Composite solid electrolyte membrane and preparation method thereof

Abstract

The invention relates to the technical field of solid-state batteries, in particular to a composite solid-state electrolyte membrane and a preparation method thereof. The composite solid electrolyte membrane provided by the invention comprises a binder and a sulfide solid electrolyte, the binder comprises modified polyisobutene and polytetrafluoroethylene, and the modified polyisobutene is prepared by carrying out polymerization reaction on an initiator, which is an oxygen anion macromolecule prepared from high-activity polyisobutene as a raw material, with methyl methacrylate and lithium acrylate; the sulfide electrolyte comprises any one of Li < 7 > P < 3 > S < 11 >, Li < 3 > P < 4 >, Li < 10 > Ge < 2 > S < 12 >, Li < 10 > Ge < 2 > S < 12 >, Li < 6 > PS < 5 > Cl and Li < 7-x > PS < 6-x > Cl < x >; the electrolyte membrane prepared by the invention effectively solves the side reaction problem of a polytetrafluoroethylene binder in a dry electrode, and has the advantages of certain mechanical strength, higher ionic conductivity, low thickness and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of solid-state batteries, and in particular to a composite solid-state electrolyte membrane and a preparation method thereof. Background Art

[0002] The solid electrolyte membrane is a core component of solid-state batteries, separating the positive and negative electrodes to prevent short circuits, allowing ions to pass through, and isolating electrons. Sulfide solid electrolytes have attracted widespread attention due to their high room-temperature ionic conductivity. Sulfide electrolytes can also form good interfacial contact with electrode materials under certain pressures. An ideal sulfide electrolyte membrane should have low thickness, good mechanical properties, and high ionic conductivity to increase battery energy density, extend battery life, and improve safety. Therefore, achieving an ideal electrolyte membrane requires a balance between ionic conductivity, mechanical strength, and thickness.

[0003] Currently, the commonly used method for preparing sulfide electrolyte membranes is wet film formation. Since sulfide electrolytes are extremely sensitive to polar solvents, the ionic conductivity of the electrolyte membranes prepared by the wet process is significantly reduced. Dry film formation is to mix the binder with solid electrolyte powder and apply shear force to fiberize the binder, thereby forming the electrolyte into a film. Compared with wet film formation, the dry process for preparing solid electrolyte membranes does not require organic solvents, is environmentally friendly, and saves costs such as materials, time, and labor. Furthermore, most sulfide electrolyte membranes currently available are usually thicker and have lower ionic conductivity, which makes it impossible to further improve the energy density of the assembled all-solid-state battery. Based on this, it is crucial to develop sulfide electrolyte membranes that have low thickness, ideal mechanical properties, and higher ionic conductivity.

[0004] Polytetrafluoroethylene (PTFE) is a common binder used in dry-process membrane production, but it is prone to reduction reactions at low potentials. Furthermore, sulfide electrolyte membranes with high PTFE content consume a large amount of active lithium on the side in contact with the anode during the lithiation process, resulting in poor contact between the electrolyte membrane and the anode. This leads to loose solid electrolyte membranes, damage to the battery structure, and decreased battery performance. However, sulfide electrolyte membranes prepared with a small amount of PTFE binder have poor mechanical properties, and their thickness cannot be reduced. Summary of the Invention

[0005] The object of the present invention is to provide a composite solid electrolyte membrane and a preparation method thereof to solve the problems raised in the above background technology.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: Step 1: In an argon environment, a modified polyisobutylene binder and sulfide electrolyte particles are ground and mixed to obtain a composite solid electrolyte powder; Step 2: A polytetrafluoroethylene binder is added to the composite solid electrolyte powder for shear mixing, and the powder is hot extruded to 150-300 μm and rolled to be thinned to 20-40 μm to obtain a composite solid electrolyte membrane.

