CN109361019A - A kind of all solid state lithium metal battery and its chemical property improvement method - Google Patents

A kind of all solid state lithium metal battery and its chemical property improvement method Download PDF

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Publication number
CN109361019A
CN109361019A CN201811077393.0A CN201811077393A CN109361019A CN 109361019 A CN109361019 A CN 109361019A CN 201811077393 A CN201811077393 A CN 201811077393A CN 109361019 A CN109361019 A CN 109361019A
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electrolyte
layer
lithium metal
solid state
solid
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武建飞
孙士美
孙晓林
刘涛
牛全海
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of all solid state lithium metal battery based on sulfide solid electrolyte and the method for making the battery.The battery includes the layer (anode layer) at least containing a positive electrode, the layer (electrolyte layer) at least containing a solid electrolyte, and the layer (negative electrode layer) at least containing a negative electrode material, each layer in three layers is obtained by mechanical cold pressing mode.The present invention has the advantages that the present invention uses cathode of the lithium metal as all-solid-state battery, sulfide solid electrolyte is avoided by the way of transition zone and is reacted with lithium metal, to improve the cyclical stability of all-solid-state battery.

Description

A kind of all solid state lithium metal battery and its chemical property improvement method
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of all solid state lithium metal battery and its electrochemistry It can improvement method.
Background technique
Lithium ion battery is considered as most competitive electrochemical energy storage skill since light-weight, specific energy are high and the service life is long One of art, and have been widely used in each field of energy storage.But existing lithium ion battery uses organic electrolyte, and battery is caused to be deposited In inflammable and explosive safety issue, and at present, lithium ion battery high and low temperature resistance is poor, cannot fully meet scale Requirement of the industrial energy storage in terms of safety.How electricity is improved on the basis of existing chemical energy storage battery cycle life and capacity The security performance and stability in pond are the key breakthrough points of energy storage field.
Organic electrolyte is substituted using solid electrolyte, solid lithium battery is developed and is expected to solve the above problems.Due to solid The special nature that there is body electrolyte ionic conductivity to be gradually increased with temperature raising, complete using sulfide as solid electrolyte Solid state battery has excellent high-low temperature resistant stability, avoids the caused safety of conventional lithium ion battery electrolyte leakage and asks Topic, the service life is longer, and applying has huge advantage in energy-storage battery field.
It at present for the research of solid lithium battery, is distinguished by solid electrolyte, mainly includes copolymer solid electrolyte With inorganic solid electrolyte two major classes.Although copolymer solid electrolyte has the characteristics that plasticity is strong, various shapes, It is limited to extremely low conductivity, in power and energy storage field by biggish limitation.In contrast, inorganic solid electrolyte has Apparent advantage: having higher ionic conductivity and mechanical strength, has wider operating temperature and voltage window.Therefore base There is better application prospect in the lithium battery of inorganic solid electrolyte.In inorganic solid electrolyte, compared with oxide, sulphur Compound solid electrolyte is received significant attention due to ionic conductivity with higher.At present the electrolyte of lithium phosphorus sulphur germanium system from Electron conductivity can reach 10-2S/cm is one of the highest system of conductivity developed at present, still, currently based on this vulcanization The solid lithium battery chemical property of object solid electrolyte is poor, electrolyte reacted with lithium metal so that cause it is biggish it is solid- Liquid/solid interface impedance, while the positive embedding de- process of lithium ion can cause material stress changes in distribution, so that all-solid-state battery cyclicity It can decay serious.
Summary of the invention
For the above-mentioned prior art, the purpose of the present invention is to provide a kind of solid lithium batteries, can reduce interface electricity Resistance improves interface stability, so that the chemical property of solid lithium battery gets a promotion.
To achieve the above object, the present invention adopts the following technical solutions: a kind of solid lithium battery, it is characterised in that: packet Include solid electrolyte layer, anode composite layer and negative electrode layer.The anode composite layer and negative electrode layer are respectively placed in solid electrolyte layer Upper and lower end face, the anode layer and negative electrode layer are in contact with electrolyte layer by machinery cold pressing or coating method.
