CN110247109A - A kind of sulfide solid electrolyte and its preparation method and application - Google Patents

A kind of sulfide solid electrolyte and its preparation method and application Download PDF

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CN110247109A
CN110247109A CN201910641764.1A CN201910641764A CN110247109A CN 110247109 A CN110247109 A CN 110247109A CN 201910641764 A CN201910641764 A CN 201910641764A CN 110247109 A CN110247109 A CN 110247109A
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solid electrolyte
sulfide solid
ball milling
sulfide
mos
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CN110247109B (en
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何天贤
吴宇鹏
高远鹏
余乐
范伟贞
赵经纬
徐三善
徐金富
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Guangzhou Tinci Materials Technology Co Ltd
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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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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Abstract

The present invention relates to a kind of sulfide solid electrolytes and its preparation method and application.The chemical composition of the sulfide solid electrolyte is xLi2S·yMoS2·zMmSn, wherein x > 0, y > 0, m > 0, n > 0, z >=0, M are metallic element.The invention also discloses a kind of preparation methods of sulfide solid electrolyte, i.e., carry out a step heat treatment to sulfidic materials.Sulfide solid electrolyte preparation process of the invention is simple, and synthesis temperature is low, has wider electrochemical window, and preferable electrochemical stability can be used as a kind of ideal macroion conductance solid electrolyte material and be applied in all-solid lithium-ion battery.

Description

A kind of sulfide solid electrolyte and its preparation method and application
Technical field
The invention belongs to solid electrolyte technical fields, and in particular to a kind of sulfide solid electrolyte and preparation method thereof And purposes.
Background technique
All-solid-state battery is the only way which must be passed of the following battery technology development, and high security and high-energy density increasingly draw Play the concern of people.All-solid-state battery is made of positive electrode, negative electrode material and solid electrolyte, and a good solid-state Electrolyte has to meet high ionic conductivity, macroion transport number, excellent mechanical property, wide electrochemical stability window, good The conditions such as good chemical/thermal stability and easy preparation.So find and develop ideal solid electrolyte become academia and The research hotspot of business circles lithium electricity people.
Consolidate currently, solid electrolyte can be divided mainly into sulfide solid electrolyte, oxide solid electrolyte and polymer State electrolyte three categories.Wherein, best with the performance of sulfide solid electrolyte in terms of ionic conductivity, ionic conductivity It can match in excellence or beauty with liquid electrolyte.Nevertheless, sulfide solid electrolyte also have the shortcomings that it is obvious, that is, chemically unstable, It is easy to react with lithium metal in cyclic process, the service life of battery is caused to reduce rapidly.Therefore, maintaining sulfide solid Under the premise of state electrolyte high ionic conductivity, novel sulfide solid electrolyte is found and excavates, to improve and improve The stability of sulfide solid electrolyte just becomes necessary.
CN108878961A discloses a kind of preparation method of sulfide solid electrolyte, the preparation method include: by Reaction raw materials are placed in the sealing container of anhydrous and oxygen-free be grated after, using microwave radiation heating after a certain period of time cooling obtain institute State sulfide solid electrolyte.But the stability of the sulfide is poor.
CN108054426A discloses a kind of sulfide solid electrolyte and preparation method thereof for being oxidized object modification, by oxygen The modified sulfide solid electrolyte chemical composition of compound is Li3PS4-xOx, wherein 0 < x < 4, the oxide dopant used include Lithium-oxygen, phosphorus-oxygen, in lithium-phosphorus-oxygen one or more of any compound combination.But the stability of the sulfide It is poor.
Therefore, this field needs a kind of new sulfide compounds solid electrolyte, the ion-conductance of the sulfide solid electrolyte Conductance is high, and the electrochemical stability with height, and preparation process is simple, can be used as a kind of ideal solid state electrolysis material Material is applied in all-solid-state battery.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of sulfide solid electrolyte and its preparation sides Method and purposes.
To achieve the above object, the present invention takes technical solution below:
One of the objects of the present invention is to provide a kind of sulfide solid electrolyte, the change of the sulfide solid electrolyte Group becomes xLi2S·yMoS2·zMmSn, wherein x > 0, y > 0, m > 0, n > 0, z >=0, M are metallic element.
