CN106684441A - Sulfur phosphide solid electrolyte and preparation method thereof - Google Patents
Sulfur phosphide solid electrolyte and preparation method thereof Download PDFInfo
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- CN106684441A CN106684441A CN201710013311.5A CN201710013311A CN106684441A CN 106684441 A CN106684441 A CN 106684441A CN 201710013311 A CN201710013311 A CN 201710013311A CN 106684441 A CN106684441 A CN 106684441A
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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
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- 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
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- 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 sulfur phosphide solid electrolyte and a preparation method thereof, and belongs to the field of solid electrolyte. The sulfur phosphide solid electrolyte is mainly prepared from the following raw materials in parts by mole: 0.1-11 parts of a lithium source, 0-15 parts of sulfur and 0.1-6 parts of phosphorous, wherein the lithium source is arbitrary one or more of LiH, LiCl, LiBr and LiI. The preparation method comprises the following steps of: (1) grinding sulfur, phosphorous and lithium source for 2-150 hours in a protective atmosphere; and (2) insulating the mixture obtained after grinding in the step (1) for 2-10 hours at 200-700 DEG C. The sulfur phosphide solid electrolyte has a stable structure and excellent performance; the preparation method is simple, has safe reaction, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of sulfur phosphide solid electrolyte and preparation method thereof, belongs to solid electrolyte field.
Background technology
At present overwhelming majority lithium ion battery battery realizes ion transmitting procedure using liquid electrolyte, but liquid is organic
, easily there is leakage, corrosion electrode and the safety problems such as oxidizing fire even occurs in thing, and largely limits use range
Continue to expand.Although the use of polymer dielectric alleviates to a certain extent this problem, due to its too low ion
Conductance, fails to tackle the problem at its root.In recent years, with the carrying out that sulfide solid electrolyte correlational study works, in a large number
Phosphorus sulfenyl solid electrolyte shows higher lithium ionic mobility.Inoganic solids lithium-ion electrolyte can not only overcome electrolysis
Matter leakage problem, and there is no the safety problem such as inflammable in solid electrolyte, and development solid state lithium battery technology is to solve liquid electric
The fundamental way of solution matter lithium battery safety problem.
The good solid lithium battery of processability it is critical only that the solid electrolyte for obtaining high room-temperature ion conductivity
And with can industrial applications inexpensive process of preparing.Substantial amounts of research concentrates on the sulfur for preparing high conductivity at room temperature rate
Compound solid electrolyte, has prepared at present the sulfide solid electricity of the high conductivity at room temperature rate that can be compared favourably with liquid electrolyte
Xie Zhi.This based solid electrolyte, generally by introducing additional constituent element, further promotes ion based on ternary Li-P-S alloy
Conductance.
Application publication number discloses a kind of amorphous state sulfide solid electrolyte for the patent of invention of CN105609870A
Preparation method, and specifically disclose it and mainly include the following steps that：1) by a certain proportion of lithium metal, elemental sulfur, germanium sulfide, five
Mixed in the hermetic container for vulcanizing two phosphorus input anhydrous and oxygen-free；2) by step 1) in mixing raw material carry out mechanical lapping,
Prepare amorphous state sulfide solid electrolyte.Technical scheme preparation process in the patent requires extremely strict, preparation cost
There is certain defect in height, electrolyte performance.Application publication number is the patent of invention of CN102959646A, discloses one kind with Li2S
And P2S5For the sulfide-based microcrystalline glass that the glass phase of main constituent coexists with crystalline phase.Tetragonal Li10GeP2S12It is existing
It is one of best solid electrolyte that stage is recognized.At ambient temperature, its lithium ionic mobility can exceed 10mScm-1,
Diffusion activation energy is between 0.22-0.285eV, and ionic conductance is suitable with liquid electrolyte.But prepare sulfur phosphide at present to consolidate
The base stock that body electrolyte is used is Li2S、P2S5It is expensive, in the patent of invention that application publication number is CN105914395A
Li in disclosed technical scheme2The preparation process of S is loaded down with trivial details, and decomposition of easily making moist, and these problems seriously constrain sulfide electricity
The commercial application of solution matter.Therefore, low cost, safety, eco-friendly sulfur phosphide solid electrolyte preparation method are developed, it is right
The commercial applications of solid electrolyte are significant.
