CN111129423B - Lithium ion battery cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery - Google Patents

Lithium ion battery cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery Download PDF

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CN111129423B
CN111129423B CN201811278630.XA CN201811278630A CN111129423B CN 111129423 B CN111129423 B CN 111129423B CN 201811278630 A CN201811278630 A CN 201811278630A CN 111129423 B CN111129423 B CN 111129423B
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lithium ion
ion battery
negative electrode
active oxide
electrode material
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CN111129423A (en
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历彪
郭姿珠
易观贵
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Shenzhen BYD Auto R&D 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M4/582—Halogenides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The disclosure relates to a lithium ion battery cathode material, which is characterized in that particles of the cathode material have a core-shell structure, the core-shell structure comprises a matrix and a shell layer coated on the outer surface of the matrix, the matrix contains a cathode active oxide, and the shell layer contains a metal oxyfluoride; the molecular general formula of the negative active oxide is LicMaObM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, a is an integer greater than 0, b is an integer greater than 0, c is an integer greater than 0, and the value of (2b-c)/a is equal to the valence of M; the molecular general formula of the metal oxyfluoride is MOxFyM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, and the numerical value of 2x + y is equal to the valence of M; wherein, the LicMaObAnd the MOxFyM in (1) are the same. The lithium ion battery prepared by the cathode material disclosed by the invention has better rate performance.

Description

Lithium ion battery cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery
Technical Field
The disclosure relates to the field of applied chemistry, in particular to a lithium ion battery cathode material and a preparation method thereof, a lithium ion battery cathode and a lithium ion battery.
Background
The lithium ion battery cathode material has important influence on the performance of the lithium ion battery, and the coating modification of the lithium ion battery cathode material is an effective means for improving the electrochemical performance of the lithium ion battery.
In the prior art, a carbon coating method is mostly adopted to modify the negative electrode material, and a fluorine-containing material is also adopted to coat the negative electrode material. Patent CN102800862A discloses a negative electrode material of lithium battery of fluoride-coated lithium titanate, which has the effect of inhibiting gas generation of battery, but the rate capability of the negative electrode of lithium ion battery prepared by the negative electrode material is poor, and the rate capability of lithium ion battery cannot be improved by the negative electrode material; patent CN101764209A discloses a lithium titanate negative electrode material with a lithium fluoride coating layer, which also has the problem of avoiding gas generation caused by the action with an electrolyte during the use of the battery, but the rate capability of the lithium ion battery prepared from the negative electrode material is also poor.
Disclosure of Invention
The invention aims to solve the problem of poor rate capability of the conventional lithium ion battery, and provides a lithium ion battery cathode material, a preparation method thereof, a lithium ion battery cathode and a lithium ion battery.
The inventors of the present disclosure found, through research, that when a negative active oxide is coated and modified with a homologous metal oxyfluoride, that is, when a metal element of the metal oxyfluoride is the same as a metal element in the negative active oxide, the homologous metal oxyfluoride has a high ionic conductivity and excellent interface compatibility with the negative active oxide, so that the rate performance of the negative active material can be significantly improved.
In order to achieve the above object, a first aspect of the present disclosure provides a lithium ion battery anode material, where particles of the anode material have a core-shell structure, where the core-shell structure includes a base body and an outer shell layer coated on an outer surface of the base body, the base body contains an anode active oxide, and the outer shell layer contains a metal oxyfluoride;
the molecular general formula of the negative active oxide is LicMaObM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, a is an integer greater than 0, b is an integer greater than 0, c is an integer greater than 0, and the value of (2b-c)/a is equal to the valence of M; the molecular general formula of the metal oxyfluoride is MOxFyM is one selected from transition metal elements and Bi, and 2x + y is equal toThe valence of M; wherein, the LicMaObAnd the MOxFyM in (1) are the same.
Optionally, the outer shell layer of the anode material has an average thickness of 10nm to 1 μm.
Optionally, the average thickness of the outer shell layer of the anode material is 30nm to 200 nm.
Optionally, the matrix is present in an amount of 90 to 99.5 wt% and the outer shell is present in an amount of 0.5 to 10 wt%, based on the total mass of the anode material.
Optionally, the transition metal element is one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, and Mt.
Optionally, the negative active oxide is Li4Ti5O12And/or TiO2The metal oxyfluoride is TiOF2(ii) a Or
The negative active oxide is Fe2O3The metal oxyfluoride is FeOOF; or
The negative active oxide is Bi2O3And the metal oxyfluoride is BiOF.
A second aspect of the present disclosure provides a method of preparing a negative electrode material for a lithium ion battery, the method comprising the steps of:
s1, mixing the negative active oxide, the metal fluoride and the solvent, and carrying out solvent heat treatment;
the molecular general formula of the negative active oxide is LicMaObM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, a is an integer greater than 0, b is an integer greater than 0, c is an integer greater than 0, and the value of (2b-c)/a is equal to the valence of M; the molecular general formula of the metal fluoride is MFzM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, and the numerical value of z is equal to the valence of M; wherein, the LicMaObAnd the MFzM in (1) are the same.
And S2, taking out the solid phase in the material subjected to the solvent heat treatment and calcining the solid phase.
Optionally, the transition metal element is one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, and Mt.
