CN108832172A - A kind of all solid state electrolyte material, preparation method and all solid lithium secondary battery - Google Patents

A kind of all solid state electrolyte material, preparation method and all solid lithium secondary battery Download PDF

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CN108832172A
CN108832172A CN201810653010.3A CN201810653010A CN108832172A CN 108832172 A CN108832172 A CN 108832172A CN 201810653010 A CN201810653010 A CN 201810653010A CN 108832172 A CN108832172 A CN 108832172A
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sulfide
solid state
state electrolyte
electrolyte material
solid
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CN108832172B (en
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姚霞银
万红利
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering 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
    • H01M10/056—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
    • 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
    • H01M10/058—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • H01M2300/0088—Composites
    • 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

Abstract

The present invention provides a kind of all solid state electrolyte material, has following below formula：(100-x)(5Li2S·A·M)·x(y1J·y2D·y3E·y4Q) formula 1；Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；M is the second sulfide, and second sulfide is P2S5And/or P2S3；J, D, E and Q are dopant, and described J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halide；0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 95,0≤y2< 95,0≤y3< 95,0≤y4< 95, and y1、y2、y3And y4In, at least two be not 0 simultaneously.The present invention also provides the preparation methods and all solid lithium secondary battery of a kind of all solid state electrolyte material.

Description

A kind of all solid state electrolyte material, preparation method and all solid lithium secondary battery
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of all solid state electrolyte materials, preparation method And all solid lithium secondary battery.
Background technique
Lithium ion battery has many advantages, such as energy density height, output voltage height, long service life, environmentally friendly, exists Consumer electronics, electric tool, medical electronics etc. can charge-discharge battery field be applied widely, future in various extensive storages There is vast potential for future development in energy.But since traditional lithium ion battery generally uses organic liquid electrolytes and gel state electricity Xie Zhi inevitably introduces volatile, inflammable, explosive organic liquid in battery system, brings seriously to battery system Security risk so that lithium ion battery application be restricted.And all solid lithium secondary battery uses all solid state electrolyte generation For organic electrolyte, battery is made to improve the energy density of battery while ensuring safety, more meets current power train in vehicle application electricity The direction of pond development.
One of core composition as all solid lithium secondary battery, solid electrolyte material is to realize the secondary electricity of all solid lithium The key of pond high performance.The inorganic solid electrolyte of most study includes sulfide solid electrolyte and oxide solid at present Electrolyte.Although solid oxide electrolyte chemical stability and ionic conductivity are high, its interface impedance between electrode Greatly.Sulfide electrolyte is compared with oxide electrolyte, due to S2-Radius ratio O2-Greatly, and polarization is strong, replaces oxygen with sulphur On the one hand oxygen in compound crystalline state electrolyte can play and increase unit cell volume, expand Li+The effect of transmission channel size；Separately On the one hand, skeleton is weakened to Li+Attraction and constraint, increase removable mobile carriers Li+Concentration.Therefore, with oxide electrolysis Matter is compared, and sulfide solid electrolyte shows higher ionic conductivity.
The conductivity of electrolyte, but the conductivity phase of the sulfide electrolyte after existing doping can be improved by adulterating To lower.Therefore, it is urgent to provide a kind of high conductance, all solid state electrolyte materials of high stability.
Summary of the invention
The purpose of the present invention is to provide a kind of all solid state electrolyte material, preparation method and the secondary electricity of all solid lithium Pond, all solid state electrolyte material ions conductivity in the present invention is high, electrochemical stability is good.
The present invention provides a kind of all solid state electrolyte material, has following below formula：
(100-x)(5Li2S·A·M)·x(y1J·y2D·y3E·y4Q) formula 1；
Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；
M is the second sulfide, and second sulfide is P2S5And/or P2S3；
J, D, E and Q are dopant, and J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halide；
0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 100,0≤y2< 100,0≤y3< 100,0≤y4< 100, and y1、y2、y3And y4In, at least two be not 0 simultaneously.
Preferably, 0.2≤x≤20.
Preferably, the lithium salts is Li3PO4、Li3BO3、Li4SiO4、Li4Ti5O12、Li3VO4、Li2SO4、Li3AlO3、 Li3GaO3、Li3InO3、Li4GeO4、Li3TaO4And Li4TeO4One of or it is a variety of.
Preferably, the oxide is P2O5、B2O3、SiO2、TiO2、V2O5、Al2O3、Ga2O3、In2O3、GeO2、TaO2、 ZnO、MnO、MnO2And TeO2One of or it is a variety of.
