Solid electrolyte membrane and its preparation method, all-solid-state lithium-ion battery and electronic device

Abstract

Improve the stability of the conductivity of the solid electrolyte membrane, enhance the air stability, improve the interfacial properties of the electrolyte / active material, and improve the lifespan and safety of the lithium battery of the all-solid-state lithium-ion battery. 【Solution means】The present invention provides a solid electrolyte membrane and a preparation method thereof, an all-solid-state lithium-ion battery, and an electronic device. The solid electrolyte membrane contains a binder and a sulfide solid electrolyte, and the chemical formula of the sulfide solid electrolyte is Li -3 , -2 , d , e P 1-b M b S c O d X e wherein, 5 < a < 6, 0 < b < 1, 1.5 < c < 5, 0 < d < 2.5, 4 < c + d < 5, 1 < e < 2, M is one or more selected from Al, Ga, In, Ti, Sc, As, Sb, Bi, As, V, or Nb, X is one or more selected from Cl, Br, or I, and the ionic conductivity of the solid electrolyte membrane is 1×10 -3 ~2×10 -2 S / cm.

Description

[Technical Field]

[0001] This invention relates to the field of lithium-ion batteries, and more specifically to solid electrolyte membranes, methods for preparing them, and their applications. [Background technology]

[0002] Currently, lithium-ion batteries are widely used in fields such as portable electronic devices, electric vehicles, and energy storage systems. However, conventional lithium-ion batteries use flammable organic liquid electrolytes, which presents safety concerns and relatively low energy density, thus limiting their further development. All-solid-state lithium batteries replace liquid electrolytes with solid electrolytes, offering higher safety, a wider operating temperature range, and higher energy density, representing a key development direction for next-generation battery technology.

[0003] Sulfide solid electrolytes are among the most promising electrolyte materials for all-solid-state lithium batteries due to their high ionic conductivity and good mechanical properties. However, most sulfide electrolytes decompose easily in air, generating toxic hydrogen sulfide gas, and their production complexity and cost are increased due to the strict manufacturing requirements. Furthermore, sulfide electrolytes have poor compatibility with lithium metal negative electrodes, leading to frequent interfacial reactions, inducing lithium dendrite formation, and causing short circuits in the battery. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] This invention provides a solid electrolyte membrane, a method for preparing the same, and its applications. The solid electrolyte membrane, its preparation method, and its applications enable improved conductivity stability, enhanced stability in air, and improved properties of the electrolyte / active material interface. This improves the lifespan and safety of lithium batteries in all-solid-state lithium-ion batteries. [Means for solving the problem]

[0005] To solve the above technical problems, the present invention provides a solid electrolyte membrane. The solid electrolyte membrane includes at least a binder, a sulfide solid electrolyte, and the chemical formula of the sulfide solid electrolyte is Li ,

[0008] ,

[0010] , , , , , , , , ,

[0007] , ,

[0009] P 1-b M b S c O d X e where in the formula, 5 < a < 6, 0 < b < 1, 1.5 < c < 5, 0 < d < 2.5, 4 < c + d < 5, 1 < e < 2, M is one or more selected from Al, Ga, In, Ti, Sc, As, Sb, Bi, As, V, or Nb, and X is one or more selected from Cl, Br, or I. the ionic conductivity of the solid electrolyte membrane is 1×10 -3 ~2×10 -2 S / cm.

[0006] In one embodiment of the present invention, M is one or more selected from Sb, In, or Bi.

[0007] In one embodiment of the present invention, X is Cl, and the allowable range of b is 0 < b ≤ 0.1.

[0008] In one embodiment of the present invention, the thickness of the solid electrolyte membrane is 1~200 μm.

[0009] In one embodiment of the present invention, the mass ratio of the binder to the sulfide solid electrolyte is 0.1:99.9~10:90.

[0010] The present invention also provides a method for preparing the above solid electrolyte membrane. The method includes based on the chemical formula of the sulfide solid electrolyte, uniformly mixing raw materials according to stoichiometry, then putting them into a ball mill pot and ball milling to obtain a sulfide solid electrolyte precursor powder, The sulfide solid electrolyte precursor powder is subjected to calcination treatment at a predetermined temperature to obtain the sulfide solid electrolyte, The method includes mixing the sulfide solid electrolyte with a binder and obtaining the solid electrolyte film by a dry or wet process.

[0011] In one embodiment of the present invention, the raw materials include a Li source, a P source, an M source, an S source, and an X source, wherein the Li source is one or more selected from LiCl, LiBr, LiI, or Li2S; the P source is one or more selected from elemental P, P2S5, P4S6, PCl5, or PBr5; the M source is one or more selected from oxides of M or sulfides of M; the S source is one or more selected from elemental S, Li2S, P2S5, P4S6, As2S5, As2S3, Sb2S5, Sb2S3, Bi2S5, Bi2S3, Al2S3, Ga2S3, In2S3, or Sc2S3; and the X source is one or more selected from LiCl, PCl5, LiBr, PBr5, LiI, or I2, wherein the O element in the chemical formula is derived from an oxide of M.

[0012] In one embodiment of the present invention, when the solid electrolyte membrane is prepared by a dry process, the binder is selected from a first binder, and the first binder is one or more selected from polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene propylene copolymer, perfluoroalkoxy resin, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, or polyvinylidene fluoride-chlorotrifluoroethylene copolymer.

[0013] In one embodiment of the present invention, when the solid electrolyte membrane is prepared by a wet process, the binder is selected from a second binder, and the second binder is polyvinylidene fluoride, carboxymethyl cellulose, styrene butadiene rubber, polyvinylpyrrolidone, polymethyl methacrylate, polyacrylonitrile, polyacrylic acid, polyurethane, polyvinyl alcohol, sodium alginate, ethylene-propylene-diene monomer, styrene-butadiene rubber, fluorine rubber, β-cyclodextrin polymer, polypropylene emulsion, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-propylene fluoride copolymer, perfluoroalkoxy resin, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride-hexafluoropropylene copolymer, or polyvinylidene fluoride-chlorotrifluoroethylene copolymer, and is one or more selected therefrom.

[0014] The present invention also provides an all-solid-state lithium-ion battery. The battery Li 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 includes a positive electrode sheet containing a halide solid electrolyte containing the same, a negative electrode sheet, and a solid electrolyte membrane disposed between the adjacent positive electrode sheet and the negative electrode sheet and selected from the above solid electrolyte membranes, and at least includes the same.

