CN114716775B - Material for electrolyte separator, preparation method and battery - Google Patents
Material for electrolyte separator, preparation method and battery Download PDFInfo
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- CN114716775B CN114716775B CN202210275210.6A CN202210275210A CN114716775B CN 114716775 B CN114716775 B CN 114716775B CN 202210275210 A CN202210275210 A CN 202210275210A CN 114716775 B CN114716775 B CN 114716775B
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- 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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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/44—Sulfenamides
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
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- H01M2300/0082—Organic polymers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a material for an electrolyte membrane, the electrolyte membrane, a preparation method and a battery, wherein the material for the electrolyte membrane comprises, by mass, 0.01-1% of perfluoroalkyl ethyl acrylate, 8-10% of polyvinylidene fluoride, 5-15% of bis (trifluoromethanesulfonyl) lithium and the balance of N, N-dimethylformamide. According to the invention, the polymer electrolyte crystallization state is regulated by controlling the polymer viscosity and the additive proportion, and the conductivity of the polymer electrolyte in a low-temperature environment is improved by blending the perfluoroalkyl ethyl acrylate, so that the activation energy of lithium ions at low temperature can be effectively reduced, the low-temperature lithium ion conductivity is improved, the energy barrier to be overcome when lithium ions migrate in an electrolyte membrane is reduced, the migration becomes easy, and the effect of improving the circulation performance of the lithium ion battery at low temperature is achieved.
Description
Technical Field
The invention relates to the technical field of electrolyte diaphragms, in particular to a material for an electrolyte diaphragm, the electrolyte diaphragm, a preparation method and a battery.
Background
The gel state polymer electrolyte is composed of a polymer, a plasticizer, an inorganic salt, etc., and is generally formed by gelation such as van der Waals force or hydrogen bonding, crystallization, chemical crosslinking between polymers, etc.; the lithium ion battery is mainly used for providing a channel for conducting lithium ions between the anode and the cathode in the lithium ion battery.
Ion transport in the polymer electrolyte occurs mainly in the amorphous region above the glass transition temperature Tg. Therefore, in a low temperature state, the transfer of lithium ions in the polymer electrolyte separator is severely blocked, resulting in difficulty in application of the lithium ion battery in a low temperature environment. Therefore, the activation energy of the polymer electrolyte membrane in the low-temperature environment is improved, so that the use condition of the lithium ion battery in the low-temperature environment is improved, and the lithium ion battery has important significance.
Disclosure of Invention
The invention aims to provide a material for an electrolyte membrane, the electrolyte membrane, a preparation method and a battery, which can improve the activation energy of the polymer electrolyte membrane in a low-temperature environment and improve the service condition of a lithium ion battery in the low-temperature environment.
The invention discloses a material for an electrolyte membrane, which comprises the following components in mass percent:
optionally, by mass, comprising:
optionally, by mass, comprising:
optionally, by mass, comprising:
optionally, by mass, comprising:
the invention also discloses an electrolyte membrane prepared from the material for the electrolyte membrane.
The invention also discloses a preparation method of the electrolyte membrane, which is applied to the preparation of the electrolyte membrane and is characterized by comprising the following steps:
adding polyvinylidene fluoride into an N, N-dimethylformamide solvent, and stirring until the polyvinylidene fluoride is semitransparent;
adding perfluoroalkyl ethyl acrylate, continuously stirring, and standing at low temperature;
adding bis (trifluoromethanesulfonyl) lithium and stirring to obtain a film-forming material;
and after the film forming material is scraped, heating, drying and forming a film.
Optionally, the step of adding polyvinylidene fluoride into the N, N-dimethylformamide solvent and stirring until the polyvinylidene fluoride is semitransparent is specifically as follows:
8 to 10 percent of polyvinylidene fluoride is added into the N, N-dimethylformamide solvent by mass, and the mixture is stirred until the mixture is semitransparent, the stirring speed is 800 to 1200rpm/min, and the stirring time is 10 to 15min.
Optionally, the step of adding perfluoroalkyl ethyl acrylate, continuously stirring and then standing at a low temperature is specifically as follows:
adding 0.01 to 1 percent of perfluoroalkyl ethyl acrylate by mass, continuously stirring, and standing at a low temperature; stirring speed is 1500-2000 rpm/min, stirring time is 10-15 min, low-temperature standing temperature is 0-10 ℃, and standing time is 1-2 h.
