A high-thermal-stability polymer solid-state electrolyte film, a preparation method and a solid-state battery

Abstract

This invention provides a high thermal stability polymer solid electrolyte membrane, its preparation method, and a solid-state battery. The high thermal stability polymer solid electrolyte membrane uses highly crystalline aliphatic polyketide (POK) as a matrix. Through active regulation of its condensed-state structure, a novel ion transport network based on grain boundary conduction is constructed while maintaining a highly crystalline framework. The preparation method of this high thermal stability polymer solid electrolyte membrane introduces thermal annealing as an active grain boundary regulation step to precisely control the crystallization behavior and grain boundary network structure of the POK matrix, constructing a continuous and efficient grain boundary conduction network. This significantly improves ionic conductivity and high-temperature dimensional stability while maintaining the high crystalline framework of POK. Both the high thermal stability polymer solid electrolyte membrane and the solid-state battery incorporating it have promising prospects for industrial application.

Description

Technical Field

[0001] This invention belongs to the field of all-solid-state battery technology, specifically, it relates to a high thermal stability polymer solid electrolyte membrane, its preparation method, and a solid-state battery. Background Technology

[0002] Solid-state polymer electrolytes (SPEs) are considered key materials for overcoming the safety bottlenecks of lithium metal batteries and achieving high energy density due to their excellent flexibility, processability, and interfacial compatibility. An ideal SPE needs to simultaneously possess high ionic conductivity, a wide electrochemical window, and excellent thermal / mechanical stability. However, in the traditional understanding of SPEs, ion conduction depends on the movement of polymer chains in the amorphous region. To improve room-temperature ionic conductivity, it is usually necessary to reduce the crystallinity of the system through blending, copolymerization, and plasticization. Reducing crystallinity inevitably sacrifices the material's mechanical strength and high-temperature dimensional stability. The inherent contradiction between these three core properties has become a key bottleneck restricting the commercial application of SPEs.

[0003] Existing technologies have improved thermal stability and mechanical properties of solid polymer electrolytes by introducing high-heat-resistant polymer backbones, cross-linking to form three-dimensional network structures, and organic-inorganic composites, while ensuring the ionic conductivity and electrochemical window of the solid polymer electrolyte. However, high-heat-resistant polymer backbones usually lack ionic conductivity and mostly have highly rigid main chains, resulting in relatively low compatibility and interfacial matching with flexible conductive components, thus limiting ionic conductivity. While constructing a three-dimensional network structure significantly improves the thermal stability of the electrolyte, it also restricts the mobility of polymer chain segments, negatively impacting ionic conductivity. Furthermore, improper control of cross-linking degree can lead to increased material brittleness, resulting in strong constraints on the control window. Inorganic fillers, on the other hand, suffer from dispersion difficulties and do not fundamentally solve the problem of size shrinkage of solid polymer electrolytes at high temperatures.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] To address the aforementioned technical problems, the first aspect of this invention provides a high thermal stability polymer solid electrolyte membrane. This electrolyte membrane uses a highly crystalline aliphatic polyketide as its matrix. By actively controlling its condensed-state structure, a novel ion transport network based on grain boundary conduction is constructed while maintaining a highly crystalline framework. This fundamentally decouples the contradiction between ionic conductivity and thermal stability, enabling it to possess high ionic conductivity, excellent dimensional stability, and structural safety under high-temperature operating conditions.

[0006] The second aspect of this invention provides a method for preparing the above-mentioned high thermal stability polymer solid electrolyte membrane. By introducing thermal annealing as an active grain boundary control step, the crystallization behavior and grain boundary network structure of the POK matrix are precisely controlled, and a continuous and efficient grain boundary conduction network is constructed. While maintaining the high crystallinity framework of POK, the ionic conductivity and high-temperature dimensional stability are significantly improved, which has good prospects for industrial application.

[0007] A third aspect of the present invention provides a solid-state battery employing the above-described high thermal stability polymer solid electrolyte membrane.

