CN117276642A - Sodium ion sulfide electrolyte and preparation method and application thereof - Google Patents

Sodium ion sulfide electrolyte and preparation method and application thereof Download PDF

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CN117276642A
CN117276642A CN202311030496.2A CN202311030496A CN117276642A CN 117276642 A CN117276642 A CN 117276642A CN 202311030496 A CN202311030496 A CN 202311030496A CN 117276642 A CN117276642 A CN 117276642A
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sodium ion
electrolyte
sodium
sulfide electrolyte
ball milling
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张怡
游佳乐
平叶子
陈炽超
赵国伟
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Huanggang Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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    • C01—INORGANIC CHEMISTRY
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    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic

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Abstract

The invention discloses a sodium ion sulfide electrolyte, a preparation method and application thereof, belonging to the field of sodium ion battery electrolyte materials, wherein the sodium ion sulfide electrolyte is Na with a cubic phase structure 6 PS 5 Cl 1‑x (BF 4 ) x The preparation method comprises the following steps: raw material Na 2 S、P 2 S 5 NaCl and NaBF 4 Pouring into a ball milling tank, uniformly mixing, pressing into compact discs under certain pressure, and placing in a vacuum environment for calcination to obtain a product which can be used as a solid electrolyte for sodium ion batteries. The invention is realized by combining BF 4 ‑ The anionic groups are introduced into the sodium ion solid electrolyte to partially replace Cl ‑ The site of the anion enlarges the transmission channel of the sodium ion, improves the solid stateThe ionic conductivity of the electrolyte, the preparation process is simple, and the sodium ion sulfide solid electrolyte with high ionic conductivity is easy to synthesize in large scale, so that the commercialization process of the sodium ion sulfide solid electrolyte is promoted.

Description

Sodium ion sulfide electrolyte and preparation method and application thereof
Technical Field
The invention relates to a sodium ion sulfide electrolyte, a preparation method and application thereof, and belongs to the field of sodium ion battery electrolyte materials.
Background
Lithium ion batteries are widely used in portable electronic devices such as mobile phones and computers nowadays due to the advantages of high energy density, long cycle life, high working voltage, no memory effect and the like. As lithium ion batteries are increasingly used in power automobiles, there is a growing demand for energy storage systems, which require a large amount of lithium source in the energy storage market. However, the price of lithium sources in recent years is in a rising trend and the lithium resources in China are extremely limited. Therefore, sodium ion batteries become one of the options for replacing lithium ion batteries.
The sodium element and the lithium element are in the same main group and have similar physical and chemical properties. As with lithium ion batteries, sodium ion batteries also have the problem of flammability because conventional sodium ion batteries use a liquid electrolyte, i.e., a mixed solution of an ester compound and a sodium salt. The electrolyte contains ester organic compounds, and is easy to burn under the conditions of high temperature or collision. Therefore, it is urgent to solve the safety problem of the power battery.
The use of solid electrolytes instead of liquid electrolytes for the preparation of all-solid batteries is an important way to improve safety performance because the solid electrolytes in all-solid batteries do not decompose and burn at high temperatures. Sodium ion solid electrolyte research is mainly focused on Na at present 3 PS 4 ，Na 11 Sn 2 PS 12 ，Na 10 GeP 2 S 12 Na and Na 3 SbS 4 And the like. In the sulfide solid state electrolyte, na 3 PS 4 The ionic conductivity is low, while other solid electrolytes need to be used for SnS 2 ，GeS 2 And Sb (Sb) 2 S 5 The equivalent raw materials with high price are not beneficial to commercial production and application. Therefore, how to prepare the sodium ion solid electrolyte with low cost and high performance becomes the key of the development of the next generation of sodium ion batteries.
Disclosure of Invention
Li of silver-sulfur-germanium ore structure 6 PS 5 Cl is a classical lithium ion sulfide solid electrolyte with ionic conductivity of 10 -3 S/m. However, literature (doi.org/10.1016/j.jpcs.2021.110269) shows that sodium-ion solid electrolyte Na 6 PS 5 The Cl ion conductivity is low, namely, only 2 multiplied by 10 -5 S/m or so, probably due to Na 6 PS 5 Cl (cubic phase structure) and Li 6 PS 5 Cl (silver sulfur germanium ore structure) has an essential difference in crystal form structure.
