CN110660976A - Lithium ion battery anode material and preparation method thereof, lithium ion battery anode and all-solid-state lithium battery - Google Patents

Lithium ion battery anode material and preparation method thereof, lithium ion battery anode and all-solid-state lithium battery Download PDF

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CN110660976A
CN110660976A CN201810715053.XA CN201810715053A CN110660976A CN 110660976 A CN110660976 A CN 110660976A CN 201810715053 A CN201810715053 A CN 201810715053A CN 110660976 A CN110660976 A CN 110660976A
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positive electrode
equal
core
shell
lithium ion
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历彪
郭姿珠
马永军
谢静
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BYD Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/36—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The disclosure relates to a lithium ion battery anode material and a preparation method thereof, a lithium ion battery anode and an all-solid-state lithium battery. The anode material comprises a core-shell structure composite material, the core-shell structure composite material comprises a core material, an inner shell material and an outer shell material, the core material comprises an anode active substance, the inner shell material is an anode active substance containing fluorine, and the outer shell material comprises oxyfluoride. The lithium ion battery anode material disclosed by the invention has the fluoride layer as the inner shell and the oxyfluoride as the outer shell, and the formed core-shell structure coated by the two layers of shells enables the coating structure to be stable, so that the interface reaction or element diffusion between the anode material and the solid electrolyte can be avoided, and the element diffusion between the anode material and the coating is reduced, thereby greatly optimizing the interface of the anode material. The method for preparing the cathode material can complete coating and fluorination in one step, has low coating temperature and simple and feasible operation, further reduces the mutual permeation condition of elements and optimizes the interface of the cathode material.

Description

Lithium ion battery anode material and preparation method thereof, lithium ion battery anode and all-solid-state lithium battery
Technical Field
The disclosure relates to the field of all-solid-state lithium batteries, in particular to a lithium ion battery anode material and a preparation method thereof, a lithium ion battery anode and an all-solid-state lithium battery.
Background
The interface of the anode material and the solid electrolyte of the all-solid-state lithium battery is easy to generate element diffusion phenomenon, so that the performance of the battery is reduced. In the prior art, a cathode material is mostly coated, so that an interface between a cathode and a solid electrolyte is improved, and a common coating is Li4Ti5O12、Al2O3、LiNbO3And the like. However, the performance improvement of the single coating on the anode material is limited, and the problem of interface diffusion between the anode material and the coating cannot be solved.
Disclosure of Invention
The purpose of the present disclosure is to provide a lithium ion battery cathode material, which solves the problem that the existing oxide-coated cathode material has limited improvement on interface performance, and has stable surface and less diffusion phenomenon of interface elements.
Through research, the inventor of the present disclosure finds that a fluorine-containing fluoride layer and a fluorine oxide layer are sequentially coated outside a positive electrode active material, and the formed composite material with a core-shell structure of two shells can provide an effective isolation layer structure between a positive electrode material and a solid electrolyte, so as to further avoid element diffusion of the positive electrode material and the solid electrolyte, thereby solving the problems of interface impedance increase and battery life reduction caused by interface element diffusion.
The first aspect of the present disclosure provides a lithium ion battery positive electrode material, which includes a core-shell structure composite material, where the core-shell structure composite material includes a core material, an inner shell material and an outer shell material, the core material includes a positive electrode active material, the inner shell material is the positive electrode active material containing fluorine, and the outer shell material includes oxyfluoride.
Optionally, the average particle size of the core-shell structure composite material is 100nm to 500 μm.
Optionally, the content of the inner shell material is 0.1-50% based on the total mass of the cathode material; the content of the shell material is 0.1-50%.
Optionally, the thickness of the inner shell of the core-shell structure composite material is 1nm to 5 μm, and the thickness of the outer shell of the core-shell structure composite material is 1nm to 5 μm.
Optionally, the oxyfluoride is selected from metal oxyfluorides, wherein the metal in the metal oxyfluoride is at least one of Fe, Ti, V, Bi, Zr, Nb, Ag, Cr, Mn, Co, Ni and Zn.
Alternatively, the fluorine-containing positive electrode active material is obtained by subjecting the surface of the positive electrode active material to a fluorination treatment.
Optionally, the fluorine-containing positive electrode active material has a fluorine content decreasing from the surface toward the inside of the particle.
Optionally, the inner shell of the core-shell structure composite completely isolates the core from the outer shell of the core-shell structure composite.
Optionally, the positive active material comprises LiCoO2、LiNiO2、LiCorNi1-rO2、LiCoxNi1-x-yAlyO2、LiMn2O4、LiFepMnqXsO4、Li1+aL1－b－cMbQcO2，LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、LiRSz、TiO2、Cr3O8、V2O5And MnO2At least one of; wherein r is more than or equal to 0 and less than or equal to 1, 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, p is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, p + q + s is equal to 1, a is more than or equal to-0.1 and less than or equal to 0.2, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and; x is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn and Mo, L, M, Q is at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, and R is at least one of Ti, Fe, Ni, Cu and Mo.