The content of the invention
The purpose of the present invention aims to provide a kind of sulfur phosphide solid electrolyte.
The purpose of the present invention another purpose is to provide a kind of sulfur phosphide method for preparing solid electrolyte.
To achieve these goals, sulfur phosphide solid electrolyte of the invention, mainly by the raw material of following molfraction
Make：0.1~11 part of lithium source, 0~15 part of sulfur, 0.1~6 part of phosphorus；The lithium source is in LiH, LiCl, LiBr, LiI
Any one or a few.
Above-mentioned lithium source, phosphorus, the molfraction ratio of sulfur are (5~11)：(1~5)：(1~13).
Above-mentioned lithium source, phosphorus, the molfraction of sulfur are than being more preferably (5~9.6)：(1~3)：(0~12).
Above-mentioned sulfur, phosphorus are powder body.
Above-mentioned raw materials also include doping simple substance powder body, and the doping simple substance powder body is the one kind in Si, Ge, Sn, Se, Te, I
Or it is several.
The doping molfraction of above-mentioned doping simple substance powder body account for for lithium source, sulphur powder, phosphorus powder total moles number 0~50%.
To achieve these goals, sulfur phosphide method for preparing solid electrolyte of the invention, including following step is prepared
Suddenly：
1) it is 2~150h by sulfur, phosphorus and lithium source milling time under protective atmosphere；
2) under protective atmosphere, by step 1) grinding after gained mixture 2~10h is incubated at 200~700 DEG C.
The above-mentioned raw material for preparing sulfur phosphide solid electrolyte is dried sulphur powder, phosphorus powder and lithium hydride.
Above-mentioned sulphur powder, phosphorus powder need to be dried under protective atmosphere or vacuum, and baking temperature is 50~100 DEG C, is dried
Time is 1~24h.
Above-mentioned lithium source need to be dried under protective atmosphere or vacuum, and baking temperature is 50~100 DEG C, and drying time is
1~24h.
Above-mentioned protective atmosphere is argon.
Above-mentioned sulfur phosphide method for preparing solid electrolyte, step 1) in, preparing raw material includes that doping simple substance powder body is
One or more in Si, Ge, Sn, Se, Te, I.
Above-mentioned sulfur phosphide method for preparing solid electrolyte, step 2) in, by step 1) grinding after gained mixture enter
Row melting-Quenching Treatment, is then incubated 2~10h at 200~700 DEG C.
Above-mentioned melting-quenching is carried out within the border in the inert material such as quartz ampoule vaccum seal ring.
Above-mentioned melting-Quenching Treatment, melt temperature is 650~900 DEG C, and the melting time is 2~20h.
Above-mentioned quenching liquid is the one kind in frozen water, liquid nitrogen.
Above-mentioned steps 1) in be ground to dry grinding or wet grinding；The solvent that the wet grinding is used is aprotic solvent.
Above-mentioned aprotic solvent is polar proton inert solvent or proton inert non-polar solvent.
Above-mentioned aprotic solvent be DMF, acetone, the one kind in heptane, ethyl acetate.Above-mentioned step
It is rapid 1) in grinding using ball milling by the way of, mechanical milling process pellet mass ratio be 1：(5~100).
Above-mentioned drum's speed of rotation is 50~1000rpm.
Above-mentioned Ball-milling Time is 2~150h.
Beneficial effects of the present invention：The present invention uses the things such as price and chemism relatively low lithium hydride, sulphur powder, phosphorus powder
Material prepares the solid electrolyte of the sulfur phosphatization lithium ion for basis of production high-lithium ion conductor, process is simple, processing cost
It is cheap.The present invention is raw materials used to be solid, and course of reaction is gentle, and whole process is carried out under an inert atmosphere or in vacuum, ring
Border is friendly, is suitable for large-scale industrial production.
