CN106532116A - Preparation method and application of high-temperature resistant solid-state polymer electrolyte - Google Patents
Preparation method and application of high-temperature resistant solid-state polymer electrolyte Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- 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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a high-temperature resistant solid-state polymer electrolyte and application of same in a lithium battery. The preparation method of the high-temperature resistant solid-state polymer electrolyte at least comprises the steps of uniformly mixing two or more polymer monomers, a conductive salt and an initiator on a molecular level to form a precursor solution according to a certain proportion, coating the precursor solution on a surface of a substrate or an electrode, and preparing the solid-state polymer electrolyte by a polymerization method. The electrolyte is directly assembled into the battery, and the battery can work in a room temperature and a high temperature. The method has the advantages of high controllability, convenience in operation, low cost and favorable application prospect. The mechanical property and the thermal stability of the polymer electrolyte obtained according to the method are maintained very well, meanwhile, the moving ability and the ionic conductivity of a polymer chain segment are improved, and thus, a synergetic enhancement effect is achieved.
Description
Technical field：
The present invention relates to a class heat-resistant polymer electrolyte and its application in lithium battery.
Background technology：
As environmental pollution is increasingly serious, Fossil fuel is increasingly deficient, and development cleaning, cheap and safe energy storage technology show
Obtain particularly important.Lithium metal battery is with its higher theoretical energy density (3860mA hg-1) more and more paid attention to, but
There is the leakage of electrolyte in lithium metal liquid state batteries, the nonuniform deposition of lithium anode and dissolving form Li dendrite and pierce through barrier film
Make battery short circuit, hot-spot and burn or the safety problem such as explode, so as to limit the development of lithium metal battery.Quan Gu
Instead of flammable electrolyte with the solid electrolyte with certain mechanical strength in state lithium metal battery, and it is loose porous every
Film, so as to solve the leakage of electrolyte present in liquid lithium metal battery, short circuit etc. caused by burning and dendrite causes
Safety problem, and the various shapes and flexible device of battery can also be realized with certain flexible polymer dielectric
Preparation.Polymer is caused to have preferable degree of crystallinity and machinery strong yet with a kind of stacking regular layer by layer of single polymer
Degree, but the sub-chain motion ability of polymer is but largely limited, with relatively low ionic conductivity, therefore occur in that
Contradiction between the mechanical performance usually mentioned in polymer dielectric and ionic conductivity.At present great majority work be all by
It is skeleton in the polymer of this higher mechanical strength, the system such as liquid electrolyte, ionic liquid is added by methods such as casting, immersions
Standby gel electrolyte, so as to reach the balance between ionic conductivity and mechanical performance, but the gel electrolyte that the method is formed
Matter does not avoid the use of electrolyte, from the safety problem without being fully solved in liquid electrolyte.Conventional casting film
When assembled battery is with positive pole and cathode contact, the contact interface of electrode and electrolyte often goes out the polymer dielectric film that method is obtained
Existing loose contact contacts unstable phenomenon, and the substantial amounts of solvent that can volatilize when such method is in casting film is produced and wasted simultaneously
And pollution is produced to environment.
The content of the invention：
First purpose of the present invention is to provide a kind of ionic conductivity height and the good polymer dielectric of heat stability, should
Polymer dielectric contain two classes and the above of mix homogeneously on a molecular scale with one or more differential responses senses
The chain of group, dendroid, star-like, comb-shaped polymer.
The solid polymer electrolyte, which is that gather on a molecular scale by equally distributed solid-state for two or more polymer
Polymer electrolyte, preparation method comprise the steps：By a certain proportion of two or more polymer monomers, conducting salt and initiation
Mix homogeneously forms precursor solution on a molecular scale for agent, precursor solution is coated on base material or electrode surface, by poly-
The method of conjunction is prepared for solid polymer electrolyte, and the polymer precursor includes one or more forerunner of 10%-90%
One or more precursor B of body A and 10%-90%, the precursor A and precursor B contain different functional groups and can not be mutual
Phase reaction, the solid polymer contain one or more chains of polyethoxy chain, polycarbonate chain and containing one or many
Individual unsaturated double-bond, unsaturated three key, the acrylate of ethylenic unsaturated bond, epoxy radicals, nitrine functional group, amino.