The present disclosure provides, in a second aspect, a method for preparing a positive electrode material for a lithium ion battery, the method comprising the steps of: mixing the positive active substance, the oxyfluoride precursor and the hydrogen fluoride in a solvent, and reacting at the temperature of 100-250 ℃ and the reaction pressure of 0.1-100 MPa.
Optionally, the oxyfluoride precursor is a metal fluoride, and the metal in the metal fluoride is at least one of Fe, Ti, V, Bi, Zr, Nb, Ag, Cr, Mn, Co, Ni, and Zn.
Optionally, the solvent is water and/or an alcohol.
Optionally, the molar ratio of the amounts of the positive electrode active material, the oxyfluoride precursor, and the hydrogen fluoride is 1: (0.0015-2): (0.001 to 1); the amount of the solvent is 0.1 to 10 parts by weight relative to 1 part by weight of the positive electrode active material.
Optionally, the method comprises mixing and reacting an aqueous HF solution with the positive electrode active material and the oxyfluoride precursor in the solvent; the volume ratio of the hydrogen fluoride to the water in the HF aqueous solution is as follows: (0.1 to 100).
Optionally, the method comprises mixing and reacting the positive electrode active material, the oxyfluoride precursor and the hydrogen fluoride in the solvent in a sealed state, and continuing the reaction in a non-sealed state when the reaction pressure is 5-100 Mpa and keeping the reaction pressure at 25-100 Mpa.
The third aspect of the present disclosure provides a lithium ion battery cathode material prepared according to the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure provides a lithium ion battery positive electrode comprising the lithium ion battery positive electrode material according to the first and third aspects of the present disclosure.
A fifth aspect of the present disclosure is an all-solid-state lithium battery including the lithium ion battery positive electrode according to the fourth aspect of the present disclosure.
Through the technical scheme, the lithium ion battery anode material disclosed by the invention has the fluoride layer as the inner shell and the oxyfluoride as the outer shell, and the formed core-shell structure coated by the two layers of shells enables the material to have a stable coating structure, so that the interface reaction or element diffusion between the anode material and a solid electrolyte can be avoided, and the element diffusion between the anode material and a coating object is reduced, thereby greatly optimizing the interface of the anode material. The method for preparing the cathode material can complete coating and fluorination in one step, has low coating temperature and simple and feasible operation, further reduces the mutual permeation condition of elements and optimizes the interface of the cathode material.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is a schematic structural diagram of one embodiment of the lithium ion battery positive electrode material of the present disclosure.
Description of the reference numerals
1 core material 2 inner shell material
3 outer shell material
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. 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.
As shown in fig. 1, in a first aspect of the present disclosure, a lithium ion battery positive electrode material is provided, where the positive electrode material includes a core-shell structure composite material, the core-shell structure composite material includes a core material 1, an inner shell material 2, and an outer shell material 3, the core material includes a positive electrode active material, the inner shell material is a positive electrode active material containing fluorine, and the outer shell material includes oxyfluoride.
The inventor of the present disclosure finds that the lithium ion battery cathode material with a core-shell structure, which is coated by two layers of shells including a fluorinated inner shell and an oxyfluoride outer shell, has a stable coating structure, and can significantly improve the electrochemical performance of the cathode material. The fluoride layer inner shell stabilizes the surface of the anode material, increases the stability of the anode material, reduces side reactions at the end of the anode material, and is beneficial to relieving negative effects caused by element diffusion; the oxyfluoride shell has higher ionic conductivity and low electronic conductivity, and the chemical potential of lithium is reduced after the shell is coated, so that the lithium ion transport is facilitated, the surface voltage of a positive electrode material in contact with a solid electrolyte material is effectively reduced, the solid electrolyte is protected, the oxidation of the solid electrolyte by the positive electrode material is avoided, the problem of lithium ion transport obstruction caused by a space charge layer is effectively relieved, and the element diffusion is facilitated to be reduced; the combined action of the inner shell of the fluoride layer and the double-layer outer shell of the oxyfluoride layer effectively reduces the side reaction of the interface, reduces the interface impedance, improves the interface of the anode and greatly optimizes the cycle stability and other electrochemical properties of the anode material.
According to the present disclosure, the average particle size of the core-shell structure composite material may vary in a wide range, and preferably, the average particle size may be 100nm to 500 μm, and more preferably 200nm to 50 μm, to further improve the electrochemical performance of the cathode material. The average particle size of the core-shell structure composite material can be measured by observing random 100 core-shell structure composite material particles through a Scanning Electron Microscope (SEM), and the average value of the particle sizes is the average particle size of the core-shell structure composite material.