[0015] <​​​​​​​As described above, the present invention provides a solid electrolyte membrane, a method for preparing the same, and its applications. It increases the intrinsic resistance of the solid electrolyte membrane to atmospheric degradation, effectively reduces H2S generation, and increases the battery's potential in actual production. This enhances the air and chemical stability of the sulfide solid electrolyte. At the electrolyte / lithium metal anode interface, alloys such as LiCl, Li2O, and Li-Sb / Li-Bi / Li-In can be formed, allowing for a uniform electric field and equilibrium of local current density. This regulates Li nucleation and growth, effectively suppressing the rapid growth of lithium dendrites at the growth interface. Therefore, it significantly improves the stability and performance of lithium-ion batteries and enhances the lifespan and safety of lithium batteries in all-solid-state lithium-ion batteries. Thus, the solid electrolyte membrane possesses relatively high stability and specific reactivity, improving the conductivity stability of the solid electrolyte membrane, enhancing air stability, and improving the electrolyte / active material interface properties, thereby improving compatibility with the active material. [Brief explanation of the drawing]

[0017] To more clearly explain the technical solutions of the embodiments of the present invention, the accompanying drawings necessary for describing the embodiments are briefly introduced below. Clearly, the accompanying drawings in the following description represent only a few embodiments of the present invention, and those skilled in the art can obtain other accompanying drawings based on these without requiring any creative work. [Figure 1] This is a schematic diagram of the process for preparing a solid electrolyte membrane by a dry process in one embodiment of the present invention. [Figure 2] The figure shows the 1C / 1C long-term cycle performance at room temperature for the all-solid-state lithium-ion battery of Example 3. [Modes for carrying out the invention]

[0018] The embodiments of the present invention will be described below with specific examples, and those skilled in the art will readily understand other advantages and effects of the present invention from the contents disclosed herein. Furthermore, the present invention can be implemented or applied in other different specific embodiments, and the details of each item herein can be modified or changed in various ways based on different perspectives and applications without departing from the spirit of the invention.

[0019] It should be understood that the present invention can be carried out in different forms and should not be construed as being limited to the embodiments presented herein. Rather, these embodiments are provided to make the disclosure thorough and complete and to fully communicate the scope of the invention to those skilled in the art.

[0020] The disclosed embodiments, which further describe the technical solutions of the present invention in combination with several examples below, represent only a portion of the embodiments of the present invention and are clearly not all embodiments. All other embodiments that a person skilled in the art could appropriately modify based on the embodiments of the present invention in accordance with the technical concept of the present invention are within the scope of the protection of the present invention.

[0021] This invention provides a solid electrolyte membrane. The solid electrolyte membrane comprises a binder and a sulfide solid electrolyte. Here, the chemical formula of the sulfide solid electrolyte is Li a P 1-b M b S c O d X eis satisfied. Here, 5 < a < 6, 0 < b < 1, 1.5 < c < 5, 0 < d < 2.5, 4 < c + d < 5, 1 < e < 2, M is one or more selected from Al, Ga, In, Ti, Sc, As, Sb, Bi, As, V, or Nb, and X is one or more selected from Cl, Br, or I. Among them, by introducing M element and O element into the sulfide solid electrolyte of rich halogen element, P - O bond and M - S bond are formed in the crystal structure, thereby increasing the inherent resistance to atmospheric decomposition, effectively reducing the generation of H2S, and enhancing the stability of the sulfide solid electrolyte. The stability of the sulfide solid electrolyte includes stability against lithium and stability against air, and can improve the convenience of preparation and operation of the sulfide solid electrolyte. Further, when assembling an all-solid-state lithium-ion battery using the sulfide solid electrolyte, alloys such as LiCl, Li2O, and Li - Sb / Li - Bi / Li - In can be formed at the interface layer of the electrolyte / lithium metal negative electrode. Among them, Li2O has a relatively high intrinsic ionic conductivity, and alloys such as Li - Sb / Li - Bi / Li - In can + promote the fast migration dynamics of Li, can make the electric field uniform, and can balance the local current density. Thereby, the nucleation and growth of Li can be regulated. Further, LiCl has a relatively high interfacial energy and can effectively suppress the rapid growth of lithium dendrites at the growth interface, significantly improving the stability and performance of the lithium-ion battery, and improving the life and safety of the lithium battery of the all-solid-state lithium-ion battery.

[0022] In one embodiment of the present invention, M is one or more selected from, for example, Sb, In, or Bi. Since the ionic radii of Sb, In, or Bi are appropriate, the ionic radii of these elements are close to the ionic radii of the main elements in the sulfide electrolyte, such as sulfur and phosphorus. During doping, they can more easily replace the positions of the main elements and do not cause excessive lattice strain. And the electronegativities of Sb, In, or Bi are appropriate, and they can form stable chemical bonds with sulfur elements in sulfides and are less susceptible to destruction by external influences. Thereby, the sulfide solid electrolyte has relatively high stability and specific reactivity, can improve the stability of the conductivity of the sulfide solid electrolyte, enhance the air stability, and improve the interfacial properties of the electrolyte / active material, so that the compatibility with the active material can be improved.

[0023] In one embodiment of the present invention, X selects a halogen element. And depending on the type of halogen, the degree of anion disorder between the 4a site and the 4c site in the sulfide solid electrolyte crystal structure varies from a small amount of antisite defects when X is I to 60% site disorder when X is Cl. The lithium conductivities of these compounds mainly depend on the degree of disorder in the occupancy of anion and cation sites. Therefore, X also selects, for example, Cl to improve the ionic conductivity and electrochemical stability of the sulfide solid electrolyte and improve the voltage stability. The allowable range of b is 0 < b ≤ 0.1. In one specific embodiment of the present invention, when M is +5 valence, b is optimally 0.04, and when M is +3 valence, b is optimally 0.02, thereby improving the cycle performance of the lithium-ion battery.

[0024] In one embodiment of the present invention, the thickness of the solid electrolyte membrane is, for example, 1 to 200 μm, and the ionic conductivity is, for example, 1×10 -3 ~2×10 -2The conductivity is S / cm. Furthermore, the ionic conductivity is relatively stable at low temperatures, allowing for batch preparation of solid electrolyte membranes in a low-dew-point drying chamber, which greatly simplifies the preparation process and reduces preparation costs. The solid electrolyte membrane provided by this invention can be well matched with lithium metal negative electrodes, enabling the preparation of high-energy-density and high-performance all-solid-state lithium batteries.

