A high ionic conductivity sulfide solid electrolyte membrane and a preparation method and application thereof

Abstract

The application discloses a high-ionic-conductivity sulfide solid electrolyte film as well as a preparation method and application thereof. 3‑x W y Sb 1‑y S4; wherein, 0

Description

Technical Field

[0001] This invention relates to the field of sodium solid electrolytes, specifically to a high ionic conductivity sulfide solid electrolyte membrane, its preparation method, and its application. Background Technology

[0002] To meet the diverse needs of various fields, multiple battery systems have flourished. Sodium-ion batteries, with their abundant resources and lower cost, are undoubtedly an ideal alternative to lithium-ion batteries. However, due to safety concerns related to the flammability and leakage of sodium-ion battery systems with organic liquid electrolytes, attention has shifted towards research into non-flammable sodium-ion solid electrolytes. This approach not only significantly improves the safety of battery systems but also reduces the overall weight of the battery.

[0003] Solid electrolytes are mainly classified into three categories: oxide solid electrolytes, sulfide solid electrolytes, and organic polymer solid electrolytes. Oxide solid electrolytes are inherently hard, and the contact between crystal particles is relatively poor. Simple cold pressing is insufficient to effectively reduce grain boundary resistance and electrolyte / electrode interface resistance. High-temperature sintering is necessary to achieve high ionic conductivity, and these stringent synthesis conditions hinder their commercialization and application. Polymer electrolytes, on the other hand, possess good flexibility and low interfacial resistance, but their room-temperature ionic conductivity is very low (<10). -4 The ion transference number (S / cm) is usually less than 0.5, which needs to be addressed by adding inorganic inactive fillers or inorganic active fillers to the polymer matrix. Even so, the ionic conductivity of the modified electrolyte still cannot meet the development requirements of all-solid-state sodium batteries at room temperature.

[0004] Compared to the former two, sulfide solid electrolytes possess excellent mechanical flexibility, allowing for good contact between the electrolyte and electrode through simple cold pressing, reducing grain boundary impedance and facilitating ion transport. Furthermore, their simple preparation process and low cost have made them a focus of attention for application in solid-state sodium batteries. However, sulfide solid electrolyte membranes are difficult to form; the thickness of a pure sulfide solid electrolyte membrane is approximately 0.5–1 mm. Excessive membrane thickness results in a low volumetric energy density, failing to meet the requirements for thinner and lighter solid-state sodium batteries.

[0005] For example, Chinese patent CN115189014A discloses a method for preparing a composite electrolyte membrane based on sodium ion sulfide solid electrolyte. This method involves adding sodium ion sulfide solid electrolyte to an organic solvent containing a polymer and sodium salt. However, the use of the organic solvent reduces the ionic conductivity of the sulfide solid electrolyte, resulting in generally low ionic conductivity in the prepared membrane, which cannot meet the requirements for commercial production of sodium batteries. Therefore, finding a thinner, higher-performance solid electrolyte membrane is urgently needed. SUMMARY OF THE INVENTION

[0006] In view of this, the object of the present invention is to provide a high ionic conductivity sulfide solid electrolyte membrane, its preparation method and application. The sulfide solid electrolyte membrane prepared by the preparation method provided by the present invention does not require the use of organic solvents, has a small binder content, and the prepared sulfide solid electrolyte membrane has high ionic conductivity and a thin thickness.

[0007] To achieve the above object of the invention, the present invention adopts the following technical solutions:

[0008] (1) The chemical general formula of the high ionic conductivity sulfide solid electrolyte membrane of the present invention is Na 3-x W y Sb 1-y S4; wherein, 0 < x < 1, 0 < y < 1, and further preferably, x = 0.1, y = 0.3.

[0009] (2) In an environment filled with inert gas, weigh the stoichiometric ratios of Na2S, Sb2S3, WS2 and S raw materials, grind and mix them, and then transfer them to a ball milling tank for high-energy mechanical ball milling. Oxygen is isolated during the ball milling process to obtain a sulfide solid electrolyte precursor.

[0010] (3) Preferably, the ball-to-material ratio of the ball milling is 10 - 70:1, the ball milling speed is 300 - 800 rpm, and the ball milling time is 10 - 30 h.

