CN110527229A - A kind of all solid state plastic crystals flexible electrolyte film and preparation method thereof - Google Patents

A kind of all solid state plastic crystals flexible electrolyte film and preparation method thereof Download PDF

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Publication number
CN110527229A
CN110527229A CN201910815268.3A CN201910815268A CN110527229A CN 110527229 A CN110527229 A CN 110527229A CN 201910815268 A CN201910815268 A CN 201910815268A CN 110527229 A CN110527229 A CN 110527229A
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lithium
solid state
electrolyte
electrolyte film
ratio
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CN110527229B (en
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谢惠东
李明亚
王晓强
朱琳
曲袖杰
吴智升
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Northeastern University Qinhuangdao Branch
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Northeastern University Qinhuangdao Branch
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Abstract

A kind of all solid state plastic crystals flexible electrolyte film of the invention and preparation method thereof, belong to solid electrolyte preparation field, the substance for including in the electrolytic thin-membrane is main are as follows: high-molecular compound, plasticizer, organic plastic crystal matrices, lithium salts, additive, auxiliary agent etc..Casting method or extrusion molding is accordingly used to can be obtained corresponding all solid state plastic crystals flexible electrolyte film when preparation.Preparation method of the invention has many advantages, such as that preparation process is simple, obtained all solid state plastic crystals flexible electrolyte film conductivity is high, resistance to solar radiation, anti-aging, ultralow shrinking percentage, permeability are good, has a good application prospect in fields such as electrochromism, solar battery, flexible display screens.

Description

A kind of all solid state plastic crystals flexible electrolyte film and preparation method thereof
Technical field:
The invention belongs to technical field of inorganic nonmetallic materials, and in particular to a kind of all solid state plastic crystals flexible electrolyte Film and preparation method thereof.
Background technique:
Laminated safety glass with its safety, sound insulation, heat-insulated, uvioresistant, etc. excellent properties be widely used in construction industry； And the property and preparation method of the laminating layer among laminated glass also gradually cause the attention and research of people.
The solid polymer gel electrolyte being made of polymer and salt etc. is because that need not encapsulate liquid, avoid leakage and safety The advantages such as performance height cause exploration deep both at home and abroad.Many scholars are for solid polymer gel electrolyte in recent years Research is concentrated mainly on the electrolyte of design different structure and makes great efforts to improve two aspect of ionic conductivity；It is solidifying according to solid polymer The conductivity principle of glue electrolyte, it is main from poly- in order to increase ionic conductivity when designing composite solid state polymer dielectric Object matrix, alkali metal salt are closed, the several respects such as additive consider.
The present invention uses the high-molecular compounds such as polyvinyl alcohol, polyvinyl butyral for matrix, and lithium salts is alkali metal salt, Inorganic nano-particle is electrolyte additive, while using two kinds of preparation methods of casting method and extrusion by melting, one prepared The all solid state plastic crystals flexible electrolyte film of kind has bigger ionic conductivity, and performance is more stable, time that can be recycled Number is more, anti-aging to use the longer time, also more preferable for the attached performance of parent of glass, while having longer service life.
Summary of the invention:
The purpose of the present invention is overcoming above-mentioned the shortcomings of the prior art, a kind of simple process, low in cost, property are provided The stable all solid state plastic crystals flexible electrolyte film and preparation method thereof of energy, mainly solving the technical problems that solid state electrolysis The stability problem of matter film.
A kind of all solid state plastic crystals flexible electrolyte film of the present invention and preparation method thereof specifically includes that high score The Non-aqueous processing of the drugs such as sub- compound, plasticizer, organic plastic crystal matrices, lithium salts, electrolyte additive, auxiliary agent, colloidal sol The preparation of electrolyte precursor, the casting of film layer, drying and the test of film layer of film layer etc..
To achieve the above object, the invention adopts the following technical scheme:
A kind of all solid state plastic crystals flexible electrolyte film, including raw material and proportion are macromolecule chemical combination in mass ratio Object: organic plastic crystal matrices: lithium salts: electrolyte additive: plasticizer: auxiliary agent=1:(0.1-0.3): (0.5-0.7): (0.02-0.04): (0.04-0.08), by mass volume ratio, high-molecular compound: solvent=1:(0-10), unit g:ml.
The all solid state plastic crystals flexible electrolyte film raw material further includes auxiliary agent, the auxiliary agent be antioxidant, The mass ratio of one or more of age resister, the auxiliary agent and high-molecular compound is (0.001-0.005): 1.
The high-molecular compound is polyvinyl alcohol, polyvinyl butyral, ethylene-vinyl acetate copolymer, poly- first Base methyl acrylate, Kynoar, polyvinyl chloride, ethylene-vinyl alcohol copolymer, polytetrafluoroethylene (PTFE) or poly- (vinylidene- One or more of co- hexafluoropropene), when for several mixing, mixing ratio is any ratio.
The organic plastic crystal matrices are neutral organic plastic crystals matrix.
The neutral organic plastic crystals matrix be acetonitrile, succinonitrile, adiponitrile, neopentane, cyclohexylamine, cyclobutane, The trifluoromethane sulfonic acid inferior amine salt, polyacrylonitrile or trifluoromethyl sulphur of 5- methyl -5,6,7,8- tetrahydro-pyrazole quinoline (1,2- α) pyridazone One or more of acid imide, when for several mixing, mixing ratio is any ratio.
The plasticizer is terephthalic acid (TPA) dibutyl ester, two formic acid esters of dipropylene glycol, polyol benzoate, polynary One or more of alcohol benzoic ether or dipropylene glycol, when for several mixing, mixing ratio is any ratio.
