A three-dimensional multi-layer heterostructure polymer electrolyte membrane, its preparation method and application

Abstract

The present invention discloses a three-dimensional multi-layered heterostructure polymer electrolyte membrane, a preparation method thereof and an application. The polymer electrolyte membrane includes an inorganic solid electrolyte layer, an intermediate interface layer and a composite gel layer, wherein the intermediate interface layer is located between the inorganic solid electrolyte layer and the composite gel layer. The heterostructure of the electrolyte membrane of the present invention combines the advantages of semi-solid gels and solid electrolytes, and there is a chemical-electrochemical double balance at the interface. The lithium-ion battery constructed using this polymer electrolyte membrane can achieve higher energy output, excellent cycle stability and safety performance.

Description

Technical Field

[0001] The present invention relates to the technical field of material chemistry. Specifically, it relates to a three-dimensional multi-layer heterostructure polymer electrolyte membrane, its preparation method and application, which can be applied to lithium-ion batteries. Background Art

[0002] Lithium-ion batteries (LIBs) dominate the consumer electronics and electric vehicle markets due to their relatively high energy density, long cycle life, small memory effect, and low self-discharge. The liquid organic electrolytes in conventional LIBs are flammable, which will lead to serious safety problems.

[0003] Therefore, solid-state batteries with inorganic solid electrolytes or polymer electrolytes have attracted increasing attention due to their non-flammability and high safety. Among them, organic gel polymer electrolyte batteries with relatively high ionic conductivity are more suitable for practical applications.

[0004] At present, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) has relatively high ionic conductivity compared to other polymer matrices and has been used in polymer lithium-ion batteries; however, it still cannot meet the demand for rapid transport of larger anions in dual-ion batteries. Therefore, it is urgent to develop composite polymer electrolytes with higher ionic conductivity. Summary of the Invention

[0005] In order to solve the above problems existing in the prior art, the present invention proposes a three-dimensional multi-layer heterostructure polymer electrolyte membrane. This heterostructure combines the advantages of semi-solid gels and solid electrolytes, and there is a chemical-electrochemical double balance at the interface. The lithium-ion battery constructed with this polymer electrolyte membrane can achieve higher energy output, excellent cycle stability, and safety performance.

[0006] One object of the present invention is to provide a three-dimensional multi-layer heterostructure polymer electrolyte membrane, including an inorganic solid electrolyte layer, an intermediate interface layer, and a composite gel layer, wherein the intermediate interface layer is located between the inorganic solid electrolyte layer and the composite gel layer.

[0007] In the three-dimensional multi-layer heterostructure polymer electrolyte membrane of the present invention, the inorganic solid electrolyte layer includes an oxide solid electrolyte and / or a sulfide solid electrolyte.

[0008] In the above inorganic solid electrolyte layer, the oxide solid electrolyte is a metal oxide solid electrolyte, preferably one or several of garnet-type solid electrolytes, sodium ion conductor-type solid electrolytes (NASICON-type solid electrolytes), lithium ion conductor-type solid electrolytes (LISICON-type solid electrolytes), perovskite-type solid electrolytes, inverse perovskite-type solid electrolytes, such as lithium lanthanum zirconium tantalum oxide solid electrolyte;

[0009] In the above inorganic solid electrolyte layer, the sulfide solid electrolyte is a sulfide electrolyte.

[0010] In the three-dimensional multi-layer heterostructure polymer electrolyte membrane of the present invention, the intermediate interface layer is prepared from components including a conductive agent, an inorganic solid electrolyte, polyvinyl formal resin, styrene-butadiene rubber, a curing agent, and polydimethylsiloxane.

[0011] The preparation steps of the intermediate interface layer may include: adding a conductive agent, an inorganic solid electrolyte, polyvinyl formal resin, styrene-butadiene rubber, a curing agent, polydimethylsiloxane, and solvent 2 into solvent 3, mixing evenly, then scraping and coating on one surface of the composite gel layer, and drying to obtain it.

[0012] In the above intermediate interface layer, the conductive agent is preferably selected from one or more of acetylene black, conductive carbon black (SP, Super P), conductive carbon nanotubes (CNT), and conductive graphite.