[0008] To achieve the above objectives, a first aspect of the present invention provides a high thermal stability polymer solid electrolyte membrane, comprising an aliphatic polyketide matrix and a lithium salt, wherein the main chain of the aliphatic polyketide matrix has alternating carbonyl and alkylene units and does not have aromatic rings; the crystallinity of the aliphatic polyketide matrix is ​​greater than or equal to 40%, and it has a continuous ion conduction network composed of polyketide grain boundaries, wherein the continuous ion conduction network achieves lithium ion conduction through the coordination-decoupling interaction between carbonyl groups on the polyketide grain boundaries and lithium ions.

[0009] Furthermore, the crystallinity of the aliphatic polyketide matrix is ​​40%-60%.

[0010] Furthermore, the C2-C10 aliphatic dicarboxylic acid is at least one of succinic acid and adipic acid; the mass ratio of the C8-C20 aromatic aliphatic polyketide matrix to the lithium salt is 1:0.3-0.6.

[0011] Furthermore, the lithium salt includes at least one of lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate.

[0012] Furthermore, the aliphatic polyketide matrix is ​​a copolymer of carbon monoxide and α-olefin; the α-olefin includes at least one of ethylene and propylene.

[0013] Furthermore, the high thermal stability polymer solid electrolyte membrane also includes nanofillers, which are dispersed at the polyketide grain boundaries and together with the polyketide grain boundaries form the continuous ion conduction network; the mass ratio of the aliphatic polyketide matrix, lithium salt and nanofillers is 1:0.3-0.6:0.05-0.3.

[0014] Furthermore, the nanofiller is at least one of garnet-type solid electrolyte nanoparticles, NASICON-type solid electrolyte nanoparticles, and inert oxide nanoparticles.

[0015] Furthermore, the thermal shrinkage rate of the high thermal stability polymer solid electrolyte membrane after heat treatment at 200°C for 1 hour is less than or equal to 3%.

[0016] A second aspect of the present invention provides a method for preparing the above-mentioned high thermal stability polymer solid electrolyte membrane, comprising the following steps: S1. An initial polymer solid electrolyte membrane is prepared using raw materials containing an aliphatic polyketide matrix and a lithium salt. S2. Anneal the initial polymer solid electrolyte membrane to obtain a polymer solid electrolyte membrane with high thermal stability.

[0017] Further, step S2 specifically involves annealing the initial polymer solid electrolyte membrane under an inert atmosphere at a temperature 20°C-50°C lower than the melting temperature of the aliphatic polyketide matrix for 0.5h-4h. After annealing, the membrane is cooled to room temperature to obtain the high thermal stability polymer solid electrolyte membrane.

[0018] Furthermore, after annealing, the sample is cooled to room temperature at a rate of 1℃ / min-10℃ / min.

[0019] Furthermore, in step S1, the raw material also includes nanofillers.

[0020] A third aspect of the present invention provides a solid-state battery, which includes a positive electrode, a negative electrode, and a high thermal stability polymer solid electrolyte membrane as described above.

[0021] By adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art.

[0022] 1. This invention transforms the grain boundaries of highly crystalline polymers from "conduction barriers" to "conduction channels" in the traditional sense. While maintaining the excellent thermal stability framework provided by the high crystallinity (≥40%) of the aliphatic polyketide matrix, it utilizes grain boundaries and phase interfaces to construct a highly efficient continuous ion conduction network, achieving a synergistic balance between high ionic conductivity and high thermal stability.

[0023] 2. The solid electrolyte membrane provided by this invention has a thermal shrinkage rate of less than or equal to 3% after heat treatment at 200°C for 1 hour. This is significantly better than the defect of traditional PEO-based electrolytes that undergo severe softening and shrinkage above the melting point. This ensures that the electrolyte membrane can maintain its structural integrity under high-temperature operation or thermal runaway scenarios, effectively preventing short circuits between the positive and negative electrodes and greatly improving the safety performance of the battery.