[0007] Furthermore, in step 1, the preparation method of the modified polyisobutylene binder comprises the following steps: S1: Add acrylic acid to lithium hydroxide in an ice-water bath at -5 to 0°C and stir for 5 to 10 minutes to obtain lithium acrylate; S2: In an ice-water bath at -5-0°C, sodium borohydride and boron trifluoride-ether solution are added to anhydrous tetrahydrofuran as solvent, and the mixture is stirred for 3-4 hours. A tetrahydrofuran solution of highly active polyisobutylene is then added and the mixture is reacted for 20-24 hours. The pH of the system is adjusted to 10-12 with sodium hydroxide solution, and a hydrogen peroxide solution is added dropwise and the mixture is reacted for 8-10 hours. The mixture is washed with water and extracted with ether. The organic layer is dried, the solvent is removed by rotary evaporation, and the mixture is dried in vacuo to obtain hydroxy-terminated polyisobutylene. S3: Disperse the hydroxy-terminated polyisobutylene in anhydrous tetrahydrofuran under a nitrogen atmosphere, stir until dissolved, add potassium hydride washed with anhydrous tetrahydrofuran, and react at 45-50°C for 10-12 hours to generate a polyisobutylene-based macroinitiator; S4: Under an argon environment, a polyisobutylene-based macromolecular initiator and methyl methacrylate are dispersed in anhydrous tetrahydrofuran, and the mixture is reacted at 25-30°C for 2-3 hours. After adding lithium acrylate and continuing the reaction for 2-3 hours, anhydrous methanol is added to terminate the reaction. The reaction solution is added to icy n-hexane for precipitation, and vacuum dried to constant weight to obtain a modified polyisobutylene adhesive.

[0008] Furthermore, the polyisobutylene-based macroinitiator, methyl methacrylate, and lithium acrylate are reacted in a weight ratio of (50-60):(5-20):(30-35).

[0009] Furthermore, in step 1, the grinding and mixing speed is 1500-2500 rpm, and the grinding and mixing time is 50-70 min.

[0010] Furthermore, in step 2, the shear mixing speed is 3000-5000 rpm, and the shear mixing time is 30-60 min.

[0011] Furthermore, in step 2, the hot extrusion temperature is 80-100°C.

[0012] Furthermore, in step 2, in the composite solid electrolyte membrane, the amounts of the components are calculated by weight percentage: 0.5-2% modified polyisobutylene binder, 0.05-0.1% polytetrafluoroethylene binder, and the balance is sulfide electrolyte particles.

[0013] Furthermore, in step 2, the sulfide electrolyte is Li7P3S 11 、Li3PS4、Li 10 GeP2S 12 、Li 10 GeP2S 12 、Li 7-x PS 6-x Cl x Any of .

[0014] Furthermore, the particle size D of the sulfide solid electrolyte 50 1~10μm.

[0015] Compared with existing technologies, the present invention achieves the following advantages: It provides a composite solid electrolyte membrane comprising a binder and a sulfide solid electrolyte; the binder is modified polyisobutylene and polytetrafluoroethylene. The sulfide solid electrolyte provides excellent ionic conductivity for the solid electrolyte membrane. Using the sulfide electrolyte as the primary raw material for the solid electrolyte membrane, adding a small amount of modified polyisobutylene binder and supplementing with a very small amount of polytetrafluoroethylene can achieve high ionic conductivity.

[0016] The modified polyisobutylene is prepared from highly reactive polyisobutylene through hydroboration, oxygen anion polymerization, and subsequent reaction with methyl methacrylate and lithium acrylate. Highly reactive polyisobutylene with a molecular weight of 900-1150 g / mol is used as the raw material, resulting in both good reactivity and excellent mechanical properties. The modified polyisobutylene exhibits excellent bonding properties, and the presence of lithium acrylate in its molecular segments creates a more conductive binder network. The moderate molecular weight and uniform binder distribution ensure minimal loss of ionic conductivity in the sulfide electrolyte particles. There are no significant side reactions between the modified polyisobutylene, polytetrafluoroethylene, and sulfide electrolyte. By applying shear force, mixing, extruding, and calendering, a self-supporting sulfide electrolyte membrane can be produced. Its high mechanical strength and flexibility maintain stable battery operation and the integrity of the electrolyte membrane structure during battery charge and discharge, improving cycle stability.