[0013] The inorganic solid electrolyte is preferably selected from one or more of perovskite-type solid electrolytes, sodium ion conductor-type solid electrolytes (NASICON-type solid electrolytes), and garnet-type solid electrolytes, such as lithium lanthanum zirconium tantalum oxide solid electrolyte.

[0014] The curing agent is preferably selected from one or more of 4,4'-methylenebis(2,6-diethylaniline), dimethylaminopropylamine, methylenebis(phenylenediamine), and metaphenylenediamine.

[0015] The solvent 2 is preferably selected from one or more of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, acetonitrile, pyridine, phenol, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0016] Solvent 3 is selected from one or more of N-methylpyrrolidone and N-methylformamide.

[0017] In the above intermediate interface layer, polyvinyl formal resin and styrene-butadiene rubber mainly play an adhesive role, and polydimethylsiloxane mainly plays a lubricating role, enabling good dispersion when the materials are mixed.

[0018] In the three-dimensional multi-layer heterostructure polymer electrolyte membrane of the present invention, the composite gel layer is a composite polymer membrane of polyethylene oxide (PEO) / polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) doped with an inorganic solid electrolyte.

[0019] Among them, the inorganic solid electrolyte is preferably selected from one or more of perovskite-type solid electrolytes, sodium ion conductor-type solid electrolytes (NASICON-type solid electrolytes), and garnet-type solid electrolytes, such as lithium lanthanum zirconium tantalum oxide solid electrolyte.

[0020] Based on the total weight of the composite gel layer, the content of the inorganic solid electrolyte is 15-25%, preferably 18-20%.

[0021] The composite gel layer is made by co-doping inorganic solid electrolyte powder and PEO / PVDF-HFP organic polymer gel.

[0022] The preparation steps of the composite gel layer may include: mixing an inorganic solid electrolyte, polyethylene oxide, polyvinylidene fluoride, hexafluoropropylene and a solvent 1, casting into a film, and removing the solvent 1 to obtain the composite gel layer.

[0023] Among them, the solvent 1 is selected from one or more of acetone, ethanol, and acetonitrile.

[0024] The PEO / PVDF-HFP organic polymer is a copolymer of polyethylene oxide / polyvinylidene fluoride and hexafluoropropylene. Among them, the polyethylene oxide polymer is interspersed in the composite polymer membrane with a microporous structure of the polyvinylidene fluoride-hexafluoropropylene copolymer. Its typical feature is having a three-dimensional network structure, and it is the main carrier and supporting structure of the three-dimensional multi-layer heterogeneous structure polymer electrolyte membrane.

[0025] In the three-dimensional multi-layer heterogeneous structure polymer electrolyte membrane of the present invention, the thickness of the inorganic solid electrolyte layer is 5-20 microns, preferably 8-12 microns.

[0026] In the three-dimensional multi-layer heterogeneous structure polymer electrolyte membrane of the present invention, the thickness of the intermediate interface layer is 5-20 microns, preferably 5-10 microns.

[0027] In the three-dimensional multi-layer heterogeneous structure polymer electrolyte membrane of the present invention, the thickness of the composite gel layer is 10-30 microns, preferably 15-20 microns.

[0028] The three-dimensional multi-layer heterogeneous structure polymer electrolyte membrane of the present invention includes an inorganic solid electrolyte layer, an intermediate interface layer and a composite gel layer close to the negative electrode on one side close to the positive electrode of the lithium ion battery, forming a structure similar to a "sandwich sandwich".

[0029] Among them, the inorganic solid electrolyte layer is arranged to be in direct contact with the positive electrode material of the lithium ion battery, which can well improve the voltage window of the battery of the polymer electrolyte membrane. The main components are oxide solid electrolytes and / or sulfide solid electrolytes.

[0030] The intermediate interface layer is made of components such as conductive agent, inorganic solid electrolyte powder, polyvinyl formal resin, styrene-butadiene rubber, curing agent, polydimethylsiloxane and solvent, etc. It has good ductility, elasticity, strength and ionic conductivity, and has good adhesiveness, like a "double-sided tape" to bond the solid electrolyte layer and the composite gel layer together.

