CN111146438B - Positive electrode active material, preparation method thereof, battery positive plate and lithium battery - Google Patents

Positive electrode active material, preparation method thereof, battery positive plate and lithium battery Download PDF

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CN111146438B
CN111146438B CN201811308884.1A CN201811308884A CN111146438B CN 111146438 B CN111146438 B CN 111146438B CN 201811308884 A CN201811308884 A CN 201811308884A CN 111146438 B CN111146438 B CN 111146438B
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positive electrode
active material
lithium battery
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electrode sheet
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CN111146438A (en
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郭姿珠
谢静
***
马永军
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BYD 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to the field of lithium batteries, and discloses a positive active material, a preparation method thereof, a battery positive plate containing the positive active material and a lithium battery. The positive electrode active material of the invention is represented by the general formula Li4MS4+xThe compound is shown in the specification, wherein M is one or more of Si, Ge and Sn, and x is 1-12. The positive active material is insensitive to moisture and can form a corresponding aqueous solution, so that hydrogen sulfide gas can not be generated or is rarely generated through aqueous solution synthesis; and, the positive electrode active material of the present invention is made by Li4MS4The sulfide solid electrolyte is formed by the reaction of elemental sulfur, a lithium ion transmission channel between the elemental sulfur and the electrolyte is perfectly constructed, and the ionic conductivity of the elemental sulfur is improved, so that the comprehensive electrochemical performance of the lithium battery is improved.

Description

Positive electrode active material, preparation method thereof, battery positive plate and lithium battery
Technical Field
The invention relates to the field of lithium batteries, in particular to a positive active material, a preparation method thereof, a battery positive plate containing the positive active material and a lithium battery.
Background
The theoretical specific capacity of elemental sulfur is 1672mAh/g, and the mass specific energy of the secondary battery assembled by the elemental sulfur and the metallic lithium is 2500Wh kg -1Far higher than the energy density available in the current commercial lithium ion battery. The higher theoretical specific capacity and energy density mean that the cell of the lithium-sulfur battery has small volume and light weightThe characteristic of the electric vehicle meets the development requirement of the electric vehicle, and the electric vehicle becomes a research hotspot of countries in the world. In addition, the elemental sulfur also has the advantages of abundant reserves, environmental friendliness, low price and the like, so that the elemental sulfur becomes one of the most ideal lithium battery positive electrode materials. However, the research finds that the lithium-sulfur battery has some problems which seriously restrict the large-scale commercial application of the lithium-sulfur battery: 1) elemental sulfur and final discharge product Li2S is ion and electron insulating. Due to Li2S has a resistivity of up to 1014Ωcm-1While Li+In Li2Ion mobility in S as low as 10-15cm2s-1Once discharged, end product Li2S is deposited on the electrode surface, Li+The migration reaction with electrons is affected, and the discharge voltage drops rapidly; 2) lithium polysulfide (Li) as an intermediate product generated during charge and discharge in liquid batteries2SnN is more than or equal to 3 and less than or equal to 8) in the electrolyte, polysulfide ions are diffused and shuttled back and forth between the anode and the cathode to form a shuttle effect, so that loss of active substances is caused; 3) lithium metal as the negative electrode is too reactive and tends to form lithium dendrites to pierce the separator, leading to safety problems.
In the existing literature reports, the solid-state lithium-sulfur battery prepared by using an inorganic solid electrolyte to replace a liquid electrolyte and a traditional diaphragm can effectively avoid the shuttle effect caused by polysulfide and can also play a role of a physical protective layer of a metal lithium cathode, and the research on the aspect has made certain progress: sulfur and Li3PS4Sulfide reacts in tetrahydrofuran solution, and sulfur atoms are added in PS4 3-An anion forming an S-S bond. Final positive electrode material Li3PS4+5And has high ionic conductivity and excellent electrochemical reversibility of all-solid-state lithium batteries (Angewandte Chemie 2013,52, 7460).
Chinese patent CN106784690A disperses carbon materials such as carbon nano tube in a mixed solution of deionized water and absolute ethyl alcohol, then gradually drops ammonium sulfate solution formed by dissolving elemental sulfur in advance into the carbon material solution to form a carbon-sulfur composite material, and then gradually drops the carbon-sulfur composite material and Li10GeP2S12And ball-milling and mixing the sulfide electrolyte and the conductive carbon material in an inert atmosphere to obtain the composite cathode material. With Li10GeP2S12Sulfides and Li2S-P2S5A sulfide electrolyte dual-electrolyte system and a metallic lithium negative electrode are assembled into an all-solid-state battery.
The prior art has the following defects: 1) the literature reports sulfur to Li 3PS4Reaction to form Li3PS4+5The ionic conductivity of sulfur can be improved, but Li3PS4The catalyst is unstable with water, hydrogen sulfide gas is easily generated, tetrahydrofuran in a reaction solvent system has strong toxicity, and the whole preparation environment needs special atmosphere protection; 2) other sulfur positive electrodes mainly work to improve the conductivity of sulfur and compound the sulfur with various carbon materials and other conductive substances, such as chinese patent CN106784690A, but how to form an effective lithium ion transmission channel at the solid-solid contact interface between the sulfur positive electrode material and the solid electrolyte has a great problem.