Further, the thicknesses of the inner shell and the outer shell of the core-shell structure composite material can be changed in a wide range, preferably, the thickness of the inner shell of the core-shell structure composite material can be 1nm to 10 μm, preferably 1nm to 5 μm, more preferably 100nm to 1 μm, and the thickness of the outer shell of the core-shell structure composite material can be 1nm to 10 μm, preferably 1nm to 5 μm, more preferably 100nm to 1 μm. In the preferable thickness range, the inner shell and the outer shell of the core-shell structure composite material have better coating and isolating effects on the positive active material of the core material, and can further prevent elements of the positive material and the electrolyte from diffusing. The thicknesses of the outer shell and the inner shell are average thicknesses, the sections can be exposed by using a FIB (focused ion beam) or direct section grinding method, then observation is performed by using a tool such as SEM, the thickness values of the inner shell and the outer shell are measured by taking any 100 positive electrode material particles, and the average value of the thicknesses of the inner shell and the outer shell is the thickness of the inner shell and the outer shell respectively.
According to the disclosure, the contents of the inner shell material and the outer shell material in the core-shell structure composite material can be respectively changed within a large range; further, in order to obtain the core-shell structure composite material with the appropriate thickness of the inner shell and the outer shell, the content of the inner shell material can be 0.1-50%, and is further preferably 0.2-20% based on the total mass of the positive electrode material; the content of the shell material may be 0.1 to 50%, and more preferably 0.2 to 20%.
According to the present disclosure, in order to further effectively protect the positive electrode active material of the core material from interfacial element diffusion between the positive electrode material and the electrolyte, the sheath material may include metal oxyfluoride, and the metal in the metal oxyfluoride may be at least one of Fe, Ti, V, Bi, Zr, Nb, Ag, Cr, Mn, Co, Ni, and Zn, i.e., the metal oxyfluoride may be selected from FeOF, TiOF, and Zn2、VO2F、VOF3、BiOF、ZrOF2、NbO2F、NbOF3、AgOF、CrOF、MnOF2CoOF, NiOF and Zn2OF2At least one of (1).
According to the present disclosure, for convenience of preparation, the positive active material containing fluorine may be obtained by subjecting the surface of the positive active material to a fluorination treatment, that is, the inner shell of the core-shell structure composite material may be a fluorine-containing film layer formed by fluorinating the original surface of the positive active material, in which case the non-fluorinated positive active material inside the fluorine-containing film layer is the core of the core-shell structure composite material. Further, the fluorine content of the positive electrode active material containing fluorine decreases from the surface toward the inside of the particles.
According to the present disclosure, in order to further prevent the interface element diffusion of the cathode material, preferably, the inner shell of the core-shell structure composite material may completely isolate the core of the core-shell structure composite material from the outer shell. Wherein, the complete isolation means that the inner shell completely covers the core and can prevent the diffusion of elements between the core and the outer shell. The manner of achieving such complete isolation may include providing the inner shell with a suitable thickness and F/O atomic ratio.
According to the present disclosure, the positive active material may be a conventional kind in the art, and preferably, the positive active material may include LiCoO2、LiNiO2、LiCorNi1-rO2、LiCoxNi1-x-yAlyO2、LiMn2O4、LiFepMnqXsO4、Li1+aL1－b－ cMbQcO2，LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、LiRSz、TiO2、Cr3O8、V2O5And MnO2At least one of; wherein r is more than or equal to 0 and less than or equal to 1, 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, p is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, p + q + s is equal to 1, a is more than or equal to-0.1 and less than or equal to 0.2, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and; x is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn and Mo, L, M, Q is at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, and R is at least one of Ti, Fe, Ni, Cu and Mo. The particle diameter of the positive electrode active material particles is not particularly limited and may be varied within a wide range, and preferably, the average particle diameter of the positive electrode active material particles is 100nm to 500 μm, more preferably 200nm to 50 μm, to further increase the boundary of the positive electrode materialSurface formation and electrochemical performance.
The present disclosure provides, in a second aspect, a method for preparing a positive electrode material for a lithium ion battery, the method comprising the steps of: mixing and reacting the positive active substance, the oxyfluoride precursor and hydrogen fluoride in a solvent, wherein the reaction temperature is 100-250 ℃, and the reaction pressure is 0.1-100 MPa.
The method disclosed by the invention is used for preparing the double-layer core-shell structure cathode material coated with the fluorinated inner shell and the oxyfluoride outer shell through one-step reaction, the coating temperature is low, the operation is simple and convenient, the prepared cathode material can reduce the diffusion phenomenon of interface elements, and a stable and good interface is provided.
And the reaction temperature is preferably 100-300 ℃, and the reaction pressure is preferably 25-80 MPa, so as to further optimize the coating structure and the surface performance of the positive electrode material.