X of the present invention such as 1,1.2,1.5,2,2.5,3,3.6,4,4.5,5,6,6.6,8,8.5,9,9.2,10,12 Or 15 etc., described y such as 1,1.2,1.5,2,2.5,3,3.6,4,4.5,5,6,6.6,7,8,10 or 12 etc., m such as 1,1.2, 2,3,3.3,4,4.5,5,5.2,6,7.3,8,10 or 15 etc., described n such as 1,2,3,4,5,6,7,8,10 or 15 etc., the z Such as 0,1,2,3,4,5,7,8,9 or 10 etc..
The present invention provides a kind of sulfide solid electrolyte, the Mo element introduces two-dimensional layer in the form of sulfide MoS2, with the high distinguishing feature of carrier mobility；Introducing of the M element in the form of sulfide, can stable sulfide it is solid The structure of state electrolyte enhances repellence of the sulfide in humid air.
Preferably, the x be 1~16, the y be 1~8, the z be 1~8, preferably x:y:z be 1~8:1~5:1~ 5, value of the x such as 2,3,4,5,6,8,9,10,12,14 or 15 etc.；Value of the y such as 2,3,4,5,6 or 7 etc.； Value of the z such as 2,3,4,5,6 or 7 etc.；The x:y:z is 1~8:1~5:1~5, such as 1:1:1,1:2:2,1:3: 3,2:3:3,1:4:4,3:2:2,3:4:5,3:2:5,4:1:3,4:2:4,5:1:2,5:2:3 or 4:2:5 etc..
The value of described x, y, m, n and z within this range, can form stable sulfide structure and ion Conductivity.
Preferably, the raw material sources of the sulfide solid electrolyte are sulfide, preferably Li2S and MoS2, or Li2S、MoS2And MmSn, M is metallic element.
Preferably, the MmSnIncluding ZnS, MnS, CuS, FeS, CaS, Ag2S、Cu2S、Ni3S2、FeS2、CoS2、WS2With Al2S3In any one or at least two combination.
M in the present inventionmSnIncluding ZnS, MnS, CuS, FeS, CaS, Ag2S、Cu2S、Ni3S2、FeS2、CoS2、WS2And Al2S3 In any one or at least two combination, because of MmSnSulfide has metastable structure, is not easy in humid air Degradation, MmSnAddition can increase the stability of sulfide solid electrolyte.
Preferably, the atomic molar ratio of Li, Mo and S be 1~16:1~5:1~20, such as 8:1:1,8:1:2,8:1:3, 8:2:4、8:3:5、9:1:1、9:1:2、9:2:3、9:3:5、10:1:8、10:1:3、10:2:5、11:1:2、11:2:8、12:1: 1,12:2:6,13:1:2,13:3:8,14:1:2,15:1:3 or 15:3:10 etc..
The atomic molar of Li, Mo and S are than that can form stable sulfide structure within this range and protect in the present invention Demonstrate,prove ionic conductivity.
The second object of the present invention is to provide a kind of preparation method of sulfide solid electrolyte described in the first purpose, institute The method of stating includes the following steps:
Sulfidic materials are heat-treated, sulfide solid electrolyte is prepared.
Preferably, the sulfidic materials are Li2S and MoS2Or Li2S、MoS2And MmSn, M is metallic element.
Preferably, the MmSnIncluding ZnS, MnS, CuS, FeS, CaS, Ag2S、Cu2S、Ni3S2、FeS2、CoS2、WS2With Al2S3In any one or at least two combination.
Preferably, the heat treatment carries out under protective gas.
Preferably, the protective gas include in argon gas, helium and neon any one or at least two combination, Preferably argon gas.
Preferably, the flow of the protective gas be 80~150sccm, such as 90sccm, 100sccm, 110sccm, 120sccm, 130sccm or 140sccm etc..
Since sulfide solid electrolyte is easily oxidized decomposition in a heated condition, to avoid sample during heat treatment Be oxidized decomposition, gas of the invention is protective gas, preferably argon gas, argon gas as a kind of inert gas, hardly with Any substance reaction can avoid the pollution to sulfide solid electrolyte sample surfaces.
