CN110137565B - Large-scale preparation method of sulfide solid electrolyte - Google Patents
Large-scale preparation method of sulfide solid electrolyte Download PDFInfo
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- CN110137565B CN110137565B CN201910419366.5A CN201910419366A CN110137565B CN 110137565 B CN110137565 B CN 110137565B CN 201910419366 A CN201910419366 A CN 201910419366A CN 110137565 B CN110137565 B CN 110137565B
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
The invention provides a large-scale preparation method of a sulfide solid electrolyte, which comprises the following steps: (1) vacuum drying Li source, Si source, P source, S source and Cl source raw materials; (2) pre-burning the dried raw materials in vacuum at low temperature; (3) crushing the pre-sintered raw materials, and controlling the particle size distribution of the raw materials; (4) screening the crushed raw materials, and controlling the particle size; (5) carrying out magnetic separation and iron removal on the screened raw materials; (6) sequentially adding the Li source, the Si source, the P source, the S source and the Cl source raw materials subjected to magnetic separation and iron removal into a reaction container in batches, wherein a material tray is in a stirring state in the feeding process; (7) premixing the raw materials added into the reaction vessel; (8) and grinding the premixed raw materials. The large-scale preparation method of the sulfide solid electrolyte has the advantages of high precision, good safety, small loss, environmental protection and energy conservation, and can be used for industrial preparation.
Description
Technical Field
The invention belongs to the field of solid electrolytes, and particularly relates to a large-scale preparation method of a sulfide solid electrolyte.
Background
In the process of industrially preparing the sulfide solid electrolyte, the input amount is large, the quality of raw materials is different, certain agglomeration phenomenon exists, the mixing process is continuous and flowing, the ratio of locally mixed materials is greatly different from the original stoichiometric ratio, and the influence of the feeding sequence and the quantity of the raw materials is large, so the expected effect in a laboratory cannot be achieved, the raw materials are not uniformly mixed, and the quality and the yield of products are influenced.
In the preparation process, equipment such as a sand mill and an air flow mill is used, continuous grinding is adopted to improve the production efficiency, the feed amount is large, the grinding effect cannot achieve the effect expected by a laboratory, the material cannot be fully ground, particularly, after the material is not uniformly mixed, the grinding process is not improved, the component proportion of the product may not be the design proportion, and the structure also has large deviation, particularly, components in the shell.
Disclosure of Invention
In view of the above, the present invention is directed to a method for mass production of a sulfide solid electrolyte.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a large-scale preparation method of a sulfide solid electrolyte comprises the following steps:
(1) vacuum drying Li source, Si source, P source, S source and Cl source raw materials;
(2) pre-burning the dried raw materials in vacuum at low temperature;
(3) crushing the pre-sintered raw materials, and controlling the particle size distribution of the raw materials;
(4) screening the crushed raw materials, and controlling the particle size;
(5) carrying out magnetic separation and iron removal on the screened raw materials;
(6) sequentially adding the Li source, the Si source, the P source, the S source and the Cl source raw materials subjected to magnetic separation and iron removal into a reaction container in batches, wherein a material tray is in a stirring state in the feeding process;
(7) premixing the raw materials added into the reaction vessel;
(8) grinding the premixed raw materials;
(9) sintering the ground material in an inert atmosphere to obtain the sulfide solid electrolyte.
Further, the molar ratio of the elements of the raw material is Li: si: p: s: cl (7-12), (0-2), (10-12), (0-1); the Li sourceIs Li2S、LiCl、Li2CO3At least one of LiOH, lithium acetate or metallic lithium; the Si source is SiS2、SiO2At least one of SiC or S; the P source is P2S5Red phosphorus, yellow phosphorus, P2O5Or phosphoric acid; the S source is Li2S、P2S5、SiS2Or S; the Cl source is at least one of LiCl, liquid chlorine, chloroform or chlorine-containing organic matters; the raw materials are LiCl and Li2S、P2S5、SiS2(ii) a The feeding sequence of the raw materials in the step (6) is as follows in sequence: LiCl, Li2S、P2S5、SiS2、LiCl。
Further, the temperature in the vacuum drying step in the step (1) is 105-120 ℃, the vacuum degree is 133Pa-1KPa, and the baking time is 3-10 h. The vacuum drying step can reduce the content of moisture and adsorbed gas in the material.