[0017] Compared with the traditional polytetrafluoroethylene preparation of sulfide electrolyte membrane, the use of mixed dual binders not only reduces the content of conventional polytetrafluoroethylene binder in the sulfide electrolyte membrane, but also allows the sulfide electrolyte to be fiberized into a membrane through the dual binder, so that the composite solid electrolyte membrane is strengthened while the thickness is further reduced. It also solves the shortcomings of polytetrafluoroethylene binder in dry electrodes and improves the adhesion and electrochemical stability of the sulfide electrolyte membrane.

[0018] In addition, the modified polyisobutylene binder and polytetrafluoroethylene binder used in the present invention have a lower operating temperature, so the composite solid electrolyte membrane has a lower film-forming temperature; the prepared solid electrolyte membrane is thinner, which can improve the energy density of the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings: Figure 1 1 is an electron microscope image of the composite solid electrolyte membrane in Example 1(a) of the present invention and Comparative Example 1(b); Figure 2 This is a long cycle test diagram of a solid-state battery made of a composite solid electrolyte membrane in Example 1 of the present invention. DETAILED DESCRIPTION

[0020] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0021] Materials and sources used in the present invention: The sulfide electrolyte is Li 5.5 PS 4.5 Cl 1.5 , particle size D 50 The particle size is 5μm and comes from Wuhan Tianshi Kefeng New Energy Technology Co., Ltd.; the high-activity polyisobutylene comes from Zhangjiagang Fengtong Chemical Co., Ltd., with an average molecular weight of 900~1150; polytetrafluoroethylene comes from DuPont of the United States, with the item number MP1300; the polyisobutylene adhesive comes from Wuxi Bingju Trading Co., Ltd., with the item number JINEX6130.

[0022] Example 1: A method for preparing a composite solid electrolyte membrane, comprising the following steps: Step 1: S1: Add acrylic acid to lithium hydroxide in an ice-water bath at -5°C and stir for 5 minutes to obtain lithium acrylate; S2: In an ice-water bath at -5°C, sodium borohydride and boron trifluoride-ether solution were added to anhydrous tetrahydrofuran as solvent, and the mixture was stirred for 3 hours. A tetrahydrofuran solution of highly active polyisobutylene was then added and reacted for 20 hours. The pH of the system was adjusted to 10 with sodium hydroxide solution, and a hydrogen peroxide solution was added dropwise and reacted for 8 hours. The mixture was washed with water and extracted with ether. The organic layer was dried, the solvent was removed by rotary evaporation, and the mixture was dried in vacuo to obtain hydroxy-terminated polyisobutylene. S3: Disperse the hydroxy-terminated polyisobutylene in anhydrous tetrahydrofuran under nitrogen atmosphere, stir until dissolved, add potassium hydride washed with anhydrous tetrahydrofuran, and react at 45°C for 10 hours to generate a polyisobutylene-based macroinitiator; S4: Under an argon atmosphere, a polyisobutylene-based macromolecular initiator and methyl methacrylate are dispersed in anhydrous tetrahydrofuran, reacted at 25°C for 2 hours, lithium acrylate is added while maintaining the temperature, and the reaction is continued for 2 hours. Anhydrous methanol is added to terminate the reaction, and the reaction solution is added to glacial n-hexane for precipitation, and vacuum dried to constant weight to obtain a modified polyisobutylene binder; wherein the polyisobutylene-based macromolecular initiator, methyl methacrylate, and lithium acrylate are reacted in a weight ratio of 50:20:30; Step 2: In an argon environment, a modified polyisobutylene binder and sulfide electrolyte particles are ground and mixed to obtain a composite solid electrolyte powder, the grinding and mixing speed is 1500 rpm, and the grinding and mixing time is 50 min; a polytetrafluoroethylene binder is added to the composite solid electrolyte powder for shear mixing, the shear mixing speed is 3000 rpm, and the shear mixing time is 30 min; hot extrusion is performed at 80°C to a thickness of 150 μm, and roller thinning is performed to obtain a composite solid electrolyte membrane; wherein, in the composite solid electrolyte membrane, the amount of each component is calculated by weight percentage, the amount of each component is calculated by weight percentage, 2% modified polyisobutylene binder, 0.1% polytetrafluoroethylene binder, and the balance is sulfide electrolyte particles.