Optionally, the negative active oxide is Li4Ti5O12And/or TiO2The metal fluoride is TiF4(ii) a Or
The negative active oxide is Fe2O3The metal fluoride is FeF3(ii) a Or
The negative active oxide is Bi2O3The metal fluoride is BiF3。
Alternatively, the amount of the metal fluoride is 5 to 135g and the amount of the solvent is 200-2000mL with respect to 1000g of the anode active oxide.
Optionally, in step S1, the temperature of the solvothermal treatment is 100-300 ℃ for 0.5-12 hours, and the solvothermal treatment is performed under the autogenous pressure in a closed condition;
in step S2, the temperature of the calcination treatment is 100-300 ℃, the time is 1-8 hours, and the calcination atmosphere is air atmosphere.
Optionally, the solvent comprises one or more of water, alcohol and hydrogen fluoride.
In a third aspect of the present disclosure, a lithium ion battery anode material prepared according to the method provided in the second aspect of the present disclosure is provided.
The fourth aspect of the present disclosure provides a lithium ion battery negative electrode containing the lithium ion battery negative electrode material provided by the first aspect of the present disclosure and the third aspect of the present disclosure.
A fifth aspect of the present disclosure provides a lithium ion battery cathode comprising a positive electrode, a negative electrode and an electrolyte, the negative electrode being the lithium ion battery cathode provided by the fourth aspect of the present disclosure.
According to the technical scheme, the lithium ion battery negative electrode material disclosed by the invention is prepared by coating and modifying the negative active oxide by adopting the metal oxyfluoride, and the metal element in the metal oxyfluoride is the same as that in the negative active oxide, so that the interface compatibility of the metal oxyfluoride and the negative active oxide is good, and Li of the metal oxyfluoride pair+The ionic conductivity is higher, so that the Li of the lithium ion battery can be ensured+The lithium ion battery of the cathode material provided by the disclosure has better rate performance.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure provides a lithium ion battery anode material, particles of the anode material have a core-shell structure, the core-shell structure comprises a base body and a shell layer coated on the outer surface of the base body, the base body contains an anode active oxide, and the shell layer contains a metal oxyfluoride;
the molecular formula of the negative active oxide is LicMaObM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, a is an integer greater than 0, b is an integer greater than 0, c is an integer greater than 0, and the value of (2b-c)/a is equal to the valence of M; the molecular general formula of the metal oxyfluoride is MOxFyM is selected from one of transition metal elements and Bi, and the value of 2x + y is equal to the valence of M; wherein LicMaObAnd the MOxFyM in (1) are the same.
The core-shell structure anode material of the present disclosure may further include a conventional C modified coating layer, which is not limited by the present disclosure.
The inventors of the present disclosure found that when a metal oxyfluoride is used to modify a negative active oxide, when a metal element in the metal oxyfluoride is the same as a metal element in the negative active oxide, the metal oxyfluoride and the negative active oxide have similar chemical potentials and good interface compatibility, and an interface structure and electrochemical properties are optimized, and the metal oxyfluoride is used to modify Li+The conductivity of the lithium ion battery is higher, and the Li of the lithium ion battery can be remarkably improved+The transmission rate of the lithium ion battery is increased, and therefore the rate performance of the lithium ion battery is effectively improved.
According to the present disclosure, the thickness of the outer shell layer of the anode material may vary within a wide range, and further, in order to provide a lithium ion battery with better rate performance, the average thickness of the outer shell layer of the anode material is preferably 10nm to 1 μm, and more preferably 30nm to 200 nm. Within the above range, the outer shell layer has an appropriate thickness, and has a good coating effect on the base material, and the outer shell layer of the negative electrode material can exert its effect on Li to the maximum extent+The rapid conduction function of the heat exchanger. If the shell layer is too thin, the continuity of the shell layer is broken, which is unfavorable for Li+The rapid conduction of (2); if the casing layer is too thick, the overall energy density of the lithium ion battery is sacrificed. Wherein the thickness is measured by a method of counting SEM (scanning Electron microscope) results of particle sections
In accordance with the present disclosure, the content of the matrix and the outer shell of the anode material may vary within a wide range, and preferably, the content of the matrix may be 90 to 99.5 wt% and the content of the outer shell may be 0.5 to 10 wt%, based on the total mass of the anode material; further, in order to obtain an outer shell layer having a suitable thickness to provide a lithium ion battery with a good rate capability, it is more preferable that the content of the matrix be 95 to 99 wt% and the content of the outer shell layer be 1 to 5 wt%, based on the total mass of the anode material.
According to the present disclosure, the metal element in the negative active oxide and the metal oxyfluoride may be selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm, and Yb, wherein the transition metal element may be one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, and Mt. Preferably, the metal element in the anode active oxide and the metal oxyfluoride may be one of Ti, Fe, and Bi.
According to the present disclosure, the anode active oxide may be Li4Ti5O12And/or TiO2The metal oxyfluoride may be TiOF2(ii) a Or the negative active oxide may be Fe2O3The metal oxyfluoride may be FeOF; or the negative active oxide may be Bi2O3The metal oxyfluoride may be a BiOF. When the cathode active metal oxide and the metal oxyfluoride are respectively the compounds, the lithium ion battery prepared from the cathode material has excellent rate performance and better cycle performance, and further greatly improves the comprehensive performance of the lithium ion battery. Further, in accordance with the present disclosure, the metal oxyfluoride may also be a modified metal oxyfluoride, which may be cationically doped and/or substituted, or anionically doped and/or substituted. The method for modifying the metal oxyfluoride by doping and/or substitution is a method conventionally used by those skilled in the art, and is not described herein again.
