CN109888373B - Organic/inorganic composite solid electrolyte and preparation method thereof - Google Patents
Organic/inorganic composite solid electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic/inorganic composite solid electrolyte and a preparation method thereof, sulfide is pretreated, the pretreated sulfide is subjected to high-temperature heat treatment to obtain a sulfur-based solid electrolyte, and the sulfur-based solid electrolyte, an organic polymer and lithium salt are added into an organic solvent to be mixed; removing the organic solvent, and drying to obtain the organic/inorganic composite solid electrolyte. The inner layer of the organic/inorganic composite solid electrolyte material is sulfur-based solid electrolyte, the organic polymer is coated on the outer side of the sulfur-based solid electrolyte, the sulfur-based solid electrolyte is of a three-phase or more structure, or the organic/inorganic composite electrolyte is composed of two-phase sulfide solid electrolyte and low decomposition temperature polymer organic matter, the activity of the obtained organic/inorganic composite solid electrolyte is improved, the conductivity is improved, and the improvement of the cycle performance of the lithium-sulfur battery is facilitated.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to preparation and application of a lithium ion battery solid electrolyte.
Background
The lithium ion battery has the characteristics of high energy density, long cycle life, no memory effect and the like, and is widely applied to the aspects of daily consumer electronics, electric automobiles, power grid energy storage and the like. At present, the commercial lithium ion battery generally adopts organic liquid electrolyte and gel electrolyte, the liquid electrolyte and the gel electrolyte have higher ionic conductivity, but the battery has serious potential safety hazard problems due to the fact that the battery contains volatile, flammable and explosive organic solvents. The solid electrolyte can effectively solve the problem of potential safety hazard caused by the liquid electrolyte of the lithium ion battery, and simultaneously, the solid electrolyte can inhibit the generation of lithium dendrite in the battery cycle process, so that the metal lithium can be used as the battery cathode, and the energy density of the lithium ion battery is further improved. The key of the development and application of the all-solid-state battery is a solid electrolyte, the current solid electrolyte mainly comprises an organic electrolyte and an inorganic electrolyte, wherein the organic solid electrolyte has the characteristics of good flexibility, good film forming property, viscoelasticity and light weight, but has the problems of poor mechanical property and low ionic conductivity at room temperature, and the inorganic solid electrolyte has the advantages of high conductivity at room temperature and wide electrochemical window, but has poor film forming property, so that the composite solid electrolyte prepared by combining the organic solid electrolyte and the inorganic solid electrolyte can effectively combine respective advantages to form the solid electrolyte with good ionic conductivity and mechanical property.
Sulfur-based solid electrolyteHas high ionic conductivity and wide electrochemical window, and is considered to be one of the most promising solid electrolytes. However, the sulfide solid electrolyte reacts with the interface of the metallic lithium cathode, so that the sulfur-based solid electrolyte is decomposed, the interface resistance of the electrolyte and the metallic lithium is increased, and the electrochemical cycle performance of the solid battery is affected. The organic solid electrolyte has good film-forming properties and flexibility, but has low ionic conductivity at room temperature. For example, patent No. CN 105680092A proposes that adding certain silicon dioxide to reduce the crystallinity of organic polymer so as to improve the ionic conductivity of organic solid electrolyte, and the ionic conductivity is 10 ℃ after 60 ℃ test-4S/cm, relative to the current commercial application of-10 at room temperature-2The ionic conductivity of S/cm is much lower. The sulfide prepared by the liquid phase method has the characteristics of simple and controllable operation, but the organic/inorganic composite solid electrolyte formed in situ by the liquid phase has certain limitation.
Disclosure of Invention
In view of the problems in the prior art described above, it is an object of the present invention to provide a method for producing a composite solid electrolyte material.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a composite solid electrolyte material comprises the following specific steps:
(1) pretreating the sulfide;
(2) carrying out heat treatment on the pretreated sulfide obtained in the step (1) at a certain high temperature to obtain a sulfur-based solid electrolyte;
(3) adding the sulfur-based solid electrolyte obtained in the step (2), an organic polymer and lithium salt into an organic solvent for mixing;
(4) removing the organic solvent and drying.