Further, the precursor A is esters of acrylic acid, formate ester, ethylene glycol compounds, and contains insatiable hunger
With double bond, unsaturated three key, nitrine functional group or epoxy functionality；The precursor B is glycerol ether compound, and
Containing epoxy functionality, unsaturated double-bond, the solid polymer is chain, dendroid, star-like, comb-shaped polymer.
Further, electrical conductivity is higher than 2.3 × 10-4S/cm, preferably above 3.5 × 10-4S/cm。
Further, heat decomposition temperature is between 100-400, preferably between 150-300, it is further preferred
150-260。
Second object of the present invention is to provide a kind of metal ion and metal battery of solid polymer, and the battery includes
Positive pole, negative pole, solid polymer electrolyte, the solid polymer electrolyte are located between positive pole and negative pole, wherein described solid
The electrolyte that state polymer dielectric is provided for the present invention.
The present invention realizes that the technical scheme adopted by above-mentioned purpose is as follows：
The present invention provides a kind of preparation method of solid polymer electrolyte, comprises the steps：By a certain proportion of two
Mix homogeneously forms precursor solution on a molecular scale for kind or multiple polymers monomer, conducting salt and initiator, by presoma
Solution is coated on base material or electrode surface, is prepared for solid polymer electrolyte by the method being polymerized, will be the electrolyte direct
Assembled battery, the battery can be worked at a room temperature and a high temperature.
In above-mentioned preparation method, the polymer precursor include one or more precursor A of 10%-90% with
One or more precursor B of 10%-90%, the precursor A and precursor B contain different functional groups and can not be mutually contrary
Should, the solid polymer contains one or more chains of polyethoxy chain, polycarbonate chain and contains one or more not
Saturation double bond, unsaturated three key, the acrylate of ethylenic unsaturated bond, epoxy radicals, nitrine functional group, amino.The monomer
Molecular weight is between 100-50000.
Further preferably precursor A is 2-butyne -1- base chloro-formates, tetrolic acid ethyl ester, two propylene of 1,3 butylene glycol
Acid esters, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, glycol diacrylate, polypropylene glycol dipropyl
Olefin(e) acid ester, polypropylene glycol dimethacrylate, methacrylates, polyethyleneglycol diacrylate, methoxyl group
Propane trimethyl acrylic ester, ethoxylated trimethylolpropane triacrylate, ethoxylation tetramethylol methane tetrapropylene
Acid esters, ethoxylated neopentylglycol double methacrylate, ethylene glycol monomethyl ether acrylate, methoxypolyethylene glycol methacrylate,
Methacrylate, 2- hydroxyethylmethacry,ates, 2- HEMAs, seven poly- second two of O- (2- azidoethyls)
One or more in alcohol, O- (2- azidoethyls)-O '-methyl-triethylene glycol.
Further preferably precursor B be 1,2,3,4- butane diepoxides, BDDE, poly- (diformazan
Radical siloxane), 2-glycidyl is ether capped, 1,7- octadiene epoxides, polyethyleneglycol diglycidylether, poly- pentanediol
Diglycidyl ether, diglycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, 1,1,1- trifluoro epoxy
Propane, epoxy iso-butane, epoxy butane, glycidyl methyl ether, ethyl polyglycidyl, 2,3- epoxy butanes, seven fluorine butyl rings
One kind or several in oxidative ethane, epoxy tetrahydrofuran, 7-oxa-bicyclo[4.1.0, epoxy mono methoxy glycol ether, phenyl expoxy propane
Kind.The molar ratio of precursor A and B described in above-mentioned preparation method can be 1：(0.1-10).Plurality of A polymer As1、
A2、……AnMolar ratio can be 1：(0.1-10)：……：(0.1-10)；Plurality of B polymer B1、B2、……Bn's
Molar ratio can be 1：(0.1-10)：……：(0.1-10).