In view of the above, the present invention provides a sodium sulfide electrolyte, a method for preparing the same and applications thereof, by enlarging Na 6 PS 5 The transport channel of sodium ions in the Cl structure to promote the ionic conductivity of the material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a sodium sulfide electrolyte belongs to a cubic phase structure, and has a chemical formula of Na 6 PS 5 Cl 1-x (BF 4 ) x ，
Where x=0.01, 0.05,0.1,0.15,0.2,0.25 or 0.3.
The invention also provides a preparation method of the sodium ion sulfide electrolyte, which comprises the following steps:
(1) Na is mixed with 2 S、P 2 S 5 NaCl and NaBF 4 Mixing according to the proportion and carrying out solid-phase ball milling;
(2) And pressing the solid-phase ball-milled material into tablets, and calcining in a vacuum environment.
As a starting material for the present application, suitable but non-limiting examples are Na 2 S、P 2 S 5 NaCl and NaBF 4 Wherein P is 2 S 5 Can also be replaced by P powder and S powder according to the metering ratio, naBF 4 NaPF can also be used 6 ，NaCN，NaBH 4 ，NaNH 2 NaSCN, naBr or NaI.
Based on the technical scheme, the invention can also be improved as follows:
further, the solid phase ball milling process in the step (1) is carried out in a protective gas environment;
the protective gas is argon, or can be nitrogen or hydrogen-argon mixed atmosphere or other inert atmosphere.
Further, the ball milling rotating speed in the step (1) is 280-400 rpm, and the ball milling time is 8-16 h.
Further, in the step (2), the solid-phase ball-milled material is a sheet-shaped material obtained by cold press molding.
Further, the pressure of the cold press molding is 10-30 MPa.
Further, the calcination process in the step (2) is only performed under a vacuum environment, and inert atmosphere protection can not be conducted, otherwise impurities are generated.
Further, the calcination temperature is 280-360 ℃ and the calcination time is 8-16 h.
The invention also provides application of the sodium ion sulfide electrolyte as a solid electrolyte in a sodium ion battery.
The invention has the beneficial effects that:
the present application utilizes the introduction of BF 4 - Radical method for electrolyte material Na 6 PS 5 And performing electrochemical modification on Cl. BF (BF) 4 - After the anionic group partially replaces the Cl-anionic site, the sodium ion transmission channel is enlarged, the ionic conductivity of the solid electrolyte is improved, and Na with high ionic conductivity can be prepared in batches at a lower temperature 6 PS 5 Cl 1-x (BF 4 ) x (x=0.01, 0.05,0.1,0.15,0.2,0.25,0.3) solid electrolyte, optimized Na 6 PS 5 Cl 1-x (BF 4 ) x The electrolyte material has ion conductivity as high as 2 x 10 through test -3 S/m or so, with unmodified Na 6 PS 5 Cl reports an increase in ionic conductivity of one to two orders of magnitude compared to Na 6 PS 5 Cl 1-x (BF 4 ) x Solid electrolytes are extremely commercially valuable in electrochemical performance.
Drawings
FIG. 1 is an XRD contrast pattern of example 5 and comparative example 5 of the present application;
FIG. 2 is a graph showing the comparison of the ionic conductivities of example 5 and comparative example 5 of the present application;
FIG. 3 is a graph showing the comparison of experimental results of experimental example 7 and comparative example 7 of the present application.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
To the extent that no conflict arises with the meaning commonly found in the related art, the present application terminology applies to the following explanations:
as used herein, "ball milling" refers to the process of pulverizing and mixing materials by impact of falling grinding bodies (e.g., steel ball beads, etc.) and grinding of the grinding bodies against the inner wall of the ball mill.
As used herein, "calcination" refers to heating a feedstock such as an inorganic substance to an elevated temperature, but not melting, in order to produce useful physical and chemical changes to convert or remove some of the unwanted substances contained therein.