Further, noncrystal or microcrystal and amorphous have been obtained also using the processing mode of melting-quenching in the present invention
Body mixture, during follow-up heat treatment, noncrystal or microcrystal and the further crystal growth of noncrystal mixture make
The crystalline structure defect that must be ultimately formed is less, Stability Analysis of Structures, it is ensured that the performance of electrolyte.
Description of the drawings
Fig. 1 is the XRD determining result of the sulfur phosphide solid electrolyte crystal structure prepared by embodiment 1；
Fig. 2 is the XRD determining result of the sulfur phosphide solid electrolyte crystal structure prepared by embodiment 3.
Specific embodiment
Below technical scheme is described further with specific embodiment, but protection scope of the present invention is not limited
In this.
Embodiment 1
Sulfur phosphide solid electrolyte is mainly made up of the following raw material in the present embodiment：Lithium hydride (LiH), phosphorus powder (P), sulfur
Powder (S), wherein, lithium hydride (LiH), phosphorus powder (P), the mol ratio of sulphur powder (S) they are 7.7:3:11, wherein lithium hydride (LiH) is excessive
10mol%.Sulfur phosphide solid electrolyte molecular formula is Li7P3S11。
Sulfur phosphide method for preparing solid electrolyte is in the present embodiment：
1) LiH, sulphur powder, phosphorus powder are dried into 24h for 50 DEG C in vacuum drying oven.In glove box under argon gas atmosphere protection,
It is 7.7 according to mol ratio by a certain amount of lithium hydride (LiH), phosphorus powder (P), sulphur powder (S):3:10mm a diameter of with 30 after 11 mixing
Zirconium oxide balls be fitted into together in ball grinder.The ball grinder for sealing tight is taken out from glove box, loads comprehensive planet
Ball milling is carried out in ball mill, drum's speed of rotation is set as 380rpm, the every ball milling of ball mill 20 minutes stands cooling 5 minutes.Always have
Effect Ball-milling Time is 40h.
2) powder body of ball milling is taken out, heat treatment is carried out in vacuum tube furnace, heat treatment temperature is 300 DEG C, during insulation
Between be 4h, heat treatment is slowly cooled to room temperature gained powder body and is composition for Li after terminating7P3S11Solid electrolyte.
Embodiment 2
Sulfur phosphide solid electrolyte is mainly made up of the following raw material in the present embodiment：Lithium hydride (LiH), phosphorus powder (P), sulfur
Powder (S), wherein lithium hydride (LiH), phosphorus powder (P), the mol ratio of sulphur powder (S) are 9.6:3:12；Sulfur phosphide solid electrolyte point
Minor is Li9.6P3S12。
Sulfur phosphide method for preparing solid electrolyte is in the present embodiment：
1) sulphur powder, phosphorus powder are dried into 18h in vacuum drying oven.In glove box under argon gas atmosphere protection, will be a certain amount of
Lithium hydride (LiH), phosphorus powder (P), sulphur powder (S) according to mol ratio be 9.6:3:The oxidation of 10mm a diameter of with 15 after 12 mixing
Zirconium abrading-ball is fitted into together in ball grinder.The ball grinder for sealing tight is taken out from glove box, loads comprehensive planetary ball mill
In carry out ball milling, set drum's speed of rotation as 350rpm, ball mill stood cooling 5 minutes per ball milling 20 minutes.Total effectively ball milling
Time is 60h.
2) powder body of ball milling is taken out, heat treatment is carried out in vacuum tube furnace, heat treatment temperature is 280 DEG C, during insulation
Between be 4h, heat treatment is slowly cooled to room temperature gained powder body and is composition for Li after terminating9.6P3S12Solid electrolyte.