Preferably, the solid electrolyte layer is sulfide solid electrolyte, and chemical formula is one of (I) ~ (II) Or it is several:
Li10+aX1+aP2-aS12(I)；
X is selected from one or more of major element of third, the 4th or the 5th；0≤a≤1；
Preferably, the X is selected from one or more of Al, Si, Ge, Sn, P and As；
bLi2S(100-b-c) P2S5CY(II)
0 < b < 100,0≤c < 100-b, Y LiI, LiBr, LiCl, Li3PO4, Li4SiO4Or P2O5
Preferably, in the formula (II), 30≤a≤90；
Preferably, the electrolyte is prepared according to the following steps to obtain:
A) the raw material ball milling of synthesizing sulfide electrolyte is uniformly mixed；
B) mixture for obtaining step A) carries out high temperature sintering under protective atmosphere, and obtaining chemical formula is in formula (I)~(II) One or more of sulfide electrolyte；
Preferably, the sulfide electrolyte with (I) formula preferably includes Li10GeP2S12, Li10SnP2S12, Li11Si2PS12, Li11AlP2S12, Li10Ge0 .95Si0 .05P2S12And Li10 .35Ge1 .35P1 .65S12One or more of；
Preferably, the sulfide electrolyte with (II) formula preferably includes 70Li2S·30P2S5, 75Li2S·25P2S5, 78Li2S·22P2S5, 80Li2S·20P2S5, 62.5Li2S·12.5P2S525LiCl, 62.5Li2S·12.5P2S5· 25LiBr, 62.5Li2S·12.5P2S5One or more of 25 LiI；
Preferably, the anode composite layer is made of positive active material, conductive agent and electrolyte；
Preferably, the positive active material includes that lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, nickel cobalt manganese aluminium are compound At least one of oxide and polyanion positive electrode；
Preferably, the positive active material passes through external sheath, to reduce active material and electrolyte contact resistance, the packet Covering object is usually oxide, lithium-containing transition metal oxide or fluoride, including LiNbO3、LiTaO3、Li2Zr O3、 Li4Ti5O12、Al2O3、BaF2Or CaF2One or more of；
Preferably, the conductive agent is conductive black, graphene, carbon nanotube, surper-P, at least one in gas phase carbon fiber Kind；
Preferably, the electrolyte in the anode composite is one or more of (I) ~ (II).
Preferably, the mass ratio of the positive active material, conductive agent and electrolyte are as follows: 60:x:(40-x), 0≤x≤ 10；
Preferably, the negative electrode layer is made of metal lithium sheet；
Preferably, the laminated structure that the solid electrolyte is 50 ~ 500 μm of thickness, the electrolyte can not only serve as diaphragm, but also energy It is effectively conducted lithium ion；
Preferably, the solid lithium battery is by anode composite layer, and solid electrolyte layer is connected by cold pressing mode, finally Battery is assembled into certain pressure with lithium piece.
Advantage for present invention:
The present invention provides a kind of all-solid-state battery, including electrode material and sulfide electrolyte, the sulfide electrolyte Chemical formula is one or more of formula (I) ~ (II)；Use the lithium metal of high specific capacity as cathode simultaneously, using transition The mode of layer avoids sulfide solid electrolyte from reacting with lithium metal, to improve the stable circulation of all-solid-state battery Property.The experimental results showed that with the solid lithium battery of the bilayer solid electrolyte assembling in the present invention, at charge and discharge cycles 20 times Afterwards, battery specific capacity drops to 126.2mAh/g by 169.1 mAh/g, and decline degree is small, illustrates double-layer electric provided by the invention Solution mass-energy effectively improves the chemical property of solid lithium battery.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention
Specific embodiment
It is as shown in Figure 1 structural schematic diagram of the invention, a kind of all-solid-state battery, including solid electrolyte layer 2, solid electricity Matter layer 3, anode layer 1 and negative electrode layer 4 are solved, anode layer 1 and negative electrode layer 4 are separately positioned on the upper and lower side of solid electrolyte layer 2 and 3 Face, and it is bonding with electrolyte 2 and 3 by way of cold pressing or binder.