Example 1
Sodium sulfide electrolyte Na 6 PS 5 Cl 1-x (BF 4 ) x The preparation method of (x=0.05) comprises the following preparation steps:
1) Under an inert atmosphere, 3.9g of Na 2 S，2.22gP 2 S 5 ，1.11gNaCl，0.11gNaBF 4 Adding the mixture into a ball milling tank, setting the ball milling rotating speed to 385rpm, and setting the ball milling time to 10 hours;
2) Collecting the mixed materials under an inert atmosphere, and then cold-pressing under 12MPa to obtain a precursor small wafer;
3) Placing the precursor small wafer in the step 2) into a tube furnace, and vacuumizing the tube furnace. The temperature was set at 280℃and the calcination time was 12h. And finally, collecting the reacted product, and carrying out XRD phase and electrochemical testing.
Example 2
Sodium sulfide electrolyte Na 6 PS 5 Cl 1-x (BF 4 ) x The preparation method of (x=0.1) comprises the following preparation steps:
1) Under an inert atmosphere, 3.9g of Na 2 S，2.22gP 2 S 5 ，1.05gNaCl，0.22gNaBF 4 Adding the mixture into a ball milling tank, setting the ball milling rotating speed to be 400rpm, and setting the ball milling time to be 12 hours;
2) Collecting the mixed materials under inert atmosphere, and then carrying out cold pressing under 15MPa to obtain a precursor small wafer;
3) Placing the precursor small wafer in the step 2) into a tube furnace, and vacuumizing the tube furnace. The temperature was set at 300℃and the calcination time was 10 hours. And finally, collecting the reacted product, and carrying out XRD phase and electrochemical testing.
Example 3
Sodium sulfide electrolyte Na 6 PS 5 Cl 1-x (BF 4 ) x The preparation method of (x=0.15) comprises the following preparation steps:
1) Under an inert atmosphere, 3.9g of Na 2 S，2.22gP 2 S 5 ，0.994gNaCl，0.33gNaBF 4 Adding the mixture into a ball milling tank, setting the ball milling rotating speed to be 380rpm, and setting the ball milling time to be 8 hours;
2) Collecting the mixed materials under an inert atmosphere, and then cold-pressing under 20MPa to obtain a precursor small wafer;
3) Placing the precursor small wafer in the step 2) into a tube furnace, and vacuumizing the tube furnace. The temperature was set at 320℃and the calcination time was 8h. And finally, collecting the reacted product, and carrying out XRD phase and electrochemical testing.
Example 4
Sodium sulfide electrolyte Na 6 PS 5 Cl 1-x (BF 4 ) x The preparation method of (x=0.2) comprises the following preparation steps:
1) Under an inert atmosphere, 3.9g of Na 2 S，2.22gP 2 S 5 ，0.935gNaCl，0.44gNaBF 4 Adding the mixture into a ball milling tank, setting the ball milling rotating speed to be 450rpm, and setting the ball milling time to be 16 hours;
2) Collecting the mixed materials under an inert atmosphere, and then carrying out cold pressing under 11MPa to obtain a precursor small wafer;
3) Placing the precursor small wafer in the step 2) into a tube furnace, and vacuumizing the tube furnace. The temperature was set at 340℃and the calcination time was 16h. And finally, collecting the reacted product, and carrying out XRD phase and electrochemical testing.
Example 5
Sodium sulfide electrolyte Na 6 PS 5 Cl 1-x (BF 4 ) x The preparation method of (x=0.25) comprises the following preparation steps:
1) Under an inert atmosphere, 3.9g of Na 2 S，2.22gP 2 S 5 ，0.876gNaCl，0.55gNaBF 4 Adding the mixture into a ball milling tank, setting the ball milling rotating speed to be 420rpm, and setting the ball milling time to be 9h;
2) Collecting the mixed materials under an inert atmosphere, and then cold-pressing under 16MPa to obtain a precursor small wafer;
3) Placing the precursor small wafer in the step 2) into a tube furnace, and vacuumizing the tube furnace. The temperature was set at 360℃and the calcination time was 15 hours. And finally, collecting the reacted product, and carrying out XRD phase and electrochemical testing.