The lithium salts is bis trifluoromethyl sulfimide lithium, lithium perchlorate, difluoro lithium borate, double-perfluoroethyl sulfonyl Imine lithium, lithium carbonate, LiBF4, hexafluoroarsenate lithium, lithium hexafluoro phosphate, lithium rhodanate, tetrafluoro lithium aluminate, lithium chloride, iodine Change one of lithium, lithium bromide, tetrafluoro oxalic acid lithium phosphate, dioxalic acid lithium phosphate, difluorine oxalic acid boracic acid lithium or trifluoromethanesulfonic acid lithium Or it is several, when for several mixing, mixing ratio is any ratio.
The solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dehydrated alcohol, propene carbonate, carbon One or more of dimethyl phthalate, ethyl cellulose, dimethyl acetamide or methyl methacrylate, when for several mixing When, mixing ratio is any ratio.
The electrolyte additive is inorganic nano-particle.
The inorganic nano-particle is Nano-meter SiO_22, nano-TiO2, nanometer Al2O3, nano-ZnO, nanometer ZrO2, nanometer Ta2O5, nano Ce O2, nanometer MoO3, nano-MgO or nanometer Nb2O5One or more of, when for several mixing, mixing ratio Arbitrarily to compare.
The all solid state plastic crystals flexible electrolyte film has 10-3-10-6Ionic conductivity, service life circulation Number reaches 100000-1000000 times, at applied voltage -3V~3V: initial volt-ampere circulation peak point current is 3.4-28mA, After circulation 100000-1000000 times, peak point current is stablized in 3.3-27mA, and decaying is no more than 10%；It is continuous in the UV lamp to shine It after penetrating 15 days, recycles 100000-1000000 times, peak point current is stablized in 3-25.5mA, and decaying is no more than 15%.
The all solid state electrolyte film with a thickness of 50-1000 μm, use different manufacture crafts or drying time Film thickness can be had some impact on temperature difference, it is bigger compared to casting method film thickness using extrusion by melting, it does The higher film thickness of dry time longer temperature is smaller, and film thickness is uniform, and flatness is high, and surface roughness is less than 10nm.
The preparation method of all solid state electrolyte film, using casting method or extrusion molding, comprising the following steps:
Step 1, stock:
In mass ratio, high-molecular compound: organic plastic crystal matrices: lithium salts: electrolyte additive: plasticizer=1: (0.1-0.3): (0.5-0.7): (0.02-0.04): (0.04-0.08), by mass volume ratio, high-molecular compound: solvent= 1:(0-10), unit g:ml, stock；
Step 2, film preparation:
When preparing film using casting method, steps are as follows:
Using first preparing electrolyte precursor, concrete operations scheme when casting method are as follows:
1, electrolyte precursor preparation:
By load weighted high-molecular compound, organic plastic crystal matrices, lithium salts, solvent, electrolyte additive and plasticising Agent mixing, is added the solvent of respective volume, is uniformly mixed, and obtains electrolyte precursor；
2, casting:
Electrolyte precursor is cast to release film, it is dry after natural levelling, all solid state electrolyte film is made；
When preparing film using extrusion by melting, steps are as follows:
After high-molecular compound, organic plastic crystal matrices, lithium salts, electrolyte additive and plasticizer are mixed, heating To molten condition, after slowly squeezing out, all solid state electrolyte film is made.
In the step two, high-molecular compound, organic plastic crystal matrices, lithium salts, electrolyte additive, plasticizer It is intended to do Non-aqueous processing, specific processing method before use with auxiliary agent are as follows: each substance is put into sealed environment, passes through vacuum pump Environment is evacuated to vacuum state, is then heated to 50-90 DEG C, keeps the temperature 24-28h.
In the step two 1, when using casting method, electrolyte precursor is cast under water-less environment.
In the step two 1, when using casting method, mass volume ratio is pressed in raw material, high-molecular compound: solvent=1: (7-10), unit g:ml.
In the step 21,
Each uniform detailed process of material mixing are as follows: after each material mixing is sealed, and start to be heated in stirring, Agitating mode is mechanical stirring or magnetic agitation, and mixing time 20-26h, heating temperature is 40-60 DEG C, heating time 1- 3h is uniformly mixed, and obtains electrolyte precursor.
In the step 22, detailed process of casting are as follows:
(1) release film is attached on glass substrate or ptfe substrate, with alcohol swab wiped clean；
(2) glass substrate or ptfe substrate of having release film are leveled with level meter；
(3) part electrolyte precursor drop is drawn on release film with rubber head dropper, repeatedly after 2-4 times, natural levelling；
(4) electrolyte precursor of levelling is covered with clean culture dish, after spontaneously drying 20-28h, is put into vacuum environment Middle heat drying 20-26h, heating temperature are 45-60 DEG C, and all solid state electrolyte film is made.
In the step two 2, when using extrusion by melting, quantity of solvent is 0 in raw material.
In the step two, when film raw material contains auxiliary agent, when using casting method, it is added and helps after heating 1-3h Agent is uniformly mixed, and obtains electrolyte precursor；When using extrusion by melting, auxiliary agent directly with high-molecular compound, organic plastic Crystal substrate, lithium salts, electrolyte additive and plasticizer mixing, after being heated to molten condition, slowly squeeze out.
Beneficial effects of the present invention:
All solid state plastic crystals flexible electrolyte film prepared by the present invention is compared to used in doubling glass on the market Electrolyte performance is more stable, and the number that can be recycled is more, anti-aging to use the longer time, attached simultaneously for the parent of glass Performance is also more preferable.
Specific embodiment:
Below with reference to embodiment, the present invention is described in further detail.
The used raw material of solid plastics crystal flexible electrolyte film is prepared in following example is purchased from lark prestige reagent Company.
