
S4, it will be uniformly mixed in 0.7 mass parts lysine diisocyanate, 1 mass parts solvent of addition, be added to previous step It obtains being uniformly mixed in mixed with polymers system, obtained mixed liquor is uniformly coated on Teflon mould, in vacuum The lower 80 DEG C of reactions 16h of drying box nitrogen atmosphere；
S4, after reaction, 95 DEG C of vacuum drying 38h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.
Embodiment 6
S1, by 70 mass parts methoxypolyethylene glycol methacrylates (molecular weight 950) and 10 mass parts polyethylene glycol oxides (molecular weight 5,000,000) is added in 300 mass parts tetrahydrofurans, maintaining nitrogen purge, is stirred with the revolving speed of 600r/min, is then added 35 mass parts dimalonic acid boric acid (LiBMB) and 0.5 mass parts 4- methyl dimethoxy acetone, after being sufficiently stirred, are uniformly coated on mould On tool, ultraviolet light 3min is carried out after removing solvent, obtains polymer B；
S2,60 mass parts polymer Bs are added in 200 mass parts tetrahydrofurans, maintaining nitrogen purge, with turning for 400r/min Speed stirring 3h, obtains mixed with polymers system；
S3, it will be uniformly mixed, be added in 0.6 mass parts lysine diisocyanate (LDI), 1 mass parts solvent of addition It is uniformly mixed in the mixed with polymers system that one step obtains, obtained mixed liquor is uniformly coated on Teflon mould, 90 DEG C of reaction 12h under vacuum oven nitrogen atmosphere；
S4, after reaction, 90 DEG C of vacuum drying 48h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.
Embodiment 7
S1, by 50 mass parts diphenol propanes and 3 mass parts 2, bis- (4- hydroxy phenyl) propionic acid of 2- are added in reactors, adopt With direct oxidation carbonylation method, is reacted under conditions of carbon monoxide, carbon dioxide, catalyst, polymer is obtained after purification A；
S2, by 60 mass parts methoxypolyethylene glycol methacrylates (molecular weight 500), 3 mass parts polyethylene glycol methyl Methyl acrylate (molecular weight 1500), 2 mass parts polypropylene carbonates (molecular weight 50000) are added in 200 parts of tetrahydrofurans, hold Continuous logical nitrogen, is stirred with the revolving speed of 400r/min, 30 mass parts malonato lithium borates, 0.4 mass parts 1- hydroxyl is then added Base-cyclohexyl -1- phenyl ketone, 2 parts of succinonitrile, add the solvent for being mixed with 1 mass parts lithium aluminosilicate, after being sufficiently stirred, It is uniformly coated on mold, carries out ultraviolet light 200min after removing solvent, obtain polymer B；
S3,10 mass parts polymer A and 50 mass parts polymer Bs are added in 200 mass parts acetonitriles, maintaining nitrogen purge, It is stirred with the revolving speed of 500r/min, 0.2 mass parts aromatic polycarbodi-imide stirring 3h is then added, obtains polyblend System；
S4, it will be uniformly mixed, be added supreme in 0.9 mass parts lysine diisocyanate (LDI), 1 mass parts solvent of addition It is uniformly mixed in the mixed with polymers system that one step obtains, obtained mixed liquor is uniformly coated on Teflon mould, 90 DEG C of reaction 12h in vacuum oven inert gas；
S5, after reaction, 98 DEG C of vacuum drying 30h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.
Embodiment 8
S1, reactor is added in 60 mass parts trimethylene carbonates and 3 mass parts 5- hydroxyl -1,3- dioxanes -2- ketone In, into reactor, maintaining nitrogen purge and the lasting revolving speed stirring with 200r/min, are then added 40 mass parts toluene and 0.04 Mass parts rare earth reacts 40min at 135 DEG C, obtains polymer A；
S2, by 10 mass parts methoxypolyethylene glycol acrylate (molecular weight 5000), 40 mass parts methoxypolyethylene glycols third Olefin(e) acid ester (molecular weight 950), 2 mass parts polyethylene glycol oxides (molecular weight 7,000,000) are added in 100 mass parts acetonitriles, persistently lead to nitrogen Gas is stirred with the revolving speed of 500r/min, and the double trifluoromethanesulfonimide lithiums of 20 mass parts, 0.5 mass parts 4- methyl is then added Benzophenone is mixed with 30 mass parts methoxy poly (ethylene glycol) Aluminates and 3 mass parts nano silica (partial sizes in addition Acetonitrile 7nm) after being sufficiently stirred, is uniformly coated on mold, is carried out ultraviolet light 30min after removing solvent, is polymerize Object B；
S3,10 mass parts polymer A and 40 mass parts polymer Bs are added in 150 mass parts solvents, maintaining nitrogen purge, 3h is stirred with the revolving speed of 500r/min, obtain mixed with polymers system；
S4, it will be uniformly mixed, be added to obtained in the previous step poly- in 0.2 mass parts Adipoyl Chloride, 1 mass parts solvent of addition It closes in object mixed system, obtained mixed liquor is uniformly coated on Teflon mould, in vacuum oven inert gas In 60 DEG C of reaction 20h；
S5, after reaction, 94 DEG C of vacuum drying 36h, obtain full solid state polymer electrolyte film in a nitrogen atmosphere.