Example 6
Sodium sulfide electrolyte Na 6 PS 5 Cl 1-x (BF 4 ) x The preparation method of (x=0.3) comprises the following preparation steps:
1) Under an inert atmosphere, 3.9g of Na 2 S，2.22gP 2 S 5 ，0.818gNaCl，0.66gNaBF 4 Adding the mixture into a ball milling tank, setting the ball milling rotating speed to be 410rpm, and setting the ball milling time to be 9 hours;
2) Collecting the mixed materials under inert atmosphere, and then carrying out cold pressing under 15MPa to obtain a precursor small wafer;
3) Placing the precursor small wafer in the step 2) into a tube furnace, and vacuumizing the tube furnace. The temperature was set at 350℃and the calcination time was 14h. And finally, collecting the reacted product, and carrying out XRD phase and electrochemical testing.
Example 7
Sodium sulfide electrolyte Na 6 PS 5 Cl 1-x (BF 4 ) x The preparation method of (x=0.01) comprises the following preparation steps:
1) Under an inert atmosphere, 3.9g of Na 2 S，2.22gP 2 S 5 ，1.157gNaCl，0.022gNaBF 4 Adding the mixture into a ball milling tank, setting the ball milling rotating speed to be 400rpm, and setting the ball milling time to be 9 hours;
2) Collecting the mixed materials under an inert atmosphere, and then cold-pressing under 16MPa to obtain a precursor small wafer;
3) Placing the precursor small wafer in the step 2) into a tube furnace, and vacuumizing the tube furnace. The temperature was set at 320℃and the calcination time was 10 hours. And finally, collecting the reacted product, and carrying out XRD phase and electrochemical testing.
Comparative example 1
The only difference from example 1 is that x=0. I.e. 3.9g Na 2 S，2.222gP 2 S 5 1.17g NaCl was charged into the milling jar. The rest steps are the same.
Comparative example 2
The only difference from example 2 is that x=0. I.e. 3.9g Na 2 S，2.222gP 2 S 5 1.17g NaCl was charged into the milling jar. The rest steps are the same.
Comparative example 3
The only difference from example 3 is that x=0. I.e. 3.9g Na 2 S，2.222gP 2 S 5 1.17g NaCl was charged into the milling jar. The rest steps are the same.
Comparative example 4
The only difference from example 4 is that x=0. I.e. 3.9g Na 2 S，2.222gP 2 S 5 1.17g NaCl was charged into the milling jar. The rest steps are the same.
Comparative example 5
The only difference from example 5 is that x=0. I.e. 3.9g Na 2 S，2.222gP 2 S 5 1.17g NaCl was charged into the milling jar. The rest steps are the same.
Comparative example 6
The only difference from example 6 is that x=0. I.e. 3.9g Na 2 S，2.222gP 2 S 5 1.17g NaCl was charged into the milling jar. The rest steps are the same.
Comparative example 7
The only difference from example 7 is that the tube furnace was not evacuated and pure Ar gas was introduced instead. The rest steps are the same.
Experimental example 1
1. Evaluation procedure
The solid electrolyte products of all the above examples and comparative examples were subjected to XRD analysis on the samples using a D8 type XRD analyzer manufactured by bruck corporation, germany. The specific operation process is as follows: the target test sample was loaded into a custom made (air isolatable) sample stage, 0.01 °/step, with a test range of 10 ° -60 °.
The sodium ion solid electrolyte products of all the above examples and comparative examples were subjected to conductivity tests. Ac impedance testing was performed using a french Bio-Logic electrochemical workstation. Firstly, weighing 300mg of solid electrolyte sample, placing the solid electrolyte sample in a die with the diameter of 10mm, pressing the solid electrolyte sample into small discs by using the pressure of 10MPa, coating gold powder slurry on two ends of the discs, and placing the discs in a test die for AC impedance test. Wherein the range of the AC impedance Hz setting interval is 100 MHz-10 mu Hz. After the impedance data are tested, the ion conductivity of the sample is calculated.