Disclosure of Invention
The present invention has been made to overcome the above problems occurring in the prior art, and an object of the present invention is to provide a novel positive active material, a method for preparing the same, a positive electrode sheet for a battery and a lithium battery including the same. The anode active material is insensitive to moisture and can form a corresponding aqueous solution, so that the anode active material can be synthesized by the aqueous solution without generating or generating hydrogen sulfide gas at a minimum; and, the positive electrode active material of the present invention is made by Li4MS4The sulfide solid electrolyte and the elemental sulfur are reacted, a lithium ion transmission channel between the elemental sulfur and the electrolyte is perfectly constructed, and the ionic conductivity of the elemental sulfur is improved, so that the comprehensive electrochemical performance of the lithium battery is improved (namely, the lithium battery is better in water stability, ionic conductivity and charge-discharge cycle performance).
In order to achieve the above object, one aspect of the present invention provides a positive electrode active material, which is represented by the general formula Li4MS4+xThe compound is shown in the specification, wherein M is one or more of Si, Ge and Sn, and x is 1-12.
Preferably, the positive electrodeThe electrode active material is Li4SiS4+1、Li4SiS4+2、Li4SiS4+3、Li4SiS4+4、Li4SiS4+5、Li4SiS4+6、Li4SiS4+7、Li4SiS4+8、Li4SiS4+9、Li4SiS4+10、Li4SiS4+11、Li4SiS4+12、Li4GeS4+1、Li4GeS4+2、Li4GeS4+3、Li4GeS4+4、Li4GeS4+5、Li4GeS4+6、Li4GeS4+7、Li4GeS4+8、Li4GeS4+9、Li4GeS4+10、Li4GeS4+11、Li4GeS4+12、Li4SnS4+1、Li4SnS4+2、Li4SnS4+3、Li4SnS4+4、Li4SnS4+5、Li4SnS4+6、Li4SnS4+7、Li4SnS4+8、Li4SnS4+9、Li4SnS4+10、Li4SnS4+11、Li4SnS4+12、Li4Si0.5Ge0.5S4+3、Li4Ge0.5Sn0.5S4+3、Li4Ge0.6Sn0.4S4+3、Li4Si0.5Sn0.5S4+3And Li4Si0.6Ge0.2Sn0.2S4+3One or more of (a).
The second aspect of the invention provides a method for producing the positive electrode active material of the invention, which comprises subjecting the general formula Li4MS4The compound is reacted with sulfur.
The third aspect of the present invention provides a positive electrode sheet for a lithium battery, which contains the general formula Li of the present invention4MS4+xThe positive electrode active material is shown.
Preferably, the positive plate of the lithium battery also contains a conductive material.
Preferably, the conductive material is one or more of carbon nanotubes, graphene, acetylene black, graphite, carbon fibers, carbon black, and metal powder.
Preferably, the conductive material is 0.5 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the positive electrode active material.
Preferably, the positive electrode sheet for a lithium battery further comprises a binder.
Preferably, the binder is one or more of styrene butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, polymethyl cellulose, sodium polymethyl cellulose, hydroxypropyl methyl cellulose and polypropylene glycol.
Preferably, the binder is contained in an amount of 0.5 to 10 parts by weight, more preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the positive electrode active material.
The invention provides a lithium battery, which comprises a negative plate, electrolyte and the lithium battery positive plate.
In a fifth aspect, the invention provides a solid lithium battery comprising a negative electrode sheet, a solid electrolyte and a positive electrode sheet of the lithium battery of the invention.
Preferably, the solid electrolyte contains a sulfide solid electrolyte and a binder.
Preferably, the sulfide solid electrolyte is Li3PS4、Li7P3S11Glassy Li2S-P2S5Crystalline LixByPSzCrystalline nLiA- (1-n) LidBSeAnd Li in a glass-ceramic state2S-P2S5Wherein C is one or more of Si, Ge and Sn, x +4y +10 is 2z, 0. ltoreq. y.ltoreq.1, A is one or more of F, Cl, Br and I, 0. ltoreq. n.ltoreq.0.5, 0<d≤4，0<e≤4。
According to the present invention, since the positive electrode active material of the present invention is resistant to moistureThe catalyst is insensitive, can be synthesized in aqueous solution, does not generate or generates little hydrogen sulfide gas, does not need special equipment to treat the hydrogen sulfide, can simplify reaction steps and reduce cost; and, the positive electrode active material of the present invention is made by Li 4MS4The sulfide solid electrolyte is formed by the reaction of elemental sulfur, a lithium ion transmission channel between the elemental sulfur and the electrolyte is perfectly constructed, and the ionic conductivity of the elemental sulfur is improved, so that the comprehensive electrochemical performance of the lithium battery is improved.
Drawings
FIG. 1 is Li4SnS4+3、Li4SnS4And XRD patterns of elemental sulfur.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, "water-stability" refers to the property of a substance that reacts with water to produce hydrogen sulfide gas when it encounters water or is in an environment with a high water content (>30 ppm).
The invention provides a positive active material, which is shown as a general formula Li4MS4+xThe compound is shown in the specification, wherein M is one or more of Si, Ge and Sn, and x is 1-12.
The positive electrode active material according to the present invention, preferably, x ═ 3 to 12; more preferably, x-5-12; further preferably, x is 8-12.
The x may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
According to the positive electrode active material of the present invention, since the positive electrode active material of the present invention is not sensitive to moisture, it can be synthesized in an aqueous solution with no or little generation of hydrogen sulfideThe hydrogen sulfide is not required to be treated by special equipment, so that the reaction steps can be simplified, and the cost is reduced; and, the positive electrode active material of the present invention is made by Li4MS4The sulfide solid electrolyte is formed by the reaction of elemental sulfur, a lithium ion transmission channel between the elemental sulfur and the electrolyte is perfectly constructed, and the ionic conductivity of the elemental sulfur is improved, so that the comprehensive electrochemical performance of the lithium battery is improved.