[0011] (4) Weigh the sulfide solid electrolyte precursor obtained in step (2) for tabletting, the tabletting pressure is 300 - 1000 Mpa, and the pressure holding time is 2 - 10 min; vacuum seal the tube and sinter at high temperature to obtain the high ionic conductivity sulfide solid electrolyte.

[0012] (5) Preferably, the annealing temperature is 200 - 600 °C, the heating rate is 1 - 5 °C min[[ID=2⑨] -1 , and the annealing time is 10 - 30 h.

[0013] (6) Grind the sulfide solid electrolyte obtained in step (4) into powder, screen out the materials with a mesh number ≤ 200, and then manually grind and mix with the fibrillated binder to make it fibrillate initially, and then transfer it to a roller press for continuous rolling to obtain the high ionic conductivity sulfide solid electrolyte membrane.

[0014] (7) Preferably, the fibrillated binder is one or more of a copolymer of polytetrafluoroethylene and other monomers (such as ethylene, hexafluoropropylene) and tetrafluoroethylene; the content of the binder in the high ionic conductivity sulfide solid electrolyte membrane is 0.1 - 5 wt.%.

[0015] (8) Preferably, in the roll pressing process, the temperature of the pressing roller is 100 - 180 °C, the rotation speed of the pressing roller is 10 - 50 rpm, and the thickness of the sulfide solid electrolyte membrane is 10 - 60 μm, more preferably 10 - 50 μm.

[0016] (9) The present invention provides an application of a sulfide solid electrolyte membrane with high ionic conductivity in a all - solid - state battery.

[0017] Compared with the prior art, the beneficial effects of the present invention are:

[0018] (1) The present invention provides a sulfide solid electrolyte membrane Na 3-x W y Sb 1-y S4 (where 0 < x < 1, 0 < y < 1), and this sulfide solid electrolyte membrane has the characteristics of high ionic conductivity, air stability and ultrathinness.

[0019] (2) The preparation process of the sulfide solid electrolyte membrane of the present invention is simple, easy to operate, and easy for industrial production, and has broad industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is a macroscopic observation diagram of the prepared sulfide solid electrolyte membrane;

[0021] Figure 2 is a SEM diagram of the prepared sulfide solid electrolyte membrane;

[0022] Figure 3 is an XRD diagram of the sulfide solid electrolyte membrane after roll pressing;

[0023] Figure 4 is an electrochemical impedance spectroscopy diagram of the obtained sulfide solid electrolyte membrane;

[0024] Figure 5 is a DC polarization spectroscopy diagram of the sulfide solid electrolyte membrane;

[0025] Figure 6 is the first - cycle charge - discharge curve of the all - solid - state battery assembled with the sulfide solid electrolyte membrane. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] The following combines the implementation cases to further describe the technical solutions in the present invention more clearly and completely. Obviously, the described implementation cases are only part of the experimental results of the present invention, rather than all the experimental results. Based on the implementation cases in the present invention, all other examples obtained by ordinary technical workers in the field without making creative labor are within the protection scope of the present invention.

[0027] In an example of the present invention, a method for preparing a sulfide solid electrolyte membrane with high ionic conductivity is provided, including the following steps:

[0028] A1. The present invention provides a sulfide solid electrolyte membrane. The chemical composition of the sulfide solid electrolyte is Na 3-x W y Sb 1-y S4; where 0 < x < 1 and 0 < y < 1. Among them, x is preferably 0 < x < 1, more preferably 0 < x < 0.3; y is preferably 0.1, 0.2, 0.3, 0.4, and 0.5.

[0029] In one embodiment, the raw material source of the sulfide solid electrolyte is Na2S, Sb2S3, WS2, and S. The sulfide solid electrolyte of the present invention introduces high-valent W ions. According to the charge compensation mechanism, hexavalent tungsten (W 6+ ) partially replaces pentavalent antimony (Sb 5+ ), which will lead to the introduction of Na vacancies in the Na3SbS4 system. A small amount of Na vacancies can generate a large number of degenerate or nearly degenerate energy states, thereby enabling the diffusion and rearrangement of sodium ions. For the undoped Na3SbS4 system, Na ions are relatively easy to propagate along the c-axis direction. This is mainly because the average Na-S bond lengths along the a-axis and b-axis are shorter, and a large energy cost is required for sodium ions to diffuse along these axes, while the average Na-S bond length along the c-axis is relatively longer, significantly reducing the diffusion energy barrier. Therefore, in the absence of external doping and sodium vacancies, the diffusion of sodium ions in the undoped Na3SbS4 system is similar to a one-dimensional ion conductor along the c-axis. In contrast, three-dimensional ion diffusion occurs in the W-doped material, manifested as the movement of individual ions to vacancies and the correlated movement of sodium ions. Sodium ion vacancies and three-dimensional fast ion conduction are also the reasons for the significant increase in ionic conductivity.