[0024] 3. The preparation method of this invention involves thermally annealing the initial electrolyte membrane at a temperature range 20°C-50°C below the melting temperature of polyketide, while controlling the cooling rate, thereby achieving active regulation of the crystallization behavior and grain boundary connectivity of the polyketide matrix. This process promotes the enrichment of lithium salts in the grain boundary region, optimizes grain size and grain boundary network structure, and significantly improves ionic conductivity and high-temperature dimensional stability even without the addition of nanofillers. Furthermore, through the synergistic effect of grain boundaries and nanofillers, ionic conductivity can be further improved while maintaining thermal stability. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below in conjunction with the embodiments of the present invention. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0026] It should be noted first that the raw materials, sources, and specifications used in the following embodiments are shown in the table below: name Specification source Manufacturer Aliphatic polyketone (M330A) Grade: M330A; Medium viscosity; Melting temperature approximately 220°C; White granular copolymer of alternating ethylene and carbon monoxide. Commercially available Hyosung Chemical (Korea) Aliphatic polyketone (M730F) Grade: M730F; Low flowability; Melting temperature approximately 205°C; White granular copolymer of alternating ethylene, propylene, and carbon monoxide. Commercially available Hyosung Chemical (Korea) Lithium bis(trifluoromethanesulfonylimide) (LiTFSI) Purity: 99.95%; white powder Commercially available Sigma-Aldrich Lithium difluoroflavinimide (LiFSI) Purity ≥ 99.9%; white powder Commercially available Sigma-Aldrich Lithium perchlorate Purity ≥ 99.99%; white powder Commercially available Sigma-Aldrich Lithium lanthanum zirconium oxide Cubic phase; purity ≥99.9%; particle size: 0.3-1µm Commercially available Alfa Chemistry Lithium titanium aluminum phosphate Purity > 99.9%; Particle size: 200nm Commercially available TCI Nano silica Particle size <50nm; 20wt.% aqueous dispersion; purity ≥99.9% Commercially available Sigma-Aldrich Nano aluminum oxide Particle size <50nm; nanopowder Commercially available Sigma-Aldrich Hexafluoroisopropanol (HFIP) Purity ≥ 99.8%; Commercially available Sigma-Aldrich Polyethylene oxide (PEO) Average molecular weight: 600,000; melting point: 65-67℃ Commercially available Sigma-Aldrich Acetonitrile (ACN) Chromatographic grade, ≥99.9% Commercially available Sigma-Aldrich The technical solution of the present invention will be further described in detail below with reference to specific embodiments. Example 1

[0027] S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0028] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0029] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm. Example 2

[0030] S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M730F was dissolved in 20 mL of a mixed solvent of hexafluoroisopropanol and chloroform at a volume ratio of 1:1 under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution, and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0031] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0032] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 170℃, and the annealing time was 3 hours. After annealing, it was slowly cooled to room temperature at a rate of 3℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm. Example 3

[0033] S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.4 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0034] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0035] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm. Example 4

[0036] S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.6 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0037] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0038] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0039] Example 5 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of about 10%; then 1 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0040] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0041] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0042] Example 6 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 1.2 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0043] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0044] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0045] Example 7 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0046] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0047] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 150℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0048] Example 8 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0049] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0050] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 170℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0051] Example 9 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0052] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0053] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 200℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0054] Example 10 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 0.1g of nano-silica was added to 5mL of hexafluoroisopropanol and ultrasonically dispersed for 30 minutes to obtain a nanofiller dispersion.

[0055] 2.0 g of aliphatic polyketone M330A was dissolved in 15 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution. The above nanofiller dispersion was mixed with the aliphatic polyketone solution, and 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added. The mixture was stirred for another 4 hours to obtain a homogeneous mixed solution.

[0056] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0057] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm containing nano-silica.

[0058] Example 11 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 0.1 g of lithium lanthanum zirconium oxide was added to 5 mL of hexafluoroisopropanol and ultrasonically dispersed for 30 minutes to obtain a nanofiller dispersion.

[0059] 2.0 g of aliphatic polyketone M330A was dissolved in 15 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution. The above nanofiller dispersion was mixed with the aliphatic polyketone solution, and 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added. The mixture was stirred for another 4 hours to obtain a homogeneous mixed solution.

[0060] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0061] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80 μm containing lithium lanthanum zirconium oxide.