From the viewpoint of further improving the overall electrochemical performance of the lithium battery, it is preferable that the positive active material is Li4SiS4+1、Li4SiS4+2、Li4SiS4+3、Li4SiS4+4、Li4SiS4+5、Li4SiS4+6、Li4SiS4+7、Li4SiS4+8、Li4SiS4+9、Li4SiS4+10、Li4SiS4+11、Li4SiS4+12、Li4GeS4+1、Li4GeS4+2、Li4GeS4+3、Li4GeS4+4、Li4GeS4+5、Li4GeS4+6、Li4GeS4+7、Li4GeS4+8、Li4GeS4+9、Li4GeS4+10、Li4GeS4+11、Li4GeS4+12、Li4SnS4+1、Li4SnS4+2、Li4SnS4+3、Li4SnS4+4、Li4SnS4+5、Li4SnS4+6、Li4SnS4+7、Li4SnS4+8、Li4SnS4+9、Li4SnS4+10、Li4SnS4+11、Li4SnS4+12、Li4Si0.5Ge0.5S4+3、Li4Ge0.5Sn0.5S4+3、Li4Ge0.6Sn0.4S4+3、Li4Si0.5Sn0.5S4+3And Li4Si0.6Ge0.2Sn0.2S4+3One or more of (a).
According to a second aspect of the present invention, there is provided a method for producing the positive electrode active material of the present invention, the method comprising subjecting Li of the general formula4MS4And (3) reacting the compound with elemental sulfur.
According to the preparation method of the anode active material, the anode active material is insensitive to moisture, can be synthesized in an aqueous solution, does not generate or generates little hydrogen sulfide gas, does not need special equipment to treat the hydrogen sulfide, can simplify reaction steps and reduce cost; and, the positive electrode active material of the present invention is made by Li4MS4The sulfide solid electrolyte is formed by the reaction of elemental sulfur, a lithium ion transmission channel between the elemental sulfur and the electrolyte is perfectly constructed, and the ionic conductivity of the elemental sulfur is improved, so that the comprehensive electrochemical performance of the lithium battery is improved.
According to the method for producing a positive electrode active material of the present invention, preferably, the method for producing a positive electrode active material of the present invention comprises adding Li of the general formula4MS4And (3) reacting the aqueous solution of the compound with sulfur. General formula Li4MS4The solvent water used in the aqueous solution of the compound is preferably deionized water.
According to the method for preparing the positive electrode active material of the present invention, Li4MS4The amount of the sulfur and the elemental sulfur may be appropriately selected depending on the finally desired positive electrode active material, for example, Li4MS4The molar ratio to elemental sulfur may be 1: 0.25-3.
According to the method for preparing the cathode active material of the present invention, preferably, the conditions of the above reaction include: the reaction temperature is 25-100 ℃, and the reaction time is 1-24 hours; more preferably, the conditions of the above reaction include: the reaction temperature is 25-40 deg.C, and the reaction time is 8-15 hr.
According to the method for preparing the cathode active material of the present invention, the cathode active material of the present invention is obtained by removing the solvent after the reaction is completed, and the method for removing the solvent may employ a method conventionally used in the art, for example, the solvent may be removed by distillation under normal pressure or reduced pressure.
The third aspect of the present invention provides a positive electrode sheet for a lithium battery, which contains the general formula Li of the present invention4MS4+xThe positive electrode active material is shown.
According to the positive electrode sheet for a lithium battery of the present invention, it is preferable that the content of the conductive agent is 0.5 to 20 parts by weight with respect to 100 parts by weight of the positive electrode active material; the content of the conductive agent is more preferably 0.5 to 10 parts by weight from the viewpoint of further improving the electrochemical performance of a lithium battery produced from the positive electrode sheet for a lithium battery.
According to the positive electrode sheet for a lithium battery of the present invention, preferably, the binder is contained in an amount of 0.5 to 10 parts by weight, relative to 100 parts by weight of the positive electrode active material; the content of the binder is more preferably 0.5 to 3 parts by weight from the viewpoint of further improving the electrochemical performance of a lithium battery produced from the positive electrode sheet for a lithium battery.
According to the present invention, the positive electrode sheet for a lithium battery further comprises other positive active materials commonly used in the art, preferably, the other positive active materials are lithium-containing transition metal oxides, and more preferably, the other positive active materials are one or more of the following compounds: LiFexMnyMzPO4Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is 1, and M is at least one of Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo; li3V2(PO4)3；Li3V3(PO4)3；LiNi0.5-xMn1.5-yMx+yO4Wherein x is more than or equal to-0.1 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1.5, and M is at least one of Li, Co, Fe, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn; LiVPO4F；Li1+xL1－y－zMyNzO2Wherein L, M, N is at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, x is more than or equal to-0.1 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y + z is more than or equal to 0 and less than or equal to 1.0; li2CuO2；Li5FeO4。
In a preferred embodiment of the present invention, the other positive electrode active material is LiFexMnyMzPO4Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is 1, and M is at least one of Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo.
In another preferred embodiment of the present invention, the other positive electrode active material is Li1+xL1－y－zMyNzO2Wherein L, M, N is at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, x is more than or equal to-0.1 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y + z is more than or equal to 0 and less than or equal to 1.0.
According to the positive electrode sheet for a lithium battery of the present invention, the content of the other positive electrode active material is preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of the positive electrode active material.
According to the positive electrode sheet for a lithium battery of the present invention, the positive electrode sheet for a lithium battery preferably further contains a conductive agent. The conductive agent may be various conventional conductive agents for lithium ion batteries in the art, for example, the conductive material may be one or more of carbon nanotubes, graphene, acetylene black, graphite, carbon fibers, carbon black and metal powder, and is preferably at least one of carbon nanotubes, graphene and acetylene black.