[0025] In one embodiment of the present invention, the mass ratio of the binder to the sulfide solid electrolyte is 0.1:99.9 to 10:90, and the binder is one or more selected from the first binder or the second binder. Here, the first binder is selected from one or more of the following: polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene (ETFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer, or polyvinylidene fluoride-chlorotrifluoroethylene copolymer.The second binder consists of PVDF, carboxymethyl cellulose (CMC), polymerized styrene butadiene rubber (SBR), polyvinyl pyrrolidone (PVP), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyacrylic acid (PAA), polyurethane, polyvinyl alcohol (PVA), and sodium alginate. The binder is selected from at least one of the following: alginate (Alg), ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, β-cyclodextrin polymer (β-cyclodextrin, β-CDp), polypropylene emulsion (LA132), PTFE, ETFE, FEP, PFA, PCTFE, ECTFE, polyvinylidene fluoride-hexafluoropropylene copolymer, or polyvinylidene fluoride-chlorotrifluoroethylene copolymer, etc. Adding a binder improves the processability of the solid electrolyte membrane, reduces volume expansion, and stabilizes the structure of the solid electrolyte membrane.

[0026] The present invention further provides a method for preparing a solid electrolyte membrane. The preparation method used to prepare the above-mentioned solid electrolyte membrane includes at least the following: Based on the chemical formula of the sulfide solid electrolyte, raw materials are mixed and homogenized according to stoichiometry, then placed in a ball mill pot and ball-milled to obtain a sulfide solid electrolyte precursor powder. The sulfide solid electrolyte precursor powder is calcined at a predetermined temperature to obtain a sulfide solid electrolyte. The sulfide solid electrolyte and a binder are mixed, and a solid electrolyte membrane is obtained by a dry process or a wet process.

[0027] In one embodiment of the present invention, the sulfide solid electrolyte has the chemical formula Li a P 1-b M b S c Od X e Based on this, the Li source, P source, M source, S source, and X source are uniformly mixed according to stoichiometry. Here, the Li source is one or more selected from LiCl, LiBr, LiI, or Li2S, etc., the P source is one or more selected from monoatomic P, P2S5, P4S6, PCl5, or PBr5, etc., the M source is one or more selected from oxides of M or sulfides of M, the S source is one or more selected from monoatomic S, Li2S, P2S5, P4S6, As2S5, As2S3, Sb2S5, Sb2S3, Bi2S5, Bi2S3, Al2S3, Ga2S3, In2S3, or Sc2S3, etc., and the X source is one or more selected from LiCl, PCl5, LiBr, PBr5, LiI, or I2, etc., and the O element in the chemical formula is derived from an oxide of M. After uniformly mixing the raw materials, they are placed in a ball mill pot and ball mill grinding is performed under an inert atmosphere. Here, the ratio of balls to raw materials is, for example, 1:1 to 100:1, the ball mill rotation speed is, for example, 50 to 1500 rpm, and the ball mill grinding time is, for example, 1 to 48 hours. A sulfide solid electrolyte precursor powder is obtained by the above method.

[0028] In one embodiment of the present invention, a sulfide solid electrolyte precursor powder is subjected to calcination treatment at a predetermined temperature. Here, the predetermined temperature is 400 to 600°C, and the calcination treatment time is 1 to 18 hours, thereby obtaining a sulfide solid electrolyte.

[0029] As shown in Figure 1, in one embodiment of the present invention, when a solid electrolyte membrane is prepared by a dry process, for example, a powder extrusion molding method is employed, and the binder is selected from the first binder. Specifically, the sulfide solid electrolyte and the first binder are mixed and homogenized, for example, by low-temperature shearing, and then the temperature is rapidly increased to perform high-temperature shearing mixing to obtain a mixed raw material. Furthermore, the mixed raw material is added to a roll mill and high-temperature roll rolling is performed to obtain a solid electrolyte membrane. Here, the mass ratio of the first binder to the sulfide solid electrolyte is, for example, 0.1:99.9 to 5:95, the low-temperature shearing temperature is, for example, -30 to 15°C, the high-temperature shearing temperature is, for example, 20 to 200°C, and the high-temperature roll rolling temperature is, for example, 20 to 200°C. In the dry process, the first binder surrounds the sulfide solid electrolyte in a mesh-like manner, which can improve the mechanical strength and chemical stability of the solid electrolyte membrane. During the battery charging and discharging process, stable contact between the electrolyte and electrode material can be maintained, thereby improving the battery's performance and lifespan.

[0030] In one embodiment of the present invention, when a solid electrolyte membrane is prepared by a wet process, for example, a wet coating method and an electrostatic spraying method are employed, and the binder is selected from a second binder. Specifically, the sulfide solid electrolyte, the second binder, and the solvent are mixed and homogenized to obtain an electrolyte slurry. The electrolyte slurry is then applied to a substrate by a wet coating method or an electrostatic spraying method, and subsequently the substrate to which the electrolyte slurry has been applied is dried and peeled to obtain a solid electrolyte membrane. Here, the solvent is selected from at least one of the following, for example, toluene, chlorobenzene, xylene, dimethyl carbonate, N-methylformamide, n-hexane, glycol dimethyl ether, dibutyl ether, ethanol, 1,2-ethylenediamine, 1,2-ethanedithiol, acetonitrile, tetrahydrofuran, methanol, isopropyl ether, acetone, hexene, ethyl acetate, benzyl acetate, butyl butyrate, or diisobutyl ketone. In the electrolyte slurry, the content of the sulfide solid electrolyte is, for example, 30 to 90% by mass, the content of the second binder is, for example, 0.1 to 10% by mass, and the content of the solvent is, for example, 10 to 50% by mass. After drying, the mass ratio of the second binder to the sulfide solid electrolyte is, for example, 0.1:30 to 10:90. The substrate is selected from, for example, polyethylene glycol terephthalate (PET) film, smooth aluminum foil, or release paper to facilitate demolding, and the drying temperature is, for example, 30 to 250°C.

[0031] The present invention also provides an all-solid-state lithium-ion battery. The all-solid-state lithium-ion battery comprises a positive electrode sheet, a negative electrode sheet, and a solid electrolyte membrane, the solid electrolyte membrane being placed between adjacent positive and negative electrode sheets. Here, the positive electrode sheet comprises a positive electrode active material and a halide solid electrolyte, the positive electrode active material being one or more selected from, for example, lithium nickel cobalt manganese oxide (NCM), lithium nickel oxide (LNO), lithium manganese oxide (LMO), lithium nickel manganese oxide (LNMO), lithium cobalt oxide (LCO), or lithium nickel cobalt aluminum oxide (NCA). The halide solid electrolyte is Li 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 The halogen solid electrolyte does not undergo an exothermic reaction with the lithium cathode active material, thereby improving the safety of the lithium-ion battery. The negative electrode sheet is one or more selected from, for example, a metallic lithium sheet, a metallic indium sheet, or a lithium indium alloy sheet, and the negative electrode sheet also contains, for example, a negative electrode active material, which is one or more selected from, for example, a graphite-based material, a silicon material, or a composite material of a graphite-based material and a silicon material. The solid electrolyte membrane is selected from the above-mentioned solid electrolyte membranes, which can improve the performance of the all-solid-state lithium-ion battery.