Preferably, the sulfide is SiS2、SnS2、SiS、SnS、TiS2、FeS、FeS2、MoS2、B2S3、Al2S3、MnS、 ZnS、NiS、Ni2S3、NiS2And MnS2One of or it is a variety of.
Preferably, the halide is one of LiCl, LiF, LiBQ and LiI or a variety of.
The present invention provides a kind of preparation method of all solid state electrolyte material, includes the following steps：
A) by Li2S, the first sulfide, the second sulfide and dopant mixed grinding, obtain initial material；
B) under an inert atmosphere, initial material obtained by step A) is heat-treated, obtains all solid state electrolyte as shown in Equation 1 Material；
(100-x)(5Li2S·A·M)·x(y1J·y2D·y3E·y4Q) formula 1；
Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；
M is the second sulfide, and second sulfide is P2S5And/or P2S3；
J, D, E and Q are dopant, and described J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halogenation Object；
0 < x < 100；y1+y2+y3+y4=100,0≤y1< 100,0≤y2< 100,0≤y3< 100,0≤y4< 100, And y1、y2、y3And y4In, at least two be not 0 simultaneously.
Preferably, described to be ground to one of hand mill, high-energy ball milling and roller mill or a variety of；
The time of the grinding is 0.5~72 hour.
Preferably, the temperature of the heat treatment is 350~1000 DEG C；
The time of the heat treatment is 0.5~24 hour.
The present invention provides a kind of all solid lithium secondary battery, including anode, cathode and electrolyte；
The electrolyte is all solid state electrolyte material described above.
The present invention provides a kind of all solid state electrolyte material, has following below formula：(100-x)(5Li2S·A·M)·x (y1J·y2D·y3E·y4Q) formula 1；Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；M is second Sulfide, second sulfide are P2S5And/or P2S3；J, D, E and Q are dopant, and described J, D, E and Q are independently Selected from lithium salts, oxide, sulfide or halide；0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 95,0≤y2< 95,0 ≤y3< 95,0≤y4< 95, and y1、y2、y3And y4In, at least two be not 0 simultaneously.All solid lithium provided by the invention is secondary Cell electrolyte materials include that a variety of dopants are introduced in electrolyte system by the synergistic effect between different dopants Vacancy or gap ion widen lithium ion transport channel, and increase can transmit lithium concentration, weaken skeleton to Li+Attraction and Constraint, further increases the lithium ion conductivity of all solid state electrolyte, improves chemical property.The result shows that the present invention mentions Conductivity is 5 × 10 to the lithium ion conductivity of all solid lithium secondary battery electrolyte of confession at room temperature-3S cm-1~1.5 ×10-2S cm-1, electrochemical window is up to 10V, and preparation method provided by the invention is easy to operate, short preparation period, utilizes Industrialized production.
Specific embodiment
The present invention provides a kind of all solid state electrolyte materials, have following below formula：
(100-x)(5Li2S·A·M)·x(y1J·y2D·y3E·y4Q) formula 1；
Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；
M is the second sulfide, and second sulfide is P2S5And/or P2S3；
J, D, E and Q are dopant, and described J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halogenation Object；
0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 95,0≤y2< 95,0≤y3< 95,0≤y4< 95, and y1、 y2、y3And y4In, at least two be not 0 simultaneously.
In the present invention, 0 < x < 100, it is preferred that 0 x≤50 <, more preferably, 0.2≤x≤20, specifically, at this In the embodiment of invention, x 5,10,15 or 20.
In the present invention, J, D, E and Q are dopant, and the dopant can be 2 kinds, 3 kinds or 4 kinds；That is, y1、y2、y3 And y4In, it can be 2 and be 0 or be not all 0. for 0,1
J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halide；
The lithium salts is preferably Li3PO4、Li3BO3、Li4SiO4、Li4Ti5O12、Li3VO4、Li2SO4、Li3AlO3、 Li3GaO3、Li3InO3、Li4GeO4、Li3TaO4And Li4TeO4One of or a variety of, more preferably Li3PO4、Li3BO3Or Li3AlO3；
The oxide is preferably P2O5、B2O3、SiO2、TiO2、V2O5、Al2O3、Ga2O3、In2O3、GeO2、TaO2、ZnO、 MnO、MnO2And TeO2One of or a variety of, more preferably P2O5、B2O3Or Al2O3；
The sulfide is preferably SiS2、SnS2、SiS、SnS、TiS2、FeS、FeS2、MoS2、B2S3、Al2S3、MnS、ZnS、 NiS、Ni2S3、NiS2And MnS2One of or a variety of, more preferably MoS2, ZnS or FeS2；
The halide is preferably one of LiCl, LiF, LiBQ and LiI or a variety of, more preferably LiBQ, LiCl or LiI。
Specifically, in the present invention, described J, D, E and Q's selects can be J as lithium salts, and D is oxide, and E is vulcanization Object, Q are halide, are selected according to this kind, y1、y2、y3And y4Value be preferably：75:0:25:0,0:50:0:50,20:0:0: 80,0:10:90:0,0:83.3:16.7:0,93.75:0:6.25:0,50:0:0:50,0:20:20:60,10:20:40:30, 30:0:20:50 or 30:0:30:40.