[0023] Example 2: A method for preparing a composite solid electrolyte membrane, comprising the following steps: Step 1: S1: Add acrylic acid to lithium hydroxide in an ice-water bath at -3°C and stir for 8 minutes to obtain lithium acrylate; S2: In an ice-water bath at -4°C, sodium borohydride and boron trifluoride-ether solution were added to anhydrous tetrahydrofuran as solvent, and the mixture was stirred for 3.5 hours. A tetrahydrofuran solution of highly active polyisobutylene was then added and the mixture was reacted for 23 hours. The pH of the system was adjusted to 11.5 with sodium hydroxide solution, and hydrogen peroxide solution was added dropwise and the mixture was reacted for 9 hours. The mixture was washed with water and extracted with ether. The organic layer was dried, the solvent was removed by rotary evaporation, and the mixture was dried in vacuo to obtain hydroxy-terminated polyisobutylene. S3: Disperse the hydroxy-terminated polyisobutylene in anhydrous tetrahydrofuran under nitrogen atmosphere, stir until dissolved, add potassium hydride washed with anhydrous tetrahydrofuran, and react at 48°C for 11 hours to generate a polyisobutylene-based macroinitiator; S4: Under an argon atmosphere, a polyisobutylene-based macromolecular initiator and methyl methacrylate are dispersed in anhydrous tetrahydrofuran, reacted at 28°C for 2.5 hours, lithium acrylate is added while maintaining the temperature, and the reaction is continued for 2.5 hours. Anhydrous methanol is added to terminate the reaction, and the reaction solution is added to glacial n-hexane for precipitation, and vacuum dried to constant weight to obtain a modified polyisobutylene binder; wherein the polyisobutylene-based macromolecular initiator, methyl methacrylate, and lithium acrylate are reacted in a weight ratio of 57:10:33; Step 2: In an argon environment, a modified polyisobutylene binder and sulfide electrolyte particles were ground and mixed to obtain a composite solid electrolyte powder, the grinding and mixing speed was 2000 rpm, and the grinding and mixing time was 60 min; a polytetrafluoroethylene binder was added to the composite solid electrolyte powder for shear mixing, the shear mixing speed was 4000 rpm, and the shear mixing time was 45 min; hot extrusion was performed at 90°C to a thickness of 280 μm, and roller thinning was performed to obtain a composite solid electrolyte membrane; wherein, in the composite solid electrolyte membrane, the amount of each component is calculated by weight percentage, 1.5% modified polyisobutylene binder, 0.08% polytetrafluoroethylene binder, and the balance is sulfide electrolyte particles.