A second aspect of the present disclosure provides a method of preparing a negative electrode material for a lithium ion battery, the method comprising the steps of:
s1, mixing the negative active oxide, the metal fluoride and the solvent, and carrying out solvent heat treatment;
the molecular formula of the negative active oxide is LicMaObM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, a is an integer greater than 0, b is an integer greater than 0, c is an integer greater than 0, and the value of (2b-c)/a is equal to the valence of M; the molecular general formula of the metal fluoride is MFzM is selected from one of transition metal elements, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm and Yb, and the numerical value of z is equal to the valence of M; wherein LicMaObAnd the MFzM in (1) are the same.
And S2, taking out the solid phase in the material after the solvent heat treatment and calcining the solid phase.
In step S1, the solvent heat treatment refers to a heat treatment process in which the solvent generates a self-generated pressure under heating conditions and the temperature is increased to a boiling point or higher. Generally, the solvothermal treatment is carried out under closed conditions, which means that the reaction can be carried out in a closed reaction vessel, which can be a reaction vessel conventionally used by those skilled in the art, such as an autoclave and a closed reactor.
The method disclosed by the invention is simple in steps, convenient and easy to implement, the thickness and content of the coating layer can be accurately controlled, the coating layer is uniform, and the prepared cathode material with the core-shell structure has good interface compatibility.
According to the present disclosure, the metal element in the negative active oxide and the metal fluoride may be selected from one of transition metal oxides, Bi, Ce, Pr, Sm, Eu, Tb, Dy, Tm, and Yb, wherein the transition metal element may be one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, and Mt.
According to the disclosure, in order to obtain a negative electrode material with good rate performance and good cycle performance and other comprehensive electrochemical characteristics, the negative electrode active oxide can be Li4Ti5O12And/or TiO2The metal fluoride may be TiF4(ii) a Or the negative active oxide may be Fe2O3The metal fluoride may be FeF3(ii) a Or the negative active oxide may be Bi2O3The metal fluoride may be BiF3。
According to the disclosure, the amount of each component can be adjusted in the preparation process to achieve sufficient reaction of reactants, the amount of the metal fluoride can be 5-135g and the amount of the solvent can be 200-2000mL relative to 1000g of the negative active oxide; preferably, the amount of the metal fluoride may be 10 to 68g, and the amount of the solvent may be 400-1500 mL. In the preferable dosage range of the components, the matrix size of the prepared cathode material with the core-shell structure is suitable for the thickness of the shell layer, and the interface compatibility is good.
In order to prepare the cathode material with definite composition and accurate component content, and further enable the cathode material to have good physical structure and electrochemical performance, the reaction conditions in the cathode material preparation process can be controlled. In step S1, the temperature of the solvent heat treatment is 100-300 ℃, the time is 0.5-12 hours, and the solvent heat treatment is carried out under the autogenous pressure of the closed condition; in step S2, the temperature of the calcination treatment is 100-300 ℃, the time is 1-8 hours, and the calcination atmosphere is air atmosphere. The temperature of solvent heat treatment is lower, and compared with the traditional physical blending method, the prepared cathode material with the core-shell structure has better interface compatibility.
According to the present disclosure, the solvent may include one or more of water, alcohol, and hydrogen fluoride. Among them, the alcohol may be an alcohol conventionally used by those skilled in the art, such as methanol, ethanol, propanol, ethylene glycol, 1, 2-propanediol, and butanol.
In a third aspect of the present disclosure, a lithium ion battery anode material prepared according to the method provided in the second aspect of the present disclosure is provided.
A fourth aspect of the present disclosure provides a lithium ion battery anode comprising the lithium ion battery anode material provided in the first and third aspects of the present disclosure.
According to the present disclosure, the lithium ion battery negative electrode may further include a first binder, wherein the content of the first binder is 0.01 to 10 wt% based on the total weight of the negative electrode material.
The first binder is a variety of negative electrode binders conventionally used by those skilled in the art, and may be selected from, for example, at least one of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethylcellulose (CMC), and styrene butadiene latex (SBR).
In order to ensure that the lithium ion battery cathode has good charge and discharge performance, according to the disclosure, the lithium ion battery cathode may further include a first conductive agent, and the content of the first conductive agent is 0.1-10 wt% based on the total weight of the cathode material. The first conductive agent may be a conductive agent conventionally used by those skilled in the art, for example: one or more of acetylene black, carbon nanotubes, carbon fibers and carbon black.
According to the present disclosure, the lithium ion battery negative electrode may further include a negative electrode current collector, and the negative electrode current collector may be used for supporting the negative electrode material, wherein the negative electrode current collector may be one or more selected from a copper foil, a copper mesh, a nickel foil, a copper foam, a stainless steel mesh, and a stainless steel band.