According to the positive electrode sheet for a lithium battery of the present invention, the positive electrode sheet for a lithium battery preferably further contains a binder. The binder may be any one of various conventional binders for lithium ion batteries in the art, such as at least one of styrene-butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, polymethyl cellulose, sodium polymethyl cellulose, hydroxypropyl methyl cellulose, and polypropylene alcohol, and preferably at least one of styrene-butadiene rubber, polyvinylidene fluoride, and polytetrafluoroethylene.
The lithium battery positive plate can be prepared according to the method comprising the following steps of:
(1) general formula Li4MS4+xThe positive electrode active material, the conductive agent and the binder are uniformly mixed in an organic solvent to form slurry;
(2) attaching the slurry obtained in the step (1) on a current collector;
(3) and (3) drying the current collector obtained in the step (2).
In step (1), the organic solvent may be any of various organic solvents in the art, and may be, for example, n-heptane.
In addition, in the step (1), the uniform mixing mode can adopt a vacuum stirrer for stirring to achieve the purpose of uniform mixing. Wherein, the stirring speed can be 100-1500rmp, and the time can be 1-48 h.
In the step (2), the current collector may be various current collectors for lithium ions in the art, and for example, may be at least one of an aluminum sheet, a carbon-coated aluminum sheet, an aluminum mesh, a carbon-coated aluminum mesh, a carbon paper, a carbon nanotube paper, and a graphene paper.
In the step (3), the drying temperature can be 80-85 ℃.
The invention provides a lithium battery, which comprises a negative plate, electrolyte and the lithium battery positive plate.
According to the lithium battery of the present invention, the electrolyte may be a characteristic electrolyte commonly used in the art, and will not be described herein again.
According to the lithium battery of the invention, the negative electrode sheet can be a negative electrode sheet for a lithium-ion battery with lithium pre-inserted or lithium-supplemented, which is conventional in the field, and can be, for example, metal lithium or lithium alloy. The lithium alloy may be a lithium alloy such as a lithium-indium alloy.
In a fifth aspect, the invention provides a solid lithium battery comprising a negative electrode sheet, a solid electrolyte and a positive electrode sheet of the lithium battery of the invention.
According to the solid lithium battery of the present invention, the solid electrolyte preferably contains a sulfide solid electrolyte and a binder; more preferably, the weight ratio of the sulfide-containing solid electrolyte to the binder is 5-49.5: 1, preferably 9 to 49.5: 1.
the solid-state lithium battery of the inventionPreferably, the sulfide solid electrolyte is Li3PS4、Li7P3S11Glassy Li2S-P2S5Crystalline LixByP2SzCrystalline nLiA- (1-n) LidBSeAnd Li in the form of a glass-ceramic2S-P2S5Wherein B is one or more of Si, Ge and Sn, x +4y +10 is 2z, y is 0-1, A is one or more of F, Cl, Br and I, n is 0-0.5, 0<d≤4，0<e≤4。
Preferably, the glassy Li2S-P2S5Selected from glassy 70Li2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5One or more of (a).
Preferably, Li in the glass-ceramic state 2S-P2S570Li selected from the glassy ceramic state2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5One or more of (a).
Preferably, the crystalline LixByP2SzSelected from Li10SnP2S12、Li10GeP2S12、Li10SiP2S12One or more of (a). The crystalline nLiA- (1-n) LidBSeSelected from Li4SiS4、Li4GeS4、Li4SnS4、Li2SiS3、Li2GeS3、Li2SnS3、LiSiS2、LiGeS2、LiSnS2、0.4Li-0.6Li4SiS4、0.4Li-0.6Li4GeS4、0.4Li-0.6Li4SnS4One or more of (a).
According to the solid-state lithium battery of the present invention, the binder may be any conventional binder for lithium ion batteries in the art, and may be at least one of styrene-butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, polymethyl cellulose, sodium polymethyl cellulose, hydroxypropyl methyl cellulose, and polypropylene alcohol, preferably at least one of styrene-butadiene rubber, polyvinylidene fluoride, and polytetrafluoroethylene.
In the present invention, the preparation method of the solid electrolyte may be various conventional solid electrolyte sheet preparation methods in the art, and may include, for example: the sulfide solid electrolyte and the binder are uniformly mixed in an organic solvent to form slurry, then the slurry is uniformly distributed on a positive plate, and then the solid electrolyte is obtained after drying at the temperature of 80-85 ℃. Wherein, the mode of misce bene can adopt vacuum mixer to stir in order to realize the purpose of misce bene. Wherein, the stirring speed can be 100-1500rmp, and the time can be 1-48 h. Here, the organic solvent may be various organic solvents in the art, and may be, for example, n-heptane.
According to the solid-state lithium battery of the present invention, the negative electrode sheet may be any one of those conventional in the art for lithium ion batteries, and may be, for example, metallic lithium or a lithium alloy. The lithium alloy may be a lithium alloy such as a lithium-indium alloy.
In the present invention, a method for manufacturing a solid lithium battery may include: and stacking and laminating the prepared positive plate, the solid electrolyte and the negative plate of the lithium battery to form the all-solid-state lithium battery. Wherein the pressure of lamination can be 220-260 MPa.
The present invention will be described in detail below by way of examples.
Styrene butadiene rubber was purchased from Ribose corporation of Japan under the designation BM-120S.
The carbon nanotube is purchased from Qingdao Hao Xin New energy Co., Ltd and is marked as carbon nanotube powder HX-N.
