High-entropy synergistic effect regulation of polymer electrolyte membranes, their preparation methods and applications

Abstract

This invention provides a high-entropy synergistic effect regulated polymer electrolyte membrane, its preparation method, and its application. The method involves dissolving boron-based lithium / sodium salts and their derivatives, lithium sulfonylimide / sodium salts and their derivatives, organic lithium sulfonate / sodium salts and their derivatives, inorganic lithium salts, and a polymer matrix in an organic solvent and mixing them. The polymer electrolyte membrane is then obtained via casting or electrospinning. This invention solves the problems of low solubility, poor thermal stability, severe corrosion of aluminum foil, poor low-temperature performance, and easy oxidation and decomposition associated with single lithium salts. The prepared polymer electrolyte membrane exhibits high room-temperature ionic conductivity, good high-voltage compatibility, good interfacial compatibility and stability, and high safety. The preparation process is simple, energy-efficient, highly controllable, and easily scalable. All-solid-state batteries assembled based on this electrolyte membrane exhibit good rate performance and cycle stability.

Description

Technical Field

[0001] This invention provides a high-entropy synergistic effect regulated polymer electrolyte membrane, its preparation method and application. It is a polymer electrolyte with high conductivity, high safety and high stability constructed based on the high-entropy synergistic effect of electrolyte salt, belonging to the field of all-solid-state battery technology. Background Technology

[0002] In recent years, with the rapid development of aerospace, electric vehicles, and large-scale energy storage, the demand for high-energy-density and high-safety rechargeable batteries has become extremely urgent. Currently, most traditional batteries use volatile, low-boiling-point, and flammable organic liquid electrolytes. These batteries exhibit poor stability at high temperatures, are prone to short circuits, and are susceptible to flammability and explosion under extreme conditions such as impact and overcharging, posing significant safety hazards. Therefore, high safety and high energy density are two major challenges currently facing commercial lithium-ion batteries. An effective solution to these problems is the solid-state development of lithium-ion batteries. Solid-state electrolytes are less prone to leakage and flammability, while also possessing a certain degree of mechanical strength. Replacing liquid electrolytes with solid-state electrolytes can eliminate safety hazards, while also being compatible with high-capacity electrode materials, including lithium, suppressing lithium dendrite growth, and reducing the weight of the battery system, thus significantly improving battery energy density. Solid-state lithium-ion batteries using solid-state electrolytes are expected to further improve battery performance indicators such as energy density and cycle life, while fundamentally solving battery safety issues, providing strong technical support for the development of high-safety, high-energy-density lithium-ion batteries.

[0003] One of the key materials for solid-state batteries is the solid electrolyte, which can conduct lithium ions while acting as a separator to block electron transport, greatly simplifying the battery construction process. Its advantages are: (1) eliminating the safety hazards of electrolyte corrosion and leakage; (2) maintaining the ability to transport ions over a wide temperature range, ensuring that all-solid-state batteries can work over a wider temperature range; (3) high mechanical strength, which can effectively suppress dendrite growth when using metallic lithium as the negative electrode, avoiding a series of safety hazards such as short circuits, thermal runaway, and even explosions caused by dendrites piercing the separator. Currently, the main solid electrolytes include oxides, sulfides, and polymers. Oxide electrolytes are relatively hard and brittle, making large-area production very difficult, and the interface contact with electrode materials is extremely poor; although sulfide electrolytes have high ionic conductivity, they have problems such as poor chemical / electrochemical stability, making development difficult; although polymer electrolytes have relatively low ionic conductivity at room temperature, they have good interfacial compatibility and stability with electrode materials, and have the greatest potential for engineering applications. Polymer solid electrolytes are composed of a polymer matrix and inorganic salts. The polymer matrix is ​​typically a polymer with a low glass transition temperature, such as polyethylene oxide (PEO), polyacrylonitrile (PAN), and polyvinylidene fluoride (PVDF). In this system, lithium / sodium salts are converted to Li via solvation. + / Na+ With anions, then Li + / Na + Lithium / sodium ions are conducted through coordination with polar groups on the polymer chain via local chain segment movement. The quantity of free lithium / sodium ions and the mobility of polymer chain segments significantly affect the Li-sodium content in the polymer electrolyte. + / Na + The migration of molecules affects the ionic conductivity of the electrolyte. Furthermore, the thermal stability and molecular orbital energy levels of the electrolyte salt directly influence the safety and electrochemical window of the polymer electrolyte. In summary, the selection and preparation of electrolyte salts are of great significance for constructing polymer solid electrolytes with high ionic conductivity and high safety.