Preferably, mixing and ball milling first is carried out to sulfidic materials before the heat treatment, the ball milling is preferably high energy machine Tool ball milling.
High-energy mechanical ball milling is to combine physical method and chemical method, the basic principle is that the mistake that crystalline solid passes through Ultrafine Grinding Cheng Zhong, the effect of mechanical force can star its chemical activity so that it is generally necessary to carry out at high temperature reaction can be in lower temperature Degree is lower to carry out.High-energy mechanical ball milling, which has easy to operate, simple process, solvent-free, energy-efficient, particle diameter distribution narrow and reduces, to be burnt The advantages that junction temperature, it can be achieved that different component evenly dispersed and mixing.
In the present invention, by high-energy mechanical ball milling to sulfidic materials (Li2S and MoS2Or Li2S、MoS2And MmSn) It is sufficiently mixed, not only may be implemented that sulfide shape can also be made to the chemical activation and crushing effect of sulfidic materials At preliminary ceramic metastable phase structure, under heat treatment of the invention, it is capable of forming fine and close ceramic phase, promotes ionic conductance Rate.
Preferably, the revolving speed of the ball milling be 200~500rpm, such as 220rpm, 250rpm, 280rpm, 300rpm, 350rpm, 400rpm or 450rpm etc..
Preferably, the time of the ball milling is 5~10h, such as 6h, 7h, 8h or 9h etc..
Be pulverized and mixed when the revolving speed of ball milling is too low in the present invention it is ineffective, and rotational speed of ball-mill improve (ball-milling medium turn Speed also increases accordingly) when reaching a certain critical value or more, the centrifugal force of abrading-ball is greater than gravity, and ball-milling medium is just tightly attached to ball milling Container inner wall, abrading-ball, powder, mill tube are in opposing stationary state, and ball action stops at this time, and ball milling material does not generate any Percussion is also unfavorable for crushing and alloying process.So the revolving speed of ball milling is unsuitable excessively high and too low, to reach good powder Broken and mixed effect, the present invention use the revolving speed of ball milling for 200~500rpm, and Ball-milling Time is 5~10 hours.
Preferably, the material particle size that the ball milling obtains is 100nm~100 μm, such as 200nm, 500nm, 800nm, 1 μ M, 5 μm, 10 μm, 20 μm, 40 μm, 50 μm, 60 μm, 80 μm or 90 μm etc..
Preferably, the temperature of the heat treatment is 250~400 DEG C, such as 260 DEG C, 280 DEG C, 300 DEG C, 320 DEG C, 350 DEG C, 360 DEG C or 380 DEG C etc..
Preferably, the time of the heat treatment is 5~10h, such as 6h, 7h, 8h or 9h etc..
The temperature that the present invention is heat-treated is 250~400 DEG C, at this temperature, can reach preferable reaction effect, and vulcanize Object loss is few；When the temperature is low, solid phase reaction is incomplete between sulfide, and impurity is more, influences ionic conductivity；When temperature compared with Gao Shi, sulfide can evaporation loss, cause to match incorrect, equally will affect ionic conductivity.
It preferably, further include that grinding and Sieving and casing are carried out to obtained sulfide solid electrolyte after the heat treatment Process.
Preferably, the grinding carries out under protective gas.
Preferably, water content < 1ppm of the protective gas, for example, 0.1ppm, 0.2ppm, 0.3ppm, 0.4ppm, 0.5ppm, 0.6ppm, 0.7ppm, 0.8ppm or 0.9ppm etc..
Preferably, oxygen content < 1ppm of the protective gas, for example, 0.1ppm, 0.2ppm, 0.3ppm, 0.4ppm, 0.5ppm, 0.6ppm, 0.7ppm, 0.8ppm or 0.9ppm etc..
The application, which is ground, to be needed to carry out at water content < 1ppm and oxygen content < 1ppm protective gas, guarantees sulfide Side reaction impurity of degrading or generate will not occur during the grinding process.
Preferably, the process of the Sieving and casing include: by the powder after grinding with the sieve of 200 mesh filter out mesh number >= 200 target materials, such as 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh or 500 mesh etc..