Further, the temperature of the low-temperature presintering step in the step (2) is 150-; after the crushing step in the step (3) is finished, the particle size of the raw material is D10 of 500nm-1um, D50 of 1um-5um and D90 of 5um-10 um; the particle size of the raw material after the screening step in the step (4) is D10 is 500nm-700nm, D50 is 1um-3um, and D90 is 5um-7 um. And (3) pre-burning the material at a low temperature to reduce organic residues adsorbed on the surface of the material.
And (4) adopting a vibrating screen as the screening equipment in the screening step in the step (4), wherein the vibrating frequency is 2000 times/min, the vibrating range is 0.5-12mm, and the inclination angle is 10-30 degrees.
Further, the magnetic strength of the magnetic separation iron removal step in the step (5) is 10000-. The iron removal by magnetic separation can reduce the content of impurity Fe brought by the reaction vessel.
In the step (6), the feeding sequence is controlled, multiple times of circulating feeding are adopted, the uniformity of the ingredients can be improved, the phenomenon that the adhesion amount of a transfer container (including a mixing container) to a single material is too large, the proportion of the material is unbalanced due to adhesion loss is avoided, the sulfur-containing compound is fully covered by LiCl, the contact surface with air is reduced, the risk of deterioration is reduced, the proportioning accuracy of the raw materials is improved, and the raw materials are proportioned according to the set stoichiometric ratio.
The particle size range of the material after the completion of the premixing step in the step (7) is as follows: d10 is 500nm-1um, D50 is 1um-5um, and D90 is 5um-10 um. The uniform granularity of the materials in the mixing process is controlled, and the problem of raw material agglomeration is reduced. The fluidity and the adhesiveness of various materials are different, the materials are easy to adhere to an impeller and a cylinder wall under the high-speed rotation of a mixer, and the prepared raw materials are premixed in order to ensure that the proportion of the raw materials entering the high-speed mixer is the feeding proportion.
The mixer in the premixing step in the step (7) adopts a vertical mixer, the mixing time is 5-10min, and the mixing is only 500-1000L. The vertical mixer is high in mixing efficiency and good in effect, and has the effects of shortening the production period and improving the subsequent grinding.
Further, the ball-to-material ratio of the grinding step in the step (8) is 2-5: 1, circularly grinding at a linear velocity of 9-15m/s and a filling rate of 70-85 percent, wherein the size of ball milling beads is 1-10 mm; the particle size range of the material after the grinding step in the step (8) is as follows: 500nm-700nm, D50 is 1um-3um, and D90 is 5um-7 um. The ball-material ratio and the grinding frequency are improved, the grinding efficiency is improved, the processes of circular grinding, step-by-step grinding and the like are adopted, the grinding efficiency and the grinding effect are improved, the specific operation is that after the material of the discharge port is collected, the material is further ground, the ball-material ratio is improved, the rotating speed of the grinding disc is improved, and the material is refined and mixed again.
Further, the grinding process in the step (8) comprises the following steps: grinding forward for 20min-1h, then grinding backward for 20min-1h, controlling the turning interval time to be 2-5min, the whole grinding time to be 30-50h, and cooling by water, the temperature of circulating water is 7-15 ℃, and the flow rate of circulating water is 80-100m3The temperature of the grinding cavity is 20-50 ℃, and the surface temperature of the powder is less than or equal to 150 ℃.
Further, the pre-sintering temperature of the sintering step in the step (9) is 120-200 ℃, the sintering temperature is 400-700 ℃, the sintering time is 8-10h, the heating rate is 5-10 ℃/min, the heat preservation temperature is 100-150 ℃, and then the temperature is cooled to the room temperature.
Further, the sintering step in the step (9) carries out preheating treatment on the inlet gas of the inert gas, and the inlet gas temperature is controlled to be 200-250 ℃; the inert gas is Ar or N2。
Further, the material advancing speed in the sintering step in the step (9) is 0.8-1.5 m/h; the temperature control precision of the sintering step in the step (9) ensures that the fluctuation is less than 0.5 ℃ within every 1 m; and (4) vibrating, turning and shaking the materials in the sintering step in the step (9) once every 0.5 h. Ensuring that the material is fired in a reasonable temperature range.