[0030] In one embodiment, the method includes the following steps: In an environment where the water content of the protective gas < 1 ppm and the oxygen content of the protective gas < 1 ppm, weigh the raw materials in a stoichiometric ratio, manually grind and mix them, and then transfer them to a ball mill jar for high-energy mechanical ball milling. Oxygen is isolated during the ball milling process to obtain a sulfide solid electrolyte precursor.

[0031] In the present invention, the ball-to-material ratio of the ball milling is 10 - 70:1, further preferably 20 - 60:1, more preferably 20 - 60:1. The ball milling speed is within 300 - 800 rpm, preferably 400 - 550 rpm. The ball milling time is controlled within the range of 10 - 30 h, preferably 10 - 20 h. The particle size of the material obtained by ball milling is 100 nm - 100 μm.

[0032] A2. The sulfide solid electrolyte precursor obtained in step A1 above is pressed into tablets and sintered. The method includes the following steps: weighing 100-200 mg of sulfide solid electrolyte precursor sample, using a manual tablet press at a pressure of 3-5 tons, maintaining constant pressure for 2-10 min, preferably 3-5 min; vacuum sealing, high-temperature sintering, to obtain the high ionic conductivity sulfide solid electrolyte.

[0033] In this invention, the material after annealing is a crystalline material, and the material without annealing is a glassy material.

[0034] In this invention, the annealing temperature is 200–600°C, preferably 400–550°C; the heating rate is 1–5°C / min. -1 Preferably select 3-5℃ min -1 The annealing time is 10-30 hours, preferably 10-20 hours; the number of annealing processes is preferably 1-2 times.

[0035] A3. Grind the crystalline sulfide solid electrolyte material obtained in step A2 into powder, sieve it with a 200-mesh sieve to select materials with a mesh size ≤200, and then manually grind and mix it with the fibrillated binder. During the mixing process, the various materials are evenly dispersed, and under the action of shear force, the binder will be physically stretched from its original spherical shape into fine filaments (that is, the so-called "fibrillation"). The formed network structure can connect the active particles together, thereby achieving a better bonding effect. Then, it is transferred to a roller press and continuously rolled to obtain the high ionic conductivity sulfide solid electrolyte membrane.

[0036] In this invention, the fibrillated binder is one or more copolymers of polytetrafluoroethylene and other monomers (such as ethylene, hexafluoropropylene) and tetrafluoroethylene, preferably polytetrafluoroethylene; the binder content in the high ionic conductivity sulfide solid electrolyte membrane is 0.1-5 wt.%, preferably 0.3-3 wt.%.

[0037] In this invention, the rolling temperature in the rolling process is 100-180℃, preferably 25-60℃; the rotation speed of the rolling roller is 10-50 rpm, preferably 10-20 rpm; and the thickness of the sulfide solid electrolyte membrane is controlled by adjusting the rolling time, with the thickness preferably being 10-60 μm, more preferably 10-30 μm.