[0062] Example 12 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. Add 0.1g of lithium titanium aluminum phosphate to 5mL of hexafluoroisopropanol and ultrasonically disperse for 30 minutes to obtain a nanofiller dispersion.

[0063] 2.0 g of aliphatic polyketone M330A was dissolved in 15 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution. The above nanofiller dispersion was mixed with the aliphatic polyketone solution, and 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added. The mixture was stirred for another 4 hours to obtain a homogeneous mixed solution.

[0064] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0065] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm containing lithium aluminum titanium phosphate.

[0066] Example 13 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 0.1 g of nano-alumina was added to 5 mL of hexafluoroisopropanol and ultrasonically dispersed for 30 minutes to obtain a nano-filler dispersion.

[0067] 2.0 g of aliphatic polyketone M330A was dissolved in 15 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution. The above nanofiller dispersion was mixed with the aliphatic polyketone solution, and 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added. The mixture was stirred for another 4 hours to obtain a homogeneous mixed solution.

[0068] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0069] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm containing nano-alumina.

[0070] Example 14 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0071] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0072] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 1℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0073] Example 15 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0074] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0075] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 10℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0076] Example 16 This embodiment is the same as Embodiment 1, except that step S2 is not performed, that is, the polymer electrolyte membrane is not subjected to thermal annealing.

[0077] Example 17 S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0078] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0079] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 210℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0080] Example 18 The high thermal stability polymer solid electrolyte membrane obtained in Example 1 was used to prepare a full battery, and the process is as follows: S1. Preparation of the positive electrode sheet.

[0081] Lithium iron phosphate positive electrode active material, conductive carbon black, and polyvinylidene fluoride binder were weighed in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone solvent was added. The mixture was then ground and mixed evenly in a mortar to obtain a positive electrode slurry. The positive electrode slurry was uniformly coated onto carbon-coated aluminum foil and vacuum dried at 80°C for 12 hours. After rolling and cutting, a positive electrode sheet with a size of 40mm×60mm was obtained, with an active material loading of approximately 1.5mg / cm².

[0082] S2, Preparation of the negative electrode sheet.

[0083] Using lithium metal foil as the negative electrode, the negative electrode sheet is cut into a size of 42mm×62mm, which is slightly larger than the positive electrode sheet, to eliminate the risk of lithium deposition at the edge of the negative electrode due to misalignment.

[0084] S3. Preparation of solid electrolyte membrane.

[0085] The high thermal stability polymer solid electrolyte membrane prepared in Example 1 was cut into sheets of 45mm × 65mm for later use.

[0086] S4, soft-pack battery assembly.

[0087] In a dry room or argon-protected glove box with a dew point below -45°C ( <0.1ppm, The positive and negative electrode sheets are stacked (with a concentration of <0.1ppm), separated by a solid electrolyte membrane. After stacking, the positive electrode tabs are stacked and welded together, and the negative electrode tabs are stacked and welded together to form a core. The core is placed in a perforated aluminum-plastic film shell, with the positive and negative tabs extending out of the shell. Top and side sealing are performed at 185°C to complete the assembly of the pouch battery.

[0088] Comparative Example 1 2.0 g of polyethylene oxide and 0.6 g of lithium bis(trifluoromethanesulfonyl)imide were dissolved in 20 mL of acetonitrile and stirred for 4 hours to obtain a homogeneous and transparent mixed solution.

[0089] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, a PEO-based solid electrolyte membrane with a thickness of 80 μm was obtained.

[0090] Comparative Example 2 This comparative example is the same as Example 1, except that the aliphatic polyketide used in step S1 is a low-crystallinity aliphatic polyketide with a crystallinity of 30%, that is, the aliphatic polyketide has a high ethylene content.

[0091] S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of low-crystallinity aliphatic polyketone (30% crystallinity) was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. 0.8 g of lithium bis(trifluoromethanesulfonyl)imide was added to the above solution, and stirring was continued for 4 hours to obtain a homogeneous and transparent mixed solution.

[0092] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0093] S2. Anneal the initial polymer solid electrolyte membrane.