[0004] CN 111162308 B discloses a method for preparing a novel low-lattice-energy lithium salt for solid-state lithium batteries. The designed molecule contains two lithium ions per molecule, allowing for a lower concentration of the lithium salt compared to conventionally used salts at the same ambient temperature, while achieving the same ionic conductivity. This effectively reduces battery costs. Another characteristic of this series of lithium salts is their molecular design, which is strikingly similar to LiTFSI. Both sides of the molecule are imines, and the negative charge on the nitrogen atom is delocalized by two sulfone groups, resulting in high lithium-ion mobility. Therefore, like LiTFSI, these lithium salts are expected to exhibit lower interionic attraction between cations and anions, resulting in lower lattice energy and thus improved ionic conductivity.

[0005] Generally speaking, TFSI - Anions under high voltage (3.7-4.0V, vs Li) + Li₂O₃ (Li₂O₃) severely corrodes the aluminum foil of the positive electrode current collector. This is mainly because it is easily adsorbed on the surface of the aluminum foil, thereby adsorbing the cation Li₂O₃. + The formation of LiF makes the passivation film porous and loose, and aluminum reduces the sulfonyl group to S. 2- It is oxidized into Al 3+ This leads to severe corrosion of the current collector; in addition, the preparation method used in this invention is relatively complicated, the process involves high temperature and low pressure environments, the preparation time is long, and the purity of the product is not easy to control; finally, the fluorinated double lithium salt system constructed by this invention has electrochemical stability below 4.2V, making it difficult to apply in high-voltage battery systems.

[0006] CN 108172900 B relates to a novel lithium salt, its preparation method and application, and the application of these novel lithium salts as electrolytes in secondary lithium (ion) batteries, etc., having the molecular structure shown in Formula 1:

[0007]

[0008] Wherein, R is one of CF3, C2F5, and C3F7. The method for preparing novel lithium salts provided by this invention has a short operation step, the product is easy to separate and purify, and the yield and purity of the product are both high. The novel lithium salts provided by this invention have good thermal stability and hydrolysis resistance. When the novel lithium salts provided by this invention are used as the main conductive salt of the electrolyte in lithium-ion batteries, they can significantly improve the cycle performance of the battery, and at the same time, they show good compatibility with widely used electrode materials.

[0009] To increase the solubility of lithium salts in solvents, this invention introduces a large number of strongly electron-withdrawing groups. With the introduction of these groups, the viscosity of the solution increases, the solvation effect is further enhanced, and the number of ion pairs increases, thereby affecting the lithium-ion transference number of the electrolyte. Furthermore, in the embodiments described in this invention, the lithium salt is used in the electrolyte in combination with high-dielectric-constant EC and low-viscosity EMC, which can effectively promote lithium salt dissociation and reasonably control viscosity. However, its application effect in polymer electrolyte systems is still unknown. Finally, the lithium salt introduces a large number of unsaturated bonds, which theoretically may affect its antioxidant properties. Summary of the Invention

[0010] The problem this invention aims to solve is to improve the overall performance of polymer electrolytes, specifically by constructing a polymer electrolyte with high ionic conductivity, high-voltage stability, and high safety. The electrolyte salts involved in the polymer electrolyte of this invention exhibit low lattice energy, low HOMO energy level, high heat resistance, and the ability to inhibit aluminum foil corrosion through a high-entropy synergistic effect. The polymer electrolyte of this invention possesses high room-temperature conductivity, a wide electrochemical window, and high safety. All-solid-state batteries assembled based on this electrolyte exhibit excellent electrochemical performance, solving the following technical problems:

[0011] Technical Issue 1: The intrinsic ionic conductivity of polymer electrolytes is relatively low. Ion conduction in polymers mainly depends on two conditions: i) the ion-dipole interaction between the polymer and lithium ions causes the lithium salt to dissociate. The dissociation capability of the lithium salt directly affects the ionic conductivity of the polymer electrolyte. By adjusting the group composition in the lithium salt, the negative charge of the anions in the lithium salt can be dispersed, shielding the force of the negative charge on the lithium ions, which is expected to improve the solvation effect of the polymer on lithium ions; ii) the free movement of polymer molecular chain segments promotes effective ion transport between polymer matrices. The movement of polymer molecular chain segments mainly occurs in the amorphous region above the glass transition temperature (Tg). Regulating the volume, flexibility, and degree of charge delocalization of anions in the electrolyte salt plays an important role in inhibiting the formation of ion pairs and crystalline complexes, reducing the crystallinity and Tg of the polymer, and improving the ionic conductivity of the polymer electrolyte.