The materials are stirred every 0.5h, the materials can also be uniformly mixed by vibration, a sagger with notches on four sides is adopted, the temperature of the materials in the sagger is ensured to be consistent, and the temperature difference of the working section is less than 3 ℃. The firing process route, the firing time, the turnover blending times and the annealing process are controlled by a computer, so that accurate control is ensured.
Further, the sulfide solid electrolyte prepared in the step (9) is one of A-M-B-C (-X) type crystal sulfide solid electrolytes, wherein A is at least one of Li, Na, Mg or Al; m is at least one of Si, Ge or Sn; b is at least one of P or Sb; c is at least one of O, S or Se; x is at least one of F, Cl, Br or I.
Compared with the prior art, the large-scale preparation method of the sulfide solid electrolyte has the following advantages:
the large-scale preparation method of the sulfide solid electrolyte adopts mechanical grinding and high-temperature treatment to obtain the sulfide solid electrolyte, has high precision of each step, good safety, small loss, environmental protection and energy conservation, and can be used for industrialized preparation.
Drawings
FIG. 1 is a STEM topography of a product in example 1 of the present invention;
FIG. 2 is the EDS results for Si of the product of example 1 of the present invention;
FIG. 3 is the EDS result of P for the product of example 1 of the present invention;
FIG. 4 is the EDS results for S for the product of example 1 of the present invention;
FIG. 5 is a diffraction pattern, calculated by simulation, characterizing a single crystal LSPS in example 1 of the present invention;
FIG. 6 is a diffraction pattern of the product of example 1 of the present invention;
FIG. 7 shows CV test results of the product of example 1 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
A large-scale preparation method of a sulfide solid electrolyte comprises the following steps:
(1) for LiCl, Li2S、P2S5、SiS2(according to the mass ratio of 2.3:38.9:29.3:29.4) vacuum drying the raw materials at the temperature of 120 ℃, the vacuum degree of 133Pa and the baking time of 5h, and then testing the moisture in the materials by using a moisture tester (Wantong switzerland);
(2) pre-burning the dried raw materials at low temperature for 3h at 150 ℃ to reduce organic residues adsorbed on the surfaces of the raw materials;
(3) crushing the pre-sintered raw materials, crushing the materials by a roller crusher (the width of a roller is 500mm, the diameter is 800mm), and controlling the particle size distribution of the raw materials (D10 is 500nm-1um, D50 is 1um-5um, and D90 is 5um-10 um);
(4) screening the crushed raw materials, controlling the particle size, (D10 is 500-700 nm, D50 is 1-3 um, and D90 is 5-7 um), wherein the screening equipment adopts a vibrating screen, the vibration frequency is 2000 times/min, the vibration range is 0.5-12mm, and the inclination angle is 10-30 ℃;
(5) carrying out magnetic separation and iron removal on the screened raw materials, reducing the content of impurity Fe brought by a reaction vessel, wherein the magnetic strength is 12000Gs, and the processing speed is 650-700 Kg/h;
(6) LiCl and Li after magnetic separation and iron removal2S、P2S5、SiS2LiCl (raw materials are sequentially added into a reaction chamber in batches according to the mass ratio of 1.0:38.9:29.3:29.4:1.3), a material tray is in a stirring state in the feeding process, the feeding sequence is controlled, multiple times of circulating feeding is adopted, the uniformity of material mixing can be improved, the problem that the proportion of a transfer container and a mixing container is unbalanced due to adhesion loss of a single material due to overlarge adhesion amount of the transfer container and the mixing container is solved, a sulfur-containing compound is fully covered by LiCl, the contact surface with air is reduced, the risk of deterioration is reduced, the proportioning accuracy of the raw materials is improved, the raw materials are proportioned according to a set stoichiometric ratio, a high-accuracy weighing sensor is selected for weighing, and the accuracy (brand: Transcell) of the weighing process is improved;
(7) premixing raw materials added into a reaction container, controlling the uniform particle size of the materials (D10 is about 600nm, D50 is about 3um and D90 is about 7um) in the mixing process, reducing the agglomeration problem of the raw materials, wherein a vertical mixer is adopted as the mixer, the mixing time is 5min, the raw materials are simply mixed at 500L, and the raw materials are subjected to sampling inspection and analysis;