The invention also discloses a battery comprising the electrolyte membrane.
According to the invention, the polymer electrolyte crystallization state is regulated by controlling the polymer viscosity and the additive proportion, and the conductivity of the polymer electrolyte in a low-temperature environment is improved by blending the perfluoroalkyl ethyl acrylate, so that the activation energy of lithium ions at low temperature can be effectively reduced, the low-temperature lithium ion conductivity is improved, the energy barrier to be overcome when lithium ions migrate in an electrolyte membrane is reduced, the migration becomes easy, and the effect of improving the circulation performance of the lithium ion battery at low temperature is achieved.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. It is evident that the figures in the following description are only some embodiments of the invention, from which other figures can be obtained without inventive effort for a person skilled in the art. In the drawings:
FIG. 1 is a 20000 times FEI-SEM image of a polymer electrolyte membrane prepared according to example 1 of the present invention;
FIG. 2 is a conductivity spectrum of the polymer electrolyte membrane prepared in example 1 of the present invention;
FIG. 3 is an activation energy spectrum of a polymer electrolyte membrane prepared in example 1 of the present invention;
FIG. 4 is a tensile strength chart of a polymer electrolyte membrane prepared in example 1 of the present invention;
FIG. 5 is a graph showing the cycle retention at 0℃after the assembly of the polymer electrolyte membrane prepared in example 1 of the present invention was buckled;
FIG. 6 is a graph showing the cycle retention at 0℃after the assembly of the polymer electrolyte membrane prepared in example 2 of the present invention was buckled;
FIG. 7 is a graph showing the cycle retention at 0℃after the assembly of the polymer electrolyte membrane prepared in example 3 according to the present invention was buckled;
FIG. 8 is a graph showing the cycle retention at 0℃after the polymer electrolyte membrane prepared in example 1 of the present invention and comparative example 1 were assembled and buckled.
Detailed Description
It is to be understood that the terminology used herein, the specific structural and functional details disclosed are merely representative for the purpose of describing particular embodiments, but that the invention may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
The invention is described in detail below with reference to the attached drawings and alternative embodiments.
As an embodiment of the present invention, a material for an electrolyte separator is disclosed, comprising, by mass, 0.01 to 1% of perfluoroalkyl ethyl acrylate, 8 to 10% of polyvinylidene fluoride, 5 to 15% of lithium bistrifluoromethylsulfonyl imide, and the balance of N, N-dimethylformamide, N-dimethylformamide as a solvent. The perfluoroalkyl ethyl acrylate may be 0.01%, 0.03%, 0.05%, 0.07%, 0.09%, 1%. The polyvinylidene fluoride can be 8%, 8.5%, 9%, 9.5%, 10%. The lithium bis (trifluoromethanesulfonyl) imide may be 5%, 7%, 9%, 11%, 13%, 15%.
Specifically, the material for the electrolyte membrane comprises, by mass, 0.03-0.09% of perfluoroalkyl ethyl acrylate, 7-9% of polyvinylidene fluoride, 4-11% of lithium bistrifluoromethane sulfonyl imide and the balance of N, N-dimethylformamide. The perfluoroalkyl ethyl acrylate may be 0.03%, 0.05%, 0.07%, 0.09%. The polyvinylidene fluoride can be 8%, 8.5%, 9%, 9.5%, 10%. The lithium bis (trifluoromethanesulfonyl) imide may be 5%, 7%, 9%, 11%, 13%, 15%.
Specifically, the material for the electrolyte separator includes, by mass, 0.048% of perfluoroalkyl ethyl acrylate, 8.57% of polyvinylidene fluoride, 4.8% of lithium bistrifluoromethylsulfonyl imide, and the balance of N, N-dimethylformamide.
Specifically, the material for the electrolyte separator includes, by mass, 0.03% of perfluoroalkyl ethyl acrylate, 7.7% of polyvinylidene fluoride, 9.1% of lithium bistrifluoromethylsulfonyl imide, and the balance of N, N-dimethylformamide.