Ultraviolet lamp model ZF-7；Illumination wavelength is 365nm；
The auxiliary agent is antioxidant or age resister；
The high-molecular compound is polyvinyl alcohol (molecular formula: [- CH2CHOH-] n, molecular weight: 44.05), polyethylene Butyral (MW25000-40000), ethylene-vinyl acetate copolymer (vinyl acetate 40wt.%, melt index 52g/10min (190 DEG C/2.16kg)) polymethyl methacrylate (molecular formula [C5H8O2] n, molecular weight Beilstein), Kynoar (molecular formula: (CH2CF2) n, purity: Mn~107,000 average MW~275,000by GPC, average, Pellets), polyvinyl chloride (MW80000-100000), ethylene-vinyl alcohol copolymer (ethylene 60wt.%), polytetrafluoroethylene (PTFE) (molecular formula-[- CF2-CF2-] n-, molecular weight 5000-15000) or poly- (vinylidene-co- hexafluoropropene) (average Mw ~400,000 (bimodal distribution), average Mn~130,000, pellets)；
The neutral organic plastic crystals matrix is acetonitrile (purity 99.9%, MW41.05), succinonitrile (purity 99% MW80.09), adiponitrile, neopentane, cyclohexylamine (purity 99.5%, molecular formula C6H13N, molecular weight 99.18), cyclobutane, 5- first The trifluoromethane sulfonic acid inferior amine salt, polyacrylonitrile ((C of base -5,6,7,8- tetrahydro-pyrazole quinoline (1,2- α) pyridazone3H3)n ) or trifluoromethane sulfonic acid imines MW150000；
The plasticizer is terephthalic acid (TPA) dibutyl ester, dipropylene glycol dibenzoate (purity 80%), polyalcohol benzene Formic acid esters or dipropylene glycol (purity 99%)；
The lithium salts is bis trifluoromethyl sulfimide lithium (anhydrous grade 99.99%), lithium perchlorate (anhydrous grade 99.99%), difluoro lithium borate, double-perfluoroethyl sulfonyl imine lithium, lithium carbonate (purity 97%), LiBF4 (purity 99%), hexafluoroarsenate lithium, lithium hexafluoro phosphate (purity > 97%), lithium rhodanate, tetrafluoro lithium aluminate, lithium chloride (purity > 99%), Lithium iodide (anhydrous grade 99.99%), lithium bromide (purity 99.99%), tetrafluoro oxalic acid lithium phosphate, dioxalic acid lithium phosphate, difluoro grass Sour lithium borate (99%, water content≤200ppm) or trifluoromethanesulfonic acid lithium (purity 98%)；
The solvent is N,N-dimethylformamide (AR 99.5%), DMAC N,N' dimethyl acetamide (AR 99%), nothing Water-ethanol (AR), propene carbonate (AR 99.5%), dimethyl carbonate (anhydrous grade, >=99%), ethyl cellulose (18- 22mPa.s, 5% toluene/isopropanol 80:20), dimethyl acetamide or methyl methacrylate (AR 99.0%, contain 30ppmMEHQ stabilizer)；
The inorganic nano-particle is Nano-meter SiO_22(15 ± 5nm of average grain diameter, 250 ± 30m of specific surface area2/ g), nanometer TiO2(average grain diameter 40nm), nanometer Al2O3(γ phase, average grain diameter 20nm), nano-ZnO (30 ± 10nm of average grain diameter), nanometer ZrO2(20 ± 5nm of average grain diameter), nanometer Ta2O5(average grain diameter 25nm), nano Ce O2(30 ± 5nm of average grain diameter), nanometer MoO3(average grain diameter 35nm), nano-MgO (average grain diameter 50nm) or nanometer Nb2O5(average grain diameter 30nm).
A kind of all solid state plastic crystals flexible electrolyte film, including raw material and proportion are macromolecule chemical combination in mass ratio Object: organic plastic crystal matrices: lithium salts: electrolyte additive: plasticizer: auxiliary agent=1:(0.1-0.3): (0.5-0.7): (0.02-0.04): (0.04-0.08), by mass volume ratio, high-molecular compound: solvent=1:(0-10), unit g:ml.
The all solid state plastic crystals flexible electrolyte film raw material further includes auxiliary agent, the auxiliary agent be antioxidant, The mass ratio of one or more of age resister, the auxiliary agent and high-molecular compound is (0.001-0.005): 1.
The high-molecular compound is polyvinyl alcohol, polyvinyl butyral, ethylene-vinyl acetate copolymer, poly- first Base methyl acrylate, Kynoar, polyvinyl chloride, ethylene-vinyl alcohol copolymer, polytetrafluoroethylene (PTFE) or poly- (vinylidene- One or more of co- hexafluoropropene), when for several mixing, mixing ratio is any ratio.
The organic plastic crystal matrices are neutral organic plastic crystals matrix.
The neutral organic plastic crystals matrix be acetonitrile, succinonitrile, adiponitrile, neopentane, cyclohexylamine, cyclobutane, The trifluoromethane sulfonic acid inferior amine salt, polyacrylonitrile or trifluoromethyl sulphur of 5- methyl -5,6,7,8- tetrahydro-pyrazole quinoline (1,2- α) pyridazone One or more of acid imide, when for several mixing, mixing ratio is any ratio.
The plasticizer is terephthalic acid (TPA) dibutyl ester, two formic acid esters of dipropylene glycol, polyol benzoate, polynary One or more of alcohol benzoic ether or dipropylene glycol, when for several mixing, mixing ratio is any ratio.
The lithium salts is bis trifluoromethyl sulfimide lithium, lithium perchlorate, difluoro lithium borate, double-perfluoroethyl sulfonyl Imine lithium, lithium carbonate, LiBF4, hexafluoroarsenate lithium, lithium hexafluoro phosphate, lithium rhodanate, tetrafluoro lithium aluminate, lithium chloride, iodine Change one of lithium, lithium bromide, tetrafluoro oxalic acid lithium phosphate, dioxalic acid lithium phosphate, difluorine oxalic acid boracic acid lithium or trifluoromethanesulfonic acid lithium Or it is several, when for several mixing, mixing ratio is any ratio.
The solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dehydrated alcohol, propene carbonate, carbon One or more of dimethyl phthalate, ethyl cellulose, dimethyl acetamide or methyl methacrylate, when for several mixing When, mixing ratio is any ratio.
The electrolyte additive is inorganic nano-particle.
The inorganic nano-particle is Nano-meter SiO_22, nano-TiO2, nanometer Al2O3, nano-ZnO, nanometer ZrO2, nanometer Ta2O5, nano Ce O2, nanometer MoO3, nano-MgO or nanometer Nb2O5One or more of, when for several mixing, mixing ratio Arbitrarily to compare.
The all solid state plastic crystals flexible electrolyte film has 10-3-10-6Ionic conductivity, service life circulation Number reaches 100000-1000000 times, at applied voltage -3V~3V: initial volt-ampere circulation peak point current is 3.4-28mA, After circulation 100000-1000000 times, peak point current is stablized in 3.3-27mA, and decaying is no more than 10%；It is continuous in the UV lamp to shine It after penetrating 15 days, recycles 100000-1000000 times, peak point current is stablized in 3-25.5mA, and decaying is no more than 15%, wherein initial Volt-ampere circulation peak point current is the peak point current after volt-ampere recycles 20 times.
The all solid state electrolyte film with a thickness of 50-1000 μm, use different manufacture crafts or drying time Film thickness can be had some impact on temperature difference, it is bigger compared to casting method film thickness using extrusion by melting, it does The higher film thickness of dry time longer temperature is smaller, and film thickness is uniform, and flatness is high, and surface roughness is less than 10nm.
The preparation method of all solid state electrolyte film, using casting method or extrusion molding, comprising the following steps:
Step 1, stock:
In mass ratio, high-molecular compound: organic plastic crystal matrices: lithium salts: electrolyte additive: plasticizer=1: (0.1-0.3): (0.5-0.7): (0.02-0.04): (0.04-0.08), by mass volume ratio, high-molecular compound: solvent= 1:(0-10), unit g:ml, stock；
Step 2, film preparation:
When preparing film using casting method, steps are as follows:
Using first preparing electrolyte precursor, concrete operations scheme when casting method are as follows:
1, electrolyte precursor preparation:
(1) by load weighted high-molecular compound, organic plastic crystal matrices, lithium salts, solvent, electrolyte additive and increasing Agent mixing is moulded, the solvent of respective volume is added, is uniformly mixed；
(2) by the medication containment mixed it is good after be put into magnetic stirring apparatus, magnetic agitation, magnetic force are carried out under heating condition Mixing time is 20-26h, and heating temperature is 40-60 DEG C, heating time 1-3h, is uniformly mixed, obtains electrolyte precursor；
2, casting:
(1) release film is attached on glass substrate or ptfe substrate, with alcohol swab wiped clean；
(2) glass substrate or ptfe substrate of having release film are leveled with level meter；
(3) part electrolyte precursor drop is drawn on release film with rubber head dropper, repeatedly after 2-4 times, natural levelling；
(4) electrolyte precursor of levelling is covered with clean culture dish, after spontaneously drying 20-28h, is put into vacuum environment Middle heat drying 20-26h, heating temperature are 45-60 DEG C, and all solid state electrolyte film is made；
When preparing film using extrusion by melting, steps are as follows:
After high-molecular compound, organic plastic crystal matrices, lithium salts, electrolyte additive and plasticizer are mixed, heating To molten condition, after slowly squeezing out, all solid state electrolyte film is made.
In the step two, high-molecular compound, organic plastic crystal matrices, lithium salts, electrolyte additive, plasticizer It is intended to do Non-aqueous processing, specific processing method before use with auxiliary agent are as follows: each substance is put into sealed environment, passes through vacuum pump Environment is evacuated to vacuum state, is then heated to 50-90 DEG C, keeps the temperature 24-28h.
In the step two, when film raw material contains auxiliary agent, when using casting method, it is added and helps after heating 1-3h Agent is uniformly mixed, and obtains electrolyte precursor；When using extrusion by melting, auxiliary agent directly with high-molecular compound, organic plastic Crystal substrate, lithium salts, electrolyte additive and plasticizer mixing, after being heated to molten condition, slowly squeeze out.
In the step two 1, when using casting method, electrolyte precursor is cast under water-less environment；Matter is pressed in raw material Measure volume ratio, high-molecular compound: solvent=1:(7-10), unit g:ml.
In the step two 2, when using extrusion by melting, quantity of solvent is 0 in raw material.
Embodiment 1
A kind of preparation method of all solid state plastic crystals flexible electrolyte film, comprising the following steps:
(1) by 1g macromolecular compound polyvinyl alcohol butyral (MW25000-4000), 0.5g bis trifluoromethyl sulphonyl is sub- Amine lithium (anhydrous grade 99.99%), 0.2g succinonitrile (purity 99%, MW80.09), 0.04g terephthalic acid (TPA) dibutyl ester, 0.03g Nanosized SiO_2 (15 ± 5nm of average grain diameter, 250 ± 30m of specific surface area2/ g) and 10ml solvent N,N-dimethylformamide (AR 99.5%) it is added in the vial that a volume is 20ml, is placed in magnetic stirring apparatus and stirs for 24 hours, and is rigid in magnetic agitation The age resister Tinuvin571 of 3.45mg is added in 50 DEG C of heating stirring 2-3h when beginning thereto, is thoroughly mixed uniformly Afterwards, it is stand-by to obtain electrolyte solution.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment Middle natural drying 22h, then 60 DEG C of heat drying 22h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film, should For electrolytic thin-membrane with a thickness of 570 μm, surface roughness 8nm, ionic conductivity is 1.2 × 10-5S/cm。
(4) electrolytic thin-membrane prepared by the case study on implementation measures cyclic voltammetry curve, initial volt-ampere under the conditions of -3v~3v Circulation peak point current is 3.5mA, is recycled 250000 times, and current peak is stablized in 3.4mA.