It should be noted that the selection and proportionate relationship above with respect to J, D, E and Q type are only preferred in the present invention Citing, it is not limited to above range.On the basis of the present invention, the reasonable selection made, for example, by the type of J, D, E and Q Mutually exchange or proportionate relationship carry out it is proportional expand or shrink, all within the scope of the present invention.
The present invention also provides a kind of preparation methods of all solid state electrolyte material, include the following steps：
A) by Li2S, the first sulfide, the second sulfide and dopant mixed grinding, obtain initial material；
B) under an inert atmosphere, initial material obtained by step A) is heat-treated, obtains all solid state electrolyte as shown in Equation 1 Material；
(100-x)(5Li2S·A·M)·x(y1J·y2D·y3E·y4Q) formula 1；
Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；
M is the second sulfide, and second sulfide is P2S5And/or P2S3；
J, D, E and Q are dopant, and described J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halogenation Object；
0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 95,0≤y2< 95,0≤y3< 95,0≤y4< 95, and y1、 y2、y3And y4In, at least two be not 0 simultaneously.
In the present invention, the type and dosage one of the type and dosage of the raw material and the above each raw material It causes, details are not described herein.
The mode of the mixed grinding is preferably one of hand mill, high-energy ball milling and roller mill or a variety of, more preferably roller The time of mill, the roller mill is preferably 0.5~72 hour, and more preferably 6~36 hours.
The heat treatment is sintering, and the temperature of the heat treatment is preferably 350~1000 DEG C, more preferably 500~800 DEG C, specifically, in an embodiment of the present invention, can be 580 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 680 DEG C, 600 DEG C or 630 ℃；The time of the heat treatment is preferably 0.5~24 hour, and more preferably 5~15 hours, specifically, in implementation of the invention In example, the time of heat treatment be can be 20 hours, 8 hours, 4 hours or 12 hours.
The present invention also provides a kind of all solid lithium secondary battery, including anode, cathode and electrolyte, all solid lithiums two Primary cell electrolyte is above-mentioned high conductance all solid state electrolyte material or prepares according to above-mentioned preparation method high electric Lead all solid state electrolyte material.It is good that above-mentioned high conductance all solid state electrolyte material can be such that all solid lithium secondary battery has Good chemical property.The present invention is not particularly limited the anode, and the anode can be oxide, sulfide and simple substance Sulphur etc., and just extremely blended anode；The present invention is not particularly limited the cathode, and the cathode can use lithium metal, carbon And its congeners etc. is made.
The present invention provides a kind of all solid state electrolyte material, has following below formula：(100-x)(5Li2S·A·M)·x (y1J·y2D·y3E·y4Q) formula 1；Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；M is second Sulfide, second sulfide are P2S5And/or P2S3；J, D, E and Q are dopant, and described J, D, E and Q are independently Selected from lithium salts, oxide, sulfide or halide；0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 95,0≤y2< 95,0 ≤y3< 95,0≤y4< 95, and y1、y2、y3And y4In, at least two be not 0 simultaneously.All solid lithium provided by the invention is secondary Cell electrolyte materials include that a variety of dopants are introduced in electrolyte system by the synergistic effect between different dopants Vacancy or gap ion widen lithium ion transport channel, and increase can transmit lithium concentration, weaken skeleton to Li+Attraction and Constraint, further increases the lithium ion conductivity of all solid state electrolyte, improves chemical property.The result shows that the present invention mentions Conductivity is 5 × 10 to the lithium ion conductivity of all solid lithium secondary battery electrolyte of confession at room temperature-3S cm-1~1.5 ×10-2S cm-1, electrochemical window is up to 10V, and preparation method provided by the invention is easy to operate, short preparation period, utilizes Industrialized production.
In order to further illustrate the present invention, with reference to embodiments to a kind of all solid state electrolyte material provided by the invention Material, preparation method and all solid lithium secondary battery are described in detail, but cannot be understood as to the scope of the present invention Restriction.