[0032] In one embodiment of the present invention, the positive electrode sheet further comprises a conductive agent and a binder, wherein the conductive agent is one or at least two of the following: conductive carbon black (Super P, SP), carbon nanotube (CNT), vapor-grown carbon fiber (VGCF), or graphene. The binder is, for example, polytetrafluoroethylene (PTFE) and its derivatives. The mass ratio of the positive electrode active material, halogen solid electrolyte, conductive agent, and binder is, for example, (65-78):(20-30):(1-3):(1-2). In this embodiment, the mass ratio of the positive electrode active material, halide solid electrolyte, conductive agent, and binder is, for example, 69:29:1:1, the conductive agent is a combination of conductive carbon black (super-P) and vapor-grown carbon fiber (VGCF), the mass ratio of conductive carbon black to vapor-grown carbon fiber is 1:1, and the binder is, for example, polytetrafluoroethylene. After uniformly mixing the positive electrode active material, halide solid electrolyte, conductive agent, and binder, a mixed powder is obtained, and a positive electrode sheet is obtained by compression using a dry process.

[0033] In one embodiment of the present invention, if the negative electrode sheet contains a negative electrode active material, the negative electrode sheet further contains a solid electrolyte, a conductive agent, and a binder. Here, the solid electrolyte is, for example, a halide solid electrolyte or a sulfide electrolyte, and the present invention does not make any specific limitations. The binder is, for example, one or more selected from polyisoprene, polyethylene or polypropylene, and the conductive agent is, for example, at least one of carbon nanotubes, carbon fibers, or acetylene black. The present invention does not limit the ratio of the negative electrode active material, conductive agent and binder, and the ratio is selected based on the requirements at the time of manufacture, and the negative electrode sheet is obtained, for example, by compression by a dry process.

[0034] In one embodiment of the present invention, the negative electrode sheet is selected as, for example, metallic lithium foil, and the positive electrode sheet, solid electrolyte membrane, and negative electrode sheet are sequentially laminated, sealed, hot-pressed, and cold-pressed. An aluminum plastic film or the like is then placed over the battery in a vacuum or inert atmosphere to obtain an all-solid-state pouch-type lithium-ion battery. The assembly process of the all-solid-state lithium-ion battery is completed, for example, in a glove box under an argon atmosphere.

[0035] The present invention will be described more specifically below with reference to the following embodiments, but these embodiments should not be understood as limiting. Appropriate modifications can be made within the scope consistent with the spirit of the present invention, and all such modifications fall within the technical scope of the present invention.

[0036] Example 1 Preparation of sulfide solid electrolytes: Precursor powder was obtained by high-energy ball milling using 2 moles of Li2S, 1.5 moles of LiCl, 0.48 moles of P2S5, and 0.02 moles of Sb2O5 as raw materials. Here, the ball-to-raw material ratio was 30:1, and the rotation speed was 500 rpm. Subsequently, the precursor powder was sintered at a temperature of 500°C for 10 hours, and after cooling, the sulfide solid electrolyte Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 I obtained it. Preparation of solid electrolyte membranes: Li, an electrolyte 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 The PTFE was uniformly mixed at -20°C according to a mass ratio of 99:1, and the temperature was raised to 80°C for further mixing to fibrousize the PTFE and obtain a mixture. The mixture was extruded into a roll press and roll-pressed to a thickness of 5 μm at 80°C by adjusting the gap of the roll press. Preparation of the positive electrode sheet: LiRing 0.8 Co 0.1 Mn0.1 O2, conductive agent, Li 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 The positive electrode sheet is prepared by a dry process using a mixture of PTFE and super-P in a mass ratio of 69:1:29:1. The conductive agents are super-P and VGCF in a mass ratio of 1:1. Negative electrode sheet: Select a metallic lithium piece for the negative electrode sheet. Assembly of all-solid-state batteries: The positive electrode sheet, solid electrolyte membrane, and negative electrode sheet prepared as described above are assembled into an all-solid-state pouch-type battery by lamination, sealing, hot pressing, and cold pressing processes. Assembling symmetric cells: Counter electrodes (Li) are placed on both sides of a solid electrolyte membrane, and the solid electrolyte membrane is assembled with these electrodes to form a Li / Li symmetric cell.

[0037] Example 2 The solid electrolyte membrane was fabricated in the same manner as in Example 1, except that the thickness was adjusted to 10 μm by adjusting the roll gap of the roll press machine.

[0038] Example 3 The solid electrolyte membrane was fabricated in the same manner as in Example 1, except that the thickness was adjusted to 30 μm by adjusting the roll gap of the roll press machine.

[0039] Example 4 The solid electrolyte membrane was fabricated in the same manner as in Example 1, except that the thickness was adjusted to 50 μm by adjusting the roll gap of the roll press machine.

[0040] Example 5 The solid electrolyte membrane was fabricated in the same manner as in Example 1, except that the thickness was adjusted to 100 μm by adjusting the roll gap of the roll press machine.

[0041] Example 6 The solid electrolyte membrane was fabricated in the same manner as in Example 1, except that the thickness was adjusted to 200 μm by adjusting the roll gap of the roll press machine.

[0042] Example 7 The chemical formula of the sulfide solid electrolyte prepared from 2 moles of Li2S, 1.5 moles of LiCl, 0.495 moles of P2S5, and 0.005 moles of Sb2O5 is Li 5.5 P 0.99 S 0.01 S 4.475 O 0.025 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0043] Example 8 The chemical formula of the sulfide solid electrolyte prepared from 2 moles of Li2S, 1.5 moles of LiCl, 0.49 moles of P2S5, and 0.01 moles of Sb2O5 is Li 5.5 P 0.98 S 0.02 S 4.45 O 0.05 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0044] Example 9 The chemical formula of the sulfide solid electrolyte prepared from 2 moles of Li2S, 1.5 moles of LiCl, 0.47 moles of P2S5, and 0.03 moles of Sb2O5 is Li 5.5 P 0.94 S 0.06 S 4.35 O 0.15 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0045] Example 10 The chemical formula of the sulfide solid electrolyte prepared from 2 moles of Li2S, 1.5 moles of LiCl, 0.46 moles of P2S5, and 0.04 moles of Sb2O5 is Li 5.5 P 0.92 S 0.08 S 4.3 O 0.20 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0046] Example 11 The chemical formula of the sulfide solid electrolyte produced from 2 moles of Li2S, 1.5 moles of LiCl, 0.45 moles of P2S5 and 0.05 moles of Sb2O5 is Li 5.5 P 0.9 Sb 0.1 S 4.25 O 0.25 Cl 1.5 It was prepared in the same manner as in Example 3 except that it is as follows.