In the following examples, Li4SnS4The preparation was carried out according to the following method
According to the following steps: molar ratio of 1 lithium sulfide (Li) was weighed2S, 99.9% by weight, Alfa Aesar) and tin disulfide (SnS)298 wt.%, Aldrich Chemical Co.Inc.) were ball milled for 1h, and the ball milled mixture was pressed at 10MPaPressing into a cylindrical sheet under force, and then sintering for 12h at 450 ℃ in an argon atmosphere to obtain Li4SnS4An electrolyte.
In the following examples, Li4SiS4The preparation was carried out according to the following method
According to the following steps: molar ratio of 1 lithium sulfide (Li) was weighed 2S, 99.9 wt%, Alfa Aesar) and silicon disulfide (SiS)299 percent by weight, Kyada) for 1 hour, pressing the ball-milled mixture into a cylindrical sheet under the pressure of 10MPa, and then sintering the cylindrical sheet for 12 hours at the temperature of 500 ℃ in the argon atmosphere to obtain Li4SiS4An electrolyte.
In the following examples, Li4GeS4The preparation was carried out according to the following method
According to the following steps: molar ratio of 1 lithium sulfide (Li) was weighed2S, 99.9 wt%, Alfa Aesar) and germanium disulfide (GeS)299 percent by weight percent of Beijing ceramic new material science and technology, Ltd.) are mixed by ball milling for 1 hour, the ball milling mixture is pressed into a cylindrical sheet under the pressure of 10MPa, and then the cylindrical sheet is sintered for 12 hours at the temperature of 550 ℃ under the argon atmosphere to obtain Li4GeS4An electrolyte.
Example 1
1) Positive electrode active material Li4SnS4+3
2.75g of Li were weighed4SnS4Dissolving the sulfide solid electrolyte in 50mL of deionized water, and magnetically stirring for 2 hours; then adding 0.96g of elemental sulfur powder into the solution, and continuing to magnetically stir for 12 hours; evaporating the aqueous solution at atmospheric pressure and then drying at 150 ℃ to obtain Li4SnS4+3Cathode material, FIG. 1 is Li4SnS4+3、Li4SnS4And XRD pattern of elemental sulfur, from which Li is known4SnS4+3Part of Li is reserved4SnS4The main diffraction peak, which is mainly so that both have similarity in crystal structure, but the minor diffraction peak disappears, indicating Li 4SnS4+3With Li4SnS4Or is different. In addition, the diffraction peak of the elemental sulfur is in Li4SnS4+3Shows that elemental sulfur is not physically mixed in Li4SnS4In (1).
2) Preparation of solid lithium ion battery
1.8g of the positive electrode active material obtained in the step 1), 0.1g of a conductive agent (carbon nano tube) and 0.1g of a binder (styrene butadiene rubber SBR) are put in anhydrous n-heptane by a vacuum stirrer, and then stirred in the vacuum stirrer to form stable and uniform slurry, wherein the stirring speed is 1000rmp, and the time is 12 hours; then coating the obtained slurry on a current collector aluminum sheet, drying at 80 ℃, and tabletting in a roller press (the tabletting condition is 800Mpa) to obtain a positive plate A1;
1.47g of sulfide solid electrolyte 75Li2S-25P2S5And 0.03g of SBR was added to anhydrous n-heptane and then stirred in a vacuum stirrer at a stirring speed of 1000rmp for 12 hours to form a stable and uniform electrolyte slurry; uniformly and intermittently coating the electrolyte slurry on the prepared positive plate A1, and drying in a drying oven at 80 ℃ to form an inorganic solid electrolyte layer on the surface of the positive electrode; and (3) attaching the lithium foil to the surface of the sulfide solid electrolyte layer, applying 240MPa of pressure to compress the lithium foil, and packaging to obtain the solid lithium ion battery S1.
Example 2
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 0.32g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+1Positive electrode active material, positive electrode sheet a2 and solid-state lithium ion battery S2 were obtained in the same manner as in example 1.
Example 3
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder used was 0.64g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+2Positive electrode active material, positive electrode sheet a3 and solid-state lithium ion battery S3 were obtained in the same manner as in example 1.
Example 4
A positive electrode active material was prepared in accordance with the method of example 1, except that the amount of elemental sulfur powder used was 1.28g, by carrying out the sameExample 1) obtaining of Li was confirmed in the same manner4SnS4+4Positive electrode active material, positive electrode sheet a4 and solid-state lithium ion battery S4 were obtained in the same manner as in example 1.
Example 5
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder used was 1.6g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+5Positive electrode active material, positive electrode sheet a5 and solid-state lithium ion battery S5 were obtained in the same manner as in example 1.
Example 6
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 1.92g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+6Positive electrode active material, positive electrode sheet a6 and solid-state lithium ion battery S6 were obtained in the same manner as in example 1.
Example 7
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 2.24g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+7Positive electrode active material, positive electrode sheet a7 and solid-state lithium ion battery S7 were obtained in the same manner as in example 1.
Example 8
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 2.56g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+8Positive electrode active material, positive electrode sheet A8 and solid-state lithium ion battery S8 were obtained in the same manner as in example 1.
Example 9
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 2.88g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+9Positive electrode active material, positive electrode sheet a9 and solid-state lithium ion battery S9 were obtained in the same manner as in example 1.
Example 10
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 3.2g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+10Positive electrode active material, positive electrode sheet a10 and solid-state lithium ion battery S10 were obtained in the same manner as in example 1.
Example 11
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 3.52g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+11Positive electrode active material, positive electrode sheet a11 and solid-state lithium ion battery S11 were obtained in the same manner as in example 1.