(5) it after electrolytic thin-membrane prepared by the case study on implementation irradiates 15 days in the UV lamp, is recycled under the conditions of -3v~3v 250000 times, current peak is stablized in 3.2mA.
Embodiment 2
(1) by 1g macromolecular compound polyvinyl alcohol (molecular formula: [- CH2CHOH-] n, molecular weight: 44.05), 0.6g high Lithium chlorate (anhydrous grade 99.99%), 0.25g acetonitrile (purity 99.9%, MW41.05), 0.05g dipropylene glycol, 0.03g receives Rice TiO2(average grain diameter 40nm) and 10ml solvent absolute ethyl alcohol (AR) is added in the vial that a volume is 20ml, places It is stirred for 24 hours in magnetic stirring apparatus, and 50 DEG C of heating stirring 2-3h when magnetic agitation just starts, is added 3.4mg's thereto Age resister Tinuvin571, it is stand-by after being thoroughly mixed uniformly.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment Middle natural drying 2h, then 70 DEG C of heat drying 22h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film, should For electrolytic thin-membrane with a thickness of 400 μm, surface roughness 7nm, ionic conductivity is 3.2 × 10-5S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 6.5mA, circulation 300000 Secondary, current peak is stablized in 6.4mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 300000 times under the conditions of -3v~3v, current peak Value is stablized in 6mA.
Embodiment 3
(1) by 1g high-molecular compound ethylene-vinyl acetate copolymer (vinyl acetate 40wt.%, melt index 52g/ 10min (190 DEG C/2.16kg)), 0.55g LiBF4 (purity 99%), 0.16g succinonitrile (purity 99%, MW80.09), 0.045g polyol benzoate, 0.04g nanometers of NbO (average grain diameter 30nm), 4mg antioxidant butylated hydroxy anisole and 10ml solvent dimethyl acetamide is added in the vial that a volume is 20ml, is placed in magnetic stirring apparatus and stirs for 24 hours, and The age resister Tinuvin571 of 3.5mg is added thereto, sufficiently stirs by 50 DEG C of heating stirring 2-3h when magnetic agitation just starts It mixes stand-by after mixing.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment For 24 hours, then for 24 hours, all solid state plastic crystals flexible electrolyte film can be obtained in 60 DEG C of heat dryings of vacuum for middle natural drying, should For electrolytic thin-membrane with a thickness of 360 μm, surface roughness 3nm, ionic conductivity is 3.6 × 10-5S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 8mA, is recycled 400000 times, Current peak is stablized in 7.7mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 400000 times under the conditions of -3v~3v, current peak Value is stablized in 7mA.
Embodiment 4
(1) by 1g macromolecular compound polyvinyl alcohol butyral polyvinyl butyral (MW25000-4000), 0.65g high Lithium chlorate (anhydrous grade 99.99%), 0.15g cyclohexylamine cyclohexylamine (purity 99.5%, molecular formula C6H13N, molecular weight 99.18), 0.02g nanometers of ZrO (20 ± 5nm of average grain diameter) and 10ml solvent methyl methyl acrylate methyl methacrylate (AR 99.0%, stabilizer containing 30ppmMEHQ) it is added in the vial that a volume is 20ml, it is placed in magnetic stirring apparatus and stirs For 24 hours, the age resister of 3.45mg is added in 55 DEG C of heating stirring 2-3h and when magnetic agitation just starts thereto Tinuvin571, it is stand-by after being thoroughly mixed uniformly.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment Middle natural drying 26h, then 70 DEG C of heat drying 26h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film, should For electrolytic thin-membrane with a thickness of 300 μm, surface roughness 5nm, ionic conductivity is 6.6 × 10-4S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 22mA, circulation 340000 Secondary, current peak is stablized in 21mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 340000 times under the conditions of -3v~3v, current peak Value is stablized in 19.5mA.
Embodiment 5
(1) by 1g macromolecular compound polyvinyl alcohol butyral (MW25000-4000), 0.65g lithium perchlorate (anhydrous grade 99.99%), 0.68g lithium carbonate (purity 97%), 0.3g cyclobutane, 0.04g nanometers of TaO (average grain diameter 25nm), 0.04g are more (individual is added in N,N-dimethylformamide (AR 99.5%) for first alcohol benzoic ether and 10ml solvent N,N-dimethylformamide Product is to be placed in magnetic stirring apparatus and stir for 24 hours, and 50 DEG C of heating stirrings when magnetic agitation just starts in the vial of 20ml The age resister Tinuvin571 of 3.45mg is added in 2-3h thereto, stand-by after being thoroughly mixed uniformly.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment For 24 hours, then for 24 hours, all solid state plastic crystals flexible electrolyte film can be obtained in 70 DEG C of heat dryings of vacuum for middle natural drying, should For electrolytic thin-membrane with a thickness of 320 μm, surface roughness 2nm, ionic conductivity is 1.1 × 10-3S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 28mA, circulation 430000 Secondary, current peak is stablized in 27mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 430000 times under the conditions of -3v~3v, current peak Value is stablized in 25.5mA.