Embodiment 1
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, Li3PO4With ZnS according to molar ratio 75：After 25 weigh, then press (5Li2S·GeS2·P2S5)：(75Li3PO425ZnS)=95：Li is added in 5 mass ratio3PO4With ZnS grinds 6h, gained presoma is fitted into quartz glass tube after mixing, is cooled to after sealed sintering 4h at 580 DEG C Room temperature obtains expecting all solid state electrolyte material eventually.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 6.8 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 2
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, P2O5With LiCl according to molar ratio 50：After 50 weigh, then press (5Li2S·GeS2·P2S5)：(50P2O550LiCl)=90：P is added in 10 mass ratio2O5With LiCl grinds 6h, gained presoma is fitted into quartz glass tube after mixing, cooling after sealed sintering 12h at 700 DEG C It obtains expecting all solid state electrolyte material eventually to room temperature.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 1.5 × 10-2S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 3
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, Li3BO3With LiI according to molar ratio 20：After 80 weigh, then press (5Li2S·GeS2·P2S5)：(20Li3BO380LiI)=80：Li is added in 20 mass ratio3BO3With LiI grinds 36h, is cooled to room temperature after sealed sintering 8h at 700 DEG C after mixing and obtains expecting all solid state electrolyte material eventually Material.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 7.5 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 4
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, B2O3With ZnS according to molar ratio 10：After 90 weigh, then press (5Li2S·GeS2·P2S5)：(10B2O390ZnS)=90：B is added in 10 mass ratio2O3And ZnS, Gained presoma for 24 hours, is fitted into quartz glass tube after mixing, is cooled to room after sealed sintering 4h at 750 DEG C by grinding Temperature obtains expecting all solid state electrolyte material eventually.
After obtaining all solid lithium electrolyte, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carry out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric Test (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 6.2 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 5
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, Al2O3And MoS2According to molar ratio 83.3：After 16.7 weigh, then press (5Li2S·GeS2·P2S5)：(83.3Al2O3·16.7MoS2)=85：15 mass ratio adds Enter Al2O3And MoS2, 20h is ground, gained presoma is fitted into quartz glass tube after mixing, the sealed sintering at 800 DEG C Room temperature is cooled to after 8h to obtain expecting all solid state electrolyte material eventually.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 5.9 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 6
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, Li3AlO3And FeS2According to mole Than 93.75：After 6.25 weigh, then press (5Li2S·GeS2·P2S5)：(93.75Li3AlO3·6.25FeS2)=90：10 matter Amount is than being added Li3AlO3And FeS2, 18h is ground, after mixing, is cooled to room temperature after being sintered 8h under open system at 700 DEG C It obtains expecting all solid state electrolyte material eventually.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 7.8 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 7
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, P2O5With LiCl according to molar ratio 50：After 50 weigh, then press (5Li2S·GeS2·P2S5)：(50P2O550LiCl)=90：P is added in 10 mass ratio2O5With LiCl grinds 6h, is cooled to room temperature in open system after sintering 8h at 680 DEG C after mixing and obtains expecting all solid state electrolysis eventually Material.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 1.3 × 10-2S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 8
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, Al2O3, FeS2, LiCl is according to rubbing That ratio 20：20：After 60 weigh, then press (5Li2S·GeS2·P2S5)：(20Al2O3·20FeS260LiCl)=85：15 matter Amount is than being added Al2O3, FeS2And LiCl, 20h is ground, gained presoma is fitted into quartz glass tube after mixing, 600 Room temperature is cooled at DEG C after sealed sintering 8h to obtain expecting all solid state electrolyte material eventually.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 6.9 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 9
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1；Li3PO4, Al2O3, ZnS, LiCl According to molar ratio 10：20：40：After 30 weigh, then press (5Li2S·GeS2·P2S5)：(10Li3PO4·20Al2O3·40ZnS· 30LiCl)=85：Li is added in 15 mass ratio3PO4, Al2O3, ZnS and LiCl grind 25h, after mixing by gained forerunner Body is fitted into quartz glass tube, is cooled to room temperature after sealed sintering 8h at 630 DEG C and is obtained expecting all solid state electrolyte material eventually.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 7.4 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 10
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1；Li3PO4, Li3BO3, MoS2, LiI According to molar ratio 10：20：20：After 50 weigh, then press (5Li2S·GeS2·P2S5)：(10Li3PO4·20Li3BO3· 20MoS250LiI)=85：Li is added in 15 mass ratio3PO4, Li3BO3, MoS2And LiI, 30h is ground, after mixing, Room temperature is cooled at 600 DEG C in open system after sintering 8h to obtain expecting all solid state electrolyte material eventually.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 8.6 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
Embodiment 11
Under argon atmosphere protection, by Li2S、GeS2And P2S5According to molar ratio 5：1：1, Li3AlO3, MoS2, LiBr according to Molar ratio 30：30：After 40 weigh, then press (5Li2S·GeS2·P2S5)：(30Li3AlO3·30MoS240LiBr)=85：15 Mass ratio be added Li3AlO3, MoS2And LiBQ, grind 20h, after mixing by gained presoma at 600 DEG C open system Room temperature is cooled to after middle sintering 8h to obtain expecting all solid state electrolyte material eventually.