In the method according to the present disclosure, the reaction may be performed in a conventional reaction vessel, such as a closed vessel or a semi-closed vessel, and in order to facilitate control of the reaction pressure, the method may include mixing and reacting the positive electrode active material, the oxyfluoride precursor, and the hydrogen fluoride in a solvent in a closed state, and continuing the reaction in a non-closed state while maintaining the reaction pressure at 25 to 100Mpa when the reaction pressure is 5 to 100 Mpa. Specifically, for example, the reaction can be performed in a container with a pressure reducing valve, the pressure reducing valve can be closed in the initial stage of the reaction, the pressure reducing valve is opened when the pressure in the reaction container reaches 25-80 Mpa, and the pressure in the container is controlled, in this embodiment, the pressure in each stage of the reaction process can be further precisely controlled, so that the reactant can perform uniform reaction on the surface of the positive electrode active material particles, and the formation of the positive electrode material with a double-layer core-shell structure in which the inner shell is a fluorinated layer and the outer shell is an oxyfluoride coating layer is more facilitated.
According to the present disclosure, the oxyfluoride precursor means a substance capable of generating an oxyfluoride after a mixed reaction of fluorination and coating of the oxyfluoride, for example, a fluoride, and in order to further enhance the coating and separation effects of the oxyfluoride and prevent diffusion of interface elements between the positive electrode material and the electrolyte, the oxyfluoride precursor may preferably be a metal fluoride, and further, the metal in the metal fluoride may be at least one of Fe, Ti, V, Bi, Zr, Nb, Ag, Cr, Mn, Co, Ni, and Zn. Under the condition, the metal fluoride precursor can obtain a metal oxyfluoride coating layer after mixed reaction so as to further effectively protect the positive active substance of the nuclear material and avoid the diffusion of interface elements between the positive material and the electrolyte.
According to the present disclosure, the solvent of the mixing reaction may be water and/or an alcohol, for example, at least one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, cyclohexanol, glycerol, and octadecenol.
According to the present disclosure, the molar ratio of the amounts of the positive electrode active material, the oxyfluoride precursor, and the hydrogen fluoride may be 1: (0.0015-2): (0.001 to 1), preferably 1: (0.003-0.8): (0.002-0.4), wherein the fluorine in the oxyfluoride precursor and the fluorine in the hydrogen fluoride can be completely converted respectively within the dosage range so as to form a core-shell structure composite material with a proper coating thickness; the solvent may be used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, based on 1 part by weight of the positive electrode active material. The positive electrode active material may be any one of those conventionally used in the art, and preferably those listed above, and will not be described herein.
According to the present disclosure, hydrogen fluoride may be added in various forms, and for convenience of operation and improvement of fluorination effect, preferably, the reaction of the present disclosure may be carried out using an aqueous HF solution, in which case the method may include mixing and reacting the aqueous HF solution with a positive electrode active material, an oxyfluoride precursor in a solvent; the volume ratio of hydrogen fluoride to water in the aqueous HF solution may be 1: (0.1 to 100), preferably 1: (5-20).
A third aspect of the present disclosure provides a lithium ion battery positive electrode material prepared according to the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure provides a lithium ion battery positive electrode comprising the lithium ion battery positive electrode material of the first and third aspects of the present disclosure.
Further, the positive electrode of the lithium ion battery may include a positive electrode current collector and a positive electrode material layer coated on the positive electrode current collector, where the positive electrode material layer may include the positive electrode material including the core-shell structure composite material, a conductive agent, and a binder, and the binder is a binder commonly used for the positive electrode, for example: fluorine-containing resins and polyolefin compounds such as one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE) and styrene-butadiene rubber (SBR). The conductive agent is a common conductive agent for the positive electrode, such as acetylene black, carbon nanotubes, carbon fibers, carbon black and the like. The content of the binder is 0.01 to 10 weight% (wt%), preferably 0.02 to 5 wt%, based on the weight of the positive electrode active material; the content of the conductive agent is 0.1 to 20 wt%, preferably 1 to 10 wt%. The solvent can be one or more selected from N-methylpyrrolidone (NMP), water, ethanol and acetone, and the dosage of the solvent is generally 50-400 wt%.
A fifth aspect of the present disclosure is an all-solid-state lithium battery including the lithium ion battery positive electrode of the fourth aspect of the present disclosure.
The structure of the all-solid-state lithium battery may be conventional in the art, and may include, for example, a positive electrode including a positive electrode current collector and a positive electrode material layer coated on the positive electrode current collector, a negative electrode including a negative electrode current collector and a negative electrode material layer coated on the negative electrode current collector, and a solid electrolyte layer including a solid electrolyte material. The solid electrolyte material may be conventional in the art, and preferably includes one or more of a NASICON type solid electrolyte, an oxide solid electrolyte, and a sulfur-based solid electrolyte. Wherein the NASICON type solid electrolyte is LiM2(PO4)3And one or more of the dopants thereof, wherein M is Ti, Zr, Ge, Sn or Pb, and the dopant adopts one or more of doping elements selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V. The chemical formula of the oxide type solid electrolyte is AxByTiO3、AxByTa2O6、AxByNb2O6、AhMkDnTiwO3Or A3B2(MO4)3Wherein x +3y is 2, h +2k +5n +4w is 6, 0 < x < 2,y is more than 0 and less than 2/3, and h, k, n and w are all more than 0; a is at least one of Li and Na elements, B is at least one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd, Nd and Al elements, M is at least one of Sr, Ca, Ba, Ir, Pt, Te and Zr elements, and D is at least one of Nb and Ta elements. Li with crystalline sulfur-based solid electrolytexMyPzSw(M is one or more of Si, Ge and Sn, wherein x +4y +5z is 2w, y is more than or equal to 0 and less than or equal to 1.5, x is more than or equal to 0 and less than or equal to 15, z is more than or equal to 0 and less than or equal to 3, and w is more than or equal to 0 and less than or equal to 18), and glassy Li2S-P2S5(including Li)7P3S11、70Li2S-30P2S5Etc.) or glass-ceramic state Li2S-P2S5And dopants thereof.