[0031] The composite gel layer is mainly made of inorganic solid electrolyte powder and functional composite gel of PEO / PVDF-HFP, and is arranged to adhere tightly to the negative electrode of the lithium-ion battery.

[0032] The second object of the present invention is to provide a method for preparing the three-dimensional multi-layer heterogeneous structure polymer electrolyte membrane, including the following steps:

[0033] (1) Mix inorganic solid electrolyte, polyethylene oxide, polyvinylidene fluoride, hexafluoropropylene with solvent 1, cast into a film, and remove solvent 1 to obtain a composite gel layer;

[0034] (2) Add conductive agent, inorganic solid electrolyte, polyvinyl formal resin, styrene-butadiene rubber, curing agent, polydimethylsiloxane and solvent 2 into solvent 3, mix evenly and then scrape and coat on one surface of the composite gel layer, and dry to obtain an intermediate interface layer;

[0035] (3) Place oxide solid electrolyte and / or sulfide solid electrolyte on the surface of the intermediate interface layer, and hot press to obtain the electrolyte membrane.

[0036] In step (1), solvent 1 is selected from one or more of acetone, ethanol, and acetonitrile.

[0037] In step (1), the mass ratio of polyethylene oxide, polyvinylidene fluoride, and hexafluoropropylene is (2-8):(2-8):1, preferably (3-5):(4-6):1.

[0038] In step (1), based on the total weight of the composite gel layer, the content of the inorganic solid electrolyte is 15-25%, preferably 18-20%.

[0039] In step (1), the step of removing solvent 1 can adopt the usual methods in the art and can vary according to the solvent 1 used, and can be 60-100 degrees Celsius, preferably 70 degrees Celsius, 80 degrees Celsius, 90 degrees Celsius, etc.

[0040] In step (2), solvent 2 is selected from one or more of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, acetonitrile, pyridine, phenol, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0041] In step (2), the solvent 3 is selected from one or more of N-methylpyrrolidone, N-methylformamide, and N-methylformamide.

[0042] In step (2), the drying is preferably carried out at 50 to 80 °C, and preferably can be 60 °C, 70 °C, etc.

[0043] Among them, the mass fractions of each component are as follows:

[0044]

[0045] More preferably, the mass fractions of each component are:

[0046]

[0047] In step (3), the hot pressing can adopt the conventional method in the art, and can be 60 to 100 °C, and preferably can be 70 °C, 80 °C, 90 °C, etc.

[0048] The third object of the present invention is to provide the application of the three-dimensional multi-layer heterostructure polymer electrolyte membrane or the polymer electrolyte membrane obtained by the preparation method in a lithium-ion battery.

[0049] Among them, the inorganic solid electrolyte layer of the polymer electrolyte membrane is close to the positive electrode side of the lithium-ion battery, and the composite gel layer is close to the negative electrode side of the lithium-ion battery.

[0050] In the ranges and any values disclosed in the present invention, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values and individual point values of each range, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article. In the following text, in principle, the various technical solutions can be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed in this article.

[0051] Advantages of the present invention:

[0052] The present invention proposes a three-dimensional multi-layer heterostructure polymer electrolyte membrane. This heterostructure combines the advantages of organic semi-solid gel and inorganic solid electrolyte, and there is a chemical-electrochemical double balance at the interface. The lithium-ion battery constructed with this polymer electrolyte membrane can achieve higher energy output, excellent cycle stability, safety performance, and durability. Description of the drawings

[0053] Figure 1 It is a schematic structural diagram of a three-dimensional multi-layer heterostructure polymer electrolyte membrane.

[0054] Figure 1 Among them, 1 - inorganic solid electrolyte layer;

[0055] 2 - intermediate interface layer;

[0056] 3 - composite gel layer.