The preparation of the organic/inorganic composite solid electrolyte material can effectively solve the problem that some sulfides can not synthesize three-phase or more sulfur-based solid electrolytes in a liquid-phase organic solvent, and simultaneously avoids the decomposition of organic polymers caused by overhigh heat treatment temperature. The method is suitable for three-phase and above sulfur-based solid electrolytes and is also suitable for organic polymer electrolytes with low decomposition temperature. The organic solid electrolyte coats the surface of the sulfur-based solid electrolyte, so that direct contact between the metal lithium and the sulfur-based solid electrolyte is isolated, and interface reaction between the sulfur-based solid electrolyte and a metal lithium cathode is inhibited, so that the solid electrolyte and the metal lithium have good interface compatibility. Meanwhile, the composite electrolyte adopts the organic solid electrolyte to carry out in-situ coating on the sulfur-based solid electrolyte, and the organic electrolyte can be filled among inorganic electrolyte particles, so that the interface resistance among the sulfur-based solid electrolyte particles is effectively reduced, and the ionic conductivity of the solid electrolyte at room temperature is further improved.
The sulfur-based solid electrolyte with the three-phase or above structure has the functions of improving the ionic conductivity of the sulfur-based solid electrolyte, expanding the electrochemical window of the electrolyte, reducing the chemical and electrochemical activity of the electrolyte and improving the stability of the electrolyte.
Preferably, the sulfide in the step (1) is a mixture of lithium sulfide and phosphorus pentasulfide.
The mixture of lithium sulfide and phosphorus pentasulfide is heat treated to form the sulfur-base solid electrolyte with two-phase structure.
Preferably, the sulfide in the step (1) is a combination of lithium sulfide, a mixture of phosphorus pentasulfide and one or more of aluminum sulfide, germanium sulfide, silicon sulfide, tin sulfide, selenium sulfide and molybdenum sulfide.
Because the sulfide activity of aluminum sulfide, germanium sulfide, silicon sulfide, tin sulfide, selenium sulfide and molybdenum sulfide is low, three-phase or above-three-phase sulfur-based solid electrolyte can not be prepared in an organic solution through liquid-phase reaction, and the problem can be effectively solved by adopting a solid-state reaction method.
Preferably, the pretreatment in step (1) is carried out by grinding or ball milling.
Preferably, the temperature of the heat treatment in the step (2) is in the range of 200 ℃ to 900 ℃; preferably 250 ℃ to 800 ℃.
The heat treatment process affects the microstructure of the obtained sulfur-based solid electrolyte, and the structure of the obtained sulfur-based solid electrolyte is three-phase or more crystal structure within the above heat treatment temperature range, and if the temperature is low or too high, the electrolyte material cannot be crystallized or cannot form a specific crystal phase, which directly affects the ionic conductivity of the electrolyte material.
Preferably, the heat treatment time in the step (2) is in the range of 2h-20 h; preferably from 2h to 12 h.
Preferably, the organic polymer in step (3) is one of PPC, PEC, PEG, PVCA, PSI, PEO, PMMA, PVA, PVDF.
The organic polymer comprises different substances with lower pyrolysis temperature and higher pyrolysis temperature, and the different pyrolysis temperatures of the organic polymer have no influence on the organic/inorganic composite solid electrolyte material in the application, because the preparation method of the application arranges the heat treatment of the sulfur-based solid electrolyte before the organic/inorganic composite solid electrolyte material is formed, the pyrolysis temperature of the organic polymer can be reduced, the realizability of the preparation method is ensured, the application range is wide, and the preparation method is simultaneously suitable for two-phase sulfide Li2S-P2S5And compounding with organic polymer with low decomposition temperature to form the organic/inorganic solid electrolyte.
Preferably, the lithium salt in the step (3) is LiClO4LiBF4, LiBOB, LiDFOB, LiDTI, LiTFSI, LiFSI.
Preferably, the molar ratio of the organic polymer to the lithium salt in the step (3) is 1:1 to 50:1, preferably 3:1 to 30: 1.