Specifically, the material for the electrolyte separator includes, by mass, 0.09% of perfluoroalkyl ethyl acrylate, 8.9% of polyvinylidene fluoride, 10.7% of lithium bistrifluoromethylsulfonyl imide, and the balance of N, N-dimethylformamide.
The invention also discloses an electrolyte membrane prepared from the material for the electrolyte membrane.
The invention also discloses a preparation method of the electrolyte membrane, which is applied to the preparation of the electrolyte membrane and comprises the following steps:
adding polyvinylidene fluoride into an N, N-dimethylformamide solvent, and stirring until the polyvinylidene fluoride is semitransparent;
adding perfluoroalkyl ethyl acrylate, continuously stirring, and standing at low temperature;
adding bis (trifluoromethanesulfonyl) lithium and stirring to obtain a film-forming material;
and after the film forming material is scraped, heating, drying and forming a film.
Specifically, the step of adding polyvinylidene fluoride into an N, N-dimethylformamide solvent and stirring until the polyvinylidene fluoride is semitransparent specifically as follows:
8 to 10 percent of polyvinylidene fluoride is added into the N, N-dimethylformamide solvent by mass, and the mixture is stirred until the mixture is semitransparent, the stirring speed is 800 to 1200rpm/min, and the stirring time is 10 to 15min.
Specifically, the step of adding perfluoroalkyl ethyl acrylate, continuously stirring and then standing at a low temperature is specifically as follows:
adding 0.01 to 1 percent of perfluoroalkyl ethyl acrylate by mass, continuously stirring, and standing at a low temperature; stirring speed is 1500-2000 rpm/min, stirring time is 10-15 min, low-temperature standing temperature is 0-10 ℃, and standing time is 1-2 h.
In the above preparation method, preferably, in the step (3), the mass percentage of the bistrifluoromethanesulfonyl lithium is controlled within a range of 5% -15%, and the stirring speed is 1500-2000 rpm/min, and the stirring time is 10-15 min.
In the above preparation method, preferably, in the step (4), the height of the four-sided molding machine is 40-60 μm, the temperature of the low-temperature drying oven is 80-100 ℃, and the drying time is 1-3 hours.
The polymer electrolyte diaphragm is prepared by a blending and stirring method, the crystallization state of the polymer electrolyte is adjusted by controlling the polymer viscosity and the proportion of additives, and the final film forming thickness is controlled by the height of a four-side mold making device; and the conductivity of the polymer electrolyte in a low-temperature environment is improved by blending perfluoroalkyl ethyl acrylate. Structurally, fluorine is the most electronegative atom of all elements (4.0), so fluorocarbon is extremely difficult to oxidize, the bond energy of C-F is 484kJ/mol, which is 69kJ/mol larger than that of C-H, and C-F bonds are not easily polarized, so C-F bonds are very strong and difficult to break. The radius of fluorine atoms is smaller, the Van der Waals radius is about 10% larger than that of hydrogen atoms, the perfluorinated carbon chain is formed into a spiral shape, the fluorine atoms can completely wrap the carbon atoms, the carbon skeleton can be protected from being broken, the attraction between fluorocarbon molecules can be reduced, after the perfluorinated alkyl ethyl acrylate is blended with polyvinylidene fluoride materials, the perfluorinated carbon chain structure can generate Lewis acid alkali effect with polyvinylidene fluoride, the long-range ordered chain segment structure of the polyvinylidene fluoride is disturbed, the activation energy of the polyvinylidene fluoride at low temperature can be effectively reduced after the blending is found through the low-temperature standing process, so that the low-temperature lithium ion conductivity is improved, the energy barrier to be overcome when lithium ions migrate in an electrolyte membrane is reduced, the migration becomes easy, and the effect of improving the circulation performance of the lithium ion battery at low temperature is achieved.
Compared with the prior art, the invention has the advantages that:
(1) The polymer electrolyte membrane prepared by the invention has higher mechanical strength and higher tensile strength, and meets the processability of the membrane in a lithium ion battery.
(2) According to the polymer electrolyte membrane prepared by the invention, through blending perfluoroalkyl ethyl acrylate, the lithium ion conductivity of the polymer electrolyte in a low-temperature environment is improved, so that the battery circulation condition in the low-temperature environment is improved.