Further, in the all solid-state lithium ion battery of the present disclosure, the negative electrode material layer may include a negative electrode active material commonly used by those skilled in the art, such as various negative electrode active materials capable of intercalating and deintercalating lithium, for example, one or more selected from carbon materials, tin alloys, silicon, tin, and germanium, and metal lithium, lithium-indium alloys, and the like may also be used. The carbon material can be non-graphitized carbon, graphite or carbon obtained by high-temperature oxidation of a polyacetylene polymer material, or one or more of pyrolytic carbon, coke, an organic polymer sinter and activated carbon. As a common knowledge of those skilled in the art, when the negative active material is a silicon-based material, the negative material layer further contains a conductive agent, and the function thereof is well known to those skilled in the art, and thus, will not be described herein again.
The all-solid-state lithium battery of the present disclosure may be prepared by the following method:
the positive electrode current collector is coated with the positive electrode material layer C, then the positive electrode active material layer is coated with the solid electrolyte material layer E, and the negative electrode active material layer A coated on the negative electrode current collector and the CE layer are laminated together to form the all-solid-state battery.
The positive electrode material layer can comprise the positive electrode material comprising the core-shell structure composite material, a conductive agent and a binder, and is prepared by the existing method: coating the slurry of the positive electrode material, the electrode adhesive and the solvent of the core-shell structure composite material on a current collector, drying, forming an active material layer on the current collector, and then carrying out rolling treatment under 0-5 MPa to obtain a pole piece C. The binder is a binder commonly used for a positive electrode, such as: fluorine-containing resins and polyolefin compounds such as one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE) and styrene-butadiene rubber (SBR). The conductive agent is a common conductive agent for the positive electrode, such as acetylene black, carbon nanotubes, carbon fibers, carbon black and the like. The content of the binder is 0.01 to 10 wt% (wt%), preferably 0.02 to 5 wt%, based on the weight of the positive electrode active material; the content of the conductive agent is 0.1-20 wt%, preferably 1-10 wt%. The solvent can be one or more selected from N-methylpyrrolidone (NMP), water, ethanol and acetone, and the dosage of the solvent is generally 50-400 wt%. The preparation process of the common positive electrode comprises the steps of mixing a positive active material, a conductive agent and a binder in a solvent according to a certain proportion, uniformly stirring to obtain required positive slurry, coating the slurry on an aluminum foil current collector, and drying and tabletting to obtain the common positive electrode C containing a positive active material layer.
The solid electrolyte material layer E may contain a solid electrolyte material and a binder. The solid electrolyte material layer E is produced by a coating method: and coating slurry containing a solid electrolyte material, a binder and a solvent on the C positive electrode active material layer, drying and rolling to form the CE. Wherein the solid electrolyte material is Li10GeP2S12A sulfur-based solid electrolyte. The binder is selected from one or more 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, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethyl cellulose (CMC) and styrene butadiene latex (SBR).
The components of the anode active material layer a are well known to those skilled in the art, and include an anode active material and a binder. The negative electrode active material used may be any of various negative electrode active materials capable of occluding and releasing lithium, which are commonly used by those skilled in the art, and may be one or more selected from carbon materials, tin alloys, silicon, tin, and germanium, and metallic lithium, lithium-indium alloys, and the like may be used. The carbon material can be non-graphitized carbon, graphite or carbon obtained by high-temperature oxidation of a polyacetylene polymer material, or one or more of pyrolytic carbon, coke, an organic polymer sinter and activated carbon. As a common knowledge of those skilled in the art, when the negative active material is a silicon-based material, the negative material layer further contains a conductive agent, and the function thereof is well known to those skilled in the art, and thus, will not be described herein again. The binder is a variety of negative electrode binders well known to those skilled in the art, and may be selected from one or more 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), styrene butadiene latex (SBR), for example. Preferably, the negative electrode material layer contains 0.01 to 10 wt% of a binder based on the weight of the negative electrode active material. The negative electrode material layer is obtained by mixing a negative electrode active material, a binder and the like in a solvent according to a certain proportion, uniformly stirring to obtain required negative electrode slurry, then coating the slurry on a copper foil current collector, and drying and tabletting to obtain the common negative electrode A containing the negative electrode active material layer. When lithium or lithium-indium alloy is used for the negative electrode, metallic lithium ribbon or lithium-indium alloy ribbon can be directly used.