Preferably, the mass ratio of the sulfur-based solid electrolyte to the mixture of organic polymer and lithium salt in step (3) is 1:1 to 250:1, preferably 10:1 to 150: 1.
Preferably, the organic solvent in step (3) is one of acetonitrile, tetrahydrofuran, dimethyl ether, N-methylformamide, 1, 2-dimethoxyethane and N-heptane.
Preferably, the mixing mode of the sulfur-based solid electrolyte, the organic polymer, the lithium salt and the organic solvent in the step (3) is magnetic stirring.
The inorganic solid electrolyte, the organic polymer and the lithium salt can be fully and uniformly mixed in the solution.
Preferably, the magnetic stirring time in the step (3) is between 20h and 60h, preferably between 24h and 40 h.
Preferably, the method for removing the organic solvent in the step (4) is suction filtration, rotary evaporation to dryness, vacuum evaporation and the like.
Preferably, the temperature for drying in the step (4) is 50-200 ℃, preferably 50-120 ℃.
Preferably, the drying time of the solution in the step (4) is in the range of 12-48h, preferably 24-40 h.
The organic/inorganic composite solid electrolyte material prepared by the preparation method has the advantages that the inner layer of the organic/inorganic composite solid electrolyte material is a sulfur-based solid electrolyte, the organic polymer solid electrolyte formed by lithium salt is coated on the outer side of the sulfur-based solid electrolyte, and the sulfur-based solid electrolyte has a three-phase structure or more.
The organic/inorganic composite solid electrolyte material is applied to lithium ion batteries, super capacitors and the like.
The all-solid-state lithium ion battery is obtained by assembling the sulfur simple substance as a positive electrode, the organic/inorganic composite solid electrolyte material as an electrolyte and the metal lithium as a negative electrode.
The invention has the beneficial effects that:
(1) according to the organic/inorganic composite solid electrolyte material prepared by the invention, the sulfur-based solid electrolyte is coated in situ by the organic solid electrolyte, and the organic electrolyte can be filled among inorganic electrolyte particles, so that the interface resistance among the sulfur-based solid electrolyte particles is effectively reduced, and the ionic conductivity of the solid electrolyte at room temperature is further improved.
(2) According to the organic/inorganic composite solid electrolyte material prepared by the invention, the sulfur-based solid electrolyte is coated on the surface by the organic solid electrolyte, so that the direct contact between the metal lithium and the sulfur-based solid electrolyte is isolated, the interface reaction between the sulfur-based solid electrolyte and the metal lithium cathode is inhibited, and the solid electrolyte and the metal lithium have good interface compatibility.
(3) The preparation method of the organic/inorganic composite solid electrolyte material can effectively solve the problem that some specific sulfides can not synthesize three-phase or more sulfur-based solid electrolytes in liquid-phase organic solution. And simultaneously avoids the decomposition of the organic polymer caused by overhigh heat treatment temperature. The method is suitable for three-phase and above sulfur-based solid electrolytes and two-phase sulfide Li2S-P2S5An organic/inorganic composite electrolyte formed by an electrolyte and an organic polymer with low decomposition temperature.
