WO2023130829A1 - Lithium-ion battery positive electrode material and preparation method therefor, and lithium-ion battery - Google Patents

Lithium-ion battery positive electrode material and preparation method therefor, and lithium-ion battery Download PDF

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WO2023130829A1
WO2023130829A1 PCT/CN2022/131105 CN2022131105W WO2023130829A1 WO 2023130829 A1 WO2023130829 A1 WO 2023130829A1 CN 2022131105 W CN2022131105 W CN 2022131105W WO 2023130829 A1 WO2023130829 A1 WO 2023130829A1
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ion battery
lithium
liao
positive electrode
lithium ion
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缪建麟
李长东
阮丁山
蔡勇
刘伟健
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/36—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Definitions

  • the invention belongs to the technical field of lithium ion batteries, and in particular relates to a lithium ion battery cathode material, a preparation method thereof and a lithium ion battery.
  • lithium-ion batteries have attracted much attention as good energy storage devices.
  • ternary cathode materials are widely used in power batteries due to their high capacity, good cycle stability and safety. has become the focus of research in recent years.
  • the formation of the negative electrode SEI film in the formation process of lithium-ion batteries needs to consume lithium ions, and this part of lithium ions comes from the positive electrode material, which leads to a decrease in the Coulombic efficiency and discharge capacity of the battery. Therefore, in the battery manufacturing process, many battery manufacturers need to perform additional pre-intercalation of lithium on the negative electrode in the battery formation stage to reduce the loss of lithium ions in the positive electrode material, but this method of additional pre-intercalation of lithium greatly improves the battery life. Production cost and difficulty are not conducive to mass production of batteries.
  • the present invention aims to solve at least one of the technical problems existing in the prior art. For this reason, the present invention proposes a lithium ion battery positive electrode material and its preparation method and lithium ion battery.
  • the lithium ion battery positive electrode material can directly pre-lithiate the negative electrode without additional steps, which is beneficial to the mass production of batteries.
  • a lithium ion battery positive electrode material the chemical formula of the lithium ion battery positive electrode material is LiAO 2 xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 ; in the chemical formula, A includes at least one of Ni and Co, so B is at least one of Ni, Co, Mn, Cu and Zn, where 0 ⁇ x ⁇ 0.05.
  • the A further includes at least one of Mn or Al.
  • the average valence state of A in the LiAO 2 ⁇ xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 is +3, and the average valence state of B is +2.
  • LiAO 2 in the LiAO 2 ⁇ xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 has a hexagonal crystal structure.
  • the Li 2 BO 2 in the LiAO 2 ⁇ xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 has an orthorhombic crystal structure.
  • the LiAO 2 is at least one of lithium nickel cobalt manganate, lithium nickel cobalt aluminate and lithium nickel cobalt manganese aluminate.
  • the particle size D50 of the positive electrode material of the lithium ion battery is 1-13 ⁇ m.
  • Li 2 BO 2 particles are evenly distributed in the LiAO 2 particles; when the chemical formula of the positive electrode material is LiAO 2 @xLi 2 BO 2 , Li 2 BO 2 is coated on the surface of the LiAO 2 particles.
  • a kind of preparation method of positive electrode material of lithium ion battery as mentioned above comprises the following steps:
  • LiAO 2 Sinter the precursor containing A and the lithium source at high temperature to obtain LiAO 