Embodiment 1
In the present invention, solid electrolyte layer 2 is selected from one of (I) formula, meets the sulfide electrolyte of chemical formula shown in formula (I) Preferably include Li10GeP2S12, Li10SnP2S12, Li11Si2PS12, Li11AlP2S12, Li10Ge0 .95Si0 .05P2S12And Li10 .35Ge1 .35P1 .65S12One or more of, it is highly preferred that being selected from the higher Li of ionic conductivity10GeP2S12(LGPS), remember Make SE1；
In the present invention, solid electrolyte layer 3 is selected from one of (II) formula, meets the sulfide electrolysis of chemical formula shown in formula (II) Matter preferably includes 70Li2S·30P2S5, 75Li2S·25P2S5, 78Li2S·22P2S5, 80Li2S·20P2S5, 62.5Li2S· 12.5P2S525LiCl, 62.5Li2S·12.5P2S525LiBr, 62.5Li2S·12.5P2S5One of 25LiI or It is several, it is highly preferred that selection 62.5Li2S·12.5P2S525 LiCl(LPSCl), it is denoted as SE2；
The electrolyte is prepared according to the following steps to obtain:
A) the raw material ball milling of synthesizing sulfide electrolyte is uniformly mixed；
B) mixture for obtaining step A) carries out high temperature sintering under protective atmosphere, and obtaining chemical formula is in formula (I)~(II) One or more of sulfide electrolyte；
Above-mentioned solid electrolyte is pressed into diameter as 10mm, the laminated structure that 50 ~ 500 μm of thickness, the electrolyte can both fill Work as diaphragm, and lithium ion can be effectively conducted.
In the present invention, the anode layer 1 includes active material, conductive agent and electrolyte；The active material includes In cobalt/cobalt oxide, lithium nickel oxide, lithium manganese oxide, nickel cobalt manganese aluminium composite oxide and polyanion positive electrode at least One kind preferably including cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), ternary NCA, NCM material, it is rich One or more of lithium manganese material, more preferably selection ternary NCA material；The positive active material passes through external sheath, To reduce active material and electrolyte contact resistance, the coating is usually oxide, lithium-containing transition metal oxide or fluorine Compound, including LiNbO3、LiTaO3、Li2ZrO3、Li4Ti5O12、Al2O3、BaF2Or CaF2One or more of；The conduction Agent is at least one of conductive black, graphene, carbon nanotube, surper-P, gas phase carbon fiber；In the anode composite Electrolyte is one or more of (I) ~ (II)；The mass ratio of the positive active material, conductive agent and electrolyte are as follows: 60: X:(40-x), 0≤x≤10；1 interface impedance of anode layer provided by the invention is small, can effectively improve the electrification of solid lithium battery Learn performance.
In the present invention, select lithium metal as negative electrode layer 4.
Above-mentioned anode is tabletted, make anode layer 1, is combined with above-mentioned electrolyte layer 2 and 3 and negative electrode layer 4, composition Solid lithium battery.
Comparative example 2
Solid lithium battery is prepared using method same as Example 1, the difference is that: electrolyte layer 3 selects LPS system sulphur Compound electrolyte, such as 70Li2S·30P2S5, 75Li2S·25P2S5, 78Li2S·22P2S5, 80Li2S·20P2S5, more preferably Ground selects 70Li2S·30P2S5(LPS), it is denoted as SE3；
Comparative example 3
Solid lithium battery is prepared using method same as Example 1, the difference is that: the selection of electrolyte layer 3 and electrolysis The identical sulfide electrolyte of matter layer 2.