The method for preparing the lithium ion battery cathode can comprise the following steps: uniformly mixing a negative electrode material, a conductive agent and a first adhesive in a first solvent to obtain negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying at 50-150 ℃ and tabletting at 0.5-3MPa to obtain the lithium ion battery negative electrode A containing the negative electrode material disclosed by the invention.
A fifth aspect of the present disclosure provides a lithium ion battery including a positive electrode, a negative electrode, and an electrolyte. The structure of the lithium ion battery is not particularly required, and may be one of an all-solid-state battery, a quasi-solid-state battery, and a liquid lithium battery, preferably a liquid lithium battery, and for example, may include a positive electrode, a negative electrode, a separator, and an electrolyte.
According to the present disclosure, the positive electrode may include a positive electrode material, a second binder, a second conductive agent, a second solvent, and a positive electrode current collector, and the content of the second binder may be 0.01 to 10 wt%, preferably 0.02 to 5 wt%, based on the total weight of the positive electrode material; the content of the second conductive agent may be 0.1 to 20% by weight, preferably 1 to 10% by weight; the content of the second solvent may be 50 to 400% by weight, preferably 70 to 300% by weight.
Wherein the positive electrode material may include LiCoO2、LiNiO2、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、LiCoxNi1-xO2、LiCoxNi1-x-yAlyO2、LiMn2O4、Li1+aL1－b－cM1dNeO2、LiFefMngMhO4X is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; -0.1. ltoreq. a.ltoreq.0.2, 0. ltoreq. b.ltoreq.1, 0. ltoreq. c.ltoreq.1, 0. ltoreq. B + c.ltoreq.1, L, M, N being at least one selected from Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B; f is more than or equal to 0 and less than or equal to 1, g is more than or equal to 0 and less than or equal to 1, h is more than or equal to 0 and less than or equal to 1, f + g + h is 1, and M1 is at least one selected from Al, Mg, Ga, Cr, Co, Ni, Cu, Zn and Mo;
the metal sulfide may include TiS2、V2S3、FeS、FeS2And LiM2SjWherein j is more than or equal to 1 and less than or equal to 2.5, and M2 is at least one selected from Ti, Fe, Ni, Cu and Mo;
the metal oxide may comprise TiO2、Cr3O8、V2O5And MnO2。
The second adhesive may include at least one of a fluorine resin and/or a polyolefin compound, wherein the polyolefin compound may be one or more selected from polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and Styrene Butadiene Rubber (SBR). The second conductive agent may be one or more of acetylene black, carbon nanotubes, carbon fibers, and carbon black. The second solvent may be one or more selected from N-methylpyrrolidone (NMP), water, ethanol and acetone. The positive electrode collector may be a positive electrode collector conventionally used by those skilled in the art, for example: aluminum foil and/or carbon-coated aluminum foil. The second conductive agent may be one or more selected from acetylene black, carbon nanotubes, carbon fibers, and carbon black.
The electrolyte may be an electrolyte solution that is conventionally used by those skilled in the art in light of the present disclosureAn electrolyte solution, which may include LiPF6Diethyl carbonate solution as solute, LiPF6Dimethyl carbonate solution as solute, LiPF6Propylene carbonate and LiPF as solutes6One or more of ethylene carbonate as solute.
The method for preparing the lithium ion battery anode disclosed by the invention can comprise the following steps of: uniformly mixing the positive electrode active material, a second conductive agent and a second binder in a second solvent to obtain positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying at 50-150 ℃ and tabletting under 0.5-3MPa to obtain the positive electrode C of the lithium ion battery.
According to the present disclosure, a method of preparing a lithium ion battery provided by the present disclosure may be: and winding the positive electrode C, the negative electrode A and the diaphragm into a battery cell, placing the battery cell into a shell of the lithium ion battery, sealing, and performing liquid injection, aging, formation and capacity grading to obtain the lithium ion battery T. Among these, the membrane is a membrane conventionally used by those skilled in the art, such as: a polypropylene separator.
The present disclosure is further described below by way of examples, but the present disclosure is not limited thereto in any way.
Example 1
(1) Preparation of anode C of lithium ion battery
930g of LiCoO2The positive electrode material (93%), 30g of binder PVDF (3%), 20g of acetylene black (2%) and 20g of conductive agent carbon fiber (2%) were added to 800g of solvent NMP (N-methylpyrrolidone) and stirred in a vacuum stirrer to form stable and uniform positive electrode slurry. The positive electrode slurry was uniformly coated intermittently on both sides of an aluminum foil (aluminum foil size: 160mm in width, 16 μm in thickness), then dried under 393K, pressed into a sheet by a roller press at a pressure of 1.5MPa, and cut into a positive electrode C of a lithium ion battery having a size of 480mm (length) × 45mm (width).
(2) Preparation of negative electrode A of lithium ion battery
Titanium oxyfluoride (TiOF)2) Coated lithium titanate (Li)4Ti5O12) Preparing a negative electrode material: 1000g of Li4Ti5O12、30gTiF4Adding 200mL of deionized water and 800mL of ethanol into a closed reaction container with the volume of 5L, heating to 200 ℃ while stirring, reacting for 1h, cleaning the obtained precipitate, and calcining for 1.5h at 120 ℃ in the air to obtain the cathode material with the core-shell structure.