(4) The invention adopts the organic/inorganic composite solid electrolyte to assemble the battery, and can avoid the potential safety hazard problem of the use of the organic electrolyte.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a scanning electron microscope image of the organic/inorganic composite solid electrolyte obtained in example 1;
FIG. 2 is an XRD pattern of the organic/inorganic composite solid electrolyte obtained in example 1;
FIG. 3 is a scanning electron microscope image of the organic/inorganic composite solid electrolyte obtained in example 2;
FIG. 4 is an XRD pattern of the organic/inorganic composite solid electrolyte obtained in example 2;
fig. 5 is a graph of electrochemical cycle performance of an all solid-state lithium sulfur battery assembled with a composite electrolyte.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention will be further illustrated by the following examples
Example 1
Grinding and mixing lithium sulfide and phosphorus pentasulfide in a molar ratio of 1:1 in a mortar, performing ball milling in a ball mill for 6h, performing heat treatment at 280 ℃ for 4h to obtain a sulfur-based solid electrolyte, and mixing PMMA polymer and LiClO4Mix in a 10:1 molar ratio, sulfide powder with polymer/lithium salt at a ratio of 9: adding the mixture into n-heptane according to the mass ratio of 1, magnetically stirring the mixture for 12 hours at the temperature of 50 ℃, removing the organic solvent by using a rotary evaporation method, and drying the mixture at the temperature of 80 ℃ to obtain the organic/inorganic composite solid electrolyte. The coating layer of organic polymer has a thickness of 20-30nm and an ionic conductivity of 10 at room temperature-4S/cm。
On one hand, the preparation method is suitable for preparing three-phase and above sulfur-based solid electrolytes and is also suitable for organic polymer electrolytes with low decomposition temperature. In addition, the composite electrolyte adopts the organic solid electrolyte to carry out in-situ coating on the sulfur-based solid electrolyte, and the organic electrolyte can be filled among inorganic electrolyte particles, so that the interface resistance among the sulfur-based solid electrolyte particles is effectively reduced, and the ionic conductivity of the solid electrolyte at room temperature is further improved. Meanwhile, the organic solid electrolyte coats the surface of the sulfur-based solid electrolyte, so that direct contact between the metal lithium and the sulfur-based solid electrolyte is isolated, and interface reaction between the sulfur-based solid electrolyte and a metal lithium cathode is inhibited, so that the solid electrolyte and the metal lithium have good interface compatibility. Meanwhile, the all-solid-state battery assembled by the composite solid electrolyte can effectively solve the interface problem of the metal lithium and the sulfur-based solid electrolyte, and avoid potential safety hazards caused by the metal lithium.
Fig. 1 is a scanning electron microscope image of the organic/inorganic composite solid electrolyte material prepared in example 1, and fig. 2 is an XRD image of the organic/inorganic composite solid electrolyte material prepared in example 1. As can be seen from fig. 1 and 2, the inorganic solid electrolyte is micron-sized particles, and the organic polymer solid electrolyte is coated on the surface of the particles.
Example 2
Performing ball milling on lithium sulfide, phosphorus pentasulfide and germanium sulfide for 12 hours in a ball mill at a molar ratio of 5:2:1, performing heat treatment for 6 hours at 600 ℃ to obtain a sulfur-based solid electrolyte, mixing PVDF polymer and LiTFSI at a molar ratio of 30:1, and mixing sulfide powder with polymer/lithium salt according to a molar ratio of 1: adding the mixture into acetonitrile according to the mass ratio of 1, magnetically stirring the mixture for 48 hours at room temperature, removing the organic solvent by using a suction filtration method, and drying the mixture at the temperature of 50 ℃ to obtain the organic/inorganic composite solid electrolyte. The thickness of the coating layer of the organic polymer is 100-120nm, and the ionic conductivity is 10 to the room temperature-3S/cm。
A scanning electron microscope image of the organic/inorganic composite solid electrolyte material prepared in example 2 and fig. 4 is an XRD image of the organic/inorganic composite solid electrolyte material prepared in example 2. As can be seen from fig. 3 and 4, the inorganic solid electrolyte is micron-sized particles, and the organic polymer solid electrolyte is coated on the surface of the particles.
Example 3
Carrying out ball milling on lithium sulfide, phosphorus pentasulfide and aluminum sulfide for 16h in a ball mill according to a molar ratio of 6:2:1, carrying out heat treatment for 10h at 400 ℃ to obtain a sulfur-based solid electrolyte, mixing a PEO polymer and LiTFSI according to a molar ratio of 5:1, adding sulfide powder and a polymer/lithium salt into tetrahydrofuran according to a mass ratio of 150:1, carrying out magnetic stirring for 36h at room temperature, removing an organic solvent by using a suction filtration method, and drying at 120 ℃ to obtain the organic/inorganic composite solid electrolyte. The coating layer of the organic polymer has a thickness of 5 to 10nm and an ionic conductivity of 10 to 10 at room temperature-5S/cm。
The organic/inorganic composite solid electrolyte prepared in example 1 was used to assemble an all-solid lithium ion battery, elemental sulfur was used as a positive electrode, and a metal lithium sheet was used to assemble an all-solid lithium sulfur battery.