Embodiment 3
Sulfur phosphide solid electrolyte is mainly made up of the raw material of following mole in the present embodiment：Lithium hydride (LiH), phosphorus
Powder (P), sulphur powder (S), wherein lithium hydride (LiH), phosphorus powder (P), the mol ratio of sulphur powder (S) are 9.6:3:12；Sulfur phosphide solid
Electrolyte molecule formula is Li9.6P3S12。
Sulfur phosphide method for preparing solid electrolyte is in the present embodiment：
1) sulphur powder, phosphorus powder are dried into 18h in vacuum drying oven.In glove box under argon gas atmosphere protection, will be a certain amount of
Lithium hydride (LiH), phosphorus powder (P), sulphur powder (S) according to mol ratio be 9.6:3:It is fitted in ball grinder after 12 mixing, it is straight by 15
Footpath is fitted in tank for the zirconia ball abrading-ball of 10mm.The spheroidal graphite tank for sealing tight is taken out from glove box, loads comprehensive row
Ball milling is carried out in celestial body grinding machine, drum's speed of rotation is set as 350rpm, the every ball milling of ball mill 20 minutes stands cooling 5 minutes.Always
Effectively Ball-milling Time is 2h.
2) powder body of ball milling is taken out, vacuum powder is encapsulated in quartz ampoule, the quartz ampoule that will be equipped with powder is put into horse
Not in stove, 700 DEG C insulation 4 hours after, rapidly by it in frozen water Quenching Treatment, then by quartz ampoule argon protection under
Open in glove box and take out powder body, and be sealed against in ball grinder, set drum's speed of rotation as 250rpm, ball mill is per ball milling
20 minutes, cooling 5 minutes are stood, total effectively Ball-milling Time is 1 hour.
3) powder body of ball milling is taken out, in the tube furnace for having argon to protect heat treatment is carried out, heat treatment temperature is 280
DEG C, temperature retention time is 4h, and heat treatment is slowly cooled to room temperature gained powder body and is composition for Li after terminating9.6P3S12Solid electrolytic
Matter.
Embodiment 4
Sulfur phosphide solid electrolyte is mainly made up of the raw material of following mole in the present embodiment：Lithium hydride (LiH), phosphorus
Powder (P), sulphur powder (S), wherein lithium hydride (LiH), phosphorus powder (P), the mol ratio of sulphur powder (S) are 8:2:9；Sulfur phosphatization in the present embodiment
Thing method for preparing solid electrolyte is：
1) sulphur powder, phosphorus powder are dried into 24h in vacuum drying oven.In glove box under argon gas atmosphere protection, will be a certain amount of
Lithium hydride (LiH), phosphorus powder (P), sulphur powder (S) according to mol ratio be 8:2:It is fitted in ball grinder after 9 uniform mixing, it is straight by 15
Footpath is fitted in tank for the zirconia ball abrading-ball of 10mm.The ball grinder for sealing tight is taken out from glove box, loads comprehensive row
Ball milling is carried out in celestial body grinding machine, drum's speed of rotation is set as 600rpm, the every ball milling of ball mill 20 minutes stands cooling 5 minutes.Always
Effectively Ball-milling Time is 30h.
2) powder body of ball milling is taken out, heat treatment is carried out in vacuum tube furnace, heat treatment temperature is 320 DEG C, during insulation
Between be 4h, heat treatment is slowly cooled to room temperature gained powder body and is composition for Li after terminating8P2S9Solid electrolyte.
Embodiment 5
Sulfur phosphide solid electrolyte is mainly made up of the following raw material in the present embodiment：Lithium hydride (LiH), phosphorus powder (P), tellurium
Powder (Te), LiCl, wherein, lithium hydride (LiH), phosphorus powder (P), tellurium powder (Te), the mol ratio of LiCl are 5:1:5:1.