[0047] Example 12 The chemical formula of the sulfide solid electrolyte produced from 1.6 moles of Li2S, 1.9 moles of LiCl, 0.48 moles of P2S5 and 0.02 moles of Sb2O5 is Li 5.1 P 0.96 Sb 0.04 S4O 0.10 Cl 1.9 It was prepared in the same manner as in Example 3 except that it is as follows.

[0048] Example 13 4The chemical formula of the sulfide solid electrolyte produced from 2.4 moles of Li2S, 1. moles of LiCl, 0.48 moles of P2S5 and 0.02 moles of Sb2O5 is Li 5.9 P 0.96 Sb 0.04 S 4.80 O 0.10 Cl 1.1 It was prepared in the same manner as in Example 3 except that it is as follows.

[0049] Example 14 The chemical formula of the sulfide solid electrolyte produced from 2 moles of Li2S, 1.4 moles of LiCl, 0.1 moles of LiBr, 0.48 moles of P2S5 and 0.02 moles of Sb2O5 is Li 5.5 P 0.96 Sb 0.04 S 4.40 O 0.10 Cl 1.4 Br 0.1 It was prepared in the same manner as in Example 3 except that it is as follows.

[0050] Example The chemical formula of the sulfide solid electrolyte prepared from 2 moles of Li2S, 1.3 moles of LiCl, 0.1 moles of LiBr, 0.1 moles of LiI, 0.48 moles of P2S5, and 0.02 moles of Sb2O5 is Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.3 Br 0.1 I 0.1 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0051] Example 16 The chemical formula of the sulfide solid electrolyte prepared from 2.01 moles of Li2S, 1.5 moles of LiCl, 0.495 moles of P2S5, and 0.005 moles of In2O3 is Li 5.52 P 0.99 In 0.01 S 4.485 O 0.015 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0052] Example 17 The chemical formula of the sulfide solid electrolyte prepared from 2.015 moles of Li2S, 1.5 moles of LiCl, 0.4925 moles of P2S5, and 0.0075 moles of In2O3 is Li 5.53 P 0.985 In 0.015 S 4.4775 O 0.0225 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0053] Example 18 The chemical formula of the sulfide solid electrolyte prepared from 2.02 moles of Li2S, 1.5 moles of LiCl, 0.49 moles of P2S5, and 0.01 moles of In2O3 is Li 5.54 P 0.98 In 0.02 S 4.47 O 0.03 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0054] Example 19 The chemical formula of the sulfide solid electrolyte prepared from 2.04 moles of Li2S, 1.5 moles of LiCl, 0.48 moles of P2S5, and 0.02 moles of In2O3 is Li 5.58 P 0.96 In 0.04 S 4.44 O 0.06 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0055] Example 20 The chemical formula of the sulfide solid electrolyte prepared from 2.06 moles of Li2S, 1.5 moles of LiCl, 0.47 moles of P2S5 and 0.03 moles of In2O3 is Li 5.62 P 0.94 In 0.06 S 4.41 O 0.09 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0056] Example 21 The chemical formula of the sulfide solid electrolyte prepared from 2.08 moles of Li2S, 1.5 moles of LiCl, 0.46 moles of P2S5 and 0.04 moles of In2O3 is Li 5.66 P 0.92 In 0.08 S 4.38 O 0.12 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0057] Example 22 The chemical formula of the sulfide solid electrolyte prepared from 2.1 moles of Li2S, 1.5 moles of LiCl, 0.45 moles of P2S5, and 0.05 moles of In2O3 is Li 5.7 P 0.9 In 0.1 S 4.35 O 0.15 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0058] Example 23 The chemical formula of the sulfide solid electrolyte prepared from 1.62 moles of Li2S, 1.9 moles of LiCl, 0.49 moles of P2S5, and 0.01 moles of In2O3 is Li 5.14 P 0.98 In 0.02 S 4.07 O 0.03 Cl 1.9 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0059] Example 24 The chemical formula of the sulfide solid electrolyte prepared from 2.42 moles of Li2S, 1.1 moles of LiCl, 0.49 moles of P2S5, and 0.01 moles of In2O3 is Li 5.94 P 0.98 In 0.02 S 4.87 O 0.03 Cl 1.1 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0060] Example 25 The chemical formula of the sulfide solid electrolyte prepared from 2.02 moles of Li2S, 1.4 moles of LiCl, 0.1 moles of LiBr, 0.49 moles of P2S5 and 0.01 moles of In2O3 is Li 5.54 P 0.98 In 0.02 S 4.47 O 0.03 Cl 1.4 Br 0.1 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0061] Example 26 The chemical formula of the sulfide solid electrolyte prepared from 2.02 moles of Li2S, 1.3 moles of LiCl, 0.1 moles of LiBr, 0.1 moles of LiI, 0.49 moles of P2S5 and 0.01 moles of In2O3 is Li 5.54 P 0.98 In 0.02 S 4.47 O 0.03 Cl 1.3 Br 0.1 I 0.1 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0062] Example 27 The chemical formula of the sulfide solid electrolyte prepared from 2.01 moles of Li2S, 1.5 moles of LiCl, 0.495 moles of P2S5, and 0.005 moles of Bi2O3 is Li 5.52 P 0.99 Bi 0.01 S 4.485 O 0.015 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0063] Example 28 The chemical formula of the sulfide solid electrolyte prepared from 2.015 moles of Li2S, 1.5 moles of LiCl, 0.4925 moles of P2S5, and 0.0075 moles of Bi2O3 is Li 5.53 P 0.985 Bi 0.015 S 4.4775 O 0.0225 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0064] Example 29 The chemical formula of the sulfide solid electrolyte prepared from 2.02 moles of Li2S, 1.5 moles of LiCl, 0.49 moles of P2S5, and 0.01 moles of Bi2O3 is Li 5.54 P 0.98 Bi 0.02 S 4.47 O 0.03 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0065] Example 30 The chemical formula of the sulfide solid electrolyte prepared from 2.04 moles of Li2S, 1.5 moles of LiCl, 0.48 moles of P2S5, and 0.02 moles of Bi2O3 is Li 5.58 P 0.96 Bi 0.04 S 4.44 O 0.06 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0066] Example 31 The chemical formula of the sulfide solid electrolyte prepared from 2.06 moles of Li2S, 1.5 moles of LiCl, 0.47 moles of P2S5, and 0.03 moles of Bi2O3 is Li 5.62 P 0.94 Bi 0.06 S 4.41 O 0.09 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0067] Example 32 The chemical formula of the sulfide solid electrolyte prepared from 2.08 moles of Li2S, 1.5 moles of LiCl, 0.46 moles of P2S5, and 0.04 moles of Bi2O3 is Li 5.66 P 0.92 Bi 0.08 S 4.38 O 0.12 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0068] Example 33 The chemical formula of the sulfide solid electrolyte prepared from 2.1 moles of Li2S, 1.5 moles of LiCl, 0.45 moles of P2S5, and 0.05 moles of Bi2O3 is Li 5.7 P 0.9 Bi 0.1 S 4.35 O 0.15 Cl 1.5 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0069] Example 34 The chemical formula of the sulfide solid electrolyte prepared from 1.62 moles of Li2S, 1.9 moles of LiCl, 0.49 moles of P2S5, and 0.01 moles of Bi2O3 is Li 5.14 P 0.98 Bi 0.02 S 4.07 O 0.03 Cl 1.9 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0070] Example 35 The chemical formula of the sulfide solid electrolyte prepared from 2.42 moles of Li2S, 1.1 moles of LiCl, 0.49 moles of P2S5, and 0.01 moles of Bi2O3 is Li 5.94 P 0.98 Bi 0.02 S 4.87 O 0.03 Cl 1.1 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0071] Example 36 The chemical formula of the sulfide solid electrolyte prepared from 2.02 moles of Li2S, 1.4 moles of LiCl, 0.1 moles of LiBr, 0.49 moles of P2S5 and 0.01 moles of Bi2O3 is Li 5.54 P 0.98 Bi 0.02 S 4.47 O 0.03 Cl 1.4 Br 0.1 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0072] Example 37 The chemical formula of the sulfide solid electrolyte prepared from 2.02 moles of Li2S, 1.3 moles of LiCl, 0.1 moles of LiBr, 0.1 moles of LiI, 0.49 moles of P2S5, and 0.01 moles of Bi2O3 is Li 5.54 P 0.98 Bi 0.02 S 4.47 O 0.03 Cl 1.3 Br 0.1 I 0.1 It was prepared in the same manner as in Example 3, except for the difference mentioned above.