2. Evaluation results
Fig. 1 is a comparison of XRD diffraction peaks of example 5 and comparative example 5. The main peak of the sample of example 5 was sharper than that of comparative example 5, but no new hetero peak was generated.
Table 1 shows the electricity of sodium-ion solid electrolyte products of all examples and all comparative examplesAs can be seen from Table 1, the ionic conductivity of the comparative examples is significantly lower than that of the examples of the present application, which illustrates the introduction of BF in the present application 4 - Anionic groups contribute to the technical contribution of sodium ion solid electrolyte ionic conductivity enhancement. The reason for this may be that BF 4 - The introduction of the anionic group expands the transmission channel of sodium ions, thereby improving the conduction migration rate of sodium ions in the lattice structure.
TABLE 1
FIG. 2 is Na 6 PS 5 Cl 1-x (BF 4 ) x Example 5 comparative example 5 ac impedance comparison. As can be seen from the graph, the load impedance of example 5 is about 300 Ω, while the load impedance of comparative example 5 is as high as 3000 Ω, which data indicates that the load resistance of the sample is lower when x=0.25 compared to x=0, and thus example 5 has higher ion conductivity.
In fig. 3, a is the appearance of comparative example 7, b is the appearance of example 7, c is the XRD comparison of the samples of comparative example 7 and example 7, the "#" symbol represents a hetero peak, and "#" represents a missing peak, as can be seen from fig. 3, when the reaction environment is protected by introducing an inert atmosphere of Ar, the product is not maintained in the original wafer shape but deformed, and the surface is provided with a reddish impurity; when the vacuum condition is adopted to protect the reaction environment, the product still keeps the original round plate shape, the color is uniformly yellow, compared with the vacuum condition, the inert atmosphere has two more peaks (the # marked position in the figure) at 27 degrees and 56 degrees, and meanwhile, a plurality of peaks are missing (the # marked position in the figure), and the reaction environment is related to the haematochrome impurities on the surface of the sample in the figure 3 (a), therefore, although the inert atmosphere and the vacuum condition are introduced into the synthesis field of the lithium ion sulfide solid electrolyte, the inert atmosphere can influence the generation of the product and even generate other substances in the synthesis field of the sodium ion sulfide solid electrolyte.
Furthermore, it was found during the experiment that the pressure gauge value of the air pressure valve increased rapidly when the temperature increased to 190 °, indicating Na 6 PS 5 Cl 1-x (BF 4 ) x The (x=0.01) precursor releases a lot of gas during heating, which has a very strong stinky egg taste, presumably related to hydrogen sulfide, which contains a sulfur source. In comparative example 7, the inert atmosphere was introduced into the glass tube to circulate, so that the hydrogen sulfide gas in the glass tube was greatly diluted, resulting in insufficient sulfur source in the reaction system and eventually Na 6 PS 5 Cl 1-x (BF 4 ) x (x=0.01) the sample was not completely vulcanized, so that the sample became a blood red substance. While the vacuum conditions in example 7 are in a closed environment, na 6 PS 5 Cl 1-x (BF 4 ) x (x=0.01) the hydrogen sulfide gas released by the precursor during heating will always be enclosed in the glass tube as Na 6 PS 5 Cl 1-x (BF 4 ) x (x=0.01) sample sulfided sulfur source, so that Na 6 PS 5 Cl 1-x (BF 4 ) x The (x=0.01) sample is vulcanized more completely, and finally, na with high purity can be obtained 6 PS 5 Cl 1-x (BF 4 ) x (x=0.01) samples.

Claims (9)

1. A sodium sulfide electrolyte is characterized in that the electrolyte belongs to a cubic phase structure, and has a chemical formula of Na 6 PS 5 Cl 1-x (BF 4 ) x ，
Where x=0.01, 0.05,0.1,0.15,0.2,0.25 or 0.3.