(3) The method for preparing the polymer electrolyte membrane is simple and feasible, and has convenient operation and lower cost.
The invention also discloses a battery comprising the electrolyte membrane.
Example 1:
a low-temperature high-retention polymer electrolyte membrane and a preparation method thereof are provided, which are prepared by adopting a blending stirring method, and comprise the following steps:
(1) Adding polyvinylidene fluoride (PVDF) powder in an amount of 0.9g into a stirring kettle, adding 9.1g of N, N-Dimethylformamide (DMF) solvent by using a dropper, stirring the powder by using a planetary stirrer at a stirring speed of 800rpm/min for 15min; stirring until the slurry is uniform and semitransparent;
(2) Adding 0.005g of perfluoroalkyl ethyl acrylate into the material obtained after stirring in the step (1), continuously stirring the powder by using a planetary stirrer at the stirring speed of 2000rpm/min for 15min, and standing at the temperature of 10 ℃ for 2 h;
(3) Adding 0.6g of bis (trifluoromethanesulfonyl) lithium into the material obtained after stirring in the step (2), continuously stirring the powder by using a planetary stirrer at a stirring speed of 1500rpm/min for 10min;
(4) Pouring the material obtained after stirring in the step (3) onto a clean glass plate, scraping and coating by using a four-side molding device, wherein the height of the four-side molding device is 60 mu m, and placing the glass plate into a vacuum drying oven to be heated at 80 ℃ for 3 hours and dried to form a film.
The polymer electrolyte membrane prepared in this example had a slurry viscosity of 3516mPa.s before film formation and a membrane thickness of 28. Mu.m after drying.
The FEI-SEM diagram of the low-temperature high-retention polymer electrolyte membrane prepared by the embodiment is shown in figure 1, and figure 1 shows that the polymer electrolyte membrane prepared by the blending stirring method has porous surface and can provide an effective channel for lithium ion transmission in a lithium ion battery; fig. 2 is a graph of the conductivity of a polymer electrolyte separator measured at 10 ℃ calculated by the formula (σ=λ/(rb×a)), the conductivity of which is 4.05 x 10 "4S/cm; FIG. 3 is an activation energy diagram of a polymer electrolyte membrane tested at different temperatures, calculated to have an activation energy of 10.72kJ mol-1; FIG. 4 is a graph of tensile strength of a polymer electrolyte membrane tested at 10℃and it can be seen that the tensile strength of the membrane is 14.80N/mm2.
The polymer electrolyte membrane punched sheet prepared in this example was then matched with 523 type lithium nickel cobalt manganese oxide material, and a CR2032 type button cell was assembled, and tested for discharge capacity at a test temperature of 0 ℃ and a test voltage range of 3-4.4V, and a test rate of 0.3C charge and 0.5C discharge, as shown in fig. 5. Through testing, after 150 weeks of power-off circulation, the capacity retention rate is 95.22%, and the circulation performance is good.
Example 2:
a low-temperature high-retention polymer electrolyte membrane and a preparation method thereof are provided, which are prepared by adopting a blending stirring method, and comprise the following steps:
(1) 0.95g of polyvinylidene fluoride (PVDF) powder was added to the stirring tank, 9.15g of N, N-Dimethylformamide (DMF) solvent was added by using a dropper, and the powder was stirred by using a planetary stirrer at a stirring speed of 850rpm/min for 12min; stirring until the slurry is uniform and semitransparent;
(2) Adding 0.003g of perfluoroalkyl ethyl acrylate into the material obtained after stirring in the step (1), continuously stirring the powder by using a planetary stirrer at a stirring speed of 1500rpm/min for 15min, and standing at 10 ℃ for 2 h;
(3) Adding 1.0g of bis (trifluoromethanesulfonyl) lithium into the material obtained after stirring in the step (2), continuously stirring the powder by using a planetary stirrer at the stirring speed of 2000rpm/min for 12min;
(4) Pouring the material obtained after stirring in the step (3) onto a clean glass plate, scraping and coating by using a four-side molding device, wherein the height of the four-side molding device is 40 mu m, and putting the glass plate into a vacuum drying oven for heating at 90 ℃ for 2 hours to dry and form a film.