[0094] The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a low-crystallinity POK solid electrolyte membrane with a thickness of approximately 80 μm.

[0095] Comparative Example 3 The preparation method of this comparative example is the same as that of Example 1, the only difference being the adjustment of the amount of lithium trifluoromethanesulfonylimide added.

[0096] S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 1.4 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0097] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0098] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 5℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0099] Comparative Example 4 The preparation method of this comparative example is the same as that of Example 1, the only difference being that the cooling rate after annealing in step S2 was adjusted.

[0100] S1. Preparation of an initial polymer solid electrolyte membrane using raw materials containing an aliphatic polyketide matrix and lithium salt. 2.0 g of aliphatic polyketone M330A was dissolved in 20 mL of hexafluoroisopropanol under stirring at 50 °C to obtain an aliphatic polyketone solution with a mass fraction of approximately 10%. Then, 0.8 g of lithium bis(trifluoromethanesulfonylimide) was added to the aliphatic polyketone solution and stirring was continued for 4 hours to obtain a uniform and transparent mixed solution.

[0101] The above mixed solution was coated onto a polytetrafluoroethylene mold and allowed to evaporate naturally in dry air at room temperature for 6 hours. It was then transferred to a vacuum oven and vacuum dried at 60°C for 12 hours to completely remove residual solvent. After peeling off the mold, the initial electrolyte membrane was obtained.

[0102] S2. Anneal the initial polymer solid electrolyte membrane to obtain a high thermal stability polymer solid electrolyte membrane. The initial electrolyte membrane was placed in a vacuum oven and subjected to thermal annealing under an argon protective atmosphere. The annealing temperature was set at 185℃, and the annealing time was 2 hours. After annealing, it was slowly cooled to room temperature at a rate of 13℃ / min to obtain a high thermal stability polymer solid electrolyte membrane with a thickness of 80μm.

[0103] Sample preparation In this invention, a blocking battery consisting of a steel-steel system made from the polymer solid electrolyte membranes prepared in the above embodiments and comparative examples is to be tested.

[0104] Experimental Example In this experimental example, the polymer solid electrolyte membranes and button-type membranes prepared in the above embodiments were subjected to the following tests: 1) Crystallinity, melting point and glass transition temperature testing Approximately 5–8 mg of the polymer solid electrolyte membranes finally prepared in each example and comparative example were placed in an aluminum crucible of a differential scanning calorimeter (DSC). Under a nitrogen atmosphere, the temperature was increased from -50°C to 200°C at a heating rate of 10°C / min, and the first heating curve was recorded. Crystallinity was calculated from the enthalpy of fusion, using 227 J / g as the baseline for 100% crystallization of pure aliphatic polyketide crystals; the melting point was taken as the peak temperature of the melting peak; and the glass transition temperature was taken as the midpoint temperature of the heat capacity change step.

[0105] 2) Measurement of ionic conductivity Electrochemical impedance spectroscopy (EIS) was performed on the steel-steel blocking cell system under isothermal conditions of 30°C, 60°C, and 100°C using an electrochemical workstation. The frequency range was 1Hz–1MHz, and the AC amplitude was 10mV. The bulk resistance R was read from the intersection of the Nyquist curve and the real axis, and then calculated according to the formula... Calculate the ionic conductivity, where L is the film thickness and A is the electrode area.

[0106] 3) Heat shrinkage rate test The polymer solid electrolyte membrane was cut into 30mm×30mm square samples, and its initial area (S0) was measured. The samples were then placed in a 200℃ oven and heat-treated in a free state for 1 hour. After the samples were removed and cooled to room temperature, the final area (S1) was measured, and the area shrinkage rate was calculated. Three samples were made for each group of samples and tested separately. The average value of the test data of the three samples was taken.