Obtained full solid state polymer electrolyte film is cut into film-making, it is entirely solid to prepare lithium ion using conventional lamination process State polymer battery.
Battery made from embodiment 1 to 8 is tested for the property, the solid electrolyte of comparative example is that polyethylene glycol oxide (divides Ten thousand) son amount 500 is made.Test method is referring to company standard, and test result is as shown in Figure 1, Figure 2 and shown in table 1.
The full solid state polymer electrolyte of embodiment 1 and embodiment 5 is assembled into the test electrode of electrochemical window, in electricity Electrochemical window detection is carried out on chem workstation, obtained electrochemical window curve graph difference is as depicted in figs. 1 and 2, from Fig. 1 It can be seen that the decomposition voltage of the full solid state polymer electrolyte of embodiment 1 is 4.8V or so, the full solid state polymer of embodiment 5 Electrolyte decomposition voltage is 5.1V or so, illustrates that the electrochemical window of the polymeric system using the method for the present invention preparation is able to satisfy High voltage, high-energy density all-solid-state battery application demand, have extraordinary industrialization prospect.
Table 1
As shown in Table 1, the conductivity at room temperature of electrolyte made from embodiment 1-8 and electrochemical window are better than routine Polyethylene oxide electrolyte.The conductivity and electrochemical window of the polymer dielectric of embodiment 1-8 preparation are carried out simultaneously Detection, most of embodiment all has the ionic conductivity close to application, and electrochemical window is greater than 5V, belongs to high voltage withstanding body Based polymer electrolyte can be matched with high voltage system anode, and the full solid state polymer battery after assembling has higher Energy density and better application range.Full solid state polymer electrolyte of the invention prospects for commercial application with higher.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article Widest range.

Claims (14)

1. a kind of preparation method of full solid state polymer electrolyte, which comprises the following steps:
The polycarbonate monomer of 5~70 mass parts is reacted with the carboxyl of 0.5~6 mass parts or the addition of isophorone diamine monomer Polymerization reaction is carried out in device, obtains polymer A；
By the polyether monomer of 10~80 mass parts, the function of the polyethylene glycol acrylmonomers of 0~5 mass parts and 0~10 mass parts Can polymer be added in 100~300 parts of solvents, persistently lead to and inert gas and stir, be then added 5~40 mass parts lithium salts, 0.05~1 mass parts initiator, 0~50 mass parts auxiliary agent, 0~5 mass parts functional stuffing carry out initiation reaction, are polymerize Object B；
0~20 mass parts polymer A and 30~80 mass parts polymer Bs are added in 100~300 mass parts solvents, persistently led to Inert gas simultaneously stirs, and 0~0.5 mass parts carboxyl crosslinking agent is then added and is uniformly mixed, obtains mixed with polymers system；
0.1~1 mass parts hydroxyl crosslinking agent is added in 1 mass parts solvent and is uniformly mixed, polymerization obtained in the previous step is added to It in object mixed system and is uniformly mixed, obtained mixed liquor is uniformly coated on mold, the inert gas in vacuum oven Cross-linking reaction is being carried out under atmosphere；
After reaction, it is dried in vacuo under atmosphere of inert gases, obtains full solid state polymer electrolyte film.
2. the preparation method of full solid state polymer electrolyte as described in claim 1, it is characterised in that: prepare polymer A's In step, the polycarbonate monomer is one or more of diphenol propane, trimethylene carbonate.
3. the preparation method of full solid state polymer electrolyte as described in claim 1, it is characterised in that: prepare polymer A's In step, the carboxyl or isophorone diamine monomer are bis- (4- hydroxy phenyl) propionic acid of 2,2-, 5- methyl -2- oxo -1,3- Dioxanes -5- carboxylic acid, 5- hydroxyl -1,3- dioxanes -2- ketone, in 5- ethyl -5- (hydroxymethyl) -1,3- dioxanes -2- ketone It is one or more of.
4. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3, it is characterised in that: urged using heat Change method prepares polymer A, and inert gas is persistently led into reactor, and with the stirring of the revolving speed of 200~900r/min, is then added 30~60 mass parts solvents and 0.01~0.9 mass parts of catalyst react 20~80min at 100~135 DEG C.