[0012] Technical Issue 2: From a thermodynamic perspective, a high-voltage stable polymer electrolyte means that all components of the electrolyte (polymer and electrolyte salt) must simultaneously possess a highest occupied molecular orbital (HOMO) energy level lower than the cathode potential. However, most polymers have high HOMO energy levels, resulting in poor high-voltage compatibility. Furthermore, due to the complex oxidation states of the cathode material during lithium insertion / extraction, the chemical potential (μc) of the cathode material may shift downwards to a state below the electrolyte's HOMO energy level, leading to interfacial side reactions. Therefore, constructing a polymer-electrolyte salt system with low HOMO energy levels is a fundamental measure to improve its high-voltage stability.

[0013] The specific technical solution is as follows:

[0014] The present invention provides a polymer electrolyte membrane based on the high entropy synergistic effect of electrolyte salts. By dissolving boron-based lithium / sodium salts and their derivatives (lithium tetrafluoroborate, lithium difluorooxalate borate, lithium dioxo-borate, etc.), lithium sulfonylimide / sodium salts and their derivatives (lithium difluorosulfonylimide, lithium bis(trifluoromethanesulfonylimide), etc.), organic lithium sulfonate / sodium salts and their derivatives (lithium trifluoromethanesulfonate, etc.), inorganic lithium salts (lithium perchlorate, lithium lanthanum zirconium oxide, etc.) and a polymer matrix in an organic solvent and stirring the mixture, a polymer electrolyte membrane with excellent comprehensive performance is finally obtained by casting or electrospinning.

[0015] The polymer electrolyte membrane obtained in this invention based on the high-entropy synergistic effect of different types of electrolyte salts has ionic conductivity, high-voltage stability, high safety and excellent interfacial compatibility stability. It can effectively suppress lithium / sodium dendrite growth and exhibits excellent cycle performance and rate performance when applied to all-solid-state batteries.

[0016] The present invention provides the following specific technical solutions:

[0017] The high-entropy synergistic effect regulates the polymer electrolyte membrane, and the preparation method is as follows:

[0018] Step 1: Under an argon atmosphere, dissolve one or more polymer matrices in an organic solvent, stir at a speed of 100-300 rpm, and stir at room temperature for 6-14 hours to obtain slurry A;

[0019] Step 2: Under an argon atmosphere, one or more boron-based lithium / sodium salts, one or more sulfonylimide lithium / sodium salts, one or more organic sulfonate lithium / sodium salts, and one or more inorganic lithium / sodium salts are mixed in a certain proportion, dissolved in a solvent, stirred at 200-800 rpm, and stirred at 60°C for 1-2 hours to obtain solution B.

[0020] Step 3: Under an argon atmosphere, mix slurry A and solution B, and stir at room temperature for 6-14 hours to obtain a uniformly mixed slurry;

[0021] Step 4: Pour the above slurry onto a polytetrafluoroethylene (PTFE) plate, place the PTFE plate on a fully automatic coating machine, and use a 350μm doctor blade for coating at a speed of 20-50mm / s. Let it stand at room temperature in a drying room for 12-20 hours, and then dry it in a vacuum drying oven at 40-60℃ for 6-12 hours to obtain a solid electrolyte film material with a controllable film thickness of 100-200μm.

[0022] In step 1, the polymer matrix can be polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polypropylene carbonate (PPC), etc.

[0023] In step 1, the solvent can be N,N-dimethylformamide (DMF), tetrahydrofuran (THF), or anhydrous acetonitrile (ACN).

