CN114524416A - Lithium sulfide coated sulfide solid electrolyte and preparation method and application thereof - Google Patents
Lithium sulfide coated sulfide solid electrolyte and preparation method and application thereof Download PDFInfo
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- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 31
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 238000000498 ball milling Methods 0.000 claims abstract description 33
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 19
- 239000011247 coating layer Substances 0.000 abstract description 15
- 210000001787 dendrite Anatomy 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000010416 ion conductor Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910009496 Li1.5Al0.5Ge1.5 Inorganic materials 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910006309 Li—Mg Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 208000020960 lithium transport Diseases 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- 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
- H01M10/056—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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of solid-state batteries, in particular to a lithium sulfide coated sulfide solid-state electrolyte and a preparation method and application thereof, wherein the lithium sulfide coated sulfide solid-state electrolyte comprises 65-80% of sulfide, 20-35% of phosphorus pentasulfide and 0.1-10% of lithium powder. The coated sulfide solid electrolyte is prepared by a ball milling method, the preparation method is simple, and large-scale production can be realized; the sulfide-coated solid electrolyte prepared by the method can inhibit the reaction of the electrolyte and a metal lithium cathode due to the existence of the coating layer, and can inhibit the growth of lithium dendrite due to the existence of the coating layer; when the lithium dendrite grows in the solid electrolyte, the lithium dendrite can also inhibit the internal generation of the lithium dendrite, thereby greatly hindering the short circuit of the battery and improving the electrochemical performance of the battery. The lithium sulfide of the coating layer is also a good lithium ion conductor, and the existence of the coating layer can also improve the ion conductivity of electrolyte, so that the lithium sulfide can be better applied to solid batteries.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a lithium sulfide coated sulfide solid-state electrolyte and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art. In recent years, lithium ion batteries have attracted attention for their application in electronic products. However, conventional lithium ion batteries cannot meet the development requirements of emerging energy storage devices due to low energy density and safety issues. The use of non-flammable solid electrolytes instead of liquid electrolytes is generally considered to be an effective strategy to solve this problem. As a core component of all-solid batteries, various types of solid electrolytes, such as sulfide electrolyte (Li), have been widely studied7P3S11、Li10GeP2S12And Li3PS4) Oxide electrolyte (Li)7La3Zr2O12And Li1.5Al0.5Ge1.5P3O12) And polymer electrolytes and the like. In particular sulfide electrolyte Li7P3S11(abbreviated as LPS) due to its high ionic conductivity (10)-3-10-2S cm-1) Are receiving increasing attention. However, the chemical reactivity to metallic lithium results in large interface resistance during cycling, which is not favorable for lithium transport between LPS and metallic lithium interface, preventing practical application. Even more fatal, lithium dendrites can grow within the solid electrolyte, eventually penetrating the electrolyte, causing short circuit failure of the battery. In recent years, researchers have been working on developing effective strategies to address the interfacial reaction between the solid electrolyte and the lithium negative electrode. One such method is to construct Li alloy negative electrodes such as Li-Cu and Li-Mg alloys. However, the energy density of the lithium alloy negative electrode is significantly reduced due to the reduction in the battery voltage. In addition, the preparation of the alloy material also increases the cost. Another approach is to introduce functional buffer layers, such as LiF and LiI, whose high interface is effective in suppressing lithium dendrites, but whose ionic conductivity is low, the kinetics of ion transport are reduced, resulting in a reduced overall electrolyte ionic conductivity, and lithium sulfide (Li)2S) has higher ionic conductivity and moderate interfacial energy, and can be used as a critical functional layer to relieveSpontaneous reactions between the metallic lithium and the solid-state electrolyte are decomposed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a lithium sulfide coated sulfide solid electrolyte, a preparation method and application thereof, wherein the preparation method of the lithium sulfide coated sulfide solid electrolyte is simple and can be used for large-scale production; high ion conductivity and high stability to lithium (electrochemical).
There are studies in the prior art on the solid electrolyte Li3PS4And a solid electrolyte interface layer rich in LiF is generated in situ by the reaction of LiFSI and Li at the interface of the lithium metal. Because LiF has high interfacial energy, the LiF-rich SEI film can inhibit penetration of lithium dendrites into the interior of the solid electrolyte, and low electronic conductance and high mechanical strength can further block subsequent reactions of the electrolyte with metallic lithium; according to the scheme, a certain solution is adopted, the solution can react with the sulfide electrolyte to reduce the ionic conductivity of the electrolyte, the introduction of the protective layer only hinders the reaction of the electrolyte and lithium metal, and the generation of lithium dendrite in the electrolyte cannot be inhibited.
In order to achieve the above object, the technical solution of the present invention is as follows:
in the first aspect of the invention, a lithium sulfide coated sulfide solid electrolyte is provided, which comprises 65-80% of sulfide, 20-35% of phosphorus pentasulfide and 0.1-10% of lithium powder.