Embodiment 6
(1) by 1g high-molecular compound ethylene-vinyl acetate copolymer (vinyl acetate 40wt.%, melt index 52g/ 10min (190 DEG C/2.16kg)), 0.6g LiBF4 (purity 99%), 0.15g trifluoromethane sulfonic acid imines, 0.03g nanometers CeO (30 ± 5nm of average grain diameter), two formic acid esters of 0.07g dipropylene glycol, 2.5mg antioxidant tertiary butyl hydroquinone and 10ml solvent absolute ethyl alcohol is added in the vial that a volume is 20ml, is placed in magnetic stirring apparatus and stirs for 24 hours, and in magnetic 50 DEG C of heating stirring 2-3h when power stirring just starts, the age resister Tinuvin571 of 3.45mg is added thereto, is sufficiently stirred It is stand-by after mixing.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment Middle natural drying 27h, then 70 DEG C of heat drying 27h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film, should For electrolytic thin-membrane with a thickness of 160 μm, surface roughness 7nm, ionic conductance is 1.02 × 10-6S/cm。
(4) electrolytic thin-membrane measures cyclic voltammetry curve under the conditions of -3v~3v, and initial volt-ampere circulation peak point current is 3.4mA is recycled 460000 times, and current peak is stablized in 3.3mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 460000 times under the conditions of -3v~3v, current peak Value is stablized in 3mA.
Embodiment 7
(1) by 1g high-molecular compound ethylene-vinyl alcohol copolymer, 0.55g lithium hexafluoro phosphate lithium hexafluoro phosphate (purity > 97%), 0.25g polyacrylonitrile ((C3H3) n MW150000), 0.03g nano-MgO (average grain diameter 50nm), the contracting of 0.065g mono- two It is 20ml's that a volume, which is added, in propylene glycol, 2.5mg antioxidant tertiary butyl hydroquinone and 10ml solvent absolute ethyl alcohol (AR) It in vial, is placed in magnetic stirring apparatus and stirs 23h, and 50 DEG C of heating stirrings 2-3h, Xiang Qi when magnetic agitation just starts The middle age resister Tinuvin571 that 3.45mg is added, it is stand-by after being thoroughly mixed uniformly.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment For 24 hours, then for 24 hours, all solid state plastic crystals flexible electrolyte film can be obtained in 65 DEG C of heat dryings of vacuum for middle natural drying, should For electrolytic thin-membrane with a thickness of 325 μm, surface roughness 6nm, ionic conductivity is 4.1 × 10-5S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 13mA, circulation 520000 Secondary, current peak is stablized in 12.5mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 520000 times under the conditions of -3v~3v, current peak Value is stablized in 11.5mA.
Embodiment 8
(1) by 1g macromolecular compound polyvinyl alcohol butyral (MW25000-40000), 0.6g trifluoromethanesulfonic acid lithium is (pure It spends 98%), 0.2g cyclobutane, 0.06g polyol benzoate, 0.04g Nano-meter SiO_22(15 ± 5nm of average grain diameter, specific surface area 250±30m2/ g) mixing after be heated to molten condition.
(2) drug of molten condition is slowly uniformly squeezed out, all solid state plastic crystals flexible electrolyte film can be obtained, For electrolytic thin-membrane with a thickness of 652 μm, surface roughness 9nm, ionic conductivity is 1.3 × 10-5S/cm。
(3) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 8.5mA, circulation 600000 Secondary, current peak is stablized in 8.3mA.
(4) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 600000 times under the conditions of -3v~3v, current peak Value is stablized in 7.9mA.
Embodiment 9
(1) by 1g macromolecular compound polyvinyl alcohol polyvinyl alcohol (molecular formula: [- CH2CHOH-] n, molecular weight: 44.05), 0.65g lithium iodide (anhydrous grade 99.99%), 0.3g adiponitrile, 0.02g nanometers of MoO (average grain diameter 35nm), 0.07g Dipropylene glycol, 3mg antioxidant dibutyl hydroxy toluene.
(2) drug of molten condition slowly uniformly squeezes out, and all solid state plastic crystals flexible electrolyte film can be obtained, electricity Solving matter film thickness is 860 μm, surface roughness 9nm, and ionic conductivity is 3 × 10-5S/cm。
(3) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 14mA, circulation 700000 Secondary, current peak is stablized in 13.5mA.
(4) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 700000 times under the conditions of -3v~3v, current peak Value is stablized in 12.4mA.
Embodiment 10
(1) by 1g high-molecular compound polytetrafluoroethylene (PTFE), 0.6g difluorine oxalic acid boracic acid lithium (99%, water content≤ 200ppm), cyclohexylamine (purity 99.5%, molecular formula C6H13N, molecular weight 99.18), 0.02g nanometers of Al2O3(γ phase, average grain Diameter 20nm), 0.065g dipropylene glycol, 4mg age resister Tinuvin571 mixing after be heated to molten condition.
(2) drug of molten condition slowly uniformly squeezes out, and all solid state plastic crystals flexible electrolyte film can be obtained, electricity Solving matter film thickness is 700 μm, surface roughness 6nm, and ionic conductivity is 2.8 × 10-5S/cm。
(3) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 13.6mA, circulation 580000 Secondary, current peak is stablized in 13mA.
(4) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 580000 times under the conditions of -3v~3v, current peak Value is stablized in 12mA.
Embodiment 11
A kind of preparation method of all solid state plastic crystals flexible electrolyte film, comprising the following steps:
(1) by 1g macromolecular compound polyvinyl alcohol butyral (MW25000-4000), 0.5g bis trifluoromethyl sulphonyl is sub- Amine lithium (anhydrous grade 99.99%), 0.5g polymethyl methacrylate (molecular formula [C5H8O2] n, molecular weight Beilstein), Two formic acid esters of 0.04g terephthalic acid (TPA) dibutyl ester and dipropylene glycol mixture of 1:1 in mass ratio, 0.03g nano-ZnO are (flat Equal 30 ± 10nm of partial size) and 10ml solvent propene carbonate (AR 99.5%) volume is added to put in the vial of 20ml It is placed in magnetic stirring apparatus and stirs for 24 hours, and 50 DEG C of heating stirring 2-3h when magnetic agitation just starts, 4.5mg is added thereto Age resister Tinuvin571, be thoroughly mixed uniformly after, obtain electrolyte solution it is stand-by.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment Middle natural drying 27h, then 70 DEG C of heat drying 28h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film, should For electrolytic thin-membrane with a thickness of 80 μm, surface roughness 7nm, ionic conductivity is 2.9 × 10-5S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 14.5mA, circulation 760000 Secondary, current peak is stablized in 14mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 760000 times under the conditions of -3v~3v, current peak Value is stablized in 13mA.