And finally, pressing the A and the CE together to form the CEA, thus obtaining the all-solid-state battery of the invention, wherein the pressing mode is preferably isostatic pressing.
The present disclosure is further described below by way of examples, but the present disclosure is not limited thereto in any way.
Example 1
This example is provided to illustrate the lithium ion battery cathode material and all solid-state lithium battery of the present disclosure, and their preparation methods.
(1) Production of Positive electrode C
Firstly, preparing a positive electrode material with a core-shell structure of a fluorinated inner shell and an oxyfluoride outer shell, wherein a positive electrode active substance used as the core material is LiCoO2The material is prepared by mixing 1000g LiCoO2And 30gFeF3Placing into a semi-closed reaction vessel with a volume of 5L, adding 100mL of deionized water, 100mL of diluted HF solution (anhydrous HF: deionized water 11.1 mL: 88.9mL) and 800mL of ethanol, stirring, sealing, heating to 170 deg.C, reacting, and allowing the pressure in the reaction vessel to reach 8 × 106Pa (80 atmospheric pressure), the pressure reducing valve is opened to ensure that the pressure in the container is 8 multiplied by 106Pa, until the reaction is finished, the LiCoO with the core-shell structure of the fluorinated inner shell and the FeOOF outer shell of the iron oxyfluoride can be obtained2And (3) a positive electrode material. Then 930g of the above LiCoO was mixed2The 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 1500g of solvent NMP (N-methylpyrrolidone), and then stirred in a vacuum stirrer to form stable and uniform positive electrode slurry. The positive electrode slurry was uniformly and intermittently coated on both sides of an aluminum foil (aluminum foil size: 160mm in width, 16 μm in thickness), and then dried at 393K, and pressed by a roll press to obtain a positive electrode C.
(2) Production of CE
In a glove box, 600g of Li were charged10GeP2S12The resulting solution was placed in 1200g of toluene solution containing 30g of butadiene rubber binder and heated with stirring to a stable, homogeneous solution. The solution was coated continuously on the C obtained in step 2, and then dried at 333K, cut into CE of 485mm (length) by 46mm (width).
(3) Production of negative electrode A
940g of negative active material artificial graphite (94%), 30g of binder CMC (3%) and 30g of binder SBR (3%) were added to 1200g of deionized water, and then stirred in a vacuum stirrer to form stable and uniform negative 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, and cut into negative electrode sheets a of size 480mm (length) × 45mm (width) after being pressed into sheets by a roll press.
(4) Preparation of CEA
And (3) in a glove box, cutting the CE obtained in the step (2) and the A obtained in the step (3), aligning, placing in a hot press, performing 423K hot pressing for 1h, vacuumizing and sealing by using an aluminum plastic film, and taking out a sample.
And pressing the pressed sample in an isostatic press for 300 seconds(s) at 200MPa to obtain the all-solid-state lithium battery of the embodiment.
Example 2
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:
in step (1), FeF3The amount of (c) is not 30g but 60g, 100mL of diluted HF solution, anhydrous HF: deionized water 22.2 mL: 77.85L, the other steps and operations are the same.
Example 3
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:
in step (1), simultaneous fluorination and TiOF are prepared2Coated LiCoO2The positive electrode material is prepared by mixing 1000g LiCoO2And 30gTiF4Placing into a semi-closed reaction vessel with a volume of 5L, adding 100mL of deionized water, 100mL of diluted HF solution (anhydrous HF: deionized water 11.1 mL: 88.9mL) and 800mL of ethanol, stirring, sealing, heating to 200 deg.C, reacting, and allowing the pressure in the reaction vessel to reach 1 × 107Pa (100 atmospheric pressure), the pressure reducing valve is opened to ensure that the pressure in the container is 1 x 107Pa, until the reaction is finished, simultaneous fluorination and TiOF can be obtained2Coated LiCoO2The anode material is directly used for assembling the solid lithium battery, and other steps andthe operation is the same.
Comparative example 1
A lithium ion battery of this comparative example was prepared using the same procedure as in example 1, except that:
FeF is not added in the process of preparing the cathode material3The resulting LiCoO2The anode material has no FeOOF outer shell and only fluorinated inner shell, and is prepared by mixing 1000g of LiCoO2Placing into a semi-closed reaction vessel with a volume of 5L, adding 100mL of diluted HF solution (anhydrous HF: deionized water 11.1 mL: 88.9mL) and 900mL of ethanol, stirring, sealing, heating to 150 deg.C, reacting until the pressure in the reaction vessel reaches 8 × 106Pa (80 atmospheric pressure), the pressure reducing valve is opened to ensure that the pressure in the container is 8 multiplied by 106Pa until the reaction is finished, and obtaining the LiCoO with fluorinated surface2And (3) directly using the cathode material to assemble the solid-state lithium battery, and keeping the rest steps and operation unchanged.