As optimal technical scheme, the preparation method of sulfide solid electrolyte of the present invention includes the following steps:
(1) chemical general formula xLi is pressed2S·yMoS2·zMmSnMole metering a ratio weigh sulfidic materials, wherein x > 0, y > 0, m > 0, n > 0, z >=0, M are metallic element, and the sulfidic materials are Li2S and MoS2Or Li2S、MoS2And MmSn, by institute It states raw material and carries out high-energy mechanical ball milling mixing, the revolving speed of ball milling is 200~500rpm, and Ball-milling Time is 5~10h；
(2) to the material after ball milling in the case where argon flow is the atmosphere of 80~150sccm, 250~400 DEG C of the pre-heat treatments 5 ~10h obtains sulfide solid electrolyte material.
The third object of the present invention is to provide a kind of purposes of sulfide solid electrolyte as described in the first purpose, institute Sulfide solid electrolyte is stated for all-solid-state battery.
The fourth object of the present invention is to provide a kind of all solid state lithium ion secondary cell, and all solid state lithium ion is secondary Battery is using sulfide solid electrolyte described in the first purpose as electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
Sulfide solid electrolyte preparation process of the invention is simple, and synthesis temperature is low, has wider electrochemical window, Preferable electrochemical stability can be used as a kind of ideal macroion conductance solid electrolyte material and be applied to all solid state lithium ion In battery.
Detailed description of the invention
Fig. 1 is the Li that embodiment 1 is prepared10MoZnS8Solid electrolyte cyclic voltammogram；
Fig. 2 is the Li that embodiment 2 is prepared10MnMoS8Solid electrolyte cyclic voltammogram；
Fig. 3 is the Li that embodiment 3 is prepared10CuMoS8Solid electrolyte cyclic voltammogram.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of sulfide solid electrolyte, chemical composition Li10MoZnS8。
By Li2S、MoS2It is mixed with ZnS according to molar ratio for 5:1:1, using high energy ball mill ball milling, high energy mechanical The revolving speed of ball milling and time are respectively 400rpm and 8 hour, to obtain Initial solid electrolyte.It is initial solid by what is obtained State electrolyte is placed in tube furnace, is heat-treated under an argon atmosphere, and the flow of argon gas is 100sccm in reaction process, The temperature and time of reaction is 300 DEG C and 8 hours respectively.Then by grinding, the solid electrolyte grind into powder that will be obtained, Grinding carries out under an argon atmosphere, and the water content of the argon atmosphere is 0.5ppm, oxygen content 0.3ppm, later with 200 mesh Sieve filter out solid electrolyte powder to get to solid electrolyte material Li10MoZnS8。
The Li that will be obtained10MoZnS8Solid electrolyte is assembled into battery, and (positive electrode active materials are sulphur, and negative electrode active material is Lithium piece, solid electrolyte is with a thickness of 1mm), at room temperature, charge and discharge evaluate and test instrument TOSCAT-3100 in the scanning electricity of 0~5V Pressure, 1mA/cm2Current density under carry out cyclic voltammetry, test results are shown in figure 1, as can be seen from Figure, tool There is the electrochemical stability of height, ac impedance measurement is carried out using AC impedence method, applied voltage is 10~100mV, scanning Frequency is 0.1Hz~10MHz, and measuring its ionic conductivity at 25 DEG C is 1 × 10-2S/cm。
Embodiment 2
The difference from embodiment 1 is that ZnS is replaced with MnS, obtained material is Li10MnMoS8。
The Li that will be obtained10MnMoS8Solid electrolyte, mode same as Example 1 are assembled into battery and are tested, and survey Test result is as shown in Fig. 2, as can be seen from Figure, the electrochemical stability with height, AC impedence method measures its ion Conductivity is 1 × 10-2S/cm。
Embodiment 3
The difference from embodiment 1 is that ZnS is replaced with CuS, obtained material is Li10CuMoS8。
The Li that will be obtained10CuMoS8Solid electrolyte, mode same as Example 1 are assembled into battery and are tested, and survey Test result is as shown in figure 3, as can be seen from Figure, the electrochemical stability with height, AC impedence method measures its ion Conductivity is 1 × 10-2S/cm。
Embodiment 4
The difference from embodiment 1 is that the temperature of the heat treatment is 250 DEG C.