940g of the negative electrode material with the core-shell structure (94%), 30g of the binder CMC (3%) and 30g of the binder SBR (3%) are added into 1200g of deionized water, and then stirred in a vacuum stirrer to form stable and uniform negative electrode slurry. The slurry was uniformly coated intermittently on both sides of a copper foil (copper foil size: width 160mm, thickness 16 μm), then dried at 393K, sheeted by a roll press, and cut into a lithium ion battery negative electrode a of size 480mm (length) × 45mm (width).
The average thickness of the shell layer of the prepared cathode material with the core-shell structure is 140 nm. The content of the matrix was 97.5 wt% and the content of the outer shell was 2.5 wt% based on the total mass of the negative electrode material.
(3) Production of lithium ion battery T
Winding the lithium ion battery anode C obtained in the steps (1) and (2), the lithium ion battery anode A and a polypropylene diaphragm with the thickness of 20 mu m into a cell of a square lithium ion battery, putting the cell into a square battery aluminum shell with the thickness of 5mm multiplied by 34mm multiplied by 50mm, sealing, preparing into an 053450 type lithium ion battery, and then carrying out liquid injection, aging, formation and capacity division to obtain the lithium ion battery of the embodiment.
During the battery manufacturing process, the amount of the positive electrode active material should be 20% more than the negative electrode active material to highlight the negative electrode's effect on the lithium ion battery.
Example 2
(1) Preparation of anode C of lithium ion battery
930g of LiCoO2The positive electrode material (93%), 30g of binder PVDF (3%), 20g of acetylene black (2%) and 20g of conductive agent carbon fiber (2%) were added to 800g of solvent NMP (N-methylpyrrolidone) and stirred in a vacuum stirrer to form stable and uniform positive electrode slurry. The positive electrode slurry was uniformly coated intermittently on both sides of an aluminum foil (aluminum foil size: width 160mm, thickness 16 μm), and then subjected to 393K conditionsDrying, pressing by a roller press with the pressure of 1.5MPa, and cutting into the positive electrode C of the lithium ion battery with the size of 480mm (length) multiplied by 45mm (width).
(2) Preparation of negative electrode A of lithium ion battery
Iron oxide coated with iron oxyfluoride (FeOOF) (Fe)2O3) Preparing a negative electrode material: 1000g of Fe2O3、10g FeF3Adding 30mL of anhydrous HF, 100mL of deionized water and 270mL of ethylene glycol into a closed reaction container with the volume of 5L, heating to 100 ℃ while stirring, reacting for 12h, cleaning the obtained precipitate, and calcining for 8h at 100 ℃ in the air to obtain the cathode material with the core-shell structure.
940g of the negative electrode material with the core-shell structure (94%), 30g of adhesive polythiophene (3%) and 30g of adhesive polytetrafluoroethylene (3%) are added into 1200g of deionized water, and then stirred in a vacuum stirrer to form stable and uniform negative electrode slurry. The slurry was uniformly coated intermittently on both sides of a copper foil (copper foil size: width 160mm, thickness 16 μm), then dried at 393K, sheeted by a roll press, and cut into a lithium ion battery negative electrode a of size 480mm (length) × 45mm (width).
The average thickness of the shell layer of the prepared cathode material with the core-shell structure is 30 nm. The content of the matrix was 99 wt% and the content of the outer shell was 1 wt% based on the total mass of the negative electrode material.
(3) Production of lithium ion battery T
And (3) winding the lithium ion battery anode C obtained in the steps (1) and (2), the lithium ion battery cathode A and the polypropylene diaphragm with the thickness of 20 mu m into a cell of a square lithium ion battery, putting the cell into a square battery aluminum shell with the thickness of 5mm multiplied by 34mm multiplied by 50mm, sealing to prepare an 053450 type lithium ion battery, and then carrying out liquid injection, aging, formation and capacity division to obtain the lithium ion battery of the embodiment.
During the battery manufacturing process, the amount of the positive electrode active material should be 20% more than the negative electrode active material to highlight the negative electrode's effect on the lithium ion battery.
Example 3
(1) Preparation of anode C of lithium ion battery
930g of LiCoO2The positive electrode material (93%), 30g of binder PVDF (3%), 20g of acetylene black (2%) and 20g of conductive agent carbon fiber (2%) were added to 800g of solvent NMP (N-methylpyrrolidone) and stirred in a vacuum stirrer to form stable and uniform positive electrode slurry. The positive electrode slurry was uniformly coated intermittently on both sides of an aluminum foil (aluminum foil size: 160mm in width, 16 μm in thickness), then dried under 393K, pressed into a sheet by a roller press at a pressure of 1.5MPa, and cut into a positive electrode C of a lithium ion battery having a size of 480mm (length) × 45mm (width).
(2) Preparation of negative electrode A of lithium ion battery
Bismuth oxyfluoride (BiOF) -coated bismuth oxide (Bi)2O3) Preparing a negative electrode material: 1000g of Bi2O3、68g BiF350mL of anhydrous HF, 500mL of deionized water and 950mL of propanol are added into a closed reaction container with the volume of 5L, the mixture is heated to 300 ℃ while stirring is started to react for 0.5h, the obtained precipitate is cleaned, and the precipitate is calcined in the air at 300 ℃ for 1h to obtain the cathode material with the core-shell structure.