Most preferably, the precursor A is BDO diacrylate, while the precursor B is BDO
Diglycidyl ether.
In such scheme, the conducting salt can be sodium salt, lithium salts, magnesium salt, aluminium salt, potassium salt, calcium salt, zinc salt.It is preferred that lithium
Salt has LiClO4、LiPF6、LiBF4、Li(CF3SO2)、LiN(CF3SO2)2、Li[B(C2O4)2], the preferred NaClO of sodium salt4、NaN
(CF3SO2)2.Further preferably lithium salt is 0.1-10 mole per liter.It is in such scheme, described to prepare what molecular level mixed
Precursor solution, can be that the polymer monomer of liquid dissolves conducting salt and initiator as solvent.Can also be that other are easily waved
Send out nonaqueous solvent, such as lactams solvent, ester solvent, carbonate solvent, ether solvent, nitrile solvents, sulfolane solvent, phosphoric acid
Class, phosphoric acid ester solvent, ionic liquid class solvent, be used alone or be used in mixed way two kinds in the solvent or two kinds with
On.The preferred nitrogen of the solvent, nitrogen-dimethylformamide (DMF), acetonitrile, diethyl carbonate, dimethyl carbonate.Easily wave containing other
50 DEG C of drying 24h under vacuum are needed when sending out nonaqueous solvent.
In such scheme preparation method, polymerization methodses can be thermal polymerization, photopolymerization, Microwave Emulsifier-Free Polymerization, electrochemical polymerization, phase
The initiator answered can be thermal initiator, light trigger or be not added with initiator, and the mass fraction of initiator can be 0.05-
20%.The mode for preparing electrolyte is precursor solution to be coated in base material or electrode surface is polymerized, or by presoma
Assembled battery is carried out after suitable polymer dielectric film is obtained after polymerisation in solution.
In such scheme preparation method, the concentration of conducting salt is 0.1-10mol/L.
Application provided by the present invention is the preparation method and application of the solid polymer electrolyte for solid state battery, special
It is not the electrolyte as solid state lithium battery.
Compared with prior art, the present invention is provided solid polymer electrolyte its ionic conductivity, heat stability and energy
The electrolyte performance that the electrochemical window of tolerance is reported in being superior to document.This has benefited from by mutually nonreactive two kinds and various poly-
The electrolyte of the molecule rank mix homogeneously that compound is formed, reduces the ability of its orderly stacking for a kind of independent polymer,
Sub-chain motion ability and electrical conductivity are improved, and preferable mechanical performance can be kept again for the structure of whole polymer,
Ionic conductivity and heat stability are enabled while being maintained.Preparation method of the present invention is simple, and raw material is cheap and easily-available, prepares
Polymer dielectric excellent performance, be conducive to large-scale production.
Describe the present invention with reference to specific embodiment.Protection scope of the present invention is not being embodied as
Mode is limited, but is defined in the claims.
Description of the drawings
Fig. 1 present examples 1 prepare the thermogravimetric analysiss of polymer dielectric.
Fig. 2 present examples 1 prepare polymer electrolyte electrochemical window.
Fig. 3 present examples 1 are prepared polymer dielectric and filling of obtaining are matched with iron phosphate lithium positive pole and lithium anode
Discharge curve.
Specific implementation method
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiments, if no special instructions, is conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
(1) prepare polymer dielectric precursor solution：By 1,4 butanediol diacrylate, LiN (CF3SO2)2, Isosorbide-5-Nitrae-
Butanediol diglycidyl ether, benzoyl peroxide are 5 according to mass ratio:1:5:After 0.02 mixing, room temperature is uniformly mixed.