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, the electrochemical stability with height, it is 1 × 10 that AC impedence method, which measures its ionic conductivity,-2S/cm。
Embodiment 5
The difference from embodiment 1 is that the temperature of the heat treatment is 400 DEG C.
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, the electrochemical stability with height, it is 1 × 10 that AC impedence method, which measures its ionic conductivity,-2S/cm。
Embodiment 6
The difference from embodiment 1 is that the temperature of the heat treatment is 150 DEG C.
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, electrochemical stability is poor, because of the reason that reaction temperature is lower, causes solid phase reaction incomplete, and impurity is more, from Subconductivity rate is 1 × 10-4S/cm。
Embodiment 7
The difference from embodiment 1 is that the temperature of the heat treatment is 500 DEG C.
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, electrochemical stability is poor, because of the higher reason of solid phase reaction temperature, sulfide is caused to be evaporated loss seriously, brilliant Body is destructurized, and ionic conductivity is 1 × 10-4S/cm。
Embodiment 8
The difference from embodiment 1 is that by Li2S、MoS2It is mixed with ZnS according to molar ratio for 5:6:2.
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, electrochemical stability is poor, because of the reason of Li ionic carrier concentration deficiency, ionic conductivity is 1 × 10-3S/ cm。
Embodiment 9
The difference from embodiment 1 is that by Li2S、MoS2With ZnS according to molar ratio be 10:2:1.
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, electrochemical stability is poor, because Li ion is excessive, causes crystal structure unstable, and ionic conductivity is 1 × 10- 3S/cm。
Embodiment 10
The present embodiment provides a kind of sulfide solid electrolyte, chemical composition Li6MoS5。
By Li2S and MoS2It is the mixing of 3:1 row according to molar ratio, using high energy ball mill ball milling, high-energy mechanical ball milling turns Speed and time are respectively 500rpm and 5 hour, to obtain Initial solid electrolyte.The Initial solid electrolyte that will be obtained Material is placed in tube furnace, is heat-treated under helium atmosphere, and the flow of helium is 80sccm, the temperature of reaction in reaction process It is 250 DEG C and 10 hours respectively with the time.Then by grinding, the solid electrolyte grind into powder that will be obtained is ground in helium It is carried out under gas atmosphere, the water content of the helium atmosphere is 0.7ppm, oxygen content 0.2ppm, is sieved later with the sieve of 200 mesh Solid electrolyte powder is selected to get solid electrolyte material Li is arrived6MoS5。
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, the electrochemical stability with height, ionic conductivity is 1 × 10-3S/cm。
Embodiment 11
The present embodiment provides a kind of sulfide solid electrolyte, chemical composition Li8Mo3W2S14。
By Li2S、MoS2And WS2It is the mixing of 4:3:2 row according to molar ratio, using high energy ball mill ball milling, high energy mechanical ball The revolving speed of mill and time are respectively 200rpm and 10 hour, to obtain Initial solid electrolyte.It is initial solid by what is obtained State electrolyte is placed in tube furnace, is heat-treated under helium atmosphere, and the flow of helium is 150sccm in reaction process, The temperature and time of reaction is 400 DEG C and 5 hours respectively.Then by grinding, the solid electrolyte grind into powder that will be obtained, Grinding carries out under helium atmosphere, and the water content of the helium atmosphere is 0.5ppm, oxygen content 0.5ppm, later with 200 mesh Sieve filter out solid electrolyte powder to get to solid electrolyte material Li8Mo3W2S14。
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, test result table Bright, the electrochemical stability with height, ionic conductivity is 1 × 10-2S/cm。
Comparative example 1
The difference from embodiment 1 is that by MoS2Replace with CrS2。
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, experimental result table Bright, ionic conductivity only has 1 × 10-4S/cm, reason are that energy gap increases, CrS2The matchmaker of carrier fast transferring is not had Jie's ability causes Li ionic mobility to be lower, and ionic conductivity reduces.