In a second aspect of the present invention, there is provided a method for producing a lithium sulfide-coated sulfide solid-state electrolyte according to the first aspect, comprising the steps of:
(1) uniformly mixing the raw materials in a mortar in an inert atmosphere;
(2) ball-milling the material obtained in the step (1) in a ball-milling tank to obtain a sulfide solid electrolyte precursor after the ball-milling is finished;
(3) sealing the precursor obtained in the step (2) and then carrying out heat treatment to obtain a sulfide solid electrolyte;
(4) and (4) carrying out ball milling on the sulfide electrolyte prepared in the step (3) and metal lithium powder to obtain the coated sulfide solid electrolyte.
In a third aspect of the present invention, there is provided a use of the lithium sulfide-coated sulfide solid electrolyte of the first aspect in the field of solid-state batteries.
The specific embodiment of the invention has the following beneficial effects:
(1) the coated sulfide solid electrolyte is prepared by a ball milling method, the preparation method is simple, and large-scale production can be realized.
(2) The sulfide-coated solid electrolyte prepared by the method is doped compared with other ball milling methods, such as ball milling method doped metal oxide (M)aOb) The presence of the coating layer can suppress the reaction between the electrolyte and the metallic lithium negative electrode, and the presence of the coating layer can suppress the growth of lithium dendrites in the electrolyte, and the presence of the coating layer can improve the density of the electrolyte and further improve the ionic conductivity of the sulfide electrolyte itself.
(3) Due to the existence of the coating layer, when the lithium dendrite grows in the solid electrolyte, the lithium dendrite can also be inhibited from generating in the solid electrolyte, so that the short circuit of the battery is greatly prevented, and the electrochemical performance of the battery is improved.
(4) The lithium sulfide of the coating layer is also a good lithium ion conductor, and the existence of the coating layer can also improve the ion conductivity of the electrolyte, so that the lithium sulfide is better applied to solid batteries.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an SEM image of the lithium sulfide-coated sulfide solid electrolyte prepared in example 1.
Fig. 2 is an electrochemical impedance spectrum of the lithium sulfide-coated sulfide solid electrolyte prepared in example 1.
Fig. 3 is a time-voltage diagram of a symmetrical cell of the lithium sulfide coated sulfide solid state electrolyte prepared in example 1.
Fig. 4 is an electrochemical performance of the all-solid battery prepared in example 1.
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.
In the embodiment of the invention, the lithium sulfide coated sulfide solid electrolyte comprises 65-80% of sulfide, 20-35% of phosphorus pentasulfide and 0.1-10% of lithium powder.
In one or more embodiments, the sulfide solid state electrolyte component is 70Li2S·30P2S5Adding lithium powder in a certain mass ratio (x%); wherein x is the mass ratio of the lithium powder;
preferably, x is 0.1 to 1.
In one or more embodiments, the sulfide is lithium sulfide or sodium sulfide.
In an embodiment of the present invention, there is provided a method for producing the above lithium sulfide-coated sulfide solid-state electrolyte, including the steps of:
(1) uniformly mixing the raw materials in a mortar in an inert atmosphere;
(2) ball-milling the material obtained in the step (1) in a ball-milling tank to obtain a sulfide solid electrolyte precursor after the ball-milling is finished;
(3) sealing the precursor obtained in the step (2) and then carrying out heat treatment to obtain a sulfide solid electrolyte;
(4) and (4) carrying out ball milling on the sulfide electrolyte prepared in the step (3) and metal lithium powder to obtain the coated sulfide solid electrolyte.
In one or more embodiments, the rotation speed of the ball milling is 300-; preferably, the rotation speed of the ball milling is 510-.
In one or more embodiments, the temperature of the heat treatment is 220-; preferably, the temperature of the heat treatment is 240-260 ℃, and the time of the heat treatment is 1.5-4 h.
In one or more embodiments, the ball milling and heat treatment are performed under an inert atmosphere, and the inert gas is nitrogen or argon.
In one or more embodiments, the ball milling jar is a zirconia ball milling jar;
in one or more embodiments, in step (2), lithium fluoride or lithium nitride is added as a protective material.
The coated sulfide solid electrolyte is prepared by a ball milling method, the preparation method is simple, and large-scale production can be realized; the sulfide-coated solid electrolyte prepared by the method can inhibit the reaction of the electrolyte and a metal lithium cathode due to the existence of the coating layer, and can inhibit the growth of lithium dendrite due to the existence of the coating layer; and because of the existence of the coating layer, when the lithium dendrite grows in the solid electrolyte, the generation of the lithium dendrite can be inhibited, the short circuit of the battery is greatly hindered, and the electrochemical performance of the battery is improved. The existence of the coating layer can also improve the ion conductivity of the electrolyte, and the coating layer is better applied to a solid-state battery.
In an embodiment of the present invention, there is provided a use of the above-described lithium sulfide-coated sulfide solid electrolyte in the field of solid-state batteries.
The invention will be further explained and illustrated with reference to specific examples.
Example 1
The method for preparing the coated sulfide solid electrolyte and assembling the lithium cobaltate all-solid-state battery comprises the following specific steps of:
step 1: raw material Li2S、P2S5According to a molar ratio of 70: 30, mixing, and placing in a mortar for grinding uniformly;
step 2: and (3) placing the material obtained in the step (1) in a zirconium oxide ball milling tank protected by argon, and carrying out ball milling for 22h at the rotating speed of 510rpm to obtain a precursor of the solid electrolyte.