2. A method for preparing a sodium sulfide electrolyte, comprising the steps of:
(1) Na is mixed with 2 S、P 2 S 5 NaCl and NaBF 4 Mixing and performing solid-phase ball milling according to the proportion of claim 1；
(2) And pressing the solid-phase ball-milled material into tablets, and calcining in a vacuum environment.
3. The method for producing a sodium sulfide electrolyte according to claim 2, wherein the solid phase ball milling process in step (1) is performed in a protective gas atmosphere;
the protective gas is argon.
4. The method for preparing a sodium sulfide electrolyte according to claim 2, wherein the ball milling speed in the step (1) is 280-400 rpm, and the ball milling time is 8-16 hours.
5. The method for preparing a sodium sulfide electrolyte according to claim 2, wherein the solid phase ball-milled material in the step (2) is a sheet-shaped material obtained by cold press molding.
6. The method for producing a sodium sulfide electrolyte according to claim 5, wherein the cold press molding is performed under a pressure of 10 to 30mpa.
7. The method for producing a sodium-ion sulfide electrolyte according to claim 2, wherein the calcination in step (2) is performed under a vacuum atmosphere.
8. The method for preparing a sodium sulfide electrolyte according to claim 7, wherein the calcination temperature is 280 to 360 ℃ and the calcination time is 8 to 16 hours.
9. Use of the sodium-ion sulfide electrolyte according to any one of claims 1 to 8 as a solid state electrolyte in a sodium-ion battery.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101821199A (en) * 2007-10-08 2010-09-01 锡根大学 Lithium argyrodite
US20160156064A1 (en) * 2013-07-25 2016-06-02 Mitsui Mining & Smelting Co., Ltd. Sulfide-Based Solid Electrolyte for Lithium Ion Battery
CN109638347A (en) * 2018-12-02 2019-04-16 桂林理工大学 A kind of preparation and application of nanoscale Argyrodite type solid electrolyte material
CN111213274A (en) * 2017-09-22 2020-05-29 帅福得电池有限公司 Solid electrolyte for lithium-ion electrochemical cells
CN112768754A (en) * 2020-12-30 2021-05-07 南方科技大学 Solid electrolyte, preparation method thereof and all-solid-state battery
CN113104813A (en) * 2021-04-08 2021-07-13 上海大学 Sulfide solid electrolyte, preparation method thereof and all-solid-state battery
CN116438681A (en) * 2020-08-04 2023-07-14 坚固力量公司 Method for manufacturing a laminated solid electrolyte-based component and electrochemical cell using the same
CN116457961A (en) * 2020-09-23 2023-07-18 坚固力量营运公司 Solid electrolyte material and solid-state battery manufactured therefrom

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101821199A (en) * 2007-10-08 2010-09-01 锡根大学 Lithium argyrodite
US20160156064A1 (en) * 2013-07-25 2016-06-02 Mitsui Mining & Smelting Co., Ltd. Sulfide-Based Solid Electrolyte for Lithium Ion Battery
CN111213274A (en) * 2017-09-22 2020-05-29 帅福得电池有限公司 Solid electrolyte for lithium-ion electrochemical cells
CN109638347A (en) * 2018-12-02 2019-04-16 桂林理工大学 A kind of preparation and application of nanoscale Argyrodite type solid electrolyte material
CN116438681A (en) * 2020-08-04 2023-07-14 坚固力量公司 Method for manufacturing a laminated solid electrolyte-based component and electrochemical cell using the same
CN116457961A (en) * 2020-09-23 2023-07-18 坚固力量营运公司 Solid electrolyte material and solid-state battery manufactured therefrom
CN112768754A (en) * 2020-12-30 2021-05-07 南方科技大学 Solid electrolyte, preparation method thereof and all-solid-state battery
CN113104813A (en) * 2021-04-08 2021-07-13 上海大学 Sulfide solid electrolyte, preparation method thereof and all-solid-state battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HENG WANG ET AL.: "Borohydride Substitution Effects of Li6PS5Cl Solid Electrolyte", ACS APPLIED ENERGY MATERIALS, vol. 4, no. 11, 7 January 2022 (2022-01-07), pages 12079 - 12083 *

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