(2) prepare solid polymer electrolyte：By gained precursor solution in step 1 according to 50 microlitres every square centimeter
Ratio uniform is coated in politef substrate, thermal polymerization 3h in 200 DEG C of baking ovens.
(3) prepare lithium iron phosphate positive material：By resulting polymers presoma in LiFePO4, step 1, conductive black,
Vingon is according to mass ratio 7:1:1:1 mixing, adds N-Methyl pyrrolidone and makes homogeneous slurry, be uniformly coated
It is in aluminum foil current collector, vacuum dried, work positive pole is obtained after section.(4) lithium metal solid polymer electrolyte steel
The assembling of piece battery：, used as reference electrode, steel disc is used as the solid polymer electrolyte to preparing in electrode, step 2 for lithium metal
For electrolyte, the assembled battery in the glove box of argon filling.
Solid polymer electrolyte electrochemical window is tested：：-- solid polymer electrolyte -- steel disc assembling to lithium metal
Battery carry out linear voltammetric scan, sweep limitss are 0V to 6V, sweep speed for 0.1mV/s.
(5) assembling of lithium metal solid polymer electrolyte ferric phosphate lithium cell：Lithium metal is used as negative pole, iron phosphate
Lithium is electrolyte as the solid polymer electrolyte prepared in positive pole, step 2, the assembling electricity in the glove box of argon filling
Pond.
The battery of above-mentioned assembling is carried out on charge-discharge test instrument charge-discharge test.It is 2.5V- that test voltage is interval
4.25V.Battery capacity and charge-discharge magnification are with the Mass Calculation of LiFePO4.Battery is (close equivalent to electric current in 0.2C multiplying powers
Spend for 34mA g-1) lower 55 DEG C carry out charge and discharge cycles.Discharge capacity is up to 157.4mAh/g firstLFP(0.2C), after 20 times
Discharge capacity is 149.2mAh/gLFP.Coulombic efficiency is up to 99.5%.Test result is listed in Table 1 below.
Embodiment 2
Except thermal initiator benzoyl peroxide in embodiment 1 (1) is changed to light trigger 1- hydroxycyclohexyl phenyl ketones
Outside, and thermal polymerization is changed to into photopolymerization, in the position polyase 13 0 minute of 2 kilowatts of distance, 10 centimetres of uviol lamp.Other conditions are complete
Complete consistent, test performance is listed in Table 1 below.
Embodiment 3
Except thermal initiator in embodiment 1 (1) is changed to microwave initiator azodiisobutyronitrile, thermal polymerization is changed to Microwave Emulsifier-Free Polymerization
Outside, be polymerized under 10GHz, the power of 1000w 20min., other conditions are completely the same, and test performance is listed in Table 1 below.
Embodiment 4
Except thermal initiator in embodiment 1 (1) is changed to electrochemical initiation agent to cyano methyl essence of Niobe, thermal polymerization changes
Outside for electrochemical polymerization, fast 6mV/s polyase 13s 0min is swept.Other conditions are completely the same, and test performance is listed in Table 1 below.
Comparative example 1
(1) prepare polymer dielectric precursor solution：By 1,4 butanediol diacrylate, LiN (CF3SO2)2, cause
Agent benzoyl peroxide is 5 according to mass ratio:1:After 0.02 mixing, room temperature is uniformly mixed.
Other conditions are identical with embodiment 1, and test performance is listed in Table 1 below.
Comparative example 2
(1) prepare polymer dielectric precursor solution：By BDO glycidyl ether, LiN (CF3SO2)2, cause
Agent benzoyl peroxide is 5 according to mass ratio:1:After 0.02 mixing, room temperature is uniformly mixed.
Other conditions are identical with embodiment 1, and test performance is listed in Table 1 below.
Embodiment 5
In addition to BDO diacrylate in embodiment 1 (1) is changed into 2-butyne -1- base chloro-formates, other
Condition is in the same manner as in Example 1, and test performance is listed in Table 1 below.