Embodiment 12
A kind of preparation method of all solid state plastic crystals flexible electrolyte film, comprising the following steps:
(1) by 1g macromolecular compound polyvinyl alcohol butyral, 0.6g lithium perchlorate (anhydrous grade 99.99%), 0.5g are poly- Vinylidene (molecular formula: (CH2CF2) n, purity: Mn~107,000 average MW~275,000by GPC, average, Pellets), 0.1g trifluoromethane sulfonic acid imines, 0.04g polyol benzoate, 0.03g nano-ZnO (average grain diameter 30 ± It 10nm) is added in the vial that a volume is 20ml with 10ml solvent n,N-dimethylacetamide (AR 99%), is placed in magnetic It is stirred for 24 hours in power blender, and 50 DEG C of heating stirring 2-3h when magnetic agitation just starts, the anti-aging of 5mg is added thereto After being thoroughly mixed uniformly, it is stand-by to obtain electrolyte solution by agent Tinuvin571.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment For 24 hours, then 60 DEG C of heat drying 26h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film for middle natural drying, should For electrolytic thin-membrane with a thickness of 315 μm, surface roughness 4nm, ionic conductivity is 3.1 × 10-5S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 14mA, is recycled 900000 times, Current peak is stablized in 13.5mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 900000 times under the conditions of -3v~3v, current peak Value is stablized in 12.7mA.
Embodiment 13
A kind of preparation method of all solid state plastic crystals flexible electrolyte film, comprising the following steps:
(1) by 1g macromolecular compound polyvinyl alcohol butyral (MW25000-4000), 0.55g lithium chloride (purity > 99%), 0.3g trifluoromethane sulfonic acid imines, 0.05g polyol benzoate, 0.03g nano-ZnO (30 ± 10nm of average grain diameter) It is added with 10ml solvent dimethyl carbonate (anhydrous grade, >=99%) in the vial that a volume is 20ml, is placed in magnetic force and stirs It mixes in device and stirs for 24 hours, and 50 DEG C of heating stirring 2-3h when magnetic agitation just starts, the age resister of 4.5mg is added thereto After being thoroughly mixed uniformly, it is stand-by to obtain electrolyte solution by Tinuvin571.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment Middle natural drying 26h, then 70 DEG C of heat drying 28h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film, electricity Solving matter film thickness is 120 μm, surface roughness 6nm, and ionic conductivity is 0.6 × 10-5S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 10mA, is recycled 880000 times, Current peak is stablized in 9.6mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 880000 times under the conditions of -3v~3v, current peak Value is stablized in 9mA.
Embodiment 14
A kind of preparation method of all solid state plastic crystals flexible electrolyte film, comprising the following steps:
(1) by 1g macromolecular compound polyvinyl alcohol butyral (MW25000-4000), 0.7g bis trifluoromethyl sulphonyl is sub- Amine lithium (anhydrous grade 99.99%), 0.7g polytetrafluoroethylene (PTFE) and poly- (vinylidene-co- hexafluoropropene) mixing of 1:1 in mass ratio Object, 0.2g trifluoromethane sulfonic acid imines, 0.08g dipropylene glycol, 0.03g nano-ZnO (30 ± 10nm of average grain diameter) and 10ml solvent n,N-dimethylacetamide (AR 99%) is added in the vial that a volume is 20ml, is placed in magnetic agitation It is stirred for 24 hours in device, and 50 DEG C of heating stirring 2-3h when magnetic agitation just starts, the age resister of 3.45mg is added thereto After Tinuvin571 is thoroughly mixed uniformly, it is stand-by to obtain electrolyte solution.
(2) substrate with release film is leveled with level meter, is then drawn in a part of step (1) with rubber head dropper Electrolyte solution, slowly drop is on release film, repeatedly for three times, allows electrolyte natural levelling on release film.
(3) the liquid electrolyte plasma membrane after levelling in step (2) is covered to clean culture dish, is placed on vacuum environment For 24 hours, then 65 DEG C of heat drying 26h of vacuum, can be obtained all solid state plastic crystals flexible electrolyte film for middle natural drying, should For electrolytic thin-membrane with a thickness of 280 μm, surface roughness 7nm, ionic conductivity is 6.2 × 10-5S/cm。
(4) electrolytic thin-membrane initial volt-ampere circulation peak point current under the conditions of -3v~3v is 18mA, is recycled 1000000 times, Current peak is stablized in 17.5mA.
(5) it after the electrolytic thin-membrane irradiates 15 days in the UV lamp, is recycled 1000000 times under the conditions of -3v~3v, current peak Value is stablized in 16mA.

Claims (9)

1. a kind of all solid state plastic crystals flexible electrolyte film, which is characterized in that high including raw material and proportion in mass ratio Molecular compound: organic plastic crystal matrices: lithium salts: electrolyte additive: plasticizer: auxiliary agent=1:(0.1-0.3): (0.5- 0.7): (0.02-0.04): (0.04-0.08), by mass volume ratio, high-molecular compound: solvent=1:(0-10), unit g: ml。
2. all solid state plastic crystals flexible electrolyte film according to claim 1, which is characterized in that described is all solid state Plastic crystals flexible electrolyte film raw material further includes auxiliary agent, and the auxiliary agent is one of antioxidant, age resister or several Kind, the mass ratio of the auxiliary agent and high-molecular compound is (0.001-0.005): 1.