[0107] The test results are shown in the table below: Crystallinity (%) Ionic conductivity at 30℃ (S / cm) Ionic conductivity at 60℃ (S / cm) Ionic conductivity at 100℃ (S / cm) Heat shrinkage rate at 200℃ / 1h (%) Example 1 48 <![CDATA[8.2×10 -6 ]]> <![CDATA[2.5×10 -5 ]]> <![CDATA[1.8×10 -4 ]]> 2.8 Example 2 43 <![CDATA[6.5×10 -6 ]]> <![CDATA[1.8×10 -5 ]]> <![CDATA[1.2×10 -4 ]]> 3.0 Example 3 52 <![CDATA[5.1×10 -6 ]]> <![CDATA[1.2×10 -5 ]]> <![CDATA[1.2×10 -4 ]]> 2.3 Example 4 49 <![CDATA[6.5×10 -6 ]]> <![CDATA[1.9×10 -5 ]]> <![CDATA[1.5×10 -4 ]]> 2.5 Example 5 45 <![CDATA[1.5×10 -5 ]]> <![CDATA[3.8×10 -5 ]]> <![CDATA[2.5×10 -4 ]]> 2.8 Example 6 42 <![CDATA[2.2×10 -5 ]]> <![CDATA[5.5×10 -5 ]]> <![CDATA[3.1×10 -4 ]]> 3.0 Example 7 50 <![CDATA[2.8×10 -6 ]]> <![CDATA[8.5×10 -6 ]]> <![CDATA[5.5×10 -5 ]]> 2.5 Example 8 49 <![CDATA[4.5×10 -6 ]]> <![CDATA[1.5×10 -5 ]]> <![CDATA[9.2×10 -5 ]]> 2.6 Example 9 46 <![CDATA[1.1×10 -5 ]]> <![CDATA[3.2×10 -5 ]]> <![CDATA[2.5×10 -4 ]]> 3.0 Example 10 47 <![CDATA[1.5×10 -5 ]]> <![CDATA[4.5×10 -5 ]]> <![CDATA[2.8×10 -4 ]]> 2.6 Example 11 46 <![CDATA[2.5×10 -5 ]]> <![CDATA[6.8×10 -5 ]]> <![CDATA[3.8×10 -4 ]]> 2.6 Example 12 45 <![CDATA[2.2×10 -5 ]]> <![CDATA[6.2×10 -5 ]]> <![CDATA[3.5×10 -4 ]]> 2.7 Example 13 47 <![CDATA[1.8×10 -5 ]]> <![CDATA[5.2×10 -5 ]]> <![CDATA[2.9×10 -4 ]]> 2.5 Example 14 52 <![CDATA[6.2×10 -6 ]]> <![CDATA[1.8×10 -5 ]]> <![CDATA[1.4×10 -4 ]]> 2.2 Example 15 45 <![CDATA[1.0×10 -5 ]]> <![CDATA[3.0×10 -5 ]]> <![CDATA[2.2×10 -4 ]]> 3.0 Example 16 42 <![CDATA[3.8×10 -6 ]]> <![CDATA[1.2×10 -5 ]]> <![CDATA[6.8×10 -5 ]]> 4.2 Example 17 43 <![CDATA[9.5×10 -6 ]]> <![CDATA[2.8×10 -5 ]]> <![CDATA[2.0×10 -4 ]]> 3.2 Comparative Example 1 25 <![CDATA[1.2×10 -6 ]]> <![CDATA[5.5×10 -5 ]]> - - Comparative Example 2 25 <![CDATA[5.5×10 -6 ]]> <![CDATA[1.8×10 -5 ]]> <![CDATA[1.1×10 -4 ]]> 8.5 Comparative Example 3 36 <![CDATA[3.5×10 -5 ]]> <![CDATA[8.2×10 -5 ]]> <![CDATA[4.2×10 -4 ]]> 5.8 Comparative Example 4 38 <![CDATA[1.5×10 -5 ]]> <![CDATA[4.2×10 -5 ]]> <![CDATA[2.4×10 -4 ]]> 5.2 As can be seen from the comparison of the above embodiments and comparative examples, when the crystallinity is less than 40%, the crystalline phase fails to form a three-dimensional continuous rigid framework network, and the chain segment movement of the amorphous phase cannot be effectively constrained at high temperatures, resulting in a significant increase in thermal shrinkage.