(8) grinding and mixing the premixed raw materials, wherein the ball material ratio is 3: 1, linear velocity of 12m/s, filling rate of 80%, collecting material after finishing, the particle size range of material after finishing grinding is: d10 is about 150nm, D50 is about 1um, D90 is about 2 um;
(9) sintering the ground material under the protection of Ar, arranging double-row three-layer saggars, wherein the temperature of the front section is about 200 ℃, the temperature of the middle section is about 470 ℃, the temperature of the tail section is about 150 ℃, the stepping speed of a material trolley is about 1.2m/h, the sintering time is 8 hours, the heating speed is about 5 ℃/min, preheating inlet air, avoiding influencing the temperature distribution in the kiln, controlling the inlet air temperature to be 250 ℃, utilizing a pressure sensor and an automatic flowmeter to realize the dynamic balance of the air inlet amount and the pressure in the kiln, uniformly distributing circulating gas in the kiln in a kiln way, particularly ensuring the temperature circulation in the multilayer saggars, selecting high-precision thermocouples (nickel-chromium-copper-nickel thermocouples, adopting platinum-rhodium thermocouples for local precise temperature control), reasonably arranging thermocouple distribution intervals, and improving the temperature balance of the ground materialControlling the temperature of the kiln, ensuring the fluctuation within 1m to be less than 0.5 ℃ by the temperature control precision, ensuring that the material is fired within a reasonable temperature range, turning the material every 0.5h, uniformly mixing by vibration, ensuring that the temperature of the material in a sagger is consistent by adopting the sagger with notches on four sides, ensuring that the temperature difference of a working section is less than 3 ℃, controlling the firing process route, the firing time, the turnover mixing frequency and the annealing process by a computer, ensuring accurate control, and obtaining the LGPS crystal sulfide solid electrolyte (Li-phase lithium sulfide) after the sintering is finished9.54Si1.74P1.44S11.7Cl0.3)。
The grinding process comprises the following steps: grinding for 1h in forward direction, grinding for 1h in reverse direction, controlling turning interval time to be 5-10min, and water cooling, circulating water temperature being 12 deg.C, circulating water flow rate being 80m3The temperature of the grinding cavity is 30 ℃, and the surface temperature of the powder cannot exceed 150 ℃.
The material transfer process adopts sealing treatment (aluminum plastic film vacuum sealing with the thickness of 0.5 mm), the material pumping pipeline is adopted in the delivery and batching process, raw materials are transported by the pipeline, the raw material loss and pollution caused by multiple transfer are avoided, the pipeline adopts a multilayer composite structure, the outer layer is made of stainless steel, the inner layer is a friction-resistant and smooth layer, and the material is Teflon or polyurethane.
The material transfer adopts wear-resistant stainless steel pipeline to convey, avoids contacting with air, and the transportation atmosphere adopts inert atmosphere (Ar/N)2) And automatic weighing and proportioning are adopted, so that the production efficiency is improved, and the material is prevented from deteriorating due to reaction with air. The gas inlet and outlet are specially recovered by pipelines in the sintering process, and are subjected to centralized purification treatment (dust removal, dehydration and H adsorption)2S, etc.), and the protective gas utilization rate is improved by reutilization. Meanwhile, the heat of the tail gas can be utilized to heat the inlet gas, which is beneficial to the temperature control in the material firing process. The humidity control is needed in the production line construction site, the dew point is generally controlled to be-40 ℃, and the side reaction of the material caused by moisture and the generation of toxic and harmful gas are avoided.
The method adopts high-precision sensors (weighing sensors, displacement sensors, pressure sensors, temperature sensors, gas sensors, water oxygen sensors and the like), automatically weighs raw materials, monitors proportioning and mixing effects, monitors the temperature and the ball-material ratio in the grinding process in real time, periodically and randomly inspects mixed materials, a laser particle size analyzer and a desktop SEM (scanning electron microscope), quickly analyzes the grinding effect (particle size distribution and surface morphology), monitors the atmosphere in a transmission pipeline and a kiln in real time (particularly water partial pressure and oxygen partial pressure), monitors the temperature and gas content in the kiln, automatically adjusts the speed of the materials entering the kiln, and ensures that all reactions are carried out according to design requirements.