5. a kind of preparation method of full solid state polymer electrolyte, which comprises the following steps:
By the polyether monomer of 10~80 mass parts, the function of the polyethylene glycol acrylmonomers of 0~5 mass parts and 0~10 mass parts Can polymer be added in 100~300 parts of solvents, persistently lead to and inert gas and stir, be then added 5~40 mass parts lithium salts, 0.05~1 mass parts initiator, 0~50 mass parts auxiliary agent, 0~5 mass parts filler carry out initiation reaction, obtain polymer B；
30~80 mass parts polymer Bs are added in 100~300 mass parts solvents, persistently leads to and inert gas and stirs, then plus Enter 0~0.5 mass parts carboxyl crosslinking agent to be uniformly mixed, obtains mixed with polymers system；
0.1~1 mass parts hydroxyl crosslinking agent is added in 1 mass parts solvent and is uniformly mixed, polymerization obtained in the previous step is added to It in object mixed system and is uniformly mixed, obtained mixed liquor is uniformly coated on mold, the inert gas in vacuum oven Cross-linking reaction is carried out under atmosphere；
After reaction, it is dried in vacuo under atmosphere of inert gases, obtains full solid state polymer electrolyte film.
6. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: system In the step of standby polymer B, the polyether monomer be molecular weight 300~20000 methoxypolyethylene glycol methacrylate or One or more of methoxypolyethylene glycol acrylate of molecular weight 480~5000.
7. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: system In the step of standby polymer B, the polyethylene glycol acrylmonomers are the polyethylene glycol methacrylic acid of molecular weight 300~2500 One or more of methyl esters or the polyethylene glycol mono allyl ether of molecular weight 100~2400.
8. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: system In the step of standby polymer B, the functional polymer is poly- (vinylidene fluoride-hexafluoropropene), high molecular polythene, poly- third One or more of alkene, polystyrene, Kynoar, polyethylene glycol oxide, polycarbonate.
9. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: system In the step of standby polymer B, the initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, mistake Benzoyl Oxide, benzoyl peroxide, Benzophenone, benzophenone, 2- hydroxy-2-methyl -1- phenyl ketone, 1- hydroxyl Base-cyclohexyl-1- phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone, benzoin dimethylether, 4- (N, N- dimethylamino) ethyl benzoate, isopropyl thioxanthone, 4- chlorobenzophenone, methyl o-benzoylbenzoate, 4- first One or more of base benzophenone, 4- phenyl benzophenone, 4- methyl dimethoxy acetone etc..
10. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: In the step of preparing polymer B, the auxiliary agent is methoxy poly (ethylene glycol) borate, methoxy poly (ethylene glycol) Aluminate, fourth two Nitrile, vinylethylene carbonate, vinylene carbonate, fluorinated ethylene carbonate, the one or more in tetraethyleneglycol dimethyl ether.
11. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: In the step of preparing polymer B, the functional stuffing is nano silica, nano-titanium dioxide, nano-aluminium oxide, receives Rice zirconium oxide, diatomite, bentonite, kaolin, attapulgite, lithium phosphate, lithium titanate, titanium phosphate lithium, titanium phosphate aluminium lithium, metatitanic acid Lanthanum lithium, tantalic acid lanthanum lithium, phosphoric acid germanium aluminium lithium, lithium aluminosilicate, silicon phosphate lithium, lanthanium titanate lithium, diboron trioxide doping phosphoric acid lithium, lanthanum platinum One or more of lithium, lanthanum lithium platinum alumina.
12. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: The carboxyl crosslinking agent is trifunctional aziridine crosslinker, two functional group's aziridine crosslinkers, trimethylolpropane tris (3- a word used for translation Third piperidinyl propionic ester), pentaerythrite three [3- (1- aziridinyl) propionic acid], aliphatic polycarbodiimide, the poly- carbonization two of aromatics One or more of imines.
13. the preparation method of the full solid state polymer electrolyte as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that: The hydroxyl crosslinking agent is toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate, two hexamethylenes Dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hexandial, glutaraldehyde, Adipoyl Chloride, The one or more of aliphatic polycarbodiimide, aromatic polycarbodi-imide, Geniposide.
14. full solid state polymer battery, including solid polymer electrolyte, it is characterised in that: the solid polymer electrolyte It is made of the preparation method of the described in any item full solid state polymer electrolytes of such as claim 1 to 13.
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CN114865097A (en) * 2022-05-25 2022-08-05 华中科技大学 Polymer electrolyte based on borate exchange reaction, preparation method and application thereof
CN115820109A (en) * 2022-12-29 2023-03-21 安徽精卓光显技术有限责任公司 Preparation method and application of coatable solid electrolyte
CN115820109B (en) * 2022-12-29 2024-02-09 安徽精卓光显技术有限责任公司 Preparation method and application of coatable solid electrolyte

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