Sulfur phosphide method for preparing solid electrolyte is in the present embodiment：
1) sulphur powder, phosphorus powder are dried into 24h in vacuum drying oven.In glove box under argon gas atmosphere protection, will be a certain amount of
Lithium hydride (LiH), phosphorus powder (P), tellurium powder (Te), LiCl according to mol ratio 5:1:5:It is fitted in ball grinder after 1 uniform mixing, will
The zirconia ball abrading-ball of 15 a diameter of 10mm is fitted in tank.The ball grinder for sealing tight is taken out from glove box, loads complete
Ball milling is carried out in azimuth planetary ball mill, drum's speed of rotation is set as 600rpm, the every ball milling of ball mill 20 minutes stands cooling 5
Minute.Total effectively Ball-milling Time is 20h.
2) powder body of ball milling is taken out, heat treatment is carried out in vacuum tube furnace, heat treatment temperature is 300 DEG C, during insulation
Between be 10h, heat treatment is slowly cooled to room temperature gained powder body and is composition for Li after terminating6PTe5Cl solid electrolytes.
Embodiment 6
Sulfur phosphide solid electrolyte is mainly made up of the following raw material in the present embodiment：Lithium hydride (LiH), phosphorus powder (P), tellurium
Powder (Te), sulphur powder (S), LiCl are according to mol ratio 5:1:1:4:1；Sulfur phosphide solid electrolyte molecular formula is Li6PTeS4Cl。
1) sulphur powder, phosphorus powder are dried into 24h in vacuum drying oven.In glove box under argon gas atmosphere protection, will be a certain amount of
Lithium hydride (LiH), phosphorus powder (P), terbium powder (Te), sulphur powder (S), LiCl according to mol ratio 5:1:1:4:Load after 1 uniform mixing
In ball grinder, the zirconia ball abrading-ball of 15 a diameter of 10mm is fitted in tank.The tight ball grinder of sealing from glove box
Take out, being fitted in comprehensive planetary ball mill carries out ball milling, sets drum's speed of rotation as 600rpm, ball mill is per 20 points of ball milling
Clock, stands cooling 5 minutes.Total effectively Ball-milling Time is 20h.
2) powder body of ball milling is taken out, heat treatment is carried out in vacuum tube furnace, heat treatment temperature is 300 DEG C, during insulation
Between be 10h, heat treatment is slowly cooled to room temperature gained powder body and is composition for Li after terminating6PTeS4Cl solid electrolytes.
Embodiment 7
Sulfur phosphide solid electrolyte is mainly made up of the following raw material in the present embodiment：Lithium hydride (LiH), phosphorus powder (P), iodine
Simple substance powder body (I), sulphur powder (S) are according to mol ratio 5:1:1:4；Sulfur phosphide solid electrolyte molecular formula is Li5PS4I。
1) sulphur powder, phosphorus powder are dried into 24h in vacuum drying oven.In glove box under argon gas atmosphere protection, will be a certain amount of
Lithium hydride (LiH), phosphorus powder (P), elemental iodine powder body (I), sulphur powder (S) according to mol ratio 5:1:1:Load ball after 4 uniform mixing
In grinding jar, the zirconia ball abrading-ball of 15 a diameter of 10mm is fitted in tank.The ball grinder for sealing tight is taken from glove box
Go out, being fitted in comprehensive planetary ball mill carries out ball milling, set drum's speed of rotation as 600rpm, the every ball milling of ball mill 20 minutes,
Stand cooling 5 minutes.Total effectively Ball-milling Time is 20h.
2) powder body of ball milling is taken out, heat treatment is carried out in vacuum tube furnace, heat treatment temperature is 300 DEG C, during insulation
Between be 10h, heat treatment is slowly cooled to room temperature gained powder body and is composition for Li after terminating5P S4I solid electrolytes.
Claims (10)
1. a kind of sulfur phosphide solid electrolyte, it is characterised in that be mainly made up of the raw material of following molfraction：0.1~11
The lithium source, 0~15 part of sulfur, 0.1~6 part of phosphorus of part；The lithium source is any one in LiH, LiCl, LiBr, LiI or several
Kind.