[0108] Furthermore, a comparison between Examples 1 and 16 shows that annealing, by eliminating internal stress, improving the crystal structure, and optimizing the grain boundary network, can further reduce the thermal shrinkage rate while maintaining a crystallinity of ≥40%. This fully demonstrates that the crystallinity control achieved through thermal annealing and grain boundary regulation as defined in this invention has a significant synergistic effect, with both ensuring the dimensional stability and structural integrity of the solid electrolyte membrane at high temperatures.

[0109] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. The implementation schemes in the above embodiments can also be further combined or replaced. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A high-thermo-stable polymer solid-state electrolyte membrane, characterized by, The invention comprises an aliphatic polyketide matrix and a lithium salt, wherein the main chain of the aliphatic polyketide matrix has alternating carbonyl and alkylene units and does not have an aromatic ring; the crystallinity of the aliphatic polyketide matrix is ​​greater than or equal to 40%, and it has a continuous ion conduction network composed of polyketide grain boundaries, wherein the continuous ion conduction network achieves lithium ion conduction through coordination-decoupling interactions between carbonyl groups on the polyketide grain boundaries and lithium ions.

2. The high-thermal-stability polymer solid-state electrolyte membrane according to claim 1, characterized by, The crystallinity of the aliphatic polyketide matrix is ​​40%-60%.

3. The high-thermal-stability polymer solid-state electrolyte membrane according to claim 1, characterized by, The mass ratio of the aliphatic polyketide matrix to the lithium salt is 1:0.3-0.

6.

4. The high-thermal-stability polymer solid-state electrolyte membrane according to claim 3, characterized by, The lithium salt includes at least one of lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate.

5. The high thermal stability polymer solid electrolyte membrane according to claim 1, characterized in that, The aliphatic polyketide matrix is ​​a copolymer of carbon monoxide and α-olefin; the α-olefin includes at least one of ethylene and propylene.

6. The high thermal stability polymer solid electrolyte membrane according to any one of claims 1-5, characterized in that, It also includes nanofillers, which are dispersed at the polyketide grain boundaries and together with the polyketide grain boundaries form the continuous ion conduction network; the mass ratio of the aliphatic polyketide matrix, lithium salt and nanofillers is 1:0.3-0.6:0.05-0.

3.

7. The high thermal stability polymer solid electrolyte membrane according to claim 6, characterized in that, The nanofiller is at least one of garnet-type solid electrolyte nanoparticles, NASICON-type solid electrolyte nanoparticles, and inert oxide nanoparticles.

8. The high thermal stability polymer solid electrolyte membrane according to any one of claims 1-7, characterized in that, The thermally stable polymer solid electrolyte membrane has a thermal shrinkage rate of less than or equal to 3% after heat treatment at 200°C for 1 hour.

9. A method for preparing a high thermal stability polymer solid electrolyte membrane as described in any one of claims 1-8, characterized in that, Includes the following steps: S1. An initial polymer solid electrolyte membrane is prepared using raw materials containing an aliphatic polyketide matrix and a lithium salt. S2. Anneal the initial polymer solid electrolyte membrane to obtain a polymer solid electrolyte membrane with high thermal stability.

10. The method for preparing a high thermal stability polymer solid electrolyte membrane according to claim 9, characterized in that, Step S2 specifically involves annealing the initial polymer solid electrolyte membrane under an inert atmosphere at a temperature 20°C-50°C lower than the melting temperature of the aliphatic polyketide matrix for 0.5-4 hours. After annealing, the membrane is cooled to room temperature to obtain the high thermal stability polymer solid electrolyte membrane.

11. The method for preparing a high thermal stability polymer solid electrolyte membrane according to claim 10, characterized in that, After annealing, cool to room temperature at a rate of 1℃ / min-10℃ / min.

12. The method for preparing a high thermal stability polymer solid electrolyte membrane according to claim 9, characterized in that, In step S1, the raw material also includes nanofillers.

13. A solid-state battery, characterized in that, It includes a positive electrode, a negative electrode, and a high thermal stability polymer solid electrolyte membrane as described in any one of claims 1-8.