940g of the negative electrode material with the core-shell structure (94%), 30g of the adhesive polyethylene (3%) and 30g of the adhesive polystyrene (3%) are added into 1200g of deionized water, and then stirred in a vacuum stirrer to form stable and uniform negative electrode slurry. The slurry was uniformly coated intermittently on both sides of a copper foil (copper foil size: width 160mm, thickness 16 μm), then dried at 393K, sheeted by a roll press, and cut into a lithium ion battery negative electrode a of size 480mm (length) × 45mm (width).
The average thickness of the shell layer of the prepared cathode material with the core-shell structure is 200 nm. The content of the matrix was 95 wt% and the content of the outer shell was 5 wt% based on the total mass of the negative electrode material.
(3) Production of lithium ion battery T
Winding the lithium battery anode C and the lithium battery cathode A obtained in the steps (1) and (2) and a polypropylene diaphragm with the thickness of 20 mu m into a battery cell of a square lithium ion battery, putting the battery cell into a square battery aluminum shell with the thickness of 5mm multiplied by 34mm multiplied by 50mm, sealing to prepare an 053450 type lithium ion battery, and then carrying out liquid injection, aging, formation and capacity division to obtain the lithium ion battery of the embodiment.
During the battery manufacturing process, the amount of the positive electrode active material should be 20% more than the negative electrode active material to highlight the negative electrode's effect on the lithium ion battery.
Example 4
The coated positive electrode material and the lithium ion battery of the present example were prepared by the same procedure as in example 1, except that:
(2) preparation of negative electrode A of lithium ion battery
Titanium oxyfluoride (TiOF)2) Coated lithium titanate (Li)4Ti5O12) Preparing a negative electrode material: 1000g of Li4Ti5O12、6gTiF4Adding 100mL of deionized water and 100mL of 1, 2-propylene glycol into a closed reaction container with the volume of 5L, heating to 100 ℃ while stirring, reacting for 2h, cleaning the obtained precipitate, and calcining for 2h in the air at 100 ℃ to obtain the cathode material with the core-shell structure.
The average thickness of the shell layer of the prepared cathode material with the core-shell structure is 25 nm. The content of the matrix was 99.5 wt% and the content of the outer shell was 0.5 wt% based on the total mass of the negative electrode material.
During the battery manufacturing process, the amount of the positive electrode active material should be 20% more than the negative electrode active material to highlight the negative electrode's effect on the lithium ion battery.
Example 5
The coated positive electrode material and the lithium ion battery of the present example were prepared by the same procedure as in example 1, except that:
(2) preparation of negative electrode A of lithium ion battery
Titanium oxyfluoride (TiOF)2) Coated lithium titanate (Li)4Ti5O12) Preparing a negative electrode material: 1000g of Li4Ti5O12、130gTiF4Adding 800mL of deionized water and 1200mL of butanol into a closed reaction vessel with the volume of 5L, heating to 200 ℃ while stirring, reacting for 2.5h, and obtainingAnd (3) cleaning the precipitate, and calcining the precipitate in the air at 200 ℃ for 2.5h to obtain the cathode material with the core-shell structure.
The average thickness of the shell layer of the prepared cathode material with the core-shell structure is 500 nm. The content of the matrix was 90 wt% and the content of the outer shell was 10 wt% based on the total mass of the negative electrode material.
Example 6
The coated positive electrode material and the lithium ion battery of the present example were prepared by the same procedure as in example 1, except that:
(2) preparation of negative electrode A of lithium ion battery
Titanium oxyfluoride (TiOF)2) Coated lithium titanate (Li)4Ti5O12) Preparing a negative electrode material: 1000g of Li4Ti5O12、2gTiF4Adding 100mL of deionized water and 200mL of methanol into a closed reaction container with the volume of 5L, heating to 250 ℃ while stirring, reacting for 2.8h, cleaning the obtained precipitate, and calcining for 2h at 240 ℃ in the air to obtain the cathode material with the core-shell structure.
The average thickness of the shell layer of the prepared cathode material with the core-shell structure is less than 10nm, and the cathode material cannot be uniformly coated. The content of the matrix was 99.8 wt% and the content of the outer shell was 0.02 wt% based on the total mass of the negative electrode material.
Example 7
The coated positive electrode material and the lithium ion battery of the present example were prepared by the same procedure as in example 1, except that:
(2) preparation of negative electrode A of lithium ion battery
Titanium oxyfluoride (TiOF)2) Coated lithium titanate (Li)4Ti5O12) Preparing a negative electrode material: 1000g of Li4Ti5O12、550gTiF4Adding 500mL of deionized water and 800mL of ethanol into a closed reaction container with the volume of 5L, heating to 280 ℃ while stirring for reaction for 3h, cleaning the obtained precipitate, and calcining at 300 ℃ in the air for 3h to obtain the cathode material with the core-shell structure.
The average thickness of the outer shell layer of the prepared cathode material with the core-shell structure is 1.3 mu m. The content of the matrix was 75 wt% and the content of the outer shell was 25 wt% based on the total mass of the negative electrode material.