[0024] In step 2, the boron-based lithium / sodium salt, sulfonamide lithium / sodium salt, organic sulfonate lithium / sodium salt, and inorganic lithium / sodium salt are collectively referred to as lithium / sodium salts; the total content of the lithium / sodium salts in the mixture of slurry A and solution B is 10-40% by mass. The components of the lithium / sodium salts are as follows by mass: 5-40 parts boron-based lithium / sodium salt, 5-40 parts sulfonamide lithium / sodium salt, 5-20 parts organic sulfonate lithium / sodium salt, and 5-30 parts inorganic lithium / sodium salt.

[0025] The boron-based lithium / sodium salt and its derivatives may be lithium tetrafluoroborate, lithium difluorooxalate borate, lithium dioxobarbital borate, etc.

[0026] Wherein, the lithium / sodium sulfonamide salt is A[R f [SO2]2N, where A is Li or Na and R is CF3, can be lithium bisfluorosulfonylimide, sodium bisfluorosulfonylimide, lithium bistrifluoromethanesulfonylimide, sodium bistrifluoromethanesulfonylimide, etc.;

[0027] Wherein, the organic lithium sulfonate / sodium salt is AR f SO3, where A is Li or Na and R is CF3, can be lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, etc.

[0028] The inorganic lithium / sodium salt can be lithium perchlorate, sodium perchlorate, lithium lanthanum zirconium oxide, etc.

[0029] The present invention also provides an all-solid-state battery, wherein the solid-state battery includes the above-mentioned high-entropy synergistic effect regulated polymer electrolyte membrane.

[0030] Among them, the high-entropy synergistic effect regulates the polymer electrolyte membrane, with a thickness of 15–200 micrometers.

[0031] Among them, the cathode materials of all-solid-state batteries are lithium iron phosphate, lithium manganese phosphate, lithium cobalt phosphate, carbon-coated lithium iron phosphate, and ternary layered electrode materials.

[0032] Among them, the anode materials of all-solid-state batteries include graphite, hard carbon, silicon / carbon, lithium / sodium sheet anode materials, silicon oxide / carbon anode materials, etc.

[0033] The positive electrode material and the negative electrode material are in the following mass ratio: 50 parts - 95 parts: 50 parts - 95 parts.

[0034] The technical solution provided in this invention, based on the high-entropy synergistic effect of electrolyte salts to regulate the performance of polymer electrolyte membranes, solves the problems of low solubility, poor thermal stability, severe corrosion of aluminum foil, poor low-temperature performance, and easy oxidation and decomposition associated with single lithium salts. The prepared polymer electrolyte membrane exhibits high room-temperature ionic conductivity, good high-voltage compatibility, good interfacial compatibility and stability, and high safety. The preparation process is simple, energy-efficient, highly controllable, and easy to scale up. All-solid-state batteries assembled based on this electrolyte membrane demonstrate excellent rate performance and cycle stability. Attached Figure Description

[0035] Figure 1 This is the electrochemical impedance spectroscopy diagram of the electrolyte membrane in Example 1;

[0036] Figure 2 It is the electrochemical window of the electrolyte membrane in Example 1;

[0037] Figure 3 These are the charge-discharge curves of the solid-state battery in Example 1;

[0038] Figure 4 This is the electrochemical impedance spectroscopy diagram of the electrolyte membrane in Example 3. Detailed Implementation

[0039] The specific technical solutions of the present invention will be described with reference to the embodiments.

[0040] Example 1:

[0041] This embodiment is used to illustrate the polymer electrolyte and solid-state battery and their preparation method provided by the present invention.

[0042] ① Under an argon atmosphere, polymers polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and polypropylene carbonate (PPC) were dissolved in organic solvent N,N-dimethylformamide (DMF) at a mass ratio of 1:1. The mixture was stirred at 200 rpm for 10 h at room temperature to obtain slurry A.

[0043] ② Under an argon atmosphere, lithium difluorooxalate borate, lithium difluorosulfonyl imide, lithium difluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, and lithium perchlorate were mixed in a mass ratio of 3:2:2:2:1 and dissolved in solvent DMF. The mixture was stirred at 400 rpm and 60°C for 2 hours to obtain solution B.