[0024] Example 3: A method for preparing a composite solid electrolyte membrane, comprising the following steps: Step 1: S1: Add acrylic acid to lithium hydroxide in an ice-water bath at 0°C and stir for 10 minutes to obtain lithium acrylate; S2: In an ice-water bath at 0°C, sodium borohydride and boron trifluoride-ether solution were added to anhydrous tetrahydrofuran as solvent, and the mixture was stirred for 4 hours. A tetrahydrofuran solution of highly active polyisobutylene was then added and the mixture was reacted for 24 hours. The pH of the system was adjusted to 12 with sodium hydroxide solution, and a hydrogen peroxide solution was added dropwise and the mixture was reacted for 10 hours. The mixture was washed with water and extracted with ether. The organic layer was dried, the solvent was removed by rotary evaporation, and the mixture was dried in vacuo to obtain hydroxy-terminated polyisobutylene. S3: Disperse the hydroxy-terminated polyisobutylene in anhydrous tetrahydrofuran under nitrogen atmosphere, stir until dissolved, add potassium hydride washed with anhydrous tetrahydrofuran, and react at 50°C for 12 hours to generate a polyisobutylene-based macroinitiator; S4: Under an argon atmosphere, a polyisobutylene-based macromolecular initiator and methyl methacrylate are dispersed in anhydrous tetrahydrofuran, reacted at 30°C for 3 hours, lithium acrylate is added while maintaining the temperature and the reaction is continued for 3 hours, anhydrous methanol is added to terminate the reaction, the reaction solution is added to glacial n-hexane for precipitation, and vacuum dried to constant weight to obtain a modified polyisobutylene binder; wherein the polyisobutylene-based macromolecular initiator, methyl methacrylate, and lithium acrylate are reacted in a weight ratio of 60:5:35; Step 2: In an argon environment, a modified polyisobutylene binder and sulfide electrolyte particles were ground and mixed to obtain a composite solid electrolyte powder, the grinding and mixing speed was 2500 rpm, and the grinding and mixing time was 70 minutes; a polytetrafluoroethylene binder was added to the composite solid electrolyte powder for shear mixing, the shear mixing speed was 5000 rpm, and the shear mixing time was 60 minutes; hot extrusion was performed at 100°C to a thickness of 300 μm, and roller thinning was performed to obtain a composite solid electrolyte membrane; wherein, in the composite solid electrolyte membrane, the amount of each component is calculated by weight percentage, 0.5% modified polyisobutylene binder, 0.1% polytetrafluoroethylene binder, and the balance is sulfide electrolyte particles.

[0025] Comparative Example 1: No modified polyisobutylene binder was added, and other parameters were the same as those in Example 1.

[0026] In an argon environment, the sulfide electrolyte particles were ground at a grinding mixing speed of 1500 rpm and a grinding mixing time of 50 minutes; a polytetrafluoroethylene binder was added for shear mixing at a shear mixing speed of 3000 rpm and a shear mixing time of 30 minutes; the composite solid electrolyte membrane was obtained by hot extrusion at 80°C to a thickness of 150 μm and roller thinning; wherein, the amount of each component in the composite solid electrolyte membrane is calculated by weight percentage: 0.1% polytetrafluoroethylene binder and 99.9% sulfide electrolyte particles.

[0027] Experiment: The performance of the composite solid electrolyte membrane was tested, and the experimental results are shown in Table 1.

[0028] Composite solid electrolyte membrane thickness test: SEM was used to test the thickness of the composite solid electrolyte membranes in Examples 1 to 3.

[0029] Ionic conductivity test: At 30° C., a blocking cell of a sulfide electrolyte membrane against a stainless steel sheet was assembled to test the ionic conductivity of the composite solid electrolyte membrane prepared in Examples 1 to 3.

[0030] Cycling performance test: At 25°C, the composite solid electrolyte membrane prepared in Example 1 was matched with the NCM90 positive electrode material and the pre-lithiated Al-based negative electrode. The assembled battery was tested on the LAND battery test system to test the long cycle specific capacity of the battery at a current density of 0.1C.

[0031] Table 1. Test results of various properties of composite solid electrolyte membrane

[0032] Conclusion: The data of Examples 1 to 3 show that the composite solid electrolyte membrane prepared by the present invention has both high ionic conductivity and low thickness.

[0033] Data from Example 1 and Comparative Example 1 demonstrate that, compared to Comparative Example 1, in which only polytetrafluoroethylene was added as a binder, the addition of the modified polyisobutylene binder in Example 1 resulted in a more uniform distribution of the moderately molecular weight modified polyisobutylene binder within the sulfide electrolyte particles, resulting in a lesser decrease in ionic conductivity. The addition of the modified polyisobutylene binder significantly reduced the thickness of the composite solid electrolyte membrane, demonstrating that the addition of the modified polyisobutylene binder improves the mechanical properties of the composite solid electrolyte membrane. During the roller-thinning process, the dual-binder fiberization system ensures that the composite electrolyte membrane is thinned without cracking, resulting in a reduced thickness.