Example 12
A positive electrode active material was prepared in the same manner as in example 1), except that the amount of elemental sulfur powder was 3.84g, and Li was confirmed to be obtained in the same manner as in example 1)4SnS4+12Positive electrode active material, positive electrode sheet a12 and solid-state lithium ion battery S12 were obtained in the same manner as in example 1.
Example 13
1) Positive electrode active material Li4SiS4+1
1.84g of Li were weighed4SiS4Dissolving the sulfide solid electrolyte in 50mL of deionized water, and magnetically stirring for 2 hours; then adding 0.32g of elemental sulfur powder into the solution, and continuing to magnetically stir for 12 hours; the aqueous solution was evaporated under normal pressure and then dried at 150 ℃ and Li formation was confirmed by the same method as in example 1) 4SiS4+1And (3) a positive electrode material.
2) Preparation of solid lithium ion battery
A positive electrode sheet a13 and a solid state lithium ion battery S13 were obtained in the same manner as in example 1.
Example 14
A positive electrode material was prepared in the same manner as in example 13, except that the amount of elemental sulfur powder was 0.64g, and Li was confirmed to be obtained in the same manner as in example 1)4SiS4+2The positive electrode material, in addition,a positive electrode sheet a14 and a solid state lithium ion battery S14 were obtained in the same manner as in example 1.
Example 15
The procedure of example 13 was followed, except that the amount of elemental sulfur powder was 0.96g, and Li was confirmed to be obtained in the same manner as in example 1)4SiS4+3Positive electrode material, positive electrode sheet a15 and solid-state lithium ion battery S15 were obtained in the same manner as in example 1.
Example 16
A positive electrode active material was prepared in accordance with the method of example 13, except that the amount of elemental sulfur powder used was 1.28g, and Li was confirmed to be obtained by the same method as in example 1)4SiS4+4Positive electrode active material, positive electrode sheet a16 and solid-state lithium ion battery S16 were obtained in the same manner as in example 1.
Example 17
A positive electrode active material was prepared in accordance with the method of example 13, except that the amount of elemental sulfur powder used was 1.6g, and Li was confirmed to be obtained by the same method as in example 1) 4SiS4+5Positive electrode active material, positive electrode sheet a17 and solid-state lithium ion battery S17 were obtained in the same manner as in example 1.
Example 18
A positive electrode active material was prepared in the same manner as in example 13, except that the amount of elemental sulfur powder was 1.92g, and Li was confirmed to be obtained in the same manner as in example 1)4SiS4+6Positive electrode active material, positive electrode sheet a18 and solid-state lithium ion battery S18 were obtained in the same manner as in example 1.
Example 19
A positive electrode active material was prepared in accordance with the method of example 13, except that the amount of elemental sulfur powder used was 2.24g, and Li was confirmed to be obtained by the same method as in example 1)4SiS4+7Positive electrode active material, positive electrode sheet a19 and solid-state lithium ion battery S19 were obtained in the same manner as in example 1.
Example 20
A positive electrode active material was prepared according to the method of example 13, except thatThe amount of elemental sulfur powder used was 2.56g, and Li was confirmed to be obtained in the same manner as in example 1)4SiS4+8Positive electrode active material, positive electrode sheet a20 and solid-state lithium ion battery S20 were obtained in the same manner as in example 1.
Example 21
A positive electrode active material was prepared in accordance with the method of example 13, except that the amount of elemental sulfur powder used was 2.88g, and Li was confirmed to be obtained by the same method as in example 1) 4SiS4+9Positive electrode active material, positive electrode sheet a21 and solid-state lithium ion battery S21 were obtained in the same manner as in example 1.
Example 22
A positive electrode active material was prepared in the same manner as in example 13, except that the amount of elemental sulfur powder was 3.2g, and Li was confirmed to be obtained in the same manner as in example 1)4SiS4+10Positive electrode active material, positive electrode sheet a22 and solid-state lithium ion battery S22 were obtained in the same manner as in example 1.
Example 23
A positive electrode active material was prepared in the same manner as in example 13, except that the amount of elemental sulfur powder was 3.52g, and Li was confirmed to be obtained in the same manner as in example 1)4SiS4+11Positive electrode active material, positive electrode sheet a23 and solid-state lithium ion battery S23 were obtained in the same manner as in example 1.
Example 24
A positive electrode active material was prepared in the same manner as in example 13, except that the amount of elemental sulfur powder was 3.84g, and Li was confirmed to be obtained in the same manner as in example 1)4SiS4+12Positive electrode active material, positive electrode sheet a24 and solid-state lithium ion battery S24 were obtained in the same manner as in example 1.
Example 25
1) Positive electrode active material Li4GeS4+1
2.29g of Li were weighed4GeS4Dissolving the sulfide solid electrolyte in 50mL of deionized water, and magnetically stirring for 2 hours; 032g of elemental sulfur powder was then added to the above solution, followed by Magnetic stirring is continued for 12 hours; the aqueous solution was removed by evaporation under normal pressure, and then dried at 150 ℃ and Li formation was confirmed by the same method as in example 1)4GeS4+1And (3) a positive electrode material.
2) Preparation of solid lithium ion battery
A positive electrode sheet a25 and a solid state lithium ion battery S25 were obtained in the same manner as in example 1.
Example 26
A positive electrode material was prepared in the same manner as in example 25, except that the amount of elemental sulfur powder used was 0.64g, and Li was confirmed to be obtained in the same manner as in example 1)4GeS4+2A positive electrode sheet a26 and a solid lithium ion battery S26 were obtained in the same manner as in example 1.
Example 27
The procedure of example 25 was followed, except that the amount of elemental sulfur powder was 0.96g, and Li formation was confirmed in the same manner as in example 1)4GeS4+3A positive electrode sheet a27 and a solid lithium ion battery S27 were obtained in the same manner as in example 1.