Comparative example 1
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the used cathode material is FeOOF coated Li4Ti5O12And (3) a negative electrode material. The preparation method comprises the following steps: 1000gLi4Ti5O12、30gFeF3Adding 15mL of anhydrous HF, 200mL of deionized water and 800mL of ethanol into a closed reaction container with the volume of 5L, heating to 250 ℃ while stirring, reacting for 1.5h, cleaning the obtained precipitate, and calcining at 120 ℃ in air for 2h to obtain the FeOOF-coated Li4Ti5O12And (3) a negative electrode material.
The average thickness of the outer shell layer of the prepared cathode material with the core-shell structure is 125 mu m. The content of the matrix was 97.5 wt% and the content of the outer shell was 2.5 wt% based on the total mass of the negative electrode material.
Comparative example 2
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the negative electrode material used is TiOF2Coated Fe2O3And (3) a negative electrode material. The preparation method comprises the following steps: 1000g of Fe2O3、30gTiF4Adding 200mL of deionized water and 800mL of ethanol into a closed reaction container with the volume of 5L, heating to 200 ℃ while stirring, reacting for 2h, cleaning the obtained precipitate, and calcining at 120 ℃ in air for 2.5h to obtain the TiOF2Coated Fe2O3And (3) a negative electrode material.
The average thickness of the outer shell layer of the prepared cathode material with the core-shell structure is 140 mu m. The content of the matrix was 97.5 wt% and the content of the outer shell was 2.5 wt% based on the total mass of the negative electrode material.
Comparative example 3
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the used cathode material is LiF-coated Li4Ti5O12And (3) a negative electrode material. The preparation method comprises the following steps: using LiF as a source, and coating about 25g of LiF on 1000g of Li by adopting a magnetron sputtering method4Ti5O12And then, directly using the negative electrode material to assemble the lithium battery, wherein other steps and operations are the same.
Comparative example 4
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the cathode material used is Al2O3Coated Li4Ti5O12And (3) a negative electrode material. The preparation method comprises using Al2O3As a source, about 25gAl is added by magnetron sputtering2O3Coating is 1000gLi4Ti5O12And then, directly using the cathode material to assemble the lithium ion battery, wherein other steps and operations are the same.
Comparative example 5
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the used cathode material is single-layer C-coated lithium titanate (Li)4Ti5O12) The preparation method of the material comprises the following steps: lithium titanate (Li)4Ti5O12) And uniformly mixing 1000g and 11.9g of sucrose in 500mL of deionized water, heating to 300 ℃ in the atmosphere of Ar gas for 3h, and then directly assembling the lithium ion battery by using the negative electrode material, wherein other steps and operations are the same.
Comparative example 6
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that: the used cathode material adopts TiOF2With Li4Ti5O12The physical blending method is adopted.
TiOF2The preparation method comprises the following steps: 1000g of TiF are taken4100mL of deionized water and 900mL of ethanol are added into a reaction vessel with the volume of 5L, and the mixture is heated to 200 ℃ while stirring is started for reaction, so that the TiOF can be obtained2And (3) obtaining the product.
TiOF2With Li4Ti5O12The physical blending method comprises the following steps: take 250gTiOF2With 1000g Li4Ti5O12Ball-milling in a ball-milling tank at the ball-milling rotation speed of 250rpm for 2h to obtain TiOF2With Li4Ti5O12A physically blended anode material. The cathode material is directly used for assembling the lithium ion battery, and other steps and operations are the same.
Comparative example 7
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the cathode material used is Li without coating treatment4Ti5O12And (3) assembling the lithium ion battery by directly using the negative electrode material, wherein other steps and operations are the same.
Comparative example 8
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the used cathode material is Fe without coating treatment2O3And (3) assembling the lithium ion battery by directly using the negative electrode material, wherein other steps and operations are the same.
Comparative example 9
The same procedure as in example 1 was used to prepare a coated positive electrode material and a lithium ion battery of this comparative example, except that:
the used cathode material is Bi without coating treatment2O3Anode material, and then directly using the anode materialAnd assembling the lithium ion battery, and performing the same other steps and operations.
Test example 1
The all-solid-state lithium ion batteries CEA1-CEA16 obtained in examples 1 to 7 and comparative examples 1 to 9 were subjected to a cycle test of the battery cell by the following method:
and (3) testing the cycle life of the battery: the batteries prepared in each example and comparative example were 20 batteries each, and the batteries were subjected to a charge-discharge cycle test at 1C under 298 ± 1K on a LAND CT 2001C secondary battery performance testing apparatus. The method comprises the following steps: standing for 10 min; charging at constant voltage to 2.8V/0.05C, and cutting off; standing for 10 min; constant current discharge to 0.5V, i.e. 1 cycle. For examples 2, 3 and comparative examples 2, 8, 9, the test procedure was a hold up of 10 min; charging at constant voltage to 4.2V/0.05C, and cutting off; standing for 10 min; constant current discharge to 0.5V, i.e. 1 cycle. Repeating the step, and when the battery capacity is lower than 80% of the first discharge capacity in the circulation process, ending the circulation, wherein the circulation times are the circulation life of the battery, and each group is averaged.