3. all solid state plastic crystals flexible electrolyte film according to claim 1, it is characterised in that:
The high-molecular compound is polyvinyl alcohol, polyvinyl butyral, ethylene-vinyl acetate copolymer, poly- methyl-prop E pioic acid methyl ester, Kynoar, polyvinyl chloride, ethylene-vinyl alcohol copolymer, polytetrafluoroethylene (PTFE) or poly- (vinylidene-co- six One or more of fluoropropene), when for several mixing, mixing ratio is any ratio；
The organic plastic crystal matrices are neutral organic plastic crystals matrix；
The neutral organic plastic crystals matrix is acetonitrile, succinonitrile, adiponitrile, neopentane, cyclohexylamine, cyclobutane, 5- first The trifluoromethane sulfonic acid inferior amine salt, polyacrylonitrile or trifluoromethane sulfonic acid of base -5,6,7,8- tetrahydro-pyrazole quinoline (1,2- α) pyridazone are sub- One or more of amine, when for several mixing, mixing ratio is any ratio；
The plasticizer is terephthalic acid (TPA) dibutyl ester, two formic acid esters of dipropylene glycol, polyol benzoate, polyalcohol benzene One or more of formic acid esters or dipropylene glycol, when for several mixing, mixing ratio is any ratio；
The lithium salts is bis trifluoromethyl sulfimide lithium, lithium perchlorate, difluoro lithium borate, double-perfluoroethyl sulfonyl imines Lithium, lithium carbonate, LiBF4, hexafluoroarsenate lithium, lithium hexafluoro phosphate, lithium rhodanate, tetrafluoro lithium aluminate, lithium chloride, lithium iodide, One of lithium bromide, tetrafluoro oxalic acid lithium phosphate, dioxalic acid lithium phosphate, difluorine oxalic acid boracic acid lithium or trifluoromethanesulfonic acid lithium are several Kind, when for several mixing, mixing ratio is any ratio；
The solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dehydrated alcohol, propene carbonate, carbonic acid two One or more of methyl esters, ethyl cellulose, dimethyl acetamide or methyl methacrylate mix when for several mixing Composition and division in a proportion is any ratio；
The electrolyte additive is inorganic nano-particle.
4. all solid state plastic crystals flexible electrolyte film according to claim 3, which is characterized in that described inorganic to receive Rice corpuscles is Nano-meter SiO_22, nano-TiO2, nanometer Al2O3, nano-ZnO, nanometer ZrO2, nanometer Ta2O5, nano Ce O2, nanometer MoO3, nano-MgO or nanometer Nb2O5One or more of, when for several mixing, mixing ratio is any ratio.
5. all solid state plastic crystals flexible electrolyte film according to claim 1, which is characterized in that described is all solid state Plastic crystals flexible electrolyte film has 10-3-10-6Ionic conductivity, service life cycle-index reach 100000- 1000000 times, at applied voltage -3V~3V: initial volt-ampere circulation peak point current is 3.4-28mA, recycles 100000- After 1000000 times, peak point current is stablized in 3.3-27mA, and decaying is no more than 10%；In the UV lamp after Continuous irradiation 15 days, follow Ring 100000-1000000 times, peak point current are stablized in 3-25.5mA, and decaying is no more than 15%.
6. all solid state plastic crystals flexible electrolyte film according to claim 1, which is characterized in that described is all solid state Electrolytic thin-membrane with a thickness of 50-1000 μm, surface roughness is less than 10nm.
7. the preparation method of all solid state electrolyte film described in claim 1, which is characterized in that use casting method or extrusion Method, comprising the following steps:
Step 1, stock:
In mass ratio, high-molecular compound: organic plastic crystal matrices: lithium salts: electrolyte additive: plasticizer=1: (0.1- 0.3): (0.5-0.7): (0.02-0.04): (0.04-0.08), by mass volume ratio, high-molecular compound: solvent=1: (0- 10), unit g:ml, stock；
Step 2, film preparation:
When preparing film using casting method, steps are as follows:
1, electrolyte precursor preparation:
Load weighted high-molecular compound, organic plastic crystal matrices, lithium salts, solvent, electrolyte additive and plasticizer are mixed It closes, the solvent of respective volume is added, be uniformly mixed, obtain electrolyte precursor；
2, casting:
Electrolyte precursor is cast to release film, it is dry after natural levelling, all solid state electrolyte film is made；
When preparing film using extrusion by melting, steps are as follows:
After high-molecular compound, organic plastic crystal matrices, lithium salts, electrolyte additive and plasticizer are mixed, it is heated to melting After melting state, after extrusion, all solid state electrolyte film is made.
8. the preparation method of all solid state electrolyte film according to claim 7, which is characterized in that the step two In, high-molecular compound, organic plastic crystal matrices, lithium salts, electrolyte additive, plasticizer and auxiliary agent are intended to do before use Non-aqueous processing.
9. the preparation method of all solid state electrolyte film according to claim 7, which is characterized in that the step two In, when using casting method, mass volume ratio is pressed in raw material, high-molecular compound: solvent=1: (7-10), unit g:ml are used When extrusion by melting, quantity of solvent is 0 in raw material.
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Publication number Priority date Publication date Assignee Title
CN111370757A (en) * 2020-03-03 2020-07-03 上海电气集团股份有限公司 Solid electrolyte containing organic ion plastic crystal and application thereof
CN111897170A (en) * 2020-08-07 2020-11-06 中国科学院广州能源研究所 All-solid-state electrochromic device and preparation method thereof
CN113176809A (en) * 2021-04-12 2021-07-27 维沃移动通信有限公司 Electronic device
CN113176809B (en) * 2021-04-12 2024-05-03 维沃移动通信有限公司 Electronic equipment
CN113410496A (en) * 2021-06-16 2021-09-17 东北大学秦皇岛分校 All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof
CN113410496B (en) * 2021-06-16 2023-02-14 东北大学秦皇岛分校 All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof

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