Example 28
A positive electrode active material was prepared in accordance with the method of example 25, except that the amount of elemental sulfur powder used was 1.28g, and Li was confirmed to be obtained by the same method as in example 1)4GeS4+4Positive electrode active material, positive electrode sheet a28 and solid-state lithium ion battery S28 were obtained in the same manner as in example 1.
Example 29
A positive electrode active material was prepared in the same manner as in example 25, except that the amount of elemental sulfur powder was 1.6g, and Li was confirmed to be obtained in the same manner as in example 1)4GeS4+5Positive electrode active material, positive electrode sheet a29 and solid-state lithium ion battery S29 were obtained in the same manner as in example 1.
Example 30
A positive electrode active material was prepared in accordance with the method of example 25, except that the amount of elemental sulfur powder used was 1.92g, and Li was confirmed to be obtained by the same method as in example 1)4GeS4+6Positive electrode active material, positive electrode sheet a30 and solid-state lithium ion battery S30 were obtained in the same manner as in example 1.
Example 31
A positive electrode active material was prepared in accordance with the method of example 25, except that the amount of elemental sulfur powder used was 2.24g, and Li was confirmed to be obtained by the same method as in example 1)4GeS4+7Positive electrode active material, positive electrode sheet a31 and solid-state lithium ion battery S31 were obtained in the same manner as in example 1.
Example 32
A positive electrode active material was prepared in accordance with the method of example 25, except that the amount of elemental sulfur powder used was 2.56g, and Li was confirmed to be obtained by the same method as in example 1)4GeS4+8Positive electrode active material, positive electrode sheet a32 and solid-state lithium ion battery S32 were obtained in the same manner as in example 1.
Example 33
A positive electrode active material was prepared in the same manner as in example 25, except that the amount of elemental sulfur powder was 2.88g, and Li was confirmed to be obtained in the same manner as in example 1)4GeS4+9Positive electrode active material, positive electrode sheet a33 and solid-state lithium ion battery S33 were obtained in the same manner as in example 1.
Example 34
A positive electrode active material was prepared in the same manner as in example 25, except that the amount of elemental sulfur powder was 3.2g, and Li was confirmed to be obtained in the same manner as in example 1)4GeS4+10Positive electrode active material, positive electrode sheet a34 and solid-state lithium ion battery S34 were obtained in the same manner as in example 1.
Example 35
A positive electrode active material was prepared in the same manner as in example 25, except that the amount of elemental sulfur powder was 3.52g, and Li was confirmed to be obtained in the same manner as in example 1)4GeS4+11Positive electrode active material, positive electrode sheet a35 and solid-state lithium ion battery S35 were obtained in the same manner as in example 1.
Example 36
A positive electrode active material was prepared in the same manner as in example 25, except that the amount of elemental sulfur powder was 3.84g, and Li was confirmed to be obtained in the same manner as in example 1)4GeS4+12Positive electrode active material, positive electrode sheet a36 and solid-state lithium ion battery S36 were obtained in the same manner as in example 1.
Comparative example 1
A lithium solid state battery D1 was fabricated by the method of example 1, except that in step (1), Li was directly used as the positive electrode active material4SnS4。
Comparative example 2
A lithium solid state battery D2 was fabricated by the method of example 15, except that in step (1), Li was directly used as the positive electrode active material4SiS4。
Comparative example 3
A lithium solid state battery D3 was fabricated by the method of example 27, except that in step (1), Li was directly used as the positive electrode active material4GeS4。
Comparative example 4
A lithium solid state battery D4 was prepared according to the method of example 27, except that S was used as it is as the positive electrode active material in step (1).
Comparative example 5
A lithium solid state battery D4 was prepared according to the method of example 27, except that in step (1), Li was directly used as the positive electrode active material3PS4+3。
Test example
The following tests were carried out for battery a 1-battery a12 obtained in the example and battery D1-battery D4 obtained in the comparative example, and the test results are shown in table 1.
1) Hydrogen sulfide gas evolution test
Weighing 0.1g sample 240MPa, pressing into 13mm diameter circular slice, and placing in 2000cm3In the dryer, a hydrogen sulfide detector (Jikco, GBL-HS) is arranged in the dryer in advance, the temperature is 24-25 ℃, the humidity is 48-51%, and the concentration of hydrogen sulfide gas in the dryer is measured by the detector after 1 min.
2) Ion conductivity test
Taking a 0.2g sample, pressing the sample into a tablet under the pressure of 800Mpa, pasting carbon-coated aluminum foils on two sides, and testing the ionic conductivity of the sample by adopting an alternating current impedance method in an electrochemical workstation (Auto Lab), wherein the testing condition is an open-circuit potential, the scanning frequency range is 10Hz-5MHz, and the amplitude is 50 mV.
3) Charge and discharge cycle test
Respectively placing a battery A1-a 12 and a battery D1-a battery D4 in a charging and discharging test cabinet (Guangzhou Lanqi), and discharging the batteries at a constant current of 0.05C until the batteries are discharged to 1.0V and cut off at the temperature of 25 +/-1 ℃; standing for 5 minutes; charging to 3.0V at constant current 0.05C; the battery was thus charged and discharged for 50 cycles.