After obtaining all solid state electrolyte material, electrochemical property test is carried out.At room temperature, to prepared All solid state electrolyte material carries out electrochemical alternate impedance spectrum (EIS) test (using carbon plate as blocking electrode) and cyclic voltammetric is surveyed Examination (using lithium metal as reference electrode, stainless steel is to electrode), the results showed that：Room temperature lithium ion conductivity is 7.2 × 10-3S cm-1, electrochemical window is 0~10V, illustrates that resulting materials have good electric conductivity and electrochemical stability.
Above-mentioned high conductance all solid state electrolyte material and lithium anode, cobalt acid lithium blended anode are assembled into all solid lithium Secondary cell, test result show：Obtained all solid lithium secondary battery has good high rate performance and cycle performance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of all solid state electrolyte material has following below formula：
(100-x)(5Li2S·A·M)·x(y1J·y2D·y3E·y4Q) formula 1；
Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；
M is the second sulfide, and second sulfide is P2S5And/or P2S3；
J, D, E and Q are dopant, and J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halide；
0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 95,0≤y2< 95,0≤y3< 95,0≤y4< 95, and y1、y2、y3 And y4In, at least two be not 0 simultaneously.
2. all solid state electrolyte material according to claim 1, which is characterized in that 0.2≤x≤20.
3. all solid state electrolyte material according to claim 1, which is characterized in that the lithium salts is Li3PO4、Li3BO3、 Li4SiO4、Li4Ti5O12、Li3VO4、Li2SO4、Li3AlO3、Li3GaO3、Li3InO3、Li4GeO4、Li3TaO4And Li4TeO4In It is one or more.
4. all solid state electrolyte material according to claim 1, which is characterized in that the oxide is P2O5、B2O3、 SiO2、TiO2、V2O5、Al2O3、Ga2O3、In2O3、GeO2、TaO2、ZnO、MnO、MnO2And TeO2One of or it is a variety of.
5. all solid state electrolyte material according to claim 1, which is characterized in that the sulfide is SiS2、SnS2、 SiS、SnS、TiS2、FeS、FeS2、MoS2、B2S3、Al2S3、MnS、ZnS、NiS、Ni2S3、NiS2And MnS2One of or it is a variety of.
6. all solid state electrolyte material according to claim 1, which is characterized in that the halide be LiCl, LiF, One of LiBQ and LiI or a variety of.
7. a kind of preparation method of all solid state electrolyte material, includes the following steps：
A) by Li2S, the first sulfide, the second sulfide and dopant mixed grinding, obtain initial material；
B) under an inert atmosphere, initial material obtained by step A) is heat-treated, obtains all solid state electrolyte material as shown in Equation 1 Material；
(100-x)(5Li2S·A·M)·x(y1J·y2D·y3E·y4Q) formula 1；
Wherein, A is the first sulfide, and first sulfide is GeS and/or GeS2；
M is the second sulfide, and second sulfide is P2S5And/or P2S3；
J, D, E and Q are dopant, and described J, D, E and Q are independently selected from lithium salts, oxide, sulfide or halide；
0 x≤50 <；y1+y2+y3+y4=100,0≤y1< 95,0≤y2< 95,0≤y3< 95,0≤y4< 95, and y1、y2、y3 And y4In, at least two be not 0 simultaneously.
8. preparation method according to claim 7, which is characterized in that described to be ground in hand mill, high-energy ball milling and roller mill It is one or more；
The time of the grinding is 0.5~72 hour.
9. preparation method according to claim 7, which is characterized in that the temperature of the heat treatment is 350~1000 DEG C；
The time of the heat treatment is 0.5~24 hour.
10. a kind of all solid lithium secondary battery, including anode, cathode and electrolyte；
The electrolyte is that all solid state electrolyte material described in claim 1~6 any one or claim 7~9 are any All solid state electrolyte material made from preparation method described in one.
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