[0044] ③ Under an argon atmosphere, slurry A and solution B are mixed and stirred at room temperature for 8 hours to obtain a uniformly mixed slurry;

[0045] ④ The above slurry is poured onto a polytetrafluoroethylene (PTFE) plate. The PTFE plate is placed on a fully automatic coating machine and coated with a 350μm scraper at a coating speed of 30mm / s. The plate is then left to stand at room temperature in a drying room for 12 hours and dried in a vacuum drying oven at 60℃ for 8 hours to obtain a solid electrolyte film material.

[0046] ⑤ In an argon-filled glove box, LiFePO4 electrode sheets are used as positive electrodes and lithium sheets as negative electrodes. After being cut to appropriate sizes, they are placed into a 2032 button mold in the order of stainless steel sheet, positive electrode, electrolyte, and lithium sheet to prepare button batteries. After being sealed with a sealing machine, they are stored in a glove box for testing.

[0047] Figure 1 This is the electrochemical impedance spectroscopy diagram of the electrolyte membrane in Example 1. Figure 2 It is the electrochemical window of the electrolyte membrane in Example 1; Figure 3 These are the charge and discharge curves of the solid-state battery in Example 3.

[0048] Example 2:

[0049] This embodiment is used to illustrate the polymer electrolyte and solid-state battery and their preparation method provided by the present invention.

[0050] The polymer electrolyte was prepared according to the method of Example 1, except that the following salts were used: sodium difluorooxalate borate, sodium bis(trifluoromethanesulfonyl)imide, sodium trifluoromethanesulfonate, sodium perchlorate, sodium vanadium phosphate as the positive electrode, and sodium sheet as the negative electrode.

[0051] Example 3:

[0052] ① Under an argon atmosphere, the polymer polyacrylonitrile (PAN) was dissolved in the organic solvent anhydrous acetonitrile (ACN) and stirred at 200 rpm for 10 h at room temperature to obtain slurry A;

[0053] ② Under an argon atmosphere, lithium dioxoborate, lithium difluorosulfonylimide, lithium trifluoromethanesulfonate, and lithium perchlorate were mixed in a mass ratio of 3.5:4:1.5:1 and dissolved in solvent ACN. The mixture was stirred at 400 rpm and 60°C for 2 hours to obtain solution B.

[0054] ③ Under an argon atmosphere, slurry A and solution B are mixed and stirred at room temperature for 8 hours to obtain a uniformly mixed slurry;

[0055] ④ The above slurry is poured onto a polytetrafluoroethylene (PTFE) plate. The PTFE plate is placed on a fully automatic coating machine and coated with a 350μm scraper at a coating speed of 30mm / s. The plate is then left to stand at room temperature in a drying room for 12 hours and dried in a vacuum drying oven at 60℃ for 8 hours to obtain a solid electrolyte film material.

[0056] ⑤ In an argon-filled glove box, LiFePO4 electrode sheets are used as positive electrodes and lithium sheets as negative electrodes. After being cut to appropriate sizes, they are placed into a 2032 button mold in the order of stainless steel sheet, positive electrode, electrolyte, and lithium sheet to prepare button batteries. After being sealed with a sealing machine, they are stored in a glove box for testing.

[0057] Figure 4 This is the electrochemical impedance spectroscopy diagram of the electrolyte membrane in Example 3.

Claims

1. A method for preparing polymer electrolyte membranes with high-entropy synergistic effect regulation, characterized in that, By dissolving boron-based lithium salts and their derivatives, sulfonylimide lithium salts and their derivatives, organic sulfonate lithium salts and their derivatives, inorganic lithium salts and polymer matrix in an organic solvent and stirring and mixing, a polymer electrolyte membrane is finally obtained by casting or electrospinning. The components of the lithium salt are as follows, by mass: 5-40 parts boron-based lithium salt, 5-40 parts sulfonylimide lithium salt, 5-20 parts organic sulfonate lithium salt, and 5-30 parts inorganic lithium salt. Alternatively, the polymer electrolyte membrane can be obtained by dissolving boron-based sodium salt and its derivatives, sulfonamide sodium salt and its derivatives, organic sulfonate sodium salt and its derivatives, inorganic sodium salt and polymer matrix in an organic solvent and stirring, and finally by casting or electrospinning. The components of the sodium salt are as follows, by mass: 5-40 parts of boron-based sodium salt, 5-40 parts of sulfonamide sodium salt, 5-20 parts of organic sulfonate sodium salt, and 5-30 parts of inorganic sodium salt.