2. as claimed in claim 1 a kind of sulfur phosphide solid electrolyte, it is characterised in that the lithium source, phosphorus, the molar part of sulfur
Number is than being (5~11)：(1~5)：(1~13).
3. as claimed in claim 1 a kind of sulfur phosphide solid electrolyte, it is characterised in that the raw material also includes doping simple substance
Powder body, the doping simple substance powder body is one or more in Si, Ge, Sn, Se, Te, I.
4. sulfur phosphide method for preparing solid electrolyte as claimed in claim 1, it is characterised in that comprise the steps：
1) under protective atmosphere, sulfur, phosphorus and lithium source are ground into 2~150h；
2) under protective atmosphere, by step 1) grinding after gained mixture 2~10h is incubated at 200~700 DEG C.
5. sulfur phosphide method for preparing solid electrolyte as claimed in claim 4, it is characterised in that step 2) in, by step
1) gained mixture carries out melting-Quenching Treatment after grinding, and 2~10h is then incubated at 200~700 DEG C.
6. sulfur phosphide method for preparing solid electrolyte as claimed in claim 5, it is characterised in that at the melting-quenching
The melt temperature of reason is 650~900 DEG C, and the melting time is 2~20h.
7. sulfur phosphide method for preparing solid electrolyte as claimed in claim 6, it is characterised in that the quenching quenching liquid
For the one kind in frozen water, liquid nitrogen.
8. sulfur phosphide method for preparing solid electrolyte as claimed in claim 4, it is characterised in that the step 1) in grinding
For dry grinding or wet grinding.
9. sulfur phosphide method for preparing solid electrolyte as claimed in claim 8, it is characterised in that the wet grinding use point
Powder is aprotic solvent.
10. sulfur phosphide method for preparing solid electrolyte as claimed in claim 9, it is characterised in that the proton inertia is molten
Agent is DMF, acetone, the one kind in heptane, ethyl acetate.
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| CN109301336A (en) * | 2018-09-18 | 2019-02-01 | 郑州新世纪材料基因组工程研究院有限公司 | Amorphous state sulfide solid electrolyte and preparation method thereof, lithium ion battery |
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| CN110911738A (en) * | 2019-12-04 | 2020-03-24 | 郑州新世纪材料基因组工程研究院有限公司 | Artificial solid electrolyte intermediate phase, preparation method thereof and solid lithium ion battery |
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| JP2019114525A (en) * | 2017-12-20 | 2019-07-11 | 現代自動車株式会社Ｈｙｕｎｄａｉ Ｍｏｔｏｒ Ｃｏｍｐａｎｙ | Solid electrolyte for all-solid battery having argyrodite crystal structure originating from single element and manufacturing method thereof |
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| CN110911738A (en) * | 2019-12-04 | 2020-03-24 | 郑州新世纪材料基因组工程研究院有限公司 | Artificial solid electrolyte intermediate phase, preparation method thereof and solid lithium ion battery |
| CN111653753A (en) * | 2020-06-28 | 2020-09-11 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of iron sulfide composite positive electrode material of sulfide all-solid-state battery |
| CN112582669A (en) * | 2020-12-11 | 2021-03-30 | 天津巴莫科技有限责任公司 | Air-stable multi-element rare earth oxide doped lithium sulfur phosphorus solid electrolyte material and preparation method thereof |
| CN113506918A (en) * | 2021-07-09 | 2021-10-15 | 郑州新世纪材料基因组工程研究院有限公司 | Preparation method of inorganic solid electrolyte |
| CN114122508A (en) * | 2021-11-26 | 2022-03-01 | 湖州昆仑先端固态电池科技有限公司 | Sulfide solid electrolyte and preparation method and application thereof |
| CN114122508B (en) * | 2021-11-26 | 2024-02-23 | 湖州昆仑先端固态电池科技有限公司 | Sulfide solid electrolyte and preparation method and application thereof |
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