[0057] The polymer electrolyte membrane includes an inorganic solid electrolyte layer, an intermediate interface layer on the side close to the positive electrode of the lithium-ion battery, and a composite gel layer on the side close to the negative electrode of the lithium-ion battery, similar to a "sandwich sandwich" structure. The heterogeneous structure of the present invention combines the advantages of semi-solid gels and solid electrolytes, and there is a chemical-electrochemical double balance at the interface. The lithium-ion battery constructed with this polymer electrolyte membrane can achieve higher energy output, excellent cycle stability, and safety performance.

[0058] Figure 2 It is a preparation flow chart of a three-dimensional multi-layer heterogeneous structure polymer electrolyte membrane.

[0059] Figure 3 It is the first efficiency diagram of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 of the present invention.

[0060] Figure 4 It is the cycle comparison diagram of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 of the present invention. Specific Embodiments

[0061] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only for further illustration of the present invention and cannot be understood as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention still fall within the protection scope of the present invention.

[0062] In addition, it should be noted that the various specific technical features described in the following specific embodiments can be combined in any suitable manner without conflict. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0063] In addition, any combination can be made between various different embodiments of the present invention as long as it does not violate the idea of the present invention. The technical solutions formed thereby belong to a part of the original public content of this specification and also fall within the protection scope of the present invention.

[0064] If there is no special limitation on the raw materials used in the examples and comparative examples, they are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0065] Example 1:

[0066] To prepare a three-dimensional multi-layer heterostructure polymer electrolyte membrane, the following steps are included:

[0067] (1) First, prepare a composite gel layer. Stir and mix lithium lanthanum zirconium tantalum oxide powder with a mass fraction of 20% with PEO, PVDF, HFP and a solvent. The ratio of PEO:PVDF:HFP = 5:4:1, and the solvent is acetone. The mixing and stirring speed is 800 rpm, and the mixing time is 6 h. Then cast the mixture into a film with a thickness of about 20 microns, and remove the solvent at 80 °C to obtain the composite gel layer.

[0068] (2) Then, components with mass fractions of: 2% conductive agent Super P, 20% lithium lanthanum zirconium tantalum oxide solid electrolyte powder, 15% polyvinyl formal resin, 30% styrene-butadiene rubber, 1.5% 4,4'-methylenebis(2,6-diethylaniline), 10% polydimethylsiloxane and 15% N,N-dimethylformamide, etc., are successively slurried and homogenized in N-methylpyrrolidone solvent. Then, the slurry is evenly scraped onto the surface of the above composite gel layer with a scraping thickness of 5 microns, and then dried at 60 °C to make a composite material of the composite gel layer and the intermediate interface layer.

[0069] (3) Finally, place the lithium lanthanum zirconium tantalum oxide solid electrolyte solid film on the intermediate layer. The thickness of the lithium lanthanum zirconium tantalum oxide inorganic solid electrolyte layer is about 10 microns, and after hot pressing at 80 °C for 24 h, the final product, the three-dimensional multi-layer heterostructure polymer electrolyte membrane, is obtained.

[0070] Apply the obtained polymer electrolyte membrane to a Li|NCM523 4.3V lithium metal half-cell. The inorganic solid electrolyte layer is close to the positive electrode side of the lithium-ion battery, and the composite gel layer is close to the negative electrode side, and its performance is evaluated. The initial efficiency of the lithium-ion half-cell using this thin film is 84.6%, and the attenuation after 100 cycles is less than 7%.

[0071] Example 2:

[0072] To prepare a three-dimensional multi-layer heterostructure polymer electrolyte membrane, the following steps are included:

[0073] (1) First, prepare a composite gel layer. Stir and mix lithium lanthanum zirconium tantalum oxide powder with a mass fraction of 20% with PEO, PVDF, HFP and a solvent. The ratio of PEO:PVDF:HFP = 3:6:1, and the solvent is acetone. The mixing and stirring speed is 600 rpm, and the mixing time is 6 h. Then cast the mixture into a film with a thickness of about 20 microns, and remove the solvent at 80 °C to obtain the composite gel layer.