[0038] Example 1

[0039] In this example 1, a method for preparing a sulfide solid electrolyte membrane with high ionic conductivity is provided. The specific steps are as follows: (1) In a glove box under an argon atmosphere, according to the chemical composition of the sulfide solid electrolyte Na 2.9 W0.3 Sb 0.7 S4 (where x = 0.1 and y = 0.3), weigh the raw materials Na2S, Sb2S3, WS2 and S in stoichiometric ratios respectively. Pour them into an agate mortar and grind them manually for 10 min. Then transfer them to a ZrO2 ball mill jar. The ball-to-material ratio of the ball mill is 40:1. Use a high-energy mechanical ball mill at 510 rpm for 10 h to obtain the sulfide solid electrolyte precursor; (2) Weigh 150 mg of the sulfide solid electrolyte precursor obtained in step (1) above, and press it under a pressure of 380 MPa for 3 min to prepare a dense sulfide solid electrolyte precursor sheet; (3) Vacuum seal the sulfide solid electrolyte precursor sheet obtained in step (2) above in a quartz tube. The preferred heating rate is 3℃ / min. -1 (3) Sinter at 500℃ for 12 hours, then cool naturally to room temperature; (4) The crystalline sulfide solid electrolyte material Na obtained in step (3) above is sintered at 500℃ for 12 hours. 2.9 W 0.3 Sb 0.7 S4 is ground into powder, and the material with a mesh size ≤200 is screened through a 200-mesh sieve. (5) The sulfide solid electrolyte powder Na obtained in step (4) above is then processed. 2.9 W 0.3 Sb 0.7 S4 and polytetrafluoroethylene (PTFE) binder are mixed in a mortar at a mass ratio of 95:5 and ground into a clay-like consistency. This mixture is then placed on a glass plate and repeatedly folded and rolled with a rolling pin to ensure the binder and electrolyte are evenly mixed. The resulting fibrous product is then pressed into an electrolyte membrane of fixed thickness using a roller press at a speed of 10 rpm, with a diameter of 10 cm and a temperature of 60°C. Figure 1 This is a macroscopic observation of a sulfide solid electrolyte membrane obtained using the technology described in this invention. Figure 1 It can be seen that the sulfide solid electrolyte membrane provided by this invention has a smooth surface and excellent self-supporting properties. Scanning electron microscopy (SEM) was performed on the sulfide solid electrolyte membrane obtained in Example 1; the resulting SEM image is shown below. Figure 2 .Depend on Figure 2 These fibrils are clearly visible distributed on the particle surface and cross-linked to form a network.

[0040] Example 2

[0041] In this embodiment 2, a method for preparing a sulfide solid electrolyte membrane with high ionic conductivity is provided. The specific steps are as follows: (1) In a glove box under an argon atmosphere, according to the chemical composition of the sulfide solid electrolyte Na 2.9 W 0.3 Sb 0.7S4 (where x = 0.1 and y = 0.3), weigh the raw materials Na2S, Sb2S3, WS2 and S in stoichiometric ratios respectively. Pour them into an agate mortar and grind them manually for 10 min. Then transfer them to a ZrO2 ball mill jar. The ball-to-material ratio of the ball mill is 40:1. Use a high-energy mechanical ball mill at 510 rpm for 10 h to obtain the sulfide solid electrolyte precursor; (2) Weigh 150 mg of the sulfide solid electrolyte precursor obtained in step (1) above, and press it under a pressure of 380 MPa for 3 min to prepare a dense sulfide solid electrolyte precursor sheet; (3) Vacuum seal the sulfide solid electrolyte precursor sheet obtained in step (2) above in a quartz tube. The preferred heating rate is 3℃ / min. -1 (3) Sinter at 500℃ for 12 hours, then cool naturally to room temperature; (4) The crystalline sulfide solid electrolyte material Na obtained in step (3) above is sintered at 500℃ for 12 hours. 2.9 W 0.3 Sb 0.7 S4 is ground into powder, and the material with a mesh size ≤200 is screened through a 200-mesh sieve. (5) The sulfide solid electrolyte powder Na obtained in step (4) above is then processed. 2.9 W 0.3 Sb 0.7 S4 and polytetrafluoroethylene (PTFE) binder were mixed in a mortar at a mass ratio of 98:2 and ground into a clay-like consistency. This mixture was placed on a glass plate and repeatedly folded and rolled with a rolling pin to ensure uniform mixing of the binder and electrolyte. The resulting fibrous product was then rolled into a film at 10 rpm using a 10 cm diameter roller at 60 °C. XRD analysis of the resulting sulfide solid electrolyte membrane yielded the following results: Figure 3 As shown, the crystal structure of the electrolyte prepared by introducing high-valence W ions into the sulfide solid electrolyte is basically consistent with that of PDF card 00-030-1154. Apart from a residual WS2 diffraction peak detected at 2θ = 14.4°, no other impurity peaks were found, indicating that the prepared sulfide solid electrolyte is relatively stable with the binder and that no side reactions occur during mixing. Furthermore, no significant structural changes occurred in the electrolyte during the entire roll forming process.