2. The method for preparing a polymer electrolyte membrane with high entropy synergistic effect according to claim 1, characterized in that, Specifically, the steps include: Step 1: Under an argon atmosphere, dissolve the polymer matrix in an organic solvent, stir at a speed of 100-300 rpm, and stir at room temperature for 6-14 h to obtain slurry A; Step 2: Under an argon atmosphere, mix boron-based lithium salt, sulfonylimide lithium salt, organic sulfonate lithium salt, and inorganic lithium salt, dissolve them in a solvent, stir at 200-800 rpm, and stir at 60°C for 1-2 h to obtain solution B; Alternatively, under an argon atmosphere, a mixture of boron-based sodium salt, sulfonamide sodium salt, organic sulfonate sodium salt, and inorganic sodium salt is dissolved in a solvent and stirred at 200–800 rpm for 1–2 h at 60°C to obtain solution B. Step 3: Under an argon atmosphere, mix slurry A and solution B, and stir at room temperature for 6–14 h to obtain a uniformly mixed slurry; Step 4: Pour the above slurry onto a polytetrafluoroethylene (PTFE) plate, place the PTFE plate on a fully automatic coating machine, and use a 350μm doctor blade to coat it at a coating speed of 20-50mm / s. Let it stand at room temperature in a drying room for 12-20 hours, and then dry it in a vacuum drying oven at 40-60℃ for 6-12 hours to obtain a solid electrolyte film material.

3. The method for preparing a polymer electrolyte membrane with high entropy synergistic effect according to claim 2, characterized in that, In step 1, the polymer matrix is ​​one or more of the following: polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and polypropylene carbonate (PPC).

4. The method for preparing a polymer electrolyte membrane with high entropy synergistic effect according to claim 2, characterized in that, In step 1, the solvent is one or a mixture of the following: N,N-dimethylformamide (DMF), tetrahydrofuran (THF), and anhydrous acetonitrile (ACN).

5. The method for preparing a polymer electrolyte membrane with high entropy synergistic effect according to claim 2, characterized in that, In step 2, the boron-based lithium salt and its derivatives are one or more of the following: lithium tetrafluoroborate, lithium difluorooxalate borate, and lithium dioxoborate. The sulfonylimide lithium salt is one or a mixture of the following: A[R] f [SO2]2N, where A is Li and R is CF3; or lithium bis(fluorosulfonyl)imide or lithium bis(trifluoromethanesulfonyl)imide; The sodium sulfonamide salt is one or a mixture of the following: A[R] f SO2]2N, where A is Na and R is CF3; or sodium bis(fluorosulfonyl)imide or sodium bis(trifluoromethanesulfonyl)imide; The organic sulfonate lithium salt is one or a mixture of the following: AR f SO3, where A is Li and R is CF3; or lithium trifluoromethanesulfonate; The organic sulfonate sodium salt is one or a mixture of the following: AR f SO3, where A is Na and R is CF3; or sodium trifluoromethanesulfonate; The inorganic lithium salt is one or a mixture of the following: lithium perchlorate; The inorganic sodium salt is sodium perchlorate.

6. The method for preparing a polymer electrolyte membrane with high entropy synergistic effect according to claim 2, characterized in that, In step 2, the boron-based lithium salt, sulfonylimide lithium salt, organic sulfonate lithium salt, and inorganic lithium salt are collectively referred to as lithium salts; the total content of the lithium salts in the mixture of slurry A and solution B is 10-40% by mass. Alternatively, the aforementioned boron-based sodium salt, sulfonamide sodium salt, organic sulfonate sodium salt, and inorganic sodium salt are collectively referred to as sodium salts; the total content of the sodium salts in the mixture of slurry A and solution B is 10-40% by mass.

7. High-entropy synergistic effect regulating polymer electrolyte membrane, characterized in that, Obtained by the preparation method according to any one of claims 1 to 5.

8. The application of the high-entropy synergistic effect regulating polymer electrolyte membrane according to claim 6, for the preparation of all-solid-state batteries.

9. An all-solid-state battery, characterized in that, Including the high-entropy synergistic effect modulated polymer electrolyte membrane as described in claim 7.

10. A solid-state battery according to claim 9, characterized in that, The high-entropy synergistic effect modulates the polymer electrolyte membrane, which has a thickness of 15-200 micrometers.

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