[0073] Example 38 The binder was prepared in the same manner as in Example 3, except that ETFE was selected.

[0074] Example 39 The binder was prepared in the same manner as in Example 3, except that PCTFE was selected.

[0075] Example 40 Preparation of sulfide solid electrolytes: Precursor powder was obtained by high-energy ball milling using 2 moles of Li2S, 1.5 moles of LiCl, 0.48 moles of P2S5, and 0.02 moles of Sb2O5 as raw materials. Here, the ball-to-raw material ratio was 30:1, and the rotation speed was 500 rpm. Subsequently, the precursor powder was sintered at a temperature of 500°C for 10 hours, and after cooling, the sulfide solid electrolyte Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 I obtained it. Preparation of solid electrolyte membranes: Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 An electrolyte slurry was prepared by uniformly mixing SBR as a binder and xylene as a solvent in a mass ratio of 49:1:50. The electrolyte slurry was coated onto a smooth aluminum foil using a coater, vacuum-dried at 80°C, and peeled off to produce a 30 μm thick solid electrolyte film. Preparation of the positive electrode sheet: LiRing 0.8 Co 0.1 Mn 0.1 O2, conductive agent, Li 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 A positive electrode sheet is prepared by a dry process using a mixture of PTFE and super-P in a mass ratio of 69:1:29:1. Here, the conductive agents are super-P and VGCF in a mass ratio of 1:1. Negative electrode sheet: Select a metallic lithium piece for the negative electrode sheet. Assembly of all-solid-state batteries: The positive electrode sheet, solid electrolyte membrane, and negative electrode sheet prepared above are assembled into an all-solid-state pouch-type battery through lamination, sealing, hot-pressing, and cold-pressing processes. Assembling symmetric cells: Counter electrodes (Li) are placed on both sides of a solid electrolyte membrane, and the solid electrolyte membrane is assembled with these electrodes to form a Li / Li symmetric cell.

[0076] Example 41 The binder was prepared in the same manner as in Example 40, except that PVDF was selected.

[0077] Example 42 The binder was prepared in the same manner as in Example 40, except that PAA was selected.

[0078] Comparative Example 1 The chemical formula of the electrolyte prepared using 2 moles of Li2S, 1.5 moles of LiCl, and 0.5 moles of P2S5 is Li 5.5 PS 4.5 Cl 1.5 Except for the above, it was prepared in the same manner as in Example 3.

[0079] Comparative Example 2 The chemical formula of the sulfide solid electrolyte prepared using 2 moles of Li2S, 1.4 moles of LiCl, 0.1 moles of LiBr, and 0.5 moles of P2S5 is Li 5.5 PS 4.5 Cl 1.4 Br 0.1 Except for the above, it was prepared in the same manner as in Example 3.

[0080] Comparative Example 3 The chemical formula of the electrolyte prepared using 2 moles of Li2S, 1.3 moles of LiCl, 0.1 moles of LiBr, 0.1 moles of LiI, and 0.5 moles of P2S5 is Li 5.5 PS 4.5 Cl 1.3 Br 0.1 I 0.1 Except for the above, it was prepared in the same manner as in Example 3.

[0081] Comparative Example 4 The solid electrolyte membrane was fabricated in the same manner as in Example 3, except that the thickness was adjusted to 1 μm by adjusting the gap between the rolls of the roll rolling mill.

[0082] In Examples 1 to 42 and Comparative Examples 1 to 4 of the present invention, different solid electrolyte membranes were used, and the ionic conductivity of the solid electrolyte membranes was measured. Then, after leaving the solid electrolyte membranes in a drying chamber at -40°C for 24 hours, the ionic conductivity was measured again. In these examples, the ionic conductivity was obtained, for example, by the AC impedance method, and the measurement results are shown in Table 1.

[0083] In this invention, lithium-ion batteries were obtained using different sulfide solid electrolytes in Examples 1 to 42 and Comparative Examples 1 to 4. Long-cycle charge-discharge was performed on the lithium-ion batteries prepared as described above under a 25°C environment, and the discharge capacity was measured and the energy density was calculated. Here, the operating voltage range for battery measurement was 2.5 to 4.3V, the charge-discharge ratio was 1C / 1C, the discharge capacity of the first cycle was recorded and taken as the 1C discharge capacity, and the measurement was terminated when the battery capacity reached 80% of the first cycle capacity (80% State of Health, 80% SOH), and the number of cycles at room temperature was obtained. Symmetric cell was measured at 1 mA / cm². 2 A constant current charge-discharge cycle test was conducted under the specified current density, and the measurement results are shown in Table 2.