Embodiment 6
Except thermal initiator benzoyl peroxide in embodiment 5 (1) is changed to light trigger 1- hydroxycyclohexyl phenyl ketones
Outside, and thermal polymerization is changed to into photopolymerization, in the position polyase 13 0 minute of 2 kilowatts of distance, 10 centimetres of uviol lamp.Other conditions are complete
Complete consistent, test performance is listed in Table 1 below.
Embodiment 7
Except thermal initiator in embodiment 5 (1) is changed to microwave initiator azodiisobutyronitrile, thermal polymerization is changed to Microwave Emulsifier-Free Polymerization
External 10GHz, be polymerized under the power of 1000w 20min., other conditions are completely the same, and test performance is listed in Table 1 below.
Embodiment 8
Except thermal initiator in embodiment 5 (1) is changed to electrochemical initiation agent to cyano methyl essence of Niobe, thermal polymerization changes
Outside for electrochemical polymerization, fast 6mV/s polyase 13s 0min is swept.Other conditions are completely the same, and test performance is listed in Table 1 below.
Comparative example 3
(1) prepare polymer dielectric precursor solution：By 2-butyne -1- base chloro-formates, LiN (CF3SO2)2, cause
Agent benzoyl peroxide is 5 according to mass ratio:1:After 0.02 mixing, room temperature is uniformly mixed.
Other conditions are identical with embodiment 5, and test performance is listed in Table 1 below.
Embodiment 9
Except changing 1,4 butanediol diacrylate in embodiment 1 (1) into O- (2- azidoethyls)-O '-methyl-three second two
Alcohol, initiator are occurred using benzoyl peroxide/DMA outside RAFT polymerizations, in other conditions and embodiment 1
Identical, test performance is listed in Table 1 below.
Embodiment 10
Except thermal initiator benzoyl peroxide in embodiment 9 (1) is changed to light trigger 1- hydroxycyclohexyl phenyl ketones
Outside, and thermal polymerization is changed to into photopolymerization, in the position polyase 13 0 minute of 2 kilowatts of distance, 10 centimetres of uviol lamp.Other conditions are complete
Complete consistent, test performance is listed in Table 1 below.
Embodiment 11
Except thermal initiator in embodiment 9 (1) is changed to microwave initiator azodiisobutyronitrile, thermal polymerization is changed to Microwave Emulsifier-Free Polymerization
Outside, be polymerized under 10GHz, the power of 1000w 20min.Other conditions are completely the same, and test performance is listed in Table 1 below.
Embodiment 12
Except thermal initiator in embodiment 9 (1) is changed to electrochemical initiation agent to cyano methyl essence of Niobe, thermal polymerization changes
Outside for electrochemical polymerization, fast 6mV/s polyase 13s 0min is swept.Other conditions are completely the same, and test performance is listed in Table 1 below.
Comparative example 4
(1) prepare polymer dielectric precursor solution：By O- (2- azidoethyls)-O '-methyl-triethylene glycol, LiN
(CF3SO2)2, initiator benzoyl peroxide/DMA according to mass ratio be 5:1:It is stirred at room temperature after 0.02 mixing
Mix homogeneously.
Other conditions are identical with embodiment 9, and test performance is listed in Table 1 below.
Embodiment 13 is except changing 1,4 butanediol diacrylate in embodiment 1 (1) into star-shape polymer ethoxylation four
Outside methylol methane tetraacrylate, other conditions are in the same manner as in Example 1, and test performance is listed in Table 1 below.
Embodiment 14
Except thermal initiator benzoyl peroxide in embodiment 13 (1) is changed to light trigger 1- hydroxycyclohexyl phenyl ketones
Outside, and thermal polymerization is changed to into photopolymerization, in the position polyase 13 0 minute of 2 kilowatts of distance, 10 centimetres of uviol lamp.Other conditions are complete
Complete consistent, test performance is listed in Table 1 below.