And step 3: and (3) sealing the precursor obtained in the step (2), and then carrying out heat treatment for 1-5h at the temperature of 220-270 ℃ in an inert atmosphere to obtain the sulfide solid electrolyte.
And 4, step 4: and uniformly mixing the obtained sulfide solid electrolyte with a certain amount of lithium powder, and placing the mixture into a ball milling tank to perform ball milling for a plurality of hours at 500rpm to obtain the sulfide solid electrolyte coated with lithium sulfide in situ.
Example 2
The preparation of coated sulfide solid electrolyte and assembled all-solid-state battery includes the following steps:
step 1: solid electrolyte Li6PS5Placing Cl and lithium powder in a mortar according to a certain molar ratio and uniformly mixing;
step 2: and (2) placing the material obtained in the step (1) in a zirconium oxide ball milling tank protected by argon, and carrying out ball milling for 1-5h at the rotating speed of 500rpm to obtain the coated solid electrolyte.
Example 3
The preparation of coated sulfide solid electrolyte and assembled all-solid-state battery includes the following steps:
step 1: mixing raw material Li10GeP2S12Mixing the lithium powder and the lithium powder according to a certain molar ratio, and placing the mixture in a mortar for uniform mixing;
step 2: and (2) placing the material obtained in the step (1) in a zirconium oxide ball milling tank protected by argon, and carrying out ball milling for 1-5h at the rotation speed of 300-.
FIG. 1 is a view of the coated sulfide solid electrolyte prepared in example 1, which is composed of particles having different sizes and cross-linked with each other. Fig. 2 is a graph of electrochemical impedance of different coating ratios prepared in example 1, and the results show that 0.5% coating ratio electrolyte has lower electrochemical impedance, corresponding to higher ion conductivity, indicating that proper coating can improve the ionic conductivity of the material. Fig. 3 is a time-voltage diagram of a symmetrical cell of the solid electrolyte prepared in example 1, and it can be seen from the results in the figure that the symmetrical cell assembled from the electrolyte after modification can be stably cycled for more than 400h and has a lower polarization voltage (40mV) relative to the unmodified sulfide electrolyte, indicating that the coating effectively suppresses the reaction between the electrolyte and the lithium metal and effectively suppresses the generation of lithium dendrites. Fig. 4 is an electrochemical performance of the all-solid battery prepared in example 1, and it can be seen that the all-solid battery of the improved solid electrolyte assembly has good electrochemical performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The lithium sulfide coated sulfide solid electrolyte is characterized by comprising 65-80% of sulfide, 20-35% of phosphorus pentasulfide and 0.1-10% of lithium powder.
2. The lithium sulfide coated sulfide solid state electrolyte of claim 1, wherein the sulfide solid state electrolyte component is 70Li2S·30P2S5Adding lithium powder in a certain mass ratio (x%); wherein x is the mass ratio of the lithium powder;
preferably, x is from 0.1 to 1.
3. The lithium sulfide coated sulfide solid state electrolyte of claim 1, wherein the sulfide is lithium sulfide or sodium sulfide.
4. A method for producing a lithium sulfide coated sulfide solid state electrolyte according to claim 1, comprising the steps of:
(1) uniformly mixing the raw materials in a mortar in an inert atmosphere;
(2) ball-milling the material obtained in the step (1) in a ball-milling tank to obtain a sulfide solid electrolyte precursor after the ball-milling is finished;
(3) sealing the precursor obtained in the step (2) and then carrying out heat treatment to obtain a sulfide solid electrolyte;
(4) and (4) carrying out ball milling on the sulfide electrolyte prepared in the step (3) and metal lithium powder to obtain the coated sulfide solid electrolyte.
5. The preparation method as claimed in claim 4, wherein the rotation speed of the ball mill is 300-800rpm, and the ball milling time is 4-8 h; preferably, the rotation speed of the ball milling is 510-.
6. The method as claimed in claim 4, wherein the heat treatment temperature is 220 ℃ and 270 ℃ and the heat treatment time is 1-5 h; preferably, the temperature of the heat treatment is 240-260 ℃, and the time of the heat treatment is 1.5-4 h.
7. The method of claim 4, wherein the ball milling and the heat treatment are performed under an inert atmosphere, and the inert gas is nitrogen or argon.
8. The method of claim 4, wherein the mill pot is a zirconia mill pot.
9. The method according to claim 4, wherein in the step (2), lithium fluoride or lithium nitride is added as a protective material.
10. Use of the lithium sulfide-coated sulfide solid electrolyte of claim 1 in the field of solid-state batteries.
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| CN111883822A (en) * | 2020-08-21 | 2020-11-03 | 山东大学 | Sulfide solid electrolyte with stable performance and preparation method and application thereof |
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| JIANWEI LI ET AL.: "In situ modified sulfide solid electrolyte enabling stable lithium metal batteries", 《JOURNAL OF POWER SOURCES》 * |
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Application publication date: 20220524 |