[0084] Table 1 summarizes the ionic conductivity of sulfide solid electrolytes in Examples 1-42 and Comparative Examples 1-4.

[0085] Table 2 summarizes the measurement results for lithium-ion batteries and symmetrical cells in Examples 1-42 and Comparative Examples 1-4.

[0086] [Table 1]

[0087] [Table 2]

[0088] Please refer to Tables 1 and 2. As can be seen from the comparison between Examples 1-6 and Comparative Example 4, as the thickness of the solid electrolyte membrane increases, the retention rate of the ion conductivity of the solid electrolyte membrane at low temperatures increases, and the cycle performance of the lithium-ion battery increases gradually first, and then decreases gradually. Also, when the solid electrolyte membrane was excessively thin, a battery short circuit was detected at a relatively low number of cycles. Therefore, considering both the retention rate of ion conductivity and cycle performance simultaneously, there is an optimal range for the thickness of the solid electrolyte membrane.

[0089] As shown in Tables 1 and 2, comparing Examples 3, 7-11, it was found that when Sb was selected as the M element in the sulfide solid electrolyte, the cycle performance of the lithium-ion battery increased gradually with increasing Sb doping, and then decreased gradually. Comparing Examples 16-22, it was found that when In was selected as the M element in the sulfide solid electrolyte, the cycle performance of the lithium-ion battery increased gradually with increasing In doping, and then decreased gradually. Comparing Examples 27-33, when Bi was selected as the M element in the sulfide solid electrolyte, the cycle performance of the lithium-ion battery increased gradually with increasing Bi doping, and then decreased gradually. When the doping amounts of Sb, In, or Bi were excessively low, a battery short circuit occurred with a small number of cycles, regardless of which element was used. Furthermore, while the ionic conductivity of the sulfide solid electrolyte decreases with increasing doping of element M, after 24 hours of exposure in a -40°C drying chamber, the retention rate of the ionic conductivity of the sulfide solid electrolyte increases, enhancing its air and chemical stability, and improving the battery's stability and performance. This indicates that appropriate doping of element M promotes the formation of a stable solid electrolyte interface (SEI) and reduces side reactions between the solid electrolyte and electrode material. If the doping amount is too low, an effective SEI film may not be formed. If the doping is too high, the lattice strain becomes excessively large, destroying the original crystal structure. This reduces the structural stability of the material, and may even lead to phase separation or amorphous phenomena, which can reduce the material's ionic conductivity. Therefore, by controlling the amount of M doping in the sulfide solid electrolyte, the cycle life and safety of lithium batteries in all-solid-state lithium-ion batteries can be improved, while simultaneously maintaining a high level of ionic conductivity, ensuring the rate performance of lithium-ion batteries, and improving charge-discharge efficiency and cycle life.

[0090] As shown in Tables 1 and 2, a comparison of Examples 3, 12-13, 18, 23-24, and 29, 34-35 revealed that, when the doping amounts of Sb, In, or Bi were the same, increasing or decreasing the Cl content significantly reduced the ionic conductivity, both of which degraded the cycle performance of the lithium-ion battery. Therefore, by controlling the Cl content, it is possible to ensure the ionic conductivity of the sulfide solid electrolyte and the performance of the lithium-ion battery.

[0091] As shown in Tables 1 and 2, a comparison of Examples 3, 14-15, 18, 25-26, and 29, 36-37 revealed that, when the doping amounts of Sb, In, or Bi were the same, adding one or more of Br or I elements degraded the battery's cycle performance. This is because the added Br or I may introduce additional lattice defects, which can hinder lithium ion transport and further reduce the ionic conductivity of the electrolyte. Therefore, selecting Cl as X can improve the ionic conductivity and electrochemical stability of the sulfide solid electrolyte, thereby improving voltage stability.

[0092] As shown in Tables 1 and 2, a comparison of Examples 3, 14-15, 18, 25-26, and 29, 36-37, as well as Comparative Examples 1-3, revealed that when M and O elements are not added to the sulfide solid electrolyte, lithium-ion batteries have almost no cycle performance and short circuits occur in a short time. This indicates that when M and O elements are deficient, the chemical stability of the sulfide solid electrolyte material is poor, the mechanical strength is insufficient, and it is difficult to guarantee the long-term cycle performance of lithium-ion batteries. By introducing M and O elements, the cycle performance of lithium-ion batteries can be improved.

[0093] As shown in Tables 1 and 2, a comparison of Examples 3 and 38-39 revealed that in the dry process preparation, selecting a different first binder affected the ionic conductivity of the solid electrolyte membrane and the performance of the lithium-ion battery. Furthermore, selecting PTFE as the first binder resulted in optimal ionic conductivity of the solid electrolyte membrane and lithium-ion battery performance. A comparison of Examples 40-42 revealed that in the wet process preparation, selecting a different second binder affected the ionic conductivity of the solid electrolyte membrane and the performance of the lithium-ion battery. Furthermore, selecting PAA as the second binder resulted in optimal ionic conductivity of the solid electrolyte membrane and lithium-ion battery performance. A comparison of Examples 3 and 40 showed that solid electrolyte membranes prepared by the dry process performed better than those prepared by the wet process. This is because the wet process uses a large amount of organic solvent, which undergoes minor reactions with the electrolyte, degrading the electrolyte membrane performance, whereas the dry process does not involve the introduction of solvents.

[0094] Please refer to Figure 2. In the room-temperature cycling process of the all-solid-state lithium-ion battery in Example 3, the current density used for constant current charging and discharging was 1C. As can be seen from Figure 2, at a current density of 1C, the all-solid-state lithium-ion battery in Example 3 still has a storage capacity of approximately 150 mAh / g even after 500 cycles, demonstrating that the sulfide solid electrolyte has excellent reaction kinetics and cycle stability. The obtained solid electrolyte membrane has a good effect on the battery's cycle stability and reaction activity ratio capacity, and the all-solid-state lithium-ion battery simultaneously satisfies excellent performance in terms of ratio capacity, rate performance, and cycle life.

[0095] The present invention further provides electronic devices, each comprising at least one of the above-described lithium-ion batteries, which are used to provide power. Here, the electronic devices can be vehicles, mobile phones, portable devices, laptop computers, ships, spacecraft, electric toys, and power tools, etc. In one embodiment of the present invention, a vehicle is, for example, a new energy vehicle, which can be a pure electric vehicle, a hybrid vehicle, or a range-extender vehicle, etc. Spacecraft include aircraft, rockets, space shuttles, and spacecraft, and electric toys include stationary or mobile electric toys, such as game consoles, electric car toys, electric boat toys, and electric aircraft toys, etc. Power tools include metal cutting power tools, polishing power tools, assembly power tools, and railway power tools, such as electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact electric drills, concrete vibrators, and electric planers, etc. Since the electronic devices include the above-described lithium-ion batteries, they include the above-described advantages of lithium-ion batteries, which are not described in detail here.