Fig. 5 shows the result of the electrochemical cycling performance test of the lithium-sulfur battery assembled with the organic/inorganic composite solid electrolyte, and it can be seen from the figure that the organic/inorganic solid electrolyte has good ionic conductivity and can improve the interface stability with the metallic lithium cathode, so that the all-solid battery has good electrochemical cycling performance.
Comparative example 1
Grinding and mixing lithium sulfide and phosphorus pentasulfide in a molar ratio of 1:1 in a mortar, performing ball milling for 6 hours in a ball mill, and mixing PMMA polymer and LiClO4Mix in a 10:1 molar ratio, sulfide powder with polymer/lithium salt at a ratio of 9: adding 1 mass ratio of the organic/inorganic composite solid electrolyte into n-heptane, magnetically stirring for 12h at 50 ℃, removing the organic solvent by using a rotary evaporation method, drying at 80 ℃, and carrying out heat treatment for 4h at 280 ℃ to obtain the organic/inorganic composite solid electrolyte.
The organic solid electrolyte obtained in example 1 is used to coat the sulfur-based solid electrolyte in situ, and can be filled between inorganic electrolyte particles to form an organic/inorganic composite electrolyte. In contrast, comparative example 1, in which the PMMA segment was decomposed at a temperature higher than the decomposition temperature of the organic polymer PMMA, the resulting sulfur-based solid electrolyte had no good polymer coating structure and had an ionic conductivity as low as 10 at room temperature-7S/cm。
Comparative example 2
Performing ball milling on lithium sulfide, phosphorus pentasulfide and germanium sulfide for 12 hours in a ball mill at a molar ratio of 5:2:1, performing heat treatment for 6 hours at 300 ℃ to obtain a sulfur-based solid electrolyte, mixing PVDF polymer and LiTFSI at a molar ratio of 30:1, and mixing sulfide powder with polymer/lithium salt according to a molar ratio of 1: adding the mixture into acetonitrile according to the mass ratio of 1, magnetically stirring the mixture for 48 hours at room temperature, removing the organic solvent by using a suction filtration method, and drying the mixture at the temperature of 50 ℃ to obtain the organic/inorganic composite solid electrolyte.
By comparing the organic/inorganic composite solid electrolytes obtained in example 2 and comparative example 2, Li in example 2, which can be three-phase by high-temperature heat treatment, can be obtained10GeP2S12A sulfur-based solid electrolyte of phase having a conductivity of-10 at room temperature- 3S/cm, and the sulfide material cannot be crystallized by heat treatment at 300 DEG CLi in three phases10GeP2S12Phase of very low ionic conductivity of 10 at room temperature-7S/cm。
Comparative example 3
Lithium sulfide, phosphorus pentasulfide and germanium sulfide are ball milled in a ball mill for 12 hours at a molar ratio of 5:2:1, PVDF polymer and LiTFSI are mixed at a molar ratio of 30:1, sulfide powder and polymer/lithium salt are mixed in a ratio of 1: adding the mixture into acetonitrile according to the mass ratio of 1, magnetically stirring the mixture for 48 hours at room temperature, removing the organic solvent by using a suction filtration method, drying the mixture at the temperature of 50 ℃, and carrying out heat treatment on the mixture for 6 hours at the temperature of 200 ℃ to obtain the organic/inorganic composite solid electrolyte.