The polymer electrolyte membrane prepared in this example had a slurry viscosity of 3648mPa.s before film formation and a membrane thickness of 22. Mu.m after drying.
The polymer electrolyte membrane punched sheet prepared in this example was then matched with 523 type lithium nickel cobalt manganese oxide material, and a CR2032 type button cell was assembled, and tested for discharge capacity at a test temperature of 0 ℃ and a test voltage range of 3-4.4V, and a test rate of 0.3C charge and 0.5C discharge, as shown in fig. 6. Through testing, after the power-on cycle is performed for 150 weeks, the capacity retention rate is 94.97%, and the cycle performance is good.
Example 3:
a low-temperature high-retention polymer electrolyte membrane and a preparation method thereof are provided, which are prepared by adopting a blending stirring method, and comprise the following steps:
(1) Adding polyvinylidene fluoride (PVDF) powder in an amount of 1.0g into a stirring kettle, adding 9.0g of N, N-Dimethylformamide (DMF) solvent by using a dropper, stirring the powder by using a planetary stirrer at a stirring speed of 800rpm/min for 10min; stirring until the slurry is uniform and semitransparent;
(2) Adding 0.01g of perfluoroalkyl ethyl acrylate into the material obtained after stirring in the step (1), continuously stirring the powder by using a planetary stirrer at a stirring speed of 1500rpm/min for 15min, and standing at 10 ℃ for 2 h;
(3) Adding 1.2g of bis (trifluoromethanesulfonyl) lithium into the material obtained after stirring in the step (2), continuously stirring the powder by using a planetary stirrer at the stirring speed of 2000rpm/min for 10min;
(4) Pouring the material obtained after stirring in the step (3) onto a clean glass plate, scraping and coating by using a four-side molding device, wherein the height of the four-side molding device is 60 mu m, and placing the glass plate into a vacuum drying oven for heating at 95 ℃ for 2 hours to dry and form a film.
The polymer electrolyte membrane prepared in this example had a viscosity of 3708mPa.s as a slurry before film formation and a thickness of 31 μm after drying.
The polymer electrolyte membrane punched sheet prepared in this example was then matched with 523 type lithium nickel cobalt manganese oxide material, and a CR2032 type button cell was assembled, and tested for discharge capacity at a test temperature of 0 ℃ and a test voltage range of 3-4.4V, and a test rate of 0.3C charge and 0.5C discharge, as shown in fig. 7. Through testing, after the power-on cycle is performed for 150 weeks, the capacity retention rate is 90.87%, and the cycle performance is good.
Comparative example 1:
a low-temperature high-retention polymer electrolyte membrane and a preparation method thereof are provided, which are prepared by adopting a blending stirring method, and comprise the following steps:
(1) Adding polyvinylidene fluoride (PVDF) powder in an amount of 1.0g into a stirring kettle, adding 9.0g of N, N-Dimethylformamide (DMF) solvent by using a dropper, stirring the powder by using a planetary stirrer at a stirring speed of 800rpm/min for 10min; stirring until the slurry is uniform and semitransparent;
(2) Adding 1.0g of bis (trifluoromethanesulfonyl) lithium into the material obtained after stirring in the step (1), continuously stirring the powder by using a planetary stirrer at the stirring speed of 2000rpm/min for 15min;
(3) Pouring the material obtained after stirring in the step (2) onto a clean glass plate, scraping and coating by using a four-side molding device, wherein the height of the four-side molding device is 60 mu m, and putting the glass plate into a vacuum drying oven for heating at 90 ℃ for 2 hours to dry and form a film.
The polymer electrolyte membrane prepared in this example had a slurry viscosity of 3664mPa.s before film formation and a membrane thickness of 25. Mu.m after drying.
The polymer electrolyte membrane sheets prepared in comparative example and example 1 were then combined with 523 type lithium nickel cobalt manganese oxide material to assemble a CR2032 type button cell, which was tested for discharge capacity at 0C, 3-4.4V in test voltage range, 0.3C charge at test rate, and 0.5C discharge, as shown in fig. 8. After 150 weeks of power-off cycle, the capacity retention rate of example 1 was 95.22%, the cycle performance was good, and the capacity retention rate of comparative example 1 was 75.82%, with a tendency to jump.