Performance test:
The solid lithium battery that will be prepared in above-described embodiment 1 and comparative example 1 ~ 2 respectively, the 0.05C testing current electricity at 60 DEG C The charge-discharge property and cycle performance in pond, the results are shown in Table 1.
The comparison of 1 different type solid lithium battery circulation volume of table
Classification Anode 1 Electrolyte layer 2 Electrolyte layer 3 Cathode Discharge capacity/(mAh/g) for the first time Discharge capacity (mAh/g) after 20 circle of circulation Capacity retention ratio
Embodiment SE1+NCA SE1 SE2 Li 169.1 126.2 74.6%
Comparative example 1 SE1+NCA SE1 SE3 Li 166.8 90.3 54.1%
Comparative example 2 SE1+NCA SE1 SE1 Li 161 78.5 48.8%
As can be seen from Table 1, it is very big to influence difference to the cycle performance of solid lithium battery for different electrolyte layers.In embodiment 1, It is 169.1mAh/g that LPSCl, which is selected, as the discharge capacity for the first time of the solid lithium battery of separation layer, and capacity reaches after 20 circle of circulation 126.2 mAh/g, circulation conservation rate can achieve 74.6%, and in comparative example 1 and 2, select LPS and without separation layer it is complete consolidate The cycle performance of state lithium battery is poor, and after 20 circulations, capacity retention ratio is only 50% or so.The above result shows that using LPSCl can be effectively reduced LGPS system sulfide solid electrolyte and react with lithium metal, reduce as separation layer Interface impedance, to improve the cycle performance of solid lithium battery.
The above is only a preferred embodiment of the present invention, it is not a limitation on the technical scheme of the present invention.It is not taking off Under the premise of from the principle of the invention, some improvements and modifications can also be made, these improvement and modification also should be regarded as of the invention Protection scope.

Claims (11)

1. a kind of all solid state lithium metal battery, it is characterised in that: including solid electrolyte layer, anode composite layer and negative electrode layer.Institute It states anode composite layer and negative electrode layer is respectively placed in the upper and lower end face of solid electrolyte layer, the anode layer and negative electrode layer and electrolyte Layer is in contact by machinery cold pressing or coating method.
2. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the electrolyte layer includes following (I) one or more of ~ (II):
Li10+aX1+aP2-aS12(I)；
X is selected from one or more of major element of third, the 4th or the 5th；0≤a≤1 ；
bLi2S(100-b-c) P2S5CY(II)
0 < b < 100,0≤c < 100-b, Y LiI, LiBr, LiCl, Li3PO4, Li4SiO4Or P2O5；
The electrolyte is prepared according to the following steps to obtain:
A) the raw material ball milling of synthesizing sulfide electrolyte is uniformly mixed；
B) mixture for obtaining step A) carries out high temperature sintering under protective atmosphere, and obtaining chemical formula is in formula (I)~(II) One or more of sulfide electrolyte.
3. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the vulcanization with (I) formula Object electrolyte preferably includes Li10GeP2S12, Li10SnP2S12, Li11Si2PS12, Li11AlP2S12, Li10Ge0 .95Si0 .05P2S12, And Li10 .35Ge1 .35P1 .65S12One or more of.
4. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the vulcanization with (II) formula Object electrolyte preferably includes 70Li2S·30P2S5, 75Li2S·25P2S5, 78Li2S·22P2S5, 80Li2S·20P2S5, 62.5Li2S·12.5P2S525LiCl, 62.5Li2S·12.5P2S525LiBr, 62.5Li2S·12.5P2S5·25 LiI One or more of.
5. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the anode composite layer is by just Pole active material, conductive agent and electrolyte are constituted, and the positive active material includes lithium and cobalt oxides, lithium nickel oxide, lithium manganese At least one of oxide, nickel cobalt manganese aluminium composite oxide and polyanion positive electrode.
6. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the positive active material passes through For external sheath to reduce active material and electrolyte contact resistance, the coating is usually oxide, lithium-containing transition metal oxygen Compound or fluoride, including LiNbO3、LiTaO3、Li2ZrO3、Li4Ti5O12、Al2O3、BaF2Or CaF2One or more of.
7. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the conductive agent is conductive charcoal At least one of black, graphene, carbon nanotube, surper-P, gas phase carbon fiber, the electrolyte are one in (I) ~ (II) Kind is several.
8. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the positive active material is led The mass ratio of electric agent and electrolyte are as follows: 60:x:(40-x), 0≤x≤10.
9. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the negative electrode layer is by lithium metal Piece is constituted.
10. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the solid electrolyte is thickness The laminated structure of 50 ~ 500 μm of degree.
11. a kind of all solid state lithium metal battery according to claim 1, it is characterised in that: the solid lithium battery is By anode composite layer, solid electrolyte layer is connected by cold pressing mode, and last and lithium piece is assembled into battery with certain pressure.
CN201811077393.0A 2018-09-15 2018-09-15 A kind of all solid state lithium metal battery and its chemical property improvement method Pending CN109361019A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110176641A (en) * 2019-06-03 2019-08-27 哈尔滨工业大学 A kind of nanometer of LiF/Fe/ graphite anode mends the preparation method and applications of lithium slurry
CN110190276A (en) * 2019-07-10 2019-08-30 河南电池研究院有限公司 A kind of preparation method of niobium, aluminium codope anode material for lithium-ion batteries
CN112018451A (en) * 2020-08-27 2020-12-01 北京科技大学 Flexible electrode electrolyte integrated structure for all-solid-state battery and preparation method
CN112242519A (en) * 2019-07-17 2021-01-19 比亚迪股份有限公司 Positive electrode material, preparation method thereof and solid-state lithium battery
CN112768761A (en) * 2021-02-25 2021-05-07 江汉大学 Sulfide solid electrolyte and preparation method and application thereof
CN112864454A (en) * 2019-11-27 2021-05-28 郑州宇通集团有限公司 Multilayer solid electrolyte, preparation method thereof and solid lithium battery
CN113948764A (en) * 2021-09-01 2022-01-18 上海屹锂新能源科技有限公司 Preparation method and application of sulfide solid electrolyte material
CN114789993A (en) * 2022-05-05 2022-07-26 上海屹锂新能源科技有限公司 Modified GeAg sulfide type solid electrolyte and preparation method and application thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110176641A (en) * 2019-06-03 2019-08-27 哈尔滨工业大学 A kind of nanometer of LiF/Fe/ graphite anode mends the preparation method and applications of lithium slurry
CN110190276A (en) * 2019-07-10 2019-08-30 河南电池研究院有限公司 A kind of preparation method of niobium, aluminium codope anode material for lithium-ion batteries
CN112242519A (en) * 2019-07-17 2021-01-19 比亚迪股份有限公司 Positive electrode material, preparation method thereof and solid-state lithium battery
CN112864454A (en) * 2019-11-27 2021-05-28 郑州宇通集团有限公司 Multilayer solid electrolyte, preparation method thereof and solid lithium battery
CN112018451A (en) * 2020-08-27 2020-12-01 北京科技大学 Flexible electrode electrolyte integrated structure for all-solid-state battery and preparation method
CN112768761A (en) * 2021-02-25 2021-05-07 江汉大学 Sulfide solid electrolyte 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
CN113948764A (en) * 2021-09-01 2022-01-18 上海屹锂新能源科技有限公司 Preparation method and application of sulfide solid electrolyte material
WO2023030026A1 (en) * 2021-09-01 2023-03-09 上海屹锂新能源科技有限公司 Method for preparing sulfide solid electrolyte material and application thereof
CN114789993A (en) * 2022-05-05 2022-07-26 上海屹锂新能源科技有限公司 Modified GeAg sulfide type solid electrolyte and preparation method and application thereof
CN114789993B (en) * 2022-05-05 2024-01-30 上海屹锂新能源科技有限公司 Modified sulfur silver germanium mineral solid electrolyte and preparation method and application thereof

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