Embodiment 15
Except thermal initiator in embodiment 13 (1) is changed to microwave initiator azodiisobutyronitrile, thermal polymerization is changed to microwave and gathers
Outside conjunction, be polymerized under 10GHz, the power of 1000w 20min.Other conditions are completely the same, and test performance is listed in Table 1 below.
Embodiment 16
Except thermal initiator in embodiment 13 (1) is changed to electrochemical initiation agent to cyano methyl essence of Niobe, thermal polymerization
It is changed to outside electrochemical polymerization, sweeps fast 6mV/s polyase 13s 0min.Other conditions are completely the same, and test performance is listed in Table 1 below.
Comparative example 5
(1) prepare polymer dielectric precursor solution：By star-shape polymer ethoxylation tetramethylol methane tetrapropylene
Acid esters, LiN (CF3SO2)2, initiator benzoyl peroxide according to mass ratio be 5:1:Mixing is stirred at room temperature after 0.02 mixing equal
It is even.
Other conditions are identical with embodiment 13, and test performance is listed in Table 1 below.
Above-described embodiment and comparative example electrochemical property test are listed in table 1
Can be seen that by thermal polymerization or photopolymerization or Microwave Emulsifier-Free Polymerization or electrochemical polymerization from above-described embodiment and comparative example
There is synergistic enhancing effect between the polymer dielectric with multiple network structures for obtaining so that polymer is keeping original
While material higher thermal is stable, ionic conductivity and cyclical stability are improve.
In sum, method system of the present invention using the synergistic enhancing effect of multiple network structures in polymer by polymerization
Standby ionic conductivity and heat stability preferable solid polymer electrolyte, the solid-state lithium metal battery of assembling show compared with
Good discharge capacity and cyclical stability.The electrolyte also shows preferable pliability simultaneously, is adapted to prepare flexible device.This
Invention has the solid state electrolysis of macroion conductance and high thermal stability simultaneously there is provided preparation a kind of simple to operate, with low cost
The method of matter, with excellent application prospect.
Claims (9)
1. a kind of solid polymer electrolyte, which is two or more polymer equally distributed solid-state polymerization on a molecular scale
Thing electrolyte, preparation method comprise the steps：By a certain proportion of two or more polymer monomers, conducting salt and initiator
Mix homogeneously forms precursor solution on a molecular scale, and precursor solution is coated on base material or electrode surface, by polymerization
Method be prepared for solid polymer electrolyte, it is characterised in that：The polymer precursor include one kind of 10%-90% or
One or more precursor B of various precursor As and 10%-90%, the precursor A contain different functional groups with precursor B
And it is unable to interreaction, one or more chains that the solid polymer contains polyethoxy chain, polycarbonate chain and contain
One or more unsaturated double-bonds, unsaturated three key, the acrylate of ethylenic unsaturated bond, epoxy radicals, nitrine functional group, ammonia
Base.
2. solid polyelectrolyte according to claim 1, it is characterised in that：The precursor A is esters of acrylic acid, first
Esters of gallic acid, ethylene glycol compounds, and contain unsaturated double-bond, unsaturated three key, nitrine functional group or epoxy functional
Group；The precursor B is glycerol ether compound, and contains epoxy functionality, unsaturated double-bond, the solid polymer
For chain, dendroid, star-like, comb-shaped polymer.