The difference between comparative example 3 and example 2 is that the heat treatment step after the drying, the temperature of the heat treatment cannot be too high because the pyrolysis temperature is low in the organic polymer to avoid decomposition of the organic polymer solid electrolyte. After heat treatment at low temperature of 200 ℃ in comparative example 3, the lithium sulfide-phosphorus pentasulfide-germanium sulfide mixed sulfide could not be crystallized to form three-phase Li10GeP2S12A phase which is substantially non-ionically conductive to lithium ions at room temperature.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (4)
1. A preparation method of a composite solid electrolyte material is characterized by comprising the following steps: the method comprises the following specific steps:
performing ball milling on lithium sulfide, phosphorus pentasulfide and germanium sulfide for 12 hours in a ball mill according to a molar ratio of 5:2:1, performing heat treatment for 6 hours at 600 ℃ to obtain a sulfur-based solid electrolyte, mixing PVDF polymer and LiTFSI according to a molar ratio of 30:1, and mixing sulfur-based solid electrolyte powder with polymer/lithium salt according to a molar ratio of 1: adding the mixture into acetonitrile according to the mass ratio of 1, magnetically stirring the mixture for 48 hours at room temperature, removing an organic solvent by using a suction filtration method, and drying the mixture at the temperature of 50 ℃ to obtain an organic/inorganic composite solid electrolyte; of organic polymersThe thickness of the coating layer is 100-120nm, and the ion conductivity is 10 at room temperature-3 S/cm。
2. The organic/inorganic composite solid electrolyte material prepared by the preparation method of claim 1, characterized in that: the inner layer of the organic/inorganic composite solid electrolyte material is a sulfur-based solid electrolyte, the outer side of the sulfur-based solid electrolyte is coated with an organic polymer, and the sulfur-based solid electrolyte is of a three-phase structure.
3. Use of the organic/inorganic composite solid electrolyte material according to claim 2 in lithium ion batteries, supercapacitors.
4. An all-solid-state lithium ion battery, which is obtained by assembling the organic/inorganic composite solid electrolyte material of claim 2 as an electrolyte, a sulfur simple substance as a positive electrode, and metallic lithium as a negative electrode.
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| CN110247112A (en) * | 2019-06-25 | 2019-09-17 | 哈尔滨工业大学 | A kind of high wettability sulfide based composite electrolyte and the preparation method and application thereof of " sandwich " structure |
| CN110247109B (en) * | 2019-07-16 | 2021-06-01 | 广州天赐高新材料股份有限公司 | Sulfide solid electrolyte and preparation method and application thereof |
| CN110444806B (en) * | 2019-08-06 | 2022-11-18 | 深圳大学 | Sulfide solid electrolyte precursor solution and preparation method and application thereof |
| CN110518279B (en) * | 2019-09-09 | 2021-11-23 | 厦门大学 | Composite solid electrolyte of PEO-coated activated nanoparticles and preparation method thereof |
| TWI737011B (en) * | 2019-10-22 | 2021-08-21 | 輝能科技股份有限公司 | Adjusting material for contact surface of solid electrolyte and composite electrolyte system thereof |
| CN114069034A (en) * | 2020-07-31 | 2022-02-18 | 北京小米移动软件有限公司 | Composite solid electrolyte, preparation method thereof, battery and terminal |
| CN111883822A (en) * | 2020-08-21 | 2020-11-03 | 山东大学 | Sulfide solid electrolyte with stable performance and preparation method and application thereof |
| CN112768761B (en) * | 2021-02-25 | 2022-06-07 | 江汉大学 | Sulfide solid electrolyte and preparation method and application thereof |
| CN112768762B (en) * | 2021-02-26 | 2023-08-22 | 浙江锋锂新能源科技有限公司 | Carbon sulfide-containing solid electrolyte for solid lithium battery and preparation method thereof |
| CN113851700A (en) * | 2021-09-24 | 2021-12-28 | 成都汉普高新材料有限公司 | Preparation method of lithium germanium phosphorus sulfur for all-solid-state battery material |
| CN113851629A (en) * | 2021-09-24 | 2021-12-28 | 成都汉普高新材料有限公司 | Preparation method of lithium phosphorus sulfur chloride used for all-solid-state battery material |
| CN114335699B (en) * | 2021-12-31 | 2024-05-14 | 深蓝汽车科技有限公司 | Core-shell structure composite solid electrolyte and preparation method thereof |
| CN114524416A (en) * | 2022-02-21 | 2022-05-24 | 山东大学 | Lithium sulfide coated sulfide solid electrolyte and preparation method and application thereof |
| CN116093420B (en) * | 2022-10-17 | 2023-11-17 | 中国科学院精密测量科学与技术创新研究院 | Seleno sulfide solid electrolyte material and preparation method thereof |
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