The above description of the invention in connection with specific alternative embodiments is further detailed and it is not intended that the invention be limited to the specific embodiments disclosed. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (10)
1. A material for an electrolyte separator, characterized by comprising, by mass:
2. the material for an electrolyte separator according to claim 1, comprising, by mass:
3. the material for an electrolyte separator according to claim 2, comprising, by mass:
4. the material for an electrolyte separator according to claim 2, comprising, by mass:
5. the material for an electrolyte separator according to claim 2, comprising, by mass:
6. an electrolyte separator, characterized by being prepared using the material for an electrolyte separator according to any one of claims 1 to 5.
7. A method for preparing an electrolyte membrane, which is applied to the preparation of the electrolyte membrane according to claim 6, and comprises the following steps:
adding polyvinylidene fluoride into an N, N-dimethylformamide solvent, and stirring until the polyvinylidene fluoride is semitransparent;
adding perfluoroalkyl ethyl acrylate, continuously stirring, and standing at low temperature;
adding bis (trifluoromethanesulfonyl) lithium and stirring to obtain a film-forming material;
and after the film forming material is scraped, heating, drying and forming a film.
8. The method for preparing an electrolyte membrane according to claim 7, wherein the step of adding polyvinylidene fluoride to an N, N-dimethylformamide solvent and stirring until semitransparent is specifically:
8 to 10 percent of polyvinylidene fluoride is added into the N, N-dimethylformamide solvent by mass, and the mixture is stirred until the mixture is semitransparent, the stirring speed is 800 to 1200rpm/min, and the stirring time is 10 to 15min.
9. The method for preparing an electrolyte membrane according to claim 7, wherein the step of adding perfluoroalkyl ethyl acrylate, continuously stirring, and then standing at a low temperature is specifically as follows:
adding 0.01 to 1 percent of perfluoroalkyl ethyl acrylate by mass, continuously stirring, and standing at a low temperature; stirring speed is 1500-2000 rpm/min, stirring time is 10-15 min, low-temperature standing temperature is 0-10 ℃, and standing time is 1-2 h.
10. A battery comprising the electrolyte separator of claim 6.
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| CN111799508A (en) * | 2020-08-04 | 2020-10-20 | 电子科技大学 | All-solid-state polymer electrolyte diaphragm, preparation method and all-solid-state lithium ion battery |
| CN112615047A (en) * | 2020-11-27 | 2021-04-06 | 曙鹏科技（深圳）有限公司 | Gel electrolyte diaphragm, preparation method thereof and lithium ion battery |
| CN114024094A (en) * | 2021-11-08 | 2022-02-08 | 山东遥米新能源科技有限公司 | Fluorine-containing lithium ion battery diaphragm and preparation method thereof |
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| US20170263908A1 (en) * | 2016-03-08 | 2017-09-14 | Giner, Inc. | Separator For Use in Electrochemical Cells and Method of Fabrication Thereof |
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| CN106910939A (en) * | 2017-04-06 | 2017-06-30 | 哈尔滨理工大学 | A kind of lithium battery method for preparing polymer electrolytes of high conductivity |
| CN109065811A (en) * | 2018-08-20 | 2018-12-21 | 湖南烁普新材料有限公司 | Aqueous PVDF coating diaphragm and its preparation method and application |
| CN111326789A (en) * | 2020-03-09 | 2020-06-23 | 天津中电新能源研究院有限公司 | Semi-interpenetrating network flame-retardant solid lithium ion electrolyte, solid lithium battery and preparation method |
| CN111799508A (en) * | 2020-08-04 | 2020-10-20 | 电子科技大学 | All-solid-state polymer electrolyte diaphragm, preparation method and all-solid-state lithium ion battery |
| CN112615047A (en) * | 2020-11-27 | 2021-04-06 | 曙鹏科技（深圳）有限公司 | Gel electrolyte diaphragm, preparation method thereof and lithium ion battery |
| CN114024094A (en) * | 2021-11-08 | 2022-02-08 | 山东遥米新能源科技有限公司 | Fluorine-containing lithium ion battery diaphragm and preparation method thereof |
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