Comparative example 2
A lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
no HF solution is added in the process of preparing the anode material, and the obtained LiCoO2The positive electrode material has no fluorinated inner shell and only FeOOF outer shell, and is prepared by mixing 1000g of LiCoO2、30gFeF3Putting the mixture into a semi-closed reaction container with the volume of 5L, adding 100mL of deionized water and 900mL of ethanol, starting stirring, heating to 180 ℃ after closing, and reacting to obtain FeOOF-coated LiCoO2And (3) directly using the cathode material to assemble the solid-state lithium battery, and keeping the rest steps and operation unchanged.
Comparative example 3
A lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
LiCoO2the positive electrode material has no fluorinated inner shell and FeOOF outer shell and is only LiCoO2The positive electrode material is prepared by physical ball milling and blending of the positive electrode material and FeOOF, and the preparation method comprises the following step of mixing 1000g of LiCoO2Putting the mixture and 29.5g FeOOF into a ball milling tank, and ball milling for 2 hours at the rotating speed of 250rpm to obtain LiCoO2And (3) a product obtained by physically ball-milling and blending the anode material and FeOOF is directly used for assembling the solid-state lithium battery, and the rest steps and operation are unchanged.
Comparative example 4
A lithium cell of this comparative example, LiCoO, was fabricated by the same procedure as in example 12The positive electrode material has a fluorinated inner shell with the difference that:
the positive electrode material is LiCoO with the surface being fluorinated2The anode material and FeOOF are physically ball-milled and blended, and the preparation method comprises the following steps of mixing 1000g of LiCoO2Placing into a semi-closed reaction vessel with a volume of 5L, adding 100mL of diluted HF solution (anhydrous HF: deionized water 11.1 mL: 88.9mL) and 900mL of ethanol, stirring, sealing, heating to 150 deg.C, reacting until the pressure in the reaction vessel reaches 8 × 106Pa (80 atmospheric pressure), the pressure reducing valve is opened to ensure that the pressure in the container is 8 multiplied by 106Pa until the reaction is finished, and obtaining the LiCoO with fluorinated surface2Positive electrode material, LiCoO with fluorinated surface2Putting the anode material and 29.5g of FeOOF into a ball milling tank together, and ball milling for 2 hours at the rotating speed of 250rpm to obtain LiCoO with the fluorinated surface2And (3) a product obtained by physically ball-milling and blending the anode material and FeOOF is directly used for assembling the solid-state lithium battery, and the rest steps and operation are unchanged.
Comparative example 5
A lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
LiCoO2the positive electrode material does not have a fluorinated inner shell and an iron oxyfluoride FeOOF outer shell, but the surface of the positive electrode material passes through Li4Ti5O12Coated LiCoO2The positive electrode material is prepared by mixing 1000g LiCoO273.4mL of tetrabutyl titanate, 12g of lithium ethoxide and 1000mL of ethanol are put into the same container, stirring is started, dilute ammonia water is gradually added, the pH range is adjusted to 9-10, the obtained precipitate is centrifuged, and the temperature is heated to 800 ℃ in the air, so that the surface of the precipitate is subjected to Li treatment4Ti5O12Coated LiCoO2And (3) directly using the cathode material to assemble the solid-state lithium battery, and keeping the rest steps and operation unchanged.
Comparative example 6
A lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
direct use of LiCoO without any treatment2The active material is assembled into the solid lithium battery, and the rest steps and operation are unchanged.
Test example 1
SEM (JSM-7600F) and XPS (PHI 5800) tests were performed on the positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 6, and data containing the content (atomic ratio) of the surface oxyfluoride cation element, the atomic ratio of surface F/O, the thickness of the coating layer (inner and outer shells), and the content of the inner and outer shells were obtained as shown in table 1, wherein the content of the inner shell was obtained by calculating the proportion of the fluorinated product, and the content of the outer shell was obtained by calculating the mass of the coated product.
Ar was applied to the positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 6+After ion etching, the surface element content and the atomic ratio of F/O were measured and the data are also shown in Table 1, wherein Ar+The step size of the ion etching is 2min, and the energy of the used ion beam is 2 keV.
TABLE 1
Figure BDA0001717435390000161
Figure BDA0001717435390000171
Test example 2
The cycle life test of the all-solid lithium batteries CEA1-CEA9 obtained in examples 1 to 3 and comparative examples 1 to 6 was carried out, and the obtained data are shown in Table 2. The test method is as follows:
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 0.1C 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 4.2V/0.05C, and cutting off; standing for 10 min; constant current discharge to 3.0V, i.e. 1 cycle. Repeating the steps, 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 service life of the battery, each group is averaged, and the data of the parameters and the average first discharge capacity of the battery are shown in table 2.