[0042] Example 3

[0043] In this embodiment 3, a method for preparing a sulfide solid electrolyte membrane with high ionic conductivity is provided. The specific steps are as follows: (1) In a glove box under an argon atmosphere, according to the chemical composition of the sulfide solid electrolyte Na 2.9 W 0.3 Sb 0.7S4 (where x = 0.1 and y = 0.3), weigh the raw materials Na2S, Sb2S3, WS2 and S in stoichiometric ratios respectively. Pour them into an agate mortar and grind them manually for 10 min. Then transfer them to a ZrO2 ball mill jar. The ball-to-material ratio of the ball mill is 40:1. Use a high-energy mechanical ball mill at 510 rpm for 10 h to obtain the sulfide solid electrolyte precursor; (2) Weigh 150 mg of the sulfide solid electrolyte precursor obtained in step (1) above, and press it under a pressure of 380 MPa for 3 min to prepare a dense sulfide solid electrolyte precursor sheet; (3) Vacuum seal the sulfide solid electrolyte precursor sheet obtained in step (2) above in a quartz tube. The preferred heating rate is 3℃ / min. -1 Sinter at 500℃ for 12 hours, then allow to cool naturally to room temperature; (4) Calcinate the crystalline sulfide solid electrolyte material Na obtained in step (3) above. 2.9 W 0.3 Sb 0.7 S4 is ground into powder, and the material with a mesh size ≤200 is screened through a 200-mesh sieve. (5) The sulfide solid electrolyte powder Na obtained in step (4) above is then processed. 2.9 W 0.3 Sb 0.7 S4 and polytetrafluoroethylene (PTFE) binder were mixed in a mortar at a mass ratio of 99.7:0.3 and ground into a clay-like consistency. This mixture was placed on a glass plate and repeatedly folded and rolled with a rolling pin to ensure uniform mixing of the binder and electrolyte. The resulting fibrous product was then rolled into a film at 10 rpm using a 10 cm diameter roller at 60 °C. The sulfide solid electrolyte film obtained in step (5) was placed in a self-made solid battery mold, with an indium sheet added to each end as a blocking electrode. Electrochemical impedance spectroscopy and DC polarization spectroscopy were then performed. The resulting impedance diagram is shown below. Figure 4 As shown, where, Figure 4 The illustrations within are corresponding enlarged views of specific areas. Figure 4 It is evident that the sulfide solid electrolyte membrane prepared by the method provided in this invention exhibits very high room temperature ionic conductivity, and the addition of a small amount of binder does not lead to a significant decrease in ionic conductivity. Furthermore, the fact that the ionic conductivity is six orders of magnitude higher than the electronic conductivity demonstrates that the prepared sulfide solid electrolyte membrane can serve as a pure ionic conductor for solid electrolytes.

[0044] Example 4

[0045] In this embodiment 4, a method for preparing a sulfide solid electrolyte membrane with high ionic conductivity is provided. The specific steps are as follows: (1) In a glove box under an argon atmosphere, according to the chemical composition of the sulfide solid electrolyte Na 2.9 W0.3 Sb 0.7 S4 (where x = 0.1 and y = 0.3), weigh the raw materials Na2S, Sb2S3, WS2 and S in stoichiometric ratios respectively. Pour them into an agate mortar and grind them manually for 10 min. Then transfer them to a ZrO2 ball mill jar. The ball-to-material ratio of the ball mill is 40:1. Use a high-energy mechanical ball mill at 510 rpm for 10 h to obtain the sulfide solid electrolyte precursor; (2) Weigh 150 mg of the sulfide solid electrolyte precursor obtained in step (1) above, and press it under a pressure of 380 MPa for 3 min to prepare a dense sulfide solid electrolyte precursor sheet; (3) Vacuum seal the sulfide solid electrolyte precursor sheet obtained in step (2) above in a quartz tube. The preferred heating rate is 3℃ / min. -1 Sinter at 500℃ for 12 hours, then allow to cool naturally to room temperature; (4) Calcinate the crystalline sulfide solid electrolyte material Na obtained in step (3) above. 2.9 W 0.3 Sb 0.7 S4 is ground into powder, and the material with a mesh size ≤200 is screened through a 200-mesh sieve. (5) The sulfide solid electrolyte powder Na obtained in step (4) above is then processed. 2.9 W 0.3 Sb 0.7 S4 and polytetrafluoroethylene (PTFE) binder are mixed in a mortar at a mass ratio of 99.7:0.3 and ground into a clay-like consistency. This mixture is placed on a glass plate and repeatedly folded and rolled with a rolling pin to ensure uniform mixing of the binder and electrolyte. The resulting fibrous product is then rolled into a film at 10 rpm using a roller press with a diameter of 10 cm and a temperature of 60°C. The high ionic conductivity sulfide solid electrolyte membrane obtained in step (5) is then applied in an all-solid-state battery, specifically including the following steps:

[0046] Preparation of mixed positive electrode: TiS2 is selected as the positive electrode active material. The positive electrode material, conductive carbon black and sodium ion sulfide solid electrolyte are mixed in a certain proportion and the mixture is made uniform by vortex mixing.

[0047] Negative electrode material preparation: Sodium and tin powder were weighed according to a certain molar ratio and transferred to a stainless steel ball mill jar for ball milling to prepare a Na-Sn alloy. The prepared Na-Sn alloy was mixed with conductive carbon black in a certain proportion and ball milled at 300 rpm for 20 hours. All preparation processes were carried out under an argon atmosphere.

[0048] All-solid-state battery assembly: The obtained high-ionic-conductivity sulfide solid electrolyte membrane was cut into 10mm diameter sheets using a cutting machine and placed in a solid mold. Then, a mixed positive electrode was placed on one side of the electrolyte membrane sheet and pressed under slight pressure. Finally, a composite negative electrode material was attached to the other side of the solid electrolyte membrane sheet, and pressure was applied to form a sandwich-structured all-solid-state battery. All of the above preparation processes were carried out in an argon atmosphere.

[0049] Battery electrochemical performance testing:

[0050] Electrochemical tests were conducted on the all-solid-state battery using the Wuhan Landian Battery Testing System, with a charge / discharge voltage range of 1.2–2.4V. Figure 6 As shown, the solid-state battery has an initial discharge capacity of 119 mAh / g at room temperature with a current density of 0.1C.

Claims

1. The application of high ionic conductivity sulfide solid electrolyte membranes in the preparation of all-solid-state batteries, characterized in that, The method for preparing the high ionic conductivity sulfide solid electrolyte membrane includes the following steps: 1) In an environment filled with inert gas, weigh the raw materials Na2S, Sb2S3, WS2 and S in stoichiometric ratio, grind and mix them, and then transfer them to a ball mill jar for mechanical ball milling to obtain a sulfide solid electrolyte precursor. The conditions for mechanical ball milling are: ball-to-material ratio of 10~70:1, ball milling speed of 300~800 rpm, ball milling time of 10~30h, and oxygen is isolated during the ball milling process; 2) The sulfide solid electrolyte precursor is pressed into tablets, then vacuum sealed and sintered at high temperature to obtain a sulfide solid electrolyte with high ionic conductivity. The tableting conditions are: tableting pressure of 300~1000Mpa, and holding time of 2~10min; The conditions for high-temperature sintering are: a heating rate of 1~5℃ min. -1 Sintering at 200~600℃ for 10~30 hours; 3) The high ionic conductivity sulfide solid electrolyte is ground into powder, sieved, and then ground and mixed with the fibrillated binder. The mixture is then transferred to a roller press and continuously rolled to obtain a high ionic conductivity sulfide solid electrolyte membrane. The chemical composition of the sulfide solid electrolyte membrane is Na. 3-x W y Sb 1-y S4, where x = 0.1, y = 0.3; The conditions for roller pressing are: roller pressing temperature of 100~180℃ and roller speed of 10~50rpm.

2. The method for preparing a high ionic conductivity sulfide solid electrolyte membrane according to claim 1, characterized in that, In step 3), materials with a mesh size ≤ 200 are sieved out and then ground and mixed with the fibrillated binder.

3. The method for preparing a high ionic conductivity sulfide solid electrolyte membrane according to claim 1, characterized in that, In step 3), the fibrillated binder is one or more of polytetrafluoroethylene, a copolymer of tetrafluoroethylene, ethylene, and hexafluoropropylene; The content of fibrillated binder in the high ionic conductivity sulfide solid electrolyte membrane is 0.1~5 wt.%.

4. The method for preparing a high ionic conductivity sulfide solid electrolyte membrane according to claim 1, characterized in that, In step 3), the thickness of the high ionic conductivity sulfide solid electrolyte membrane is 10~60μm.

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