TABLE 1
Figure BDA0001854447290000201
From the results of the above experiments in Table 1, it was found that the hydrogen sulfide content in battery A1-battery A36 and battery D1-battery D3 was very low, 0.001cm3/(g.min), elemental sulfur in cell D4 was stable to moisture and therefore no hydrogen sulfide gas was produced, and the hydrogen sulfide content in cell D5 was 0.8cm3(g min), the results of the above experiment show that: with Li4MS4Sulfide phase ratio, Li4MS4+xSulfide (M ═ Si \ Ge \ Sn, x ═ 1-12) is more stable with moisture. In addition, the ionic conductivity was generally higher than that of pure elemental sulfur of comparative battery D4, but with increasing x, Li4MS4+xThe ionic conductivity of sulfide is reduced, but on the other hand, the capacity is increased due to the increase of the component of the S, and the lower ionic conductivity affects the capacity exertion when x is 12 due to the lower ionic conductivity of sulfur. The first discharge capacity of the battery A1-the battery A36 is superior to that of the battery D1-the battery D4, the capacity retention rate of the battery D1-the battery D3 for 50 times is close to that of the battery D1-the battery D3, the capacity exertion and the retention rate of pure elemental sulfur are lower than those of experimental results of the embodiment, the first discharge specific capacity and the capacity retention rate of the battery D5 are both close to those of the battery A1-the battery A36, but the battery A8932 is very unstable with water, and sulfide gas is easily generated, so that potential safety hazards exist. In conclusion, battery A1-battery A36 The comprehensive electrochemical performance of the lithium battery on the cyclicity, the ionic conductivity and the water stability is improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (17)

1. The positive electrode active material is characterized in that the positive electrode active material is represented by a general formula Li4MS4+xWherein M is one or more of Si, Ge and Sn, and x is 1-12, and the cathode active material is prepared by mixing Li with a solvent of the general formula4MS4The aqueous solution of the compound reacts with sulfur to form the compound.
2. The positive electrode active material according to claim 1, wherein the positive electrode active material is Li4SiS4+1、Li4SiS4+2、Li4SiS4+3、Li4SiS4+4、Li4SiS4+5、Li4SiS4+6、Li4SiS4+7、Li4SiS4+8、Li4SiS4+9、Li4SiS4+10、Li4SiS4+11、Li4SiS4+12、Li4GeS4+1、Li4GeS4+2、Li4GeS4+3、Li4GeS4+4、Li4GeS4+5、Li4GeS4+6、Li4GeS4+7、Li4GeS4+8、Li4GeS4+9、Li4GeS4+10、Li4GeS4+11、Li4GeS4+12、Li4SnS4+1、Li4SnS4+2、Li4SnS4+3、Li4SnS4+4、Li4SnS4+5、Li4SnS4+6、Li4SnS4+7、Li4SnS4+8、Li4SnS4+9、Li4SnS4+10、Li4SnS4+11、Li4SnS4+12、Li4Si0.5Ge0.5S4+3、Li4Ge0.5Sn0.5S4+3、Li4Ge0.6Sn0.4S4+3、Li4Si0.5Sn0.5S4+3And Li4Si0.6Ge0.2Sn0.2S4+3One or more of (a).
3. The method for producing a positive electrode active material according to claim 1 or 2, characterized in that the method comprises subjecting Li of the general formula4MS4And (3) reacting the aqueous solution of the compound with sulfur.
4. A positive electrode sheet for a lithium battery, comprising the positive active material according to claim 1 or 2.
5. The positive electrode sheet for a lithium battery as claimed in claim 4, wherein the positive electrode sheet for a lithium battery further comprises a conductive material.
6. The positive electrode sheet for a lithium battery according to claim 5, wherein the conductive material is one or more of carbon nanotubes, graphene, acetylene black, graphite, carbon fibers, carbon black, and metal powder.
7. The positive electrode sheet for a lithium battery as claimed in claim 5, wherein the conductive material is 0.5 to 20 parts by weight with respect to 100 parts by weight of the positive active material.
8. The positive electrode sheet for a lithium battery as claimed in claim 7, wherein the conductive material is 0.5 to 10 parts by weight with respect to 100 parts by weight of the positive active material.
9. The positive electrode sheet for a lithium battery as claimed in claim 5, wherein the positive electrode sheet for a lithium battery further comprises a binder.
10. The positive electrode sheet for a lithium battery according to claim 9, wherein the binder is one or more of styrene-butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, polymethyl cellulose sodium, hydroxypropyl methyl cellulose, and polyallyl alcohol.
11. The positive electrode sheet for a lithium battery as claimed in claim 9, wherein the binder is contained in an amount of 0.5 to 10 parts by weight, relative to 100 parts by weight of the positive electrode active material.
12. The positive electrode sheet for a lithium battery as claimed in claim 11, wherein the binder is contained in an amount of 0.5 to 3 parts by weight, relative to 100 parts by weight of the positive electrode active material.
13. A lithium battery comprising a negative electrode sheet, an electrolyte, and a positive electrode sheet for a lithium battery according to any one of claims 4 to 12.
14. A solid lithium battery comprising a negative electrode sheet, a solid electrolyte, and a positive electrode sheet for a lithium battery according to any one of claims 4 to 12.
15. The solid state lithium battery of claim 14, wherein the solid state electrolyte contains a sulfide solid electrolyte and a binder.
16. The solid state lithium battery of claim 15, wherein the sulfide solid electrolyte is Li3PS4、Li7P3S11Glassy Li2S-P2S5Crystalline LixByP2SzCrystalline nLiA- (1-n) LidBSeAnd Li in a glass-ceramic state2S-P2S5Wherein B is one or more of Si, Ge and Sn, x +4y +10 is 2z, 0. ltoreq. y.ltoreq.1, A is one or more of F, Cl, Br and I, 0. ltoreq. n.ltoreq.0.5, 0<d≤4，0<e≤4。
17. The solid state lithium battery of any one of claims 14-16, wherein the negative electrode sheet is metallic lithium or a lithium alloy.
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