Comparative example 2
The difference from embodiment 1 is that by MoS2Replace with WS2。
The solid electrolyte that will be obtained, mode same as Example 1 are assembled into battery and are tested, experimental result table Bright, ionic conductivity only has 1 × 10-4S/cm, reason are that energy gap increases, WS2The matchmaker of carrier fast transferring is not had Jie's ability causes Li ionic mobility to be lower, and ionic conductivity reduces.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention, But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention Within protection scope and the open scope.

Claims (10)

1. a kind of sulfide solid electrolyte, which is characterized in that the chemical composition of the sulfide solid electrolyte is xLi2S· yMoS2·zMmSn, wherein x > 0, y > 0, m > 0, n > 0, z >=0, M are metallic element.
2. sulfide solid electrolyte according to claim 1, which is characterized in that the x be 1~16, the y be 1~ 8, the z are 1~8, and preferably x:y:z is 1~8:1~5:1~5.
3. sulfide solid electrolyte according to claim 1 or 2, which is characterized in that the sulfide solid electrolyte Raw material sources be sulfide, preferably Li2S and MoS2Or Li2S、MoS2And MmSn, M is metallic element；
Preferably, the MmSnIncluding ZnS, MnS, CuS, FeS, CaS, Ag2S、Cu2S、Ni3S2、FeS2、CoS2、WS2And Al2S3In Any one or at least two combination.
4. described in any item sulfide solid electrolytes according to claim 1~3, which is characterized in that the atom of Li, Mo and S Molar ratio is 1~16:1~5:1~20.
5. a kind of preparation method of any one according to claim 1~4 sulfide solid electrolyte, which is characterized in that institute The method of stating includes the following steps:
Sulfidic materials are heat-treated, sulfide solid electrolyte is prepared.
6. preparation method according to claim 5, which is characterized in that the sulfidic materials are Li2S and MoS2, or Li2S、MoS2And MmSn, M is metallic element；
Preferably, the MmSnIncluding ZnS, MnS, CuS, FeS, CaS, Ag2S、Cu2S、Ni3S2、FeS2、CoS2、WS2And Al2S3In Any one or at least two combination.
7. method according to claim 5 or 6, which is characterized in that the heat treatment carries out under protective gas；
Preferably, the protective gas include in argon gas, helium and neon any one or at least two combination, preferably For argon gas；
Preferably, the flow of the protective gas is 80~150sccm；
Preferably, mixing and ball milling first is carried out to sulfidic materials before the heat treatment, the ball milling is preferably high energy mechanical ball Mill；
Preferably, the revolving speed of the ball milling is 200~500rpm；
Preferably, the time of the ball milling is 5~10h；
Preferably, the material particle size that the ball milling obtains is 100nm~100 μm；
Preferably, the temperature of the heat treatment is 250~400 DEG C；
Preferably, the time of the heat treatment is 5~10h；
It preferably, further include the mistake that grinding and Sieving and casing are carried out to obtained sulfide solid electrolyte after the heat treatment Journey；
Preferably, the grinding carries out under protective gas；
Preferably, water content < 1ppm of the protective gas；
Preferably, oxygen content < 1ppm of the protective gas；
Preferably, the process of the Sieving and casing includes: that the powder after grinding is filtered out mesh number >=200 with the sieve of 200 mesh Target material.
8. according to the described in any item methods of claim 5-7, which is characterized in that described method includes following steps:
(1) chemical general formula xLi is pressed2S·yMoS2·zMmSnMole metering a ratio weigh sulfidic materials, wherein x > 0, y > 0, m > 0, n > 0, z >=0, M are metallic element, and the sulfidic materials are Li2S and MoS2Or Li2S、MoS2And MmSn, by the original Material carries out high-energy mechanical ball milling mixing, and the revolving speed of ball milling is 200~500rpm, and Ball-milling Time is 5~10h；
(2) to the material after ball milling in the case where argon flow is the atmosphere of 80~150sccm, 250~400 DEG C of the pre-heat treatments 5~ 10h obtains sulfide solid electrolyte material.
9. a kind of purposes of sulfide solid electrolyte according to claim 1-4, which is characterized in that the sulphur Compound solid electrolyte is used for all-solid-state battery.
10. a kind of all solid state lithium ion secondary cell, which is characterized in that all solid state lithium ion secondary cell is with claim The described in any item sulfide solid electrolytes of 1-4 are as electrolyte.
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