3. the preparation method of solid polymer electrolyte according to claim 1, comprises the steps：By a certain proportion of two kinds
Or multiple polymers monomer, conducting salt and initiator on a molecular scale mix homogeneously formed precursor solution, presoma is molten
Liquid is coated on base material or electrode surface, is prepared for solid polymer electrolyte by the method being polymerized, it is characterised in that：It is described poly-
Compound presoma includes one or more precursor A of 10%-90% and one or more precursor B of 10%-90%, described
Precursor A contains different functional groups and is unable to interreaction with precursor B, and the solid polymer contains polyethoxy chain, gathers
One or more chains of chain carbonic ester and containing one or more unsaturated double-bonds, unsaturated three key, ethylenic unsaturated bond
Acrylate, epoxy radicals, nitrine functional group, amino；Preferred A is esters of acrylic acid material, and B is epoxy types；Further
Preferably, between 100-50000, precursor A is 2-butyne -1- base chloro-formates, 2-butyne to the molecular weight of the monomer
Acetoacetic ester, 1,3 butyleneglycol diacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, ethylene glycol
It is diacrylate, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, methacrylates, poly-
Glycol diacrylate, methoxy propane trimethyl acrylic ester, ethoxylated trimethylolpropane triacrylate, ethoxy
Base tetramethylol methane tetraacrylate, ethoxylated neopentylglycol double methacrylate, ethylene glycol monomethyl ether acrylate, poly- second
Glycol methyl ether methacrylate, methacrylate, 2- hydroxyethylmethacry,ates, 2- HEMAs,
One or more in O- (2- azidoethyls) seven Polyethylene Glycol, O- (2- azidoethyls)-O '-methyl-triethylene glycol, presoma
B is 1,2,3,4- butane diepoxides, BDDE, poly- (dimethyl siloxane), diglycidyl ether envelope
End, 1,7- octadiene epoxides, polyethyleneglycol diglycidylether, poly- pentanediol diglycidyl ether, 2-glycidyl
Ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, 1,1,1- trifluoro-epoxy propane, epoxy iso-butane, epoxy fourth
Alkane, glycidyl methyl ether, ethyl polyglycidyl, 2,3- epoxy butanes, seven fluorine butyl ethylene oxides, epoxy tetrahydrofuran, ring
One or more in oxygen hexamethylene, epoxy mono methoxy glycol ether, phenyl expoxy propane.
4. preparation method according to claim 3, it is characterised in that the molar ratio of the precursor A and B is 1：
(0.1-10), the A of plurality of precursor A1、A2、……AnMolar ratio be 1：(0.1-10)：……：(0.1-10)；Its
In multiple precursor Bs B1、B2、……BnMolar ratio be 1：(0.1-10)：……：(0.1-10).
5. the preparation method according to any one of claim 3-4, it is characterised in that the conducting salt is selected from sodium salt, lithium salts, magnesium
Salt, aluminium salt, potassium salt, calcium salt and zinc salt, preferred lithium salts are selected from LiClO4、LiPF6、LiBF4、Li(CF3SO2)、LiN(CF3SO2)2、
Li[B(C2O4)2], the preferred NaClO of sodium salt4、NaN(CF3SO2)2.Further preferably lithium salt is 0.1-10mol/l.
6. the preparation method described in any one of claim 3-5, it is characterised in that the presoma for preparing molecular level mixing is molten
Liquid, is that the polymer monomer of liquid dissolves conducting salt and initiator as solvent, or uses volatile nonaqueous solvent, such as interior acyl
Amine solvent, ester solvent, carbonate solvent, ether solvent, nitrile solvents, sulfolane solvent, phosphoric acid class, phosphoric acid ester solvent,
Ionic liquid class solvent, is used alone or is used in mixed way two kinds in the solvent or two or more；The solvent is preferred
DMF (DMF), acetonitrile, diethyl carbonate, dimethyl carbonate；Need true during other volatile nonaqueous solvents
The lower 50 DEG C of drying 24h of empty condition.
7. the preparation method described in any one of claim 3-6, it is characterised in that polymerization methodses are thermal polymerization, photopolymerization, microwave
Polymerization, electrochemical polymerization, corresponding initiator are thermal initiator, light trigger, microwave initiator, electrochemical initiation agent or not
Plus initiator, the mass fraction of initiator is 0.05-20%.
8. the preparation method described in any one of claim 3-7, it is characterised in that the concentration of conducting salt accounts for the concentration of total polymer
For 0.1-10mol/g.
9. the polymer dielectric that any one of claim 3-8 preparation method is prepared is used for the purposes of metal secondary batteries.
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