TABLE 2
Figure BDA0001717435390000181
As can be seen from the data in tables 1 and 2, compared with the general oxide-coated cathode material (comparative example 5) or the cathode material without any treatment (comparative example 6), the cathode material with the double-layer-coated core-shell structure of the fluorinated inner shell and the oxyfluoride outer shell according to the present disclosure can effectively improve the first discharge specific capacity and the cycle number of the all-solid-state lithium battery, and can significantly prolong the battery life; also, the battery life of the cathode material of the present disclosure is more advantageous than that of the cathode material having no inner casing of the fluorinated layer (comparative example 2) or no outer casing of oxyfluoride (comparative example 1) or the oxyfluoride is combined with the cathode active material only in a blended form (comparative examples 3 to 4), which shows that the battery material having both the inner casing of the fluorinated layer and the outer casing of the oxyfluoride further improves the interfacial properties of the cathode material, reduces the diffusion of elements, and is more advantageous to extend the life of the battery.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, 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 belong to the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
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 (18)

1. The lithium ion battery positive electrode material is characterized by comprising a core-shell structure composite material, wherein the core-shell structure composite material comprises a core material, an inner shell material and an outer shell material, the core material comprises a positive electrode active substance, the inner shell material is a positive electrode active substance containing fluorine, and the outer shell material comprises oxyfluoride.
2. The positive electrode material according to claim 1, wherein the core-shell structure composite material has an average particle diameter of 100nm to 500 μm.
3. The cathode material according to claim 1 or 2, wherein the thickness of the inner shell of the core-shell structure composite material is 1nm to 5 μm, and the thickness of the outer shell of the core-shell structure composite material is 1nm to 5 μm.
4. The cathode material according to claim 1, wherein the content of the inner shell material is 0.1% to 50% based on the total mass of the cathode material; the content of the shell material is 0.1-50%.
5. The positive electrode material according to claim 1, wherein the oxyfluoride is selected from metal oxyfluorides in which the metal is at least one of Fe, Ti, V, Bi, Zr, Nb, Ag, Cr, Mn, Co, Ni, and Zn.
6. The positive electrode material according to claim 1, wherein the fluorine-containing positive electrode active material is obtained by subjecting a surface of the positive electrode active material to a fluorination treatment.
7. The positive electrode material according to claim 6, wherein the fluorine-containing positive electrode active material has a fluorine content that decreases from the surface toward the inside of the particles.
8. The positive electrode material according to claim 1, wherein the inner shell of the core-shell structure composite material completely isolates the core from the outer shell of the core-shell structure composite material.
9. The positive electrode material according to claim 1 or 6, wherein the positive electrode active material comprises LiCoO2、LiNiO2、LiCorNi1-rO2、LiCoxNi1-x-yAlyO2、LiMn2O4、LiFepMnqXsO4、Li1+aL1－b－cMbQcO2，LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、LiRSz、TiO2、Cr3O8、V2O5And MnO2At least one of;
wherein r is more than or equal to 0 and less than or equal to 1, 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, p is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, p + q + s is equal to 1, a is more than or equal to-0.1 and less than or equal to 0.2, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and;
x is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn and Mo, L, M, Q is at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, and R is at least one of Ti, Fe, Ni, Cu and Mo.
10. A method for preparing a positive electrode material of a lithium ion battery is characterized by comprising the following steps:
mixing and reacting the positive active substance, the oxyfluoride precursor and hydrogen fluoride in a solvent, wherein the reaction temperature is 100-250 ℃, and the reaction pressure is 0.1-100 MPa.
11. The method of claim 10, wherein the oxyfluoride precursor is a metal fluoride, and the metal in the metal fluoride is at least one of Fe, Ti, V, Bi, Zr, Nb, Ag, Cr, Mn, Co, Ni, and Zn.
12. The method of claim 10, wherein the solvent is water and/or an alcohol.
13. The method according to claim 10, wherein the molar ratio of the amounts of the positive electrode active material, the oxyfluoride precursor, and the hydrogen fluoride is 1: (0.0015-2): (0.001 to 1); the amount of the solvent is 0.1 to 10 parts by weight relative to 1 part by weight of the positive electrode active material.
14. The method according to claim 10, wherein the method comprises a mixed reaction of an aqueous HF solution with the positive electrode active material, the oxyfluoride precursor in the solvent; the volume ratio of hydrogen fluoride to water in the HF aqueous solution is 1: (0.1 to 100).
15. The method according to claim 10, wherein the method comprises a step of mixing and reacting the positive electrode active material, the oxyfluoride precursor and the hydrogen fluoride in the solvent under a sealed state, and a step of continuing the reaction under a non-sealed state while maintaining a reaction pressure of 25 to 100Mpa when the reaction pressure is 5 to 100 Mpa.
16. The positive electrode material of the lithium ion battery prepared by the method according to any one of claims 10 to 15.
17. A positive electrode for a lithium ion battery, characterized by comprising the positive electrode material for a lithium ion battery according to any one of claims 1 to 9 and 16.
18. An all solid-state lithium battery comprising the lithium ion battery positive electrode according to claim 17.
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Application publication date: 20200107