[0034] Electrochemical data from Example 1 demonstrate that the composite solid electrolyte membrane prepared in this invention maintains structural integrity and minimizes capacity loss over extended battery cycles. However, the battery assembled with the composite solid electrolyte membrane from Comparative Example 1, due to its poor strength, short-circuited in the first cycle and failed to maintain stability over extended battery cycles.

[0035] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0036] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a composite solid electrolyte membrane, characterized in that: The following steps are involved: Step 1: In an argon environment, a modified polyisobutylene binder and sulfide electrolyte particles are ground and mixed to obtain a composite solid electrolyte powder; Step 2: A polytetrafluoroethylene binder is added to the composite solid electrolyte powder for shear mixing, and the powder is hot extruded to 150-300 μm and rolled to be thinned to 20-40 μm to obtain a composite solid electrolyte membrane.

2. The method for preparing a composite solid electrolyte membrane according to claim 1, wherein: In step 1, the preparation method of the modified polyisobutylene binder comprises the following steps: S1: Add acrylic acid to lithium hydroxide in an ice-water bath at -5 to 0°C and stir for 5 to 10 minutes to obtain lithium acrylate; S2: In an ice-water bath at -5-0°C, sodium borohydride and boron trifluoride-ether solution are added to anhydrous tetrahydrofuran as solvent, and the mixture is stirred for 3-4 hours. A tetrahydrofuran solution of highly active polyisobutylene is then added and the mixture is reacted for 20-24 hours. The pH of the system is adjusted to 10-12 with sodium hydroxide solution, and a hydrogen peroxide solution is added dropwise and the mixture is reacted for 8-10 hours. The mixture is washed with water and extracted with ether. The organic layer is dried, the solvent is removed by rotary evaporation, and the mixture is dried in vacuo to obtain hydroxy-terminated polyisobutylene. S3: Disperse the hydroxy-terminated polyisobutylene in anhydrous tetrahydrofuran under a nitrogen atmosphere, stir until dissolved, add potassium hydride washed with anhydrous tetrahydrofuran, and react at 45-50°C for 10-12 hours to generate a polyisobutylene-based macroinitiator; S4: Under an argon environment, a polyisobutylene-based macromolecular initiator and methyl methacrylate are dispersed in anhydrous tetrahydrofuran, and the mixture is reacted at 25-30°C for 2-3 hours. After adding lithium acrylate and continuing the reaction for 2-3 hours, anhydrous methanol is added to terminate the reaction. The reaction solution is added to icy n-hexane for precipitation, and vacuum dried to constant weight to obtain a modified polyisobutylene adhesive.

3. The method for preparing a composite solid electrolyte membrane according to claim 2, wherein: The polyisobutylene macroinitiator, methyl methacrylate, and lithium acrylate are reacted in a weight ratio of (50-60): (5-20): (30-35).

4. The method for preparing a composite solid electrolyte membrane according to claim 1, wherein: In step 1, the grinding and mixing speed is 1500-2500 rpm, and the grinding and mixing time is 50-70 min.

5. The method for preparing a composite solid electrolyte membrane according to claim 1, wherein: In step 2, the shear mixing speed is 3000-5000 rpm, and the shear mixing time is 30-60 min.

6. The method for preparing a composite solid electrolyte membrane according to claim 1, wherein: In step 2, the hot extrusion temperature is 80-100°C.

7. The method for preparing a composite solid electrolyte membrane according to claim 1, wherein: In step 2, the amount of each component in the composite solid electrolyte membrane is calculated by weight percentage: 0.5-2% modified polyisobutylene binder, 0.05-0.1% polytetrafluoroethylene binder, and the balance is sulfide electrolyte particles.

8. The method for preparing a composite solid electrolyte membrane according to claim 1, wherein: In step 2, the sulfide electrolyte is Li7P3S 11 、Li3PS4、Li 10 GeP2S 12 、Li 10 GeP2S 12 、Li 7-x PS 6-x Cl x Any of .

9. The method for preparing a composite solid electrolyte membrane according to claim 1, wherein: In step 2, the particle size D of the sulfide solid electrolyte 50 1~10μm. 10 . The composite solid electrolyte membrane prepared by the preparation method according to claim 1 .

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