[0096] As described above, the present invention provides a solid electrolyte membrane, a method for preparing the same, and its applications. As described above, by providing a solid electrolyte membrane, a method for preparing the same, and its applications, the present invention increases the intrinsic resistance of the solid electrolyte membrane to atmospheric degradation, effectively reduces H2S generation, and increases the potential of batteries in actual production. This enhances the air stability and chemical stability of the sulfide solid electrolyte. At the electrolyte / lithium metal anode interface layer, alloys such as LiCl, Li2O, and Li-Sb / Li-Bi / Li-In can be formed, allowing for a uniform electric field and equilibrium of local current density. This regulates Li nucleation and growth and effectively suppresses the rapid growth of lithium dendrites at the growth interface. Therefore, the stability and performance of lithium-ion batteries can be significantly improved, and the lifespan and safety of lithium batteries in all-solid-state lithium-ion batteries can be enhanced. Therefore, the solid electrolyte membrane has relatively high stability and specific reactivity, improving the conductivity stability of the solid electrolyte membrane, enhancing air stability, and improving the interfacial properties of the electrolyte / active material, thereby improving compatibility with the active material.

[0097] The above description is merely a description of preferred embodiments and the technical principles in which the present invention is applied. Those skilled in the art should understand that the scope of the invention is not limited to technical solutions formed by specific combinations of the above technical features, but also includes other technical solutions formed by arbitrarily combining the above technical features or their equivalents, without departing from the conceptual framework of the invention. For example, technical solutions formed by substituting the above features with similar functional technical features disclosed in the present invention (but not limited to these).

[0098] Other technical features not described in the specification are known to those skilled in the art, and in order to highlight the innovative features of the present invention, these other technical features will not be described in detail here. [Industrial applicability]

[0099] The solid electrolyte membrane of the present invention can be used in lithium batteries.

Claims

1. at least, Binder and, A sulfide solid electrolyte is included, The chemical formula of the sulfide solid electrolyte is Li ａ P １－ｂ M ｂ S ｃ O ｄ X ｅ And, In the formula, 5 < a < 6, 0 < b < 1, 1.5 < c < 5, 0 < d < 2.5, 4 < c + d < 5, 1 < e < 2, M is one or more selected from Al, Ga, In, Ti, Sc, As, Sb, Bi, As, V, or Nb, and X is one or more selected from Cl, Br, or I. Ionic conductivity is 1 × 10⁻⁶ －３ ~2 x 10 －２ It is S / cm. A solid electrolyte membrane characterized by the following features.

2. M is one or more selected from Sb, In, or Bi. The solid electrolyte membrane according to claim 1, characterized in that...

3. X is Cl, The acceptable range for b is 0 < b ≤ 0.

1. The solid electrolyte membrane according to claim 1, characterized in that...

4. The thickness of the solid electrolyte membrane is 1 to 200 μm. The solid electrolyte membrane according to claim 1, characterized in that...

5. The mass ratio of the binder to the sulfide solid electrolyte is 0.1:99.9 to 10:

90. The solid electrolyte membrane according to claim 1, characterized in that...

6. A method for preparing a solid electrolyte membrane according to any one of claims 1 to 5, Based on the chemical formula of the sulfide solid electrolyte, the raw materials are uniformly mixed according to stoichiometry, then placed in a ball mill pot and ground using a ball mill to obtain a sulfide solid electrolyte precursor powder. The sulfide solid electrolyte precursor powder is subjected to calcination treatment at a predetermined temperature to obtain the sulfide solid electrolyte, This includes mixing the sulfide solid electrolyte with a binder and obtaining the solid electrolyte film by a dry or wet process. A method for preparing a solid electrolyte membrane, characterized by the following features.

7. The aforementioned raw materials include a Li source, a P source, an M source, an S source, and an X source. The Li source is one or more selected from LiCl, LiBr, LiI, or Li ２ S, and The aforementioned P source is a single P, P ２ S ５ , P ４ S ６ , PCL ５ , or PBr ５ One or more selected from, The M source is one or more selected from oxides of M or sulfides of M. The S source is a single S, Li ２ S, P ２ S ５ , P ４ S ６ As ２ S ５ As ２ S ３ Sb ２ S ５ Sb ２ S ３ , Bi ２ S ５ , Bi ２ S ３ Al ２ S ３ Ga ２ S ３ In ２ S ３ , or Sc ２ S ３ One or more selected from, The X source is LiCl, PCl ５ LiBr, PBr ５ , LiI, or I ２ One or more selected from, The element O in the chemical formula originates from an oxide of M. A method for preparing a solid electrolyte membrane according to claim 6, characterized in that...

8. When the solid electrolyte membrane is prepared by a dry process, the binder is selected from the first binder. The first binder is one or more selected from polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene propylene copolymer, perfluoroalkoxy resin, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, or polyvinylidene fluoride-chlorotrifluoroethylene copolymer. A method for preparing a solid electrolyte membrane according to claim 6, characterized in that...

9. When the solid electrolyte membrane is prepared by a wet process, the binder is selected from the second binder. The second binder is one or more selected from polyvinylidene fluoride, carboxymethylcellulose, styrene-butadiene rubber, polyvinylpyrrolidone, polymethyl methacrylate, polyacrylonitrile, polyacrylic acid, polyurethane, polyvinyl alcohol, sodium alginate, ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, β-cyclodextrin polymer, polypropylene emulsion, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene-propylene copolymer, perfluoroalkoxy resin, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride-hexafluoropropylene copolymer, or polyvinylidene fluoride-chlorotrifluoroethylene copolymer. A method for preparing a solid electrolyte membrane according to claim 6, characterized in that...

10. Li ２．３５ Zr ０．６５ Fe ０．３５ Cl ５ Br ０．５ I ０．５ A positive electrode sheet containing a halogenated solid electrolyte containing, Negative electrode sheet and The solid electrolyte membrane is installed between adjacent positive electrode sheets and negative electrode sheets and is selected from the solid electrolyte membranes described in any one of claims 1 to 5, and includes at least one of these. A solid-state lithium-ion battery characterized by the following features.

11. Includes the all-solid-state lithium-ion battery described in claim 10 An electronic device characterized by the following features.

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