And (3) battery rate performance test: the batteries prepared in each example and comparative example were 20 batteries each, and the batteries were subjected to a charge-discharge cycle test at 10C under 298 ± 1K on a LAND CT 2001C secondary battery performance testing apparatus. The method comprises the following steps: standing for 10 min; charging at constant voltage to 2.8V/0.05C, and cutting off; standing for 10 min; constant current discharge to 0.5V, i.e. 1 cycle. For examples 2, 3 and comparative examples 2, 8, 9, the test procedure was a hold up of 10 min; charging at constant voltage to 4.2V/0.05C, and cutting off; standing for 10 min; constant current discharge to 0.5V, i.e. 1 cycle. And when the battery capacity is lower than 80% of the first discharge capacity in the circulation process, the circulation is terminated, the circulation times are the circulation life of the battery, and each group is averaged. The test results are shown in table 1.
TABLE 1
Figure BDA0001847581910000181
Figure BDA0001847581910000191
The high-rate lithium ion battery has the characteristic of excellent cycle performance, and as can be seen from the data in table 1, the rate performance of the cathode material provided by the disclosure for preparing the lithium ion battery is excellent. The possible reasons for this are: on one hand, the metal oxyfluoride in the negative electrode material and the metal element in the negative active oxide are the same, the chemical formulas of the metal oxyfluoride and the metal element are similar, the interface compatibility is good, and the electrochemical performance of the negative electrode material is further improved; on the other hand, metal oxyfluoride vs Li+Has higher conductivity and effectively improves Li+The transmission rate of the lithium ion battery improves the rate capability of the lithium ion battery prepared from the cathode material. When the thickness of the shell layer material is preferably 30nm-200nm, the rate capability of the lithium ion battery is remarkably improved; based on the total mass of the negative electrode material, the content of the matrix is preferably 95-99 wt%, the content of the shell layer is preferably 1-5 wt%, and the lithium ion battery has better rate performance.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. The lithium ion battery negative electrode material is characterized in that particles of the negative electrode material have a core-shell structure, the core-shell structure comprises a base body and a shell layer coated on the outer surface of the base body, the base body contains a negative electrode active oxide, and the shell layer contains a metal oxyfluoride;
the molecular general formula of the negative active oxide is LicMaObM is selected from one of Fe, Bi, Ti, V, Cr, Mn, Co, Ni, W, Mo, Cu, Zn, Ag, Cd and Au, a is an integer greater than 0, b is an integer greater than 0, c is an integer greater than 0, and the value of (2b-c)/a is equal to the valence of M; the molecular general formula of the metal oxyfluoride is MOxFyThe value of 2x + y is equal to the valence of M; wherein, the LicMaObAnd the MOxFyM in (1) are the same;
wherein the average thickness of the outer shell layer of the anode material is 10nm-1 μm.
2. The anode material according to claim 1, wherein the average thickness of the outer shell layer of the anode material is 30nm to 200 nm.
3. The negative electrode material as claimed in claim 1, wherein the matrix is contained in an amount of 90 to 99.5 wt% and the outer shell is contained in an amount of 0.5 to 10 wt%, based on the total mass of the negative electrode material.
4. The anode material according to any one of claims 1 to 3, wherein the anode active oxide is Li4Ti5O12And/or TiO2The metal oxyfluoride is TiOF2(ii) a Or
The negative active oxide is Fe2O3The metal oxyfluoride is FeOOF; or
The negative active oxide is Bi2O3And the metal oxyfluoride is BiOF.
5. A method for preparing a negative electrode material of a lithium ion battery is characterized by comprising the following steps:
s1, mixing the negative active oxide, the metal fluoride and the solvent, and carrying out solvent heat treatment;
the molecular general formula of the negative active oxide is LicMaObM is selected from one of Fe, Bi, Ti, V, Cr, Mn, Co, Ni, W, Mo, Cu, Zn, Ag, Cd and Au, a is an integer greater than 0, b is an integer greater than 0, c is an integer greater than 0, and the value of (2b-c)/a is equal to the valence of M; the molecular general formula of the metal fluoride is MFzZ is equal to the valence of M; wherein, the LicMaObAnd the MFzM in (1) are the same;
s2, taking out the solid phase in the material subjected to the solvent heat treatment and calcining the solid phase;
wherein, relative to 1000g of the anode active oxide, the dosage of the metal fluoride is 5-135g, and the dosage of the solvent is 200-2000 mL;
wherein, in the step S1, the temperature of the solvent heat treatment is 100-300 ℃, the time is 0.5-12 hours, and the solvent heat treatment is carried out under the autogenous pressure of the closed condition;
in step S2, the temperature of the calcination treatment is 100-300 ℃, the time is 1-8 hours, and the calcination atmosphere is air atmosphere.
6. The method according to claim 5, wherein the negative active oxide is Li4Ti5O12And/or TiO2The metal fluoride is TiF4(ii) a Or
The negative active oxide is Fe2O3The metal fluoride is FeF3(ii) a Or
The negative active oxide is Bi2O3The metal fluoride is BiF3。
7. The method of claim 5, wherein the solvent comprises one or more of water, an alcohol, and hydrogen fluoride.
8. The lithium ion battery negative electrode material prepared by the method of any one of claims 5 to 7.
9. A lithium ion battery negative electrode, characterized in that the lithium ion battery negative electrode comprises the lithium ion battery negative electrode material provided in any one of claims 1 to 4 and claim 8.
10. A lithium ion battery, comprising a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode is the lithium ion battery negative electrode provided in claim 9.
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