[0074] (2) Then, components with mass fractions of 4% of conductive agent Super P, 20% of lithium lanthanum zirconium tantalum oxide solid electrolyte powder, 10% of polyvinyl formal resin, 25% of styrene-butadiene rubber, 3% of 4,4'-methylenebis(2,6-diethylaniline), 15% of polydimethylsiloxane, and 10% of N,N-dimethylformamide, etc., are successively slurried evenly in N-methylpyrrolidone solvent. Then, the slurry is evenly blade-coated on the surface of the above composite gel layer with a coating thickness of 5 microns, and then dried at 60 °C to make a composite gel layer and intermediate interface layer hybrid material.

[0075] (3) Finally, the lithium lanthanum zirconium tantalum oxide solid electrolyte solid film is placed on the intermediate layer. The thickness of the lithium lanthanum zirconium tantalum oxide inorganic solid electrolyte layer is about 10 microns. After hot pressing at 80 °C for 24 h, the final product, a multi-layer heterogeneous structure polymer electrolyte membrane, is formed.

[0076] The performance of the obtained polymer electrolyte membrane was evaluated in a Li|NCM523 4.3V lithium metal half-cell. The inorganic solid electrolyte layer is on the side close to the positive electrode of the lithium-ion battery, and the composite gel layer is on the side close to the negative electrode. The initial efficiency of the lithium-ion half-cell using this thin film is 83.7%, and the decay after 100 cycles is less than 5%.

[0077] Comparative Example 1:

[0078] Directly use the lithium lanthanum zirconium tantalum oxide solid electrolyte as the solid film for testing.

[0079] The performance was evaluated in a Li|NCM523 lithium metal half-cell.

[0080] The performance of the solid film was evaluated in a Li|NCM523 4.3V lithium metal half-cell. The initial efficiency of the lithium-ion half-cell using this thin film is 82.1%, and the decay after 100 cycles is greater than 15%.

[0081] Comparative Example 2:

[0082] Prepare a gel electrolyte membrane, including the following steps:

[0083] Mix 20% by mass of lithium lanthanum zirconium tantalum oxide powder with PEO, PVDF, HFP, and a solvent. PEO:PVDF:HFP = 3:6:1, and the solvent is acetone. The mixing and stirring speed is 600 rpm, and the mixing time is 6 h; then cast into a film with a film thickness of about 20 microns, and remove the solvent at 80 °C to obtain a gel film.

[0084] The performance of the gel film was evaluated in a Li|NCM523 4.3V lithium metal half-cell. The initial efficiency of the lithium-ion half-cell using this thin film is 84.9%, and the decay after 100 cycles is greater than 10%.

Claims

1. A three-dimensional multi-layer heterostructure polymer electrolyte membrane, comprising an inorganic solid electrolyte layer, an intermediate interface layer, and a composite gel layer, wherein the intermediate interface layer is located between the inorganic solid electrolyte layer and the composite gel layer; the intermediate interface layer is prepared from components including a conductive agent, an inorganic solid electrolyte, polyvinyl formal resin, styrene-butadiene rubber, a curing agent, and polydimethylsiloxane; the composite gel layer is a composite polymer membrane of polyethylene oxide / polyvinylidene fluoride-hexafluoropropylene copolymer doped with an inorganic solid electrolyte.

2. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 1, wherein: The inorganic solid electrolyte layer comprises an oxide solid electrolyte and / or a sulfide solid electrolyte.

3. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 2, wherein: The oxide solid electrolyte is a metal oxide solid electrolyte; and / or, The sulfide solid electrolyte is a sulfide electrolyte.

4. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 3, wherein: The oxide solid electrolyte is one or more of garnet-type solid electrolyte, sodium ion conductor-type solid electrolyte, lithium ion conductor-type solid electrolyte, perovskite-type solid electrolyte, and inverse perovskite-type solid electrolyte.

5. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 1, wherein: The conductive agent is selected from one or more of acetylene black, conductive carbon black, conductive carbon nanotubes, and conductive graphite; and / or, The inorganic solid electrolyte is selected from one or more of perovskite-type solid electrolyte, sodium ion conductor-type solid electrolyte, and garnet-type solid electrolyte; and / or, The curing agent is selected from one or more of 4,4'-methylenebis(2,6-diethylaniline), dimethylaminopropylamine, methylenebisbenzene diamine, and metaphenylenediamine.

6. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 1, wherein: The inorganic solid electrolyte is selected from one or more of perovskite-type solid electrolyte, sodium ion conductor-type solid electrolyte, and garnet-type solid electrolyte.

7. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 1, wherein: Based on the total weight of the composite gel layer, the content of the inorganic solid electrolyte is 15-25%.

8. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 7, wherein: Based on the total weight of the composite gel layer, the content of the inorganic solid electrolyte is 18-20%.

9. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to any one of claims 1-8, wherein: The thickness of the inorganic solid electrolyte layer is 5-20 microns; and / or, The thickness of the intermediate interface layer is 5-20 microns; and / or, The thickness of the composite gel layer is 10-30 microns.

10. The three-dimensional multi-layer heterostructure polymer electrolyte membrane according to claim 9, wherein: The thickness of the inorganic solid electrolyte layer is 8-12; and / or, The thickness of the intermediate interface layer is 5 to 10 microns; and / or, the thickness of the composite gel layer is 15 to 20 microns.

11. A method for preparing a three-dimensional multi-layered heterogeneous structure polymer electrolyte membrane according to any one of claims 1 to 10, comprising the following steps: (1) Mix an inorganic solid electrolyte, polyethylene oxide, polyvinylidene fluoride, hexafluoropropylene with solvent 1, cast into a film, and remove solvent 1 to obtain a composite gel layer; (2) Add a conductive agent, an inorganic solid electrolyte, polyvinyl formal resin, styrene-butadiene rubber, a curing agent, polydimethylsiloxane and solvent 2 into solvent 3, mix evenly and then scrape and coat on one surface of the composite gel layer, and dry to obtain an intermediate interface layer; (3) Place an oxide solid electrolyte and / or a sulfide solid electrolyte on the surface of the intermediate interface layer, and hot press to obtain the polymer electrolyte membrane.

12. The method for preparing a polymer electrolyte membrane according to claim 11, wherein: in step (1), solvent 1 is selected from one or more of acetone, ethanol, and acetonitrile; and / or, in step (2), solvent 2 is selected from one or more of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, acetonitrile, pyridine, phenol, N,N-dimethylformamide, and N,N-dimethylacetamide; and / or, in step (2), solvent 3 is selected from one or more of N-methylpyrrolidone and N-methylformamide.

13. The method for preparing a polymer electrolyte membrane according to claim 11, wherein: in step (1), the mass ratio of polyethylene oxide, polyvinylidene fluoride, and hexafluoropropylene is (2 to 8):(2 to 8):

1.

14. The method for preparing a polymer electrolyte membrane according to claim 13, wherein: the mass ratio of polyethylene oxide, polyvinylidene fluoride, and hexafluoropropylene is (3 to 5):(4 to 6):

1.

15. The method for preparing a polymer electrolyte membrane according to claim 11, wherein: in step (2), the mass fractions of each component are: 2 to 5% conductive agent, 15 to 20% inorganic solid electrolyte, 10 to 15% polyvinyl formal resin, 20 to 30% styrene-butadiene rubber, 1 to 3% curing agent, 5 to 20% polydimethylsiloxane, 10 to 15% solvent 2, and the balance is solvent 3.

16. The method for preparing a polymer electrolyte membrane according to claim 15, wherein: 2 to 3% conductive agent, 18 to 20% inorganic solid electrolyte, 10 to 12% polyvinyl formal resin, 20 to 25% styrene-butadiene rubber, 2 to 3% curing agent, 15 to 20% polydimethylsiloxane, 12 to 15% solvent 2, and the balance is solvent 3.

17. Application of the polymer electrolyte membrane according to any one of claims 1 to 10 or the polymer electrolyte membrane obtained by the preparation method according to any one of claims 11 to 16 in a lithium-ion battery.

18. The application of the polymer electrolyte membrane according to claim 17 in lithium ions, wherein: The inorganic solid electrolyte layer of the polymer electrolyte membrane is close to the positive electrode side of the lithium-ion battery, and the composite gel layer is close to the negative electrode side of the lithium-ion battery.

Images