The LGPS type crystalline sulfide solid electrolyte (Li) prepared in example 19.54Si1.74P1.44S11.7Cl0.3) The shape, components, particle size, crystal structure and electrochemical performance of the material are accurately characterized by using various detection methods, and the results are as follows:
1. and acquiring the information of the shape, the composition and the particle size of the product by using a Scanning Transmission Electron Microscope (STEM) technology and an energy dispersive X-ray spectroscopy (EDS) technology. The interference of air to the sample is reduced or eliminated during the transferring process of the sample. Specific results are shown in FIGS. 1-4. From the STEM results in fig. 1, it can be known that the material is mainly divided into two parts, the center is the core structure of the sample, the outer part of the core structure is uniformly wrapped with a thin layer of shell structure, and the outer shape of the shell has smooth radian and uniform thickness, so as to form a good sphere. From the EDS plots of fig. 2-4, it is known that the compositions of the "core" and "shell" of the samples are Si, P, S (Li cannot be detected by EDS, not shown), but the shell is very thin in the direction of electron beam travel relative to the core, and the X-ray signal generated is much weaker than the core, and therefore the EDS signal is weak. The EDS results were consistent with the experimental design material composition. In addition, the particle size of the "core" is about 6um, the thickness of the shell is about 1.5um, and the particle size of the LSPS bulk particle is about 9 um.
2. The crystal structure information of the sample was acquired using an X-ray diffractometer (XRD). Testing main parameters: the Cu target has a scanning step of 0.02 degrees and a scanning range of 10-70 degrees, and specific results are shown in FIGS. 5-6. The standard diffraction peak spectrum of the LSPS simulated by software and the diffraction peak spectrum of the experimental product are contrastively analyzed, all peak positions of the standard diffraction peak spectrum and the diffraction peak spectrum of the experimental product can correspond to each other, and the standard diffraction peak spectrum and the diffraction peak spectrum belong to a space group P42/nmc,137, crystal structures of the experimental products andthe LSPS single crystal structure is completely consistent. The results of experimental analysis by STEM-EDS are combined, so that the synthesized product can be judged to be LSPS, and the main part of the synthesized product is crystalline. After the XRD diffraction peak of the product is refined, fitted and analyzed, the lattice parameter a is 8.7008667, and c is 12.6071594, which is completely consistent with the lattice parameter in the standard structure of software simulation LSPS, so that the synthesized product is pure LSPS and is consistent with the experimental design.
3. And acquiring electrochemical stability information of the sample by using Cyclic Voltammetry (CV). Testing main parameters: the voltage range is 2.5-4.0V, the scanning rate is 0.1mV/s, the electrochemical cell system is Li/glass fiber/LSPS-Cl + C/Au, and the specific results are shown in FIG. 7. From the results, it can be seen that the initial oxidative decomposition voltage of the product synthesized by the method described in example 1 is increased to about 3.09V, which is much higher than the currently generally accepted initial oxidative decomposition voltage (2.1V) of LSPS material. And the product has small oxidative decomposition current density in a high voltage range of 3-5V, and the high voltage resistance is relatively excellent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A large-scale preparation method of a sulfide solid electrolyte is characterized by comprising the following steps: the method comprises the following steps:
(1) vacuum drying Li source, Si source, P source, S source and Cl source raw materials; the molar ratio of the elements of the raw material is Li: si: p: s: cl (7-12) (0-2) (10-12) (0-1), and the lower limit does not include 0;
(2) carrying out low-temperature vacuum pre-sintering on the dried raw materials at the temperature of 150-;
(3) crushing the pre-sintered raw materials, and controlling the particle size distribution of the raw materials;
(4) screening the crushed raw materials, and controlling the particle size D50 to be 1-3 um after screening;
(5) carrying out magnetic separation and iron removal on the screened raw materials;
(6) sequentially adding the Li source, the Si source, the P source, the S source and the Cl source raw materials subjected to magnetic separation and iron removal into a reaction container in batches, wherein a material tray is in a stirring state in the feeding process;
(7) premixing the raw materials added into the reaction vessel;
(8) carrying out circulating grinding on the premixed raw materials, controlling the surface temperature of the powder to be less than or equal to 150 ℃, and the particle size range after grinding is as follows: d50 is 200nm-1 um;
(9) sintering the ground material in an inert atmosphere to obtain the sulfide solid electrolyte.
2. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: the Li source is Li2S、LiCl、Li2CO3At least one of LiOH, lithium acetate or metallic lithium; the Si source is SiS2、SiO2At least one of SiC or S; the P source is P2S5Red phosphorus, yellow phosphorus, P2O5Or phosphoric acid; the S source is Li2S、P2S5、SiS2Or S; the Cl source is at least one of LiCl, liquid chlorine, chloroform or chlorine-containing organic matters; the raw materials are LiCl and Li2S、P2S5、SiS2(ii) a The feeding sequence of the raw materials in the step (6) is as follows in sequence: LiCl, Li2S、P2S5、SiS2、LiCl。
3. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: in the step (1), the temperature in the vacuum drying step is 105-; the pre-sintering time of the low-temperature pre-sintering step in the step (2) is 1-5 h; after the crushing step in the step (3) is finished, the particle size of the raw material is D10 of 500nm-1um, D50 of 1um-5um and D90 of 5um-10 um; the particle size of the raw material after the screening step in the step (4) is 500nm-700nm D10, and 5um-7um D90.
4. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: the magnetic strength of the magnetic separation iron removal step in the step (5) is 10000-; the particle size range of the material after the completion of the premixing step in the step (7) is as follows: d10 is 500nm-700nm, D50 is 1um-3um, and D90 is 5um-7 um.
5. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: the ball-material ratio of the grinding step in the step (8) is 2-5: 1, circularly grinding at a linear velocity of 9-15m/s and a filling rate of 70-85 percent, wherein the size of ball milling beads is 1-10 mm; the particle size range of the material after the grinding step in the step (8) is as follows: d10 is 50-200nm, and D90 is 1-2 um.
6. The large-scale production method of a sulfide solid electrolyte according to claim 5, characterized in that: the grinding process in the step (8) comprises the following steps: grinding forward for 20min-1h, then grinding backward for 20min-1h, controlling the turning interval time to be 2-5min, the whole grinding time to be 30-50h, and cooling by water, the temperature of circulating water is 7-15 ℃, and the flow rate of circulating water is 80-100m3The temperature of the grinding cavity is 20-50 ℃.
7. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: the presintering temperature of the sintering step in the step (9) is 200 ℃ plus 120 ℃, the sintering temperature is 700 ℃ plus 400 ℃, the sintering time is 8-10h, the heating rate is 5-10 ℃/min, the heat preservation temperature is 150 ℃ plus 100 ℃, and then the temperature is cooled to the room temperature.
8. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: in the step (9), the sintering step carries out preheating treatment on the inlet gas of the inert gas, and the inlet gas temperature is controlled to be 200-250 ℃; the inert gasThe body is Ar or N2。
9. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: the material advancing speed in the sintering step in the step (9) is 0.8-1.5 m/h; the temperature control precision of the sintering step in the step (9) ensures that the fluctuation is less than 0.5 ℃ within every 1 m; and (4) vibrating, turning and shaking the materials in the sintering step in the step (9) once every 0.5 h.
10. The large-scale production method of a sulfide solid electrolyte according to claim 1, characterized in that: the sulfide solid electrolyte prepared in the step (9) is one of A-M-B-C (-X) type crystal sulfide solid electrolytes, wherein A is at least one of Li, Na, Mg or Al; m is at least one of Si, Ge or Sn; b is at least one of P or Sb; c is at least one of O, S or Se; x is at least one of F, Cl, Br or I.
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| JP7243662B2 (en) * | 2020-02-21 | 2023-03-22 | トヨタ自動車株式会社 | Method for producing sulfide solid electrolyte |
| CN111943263B (en) * | 2020-08-24 | 2022-11-11 | 中创新航技术研究院(江苏)有限公司 | Solid electrolyte, preparation method thereof and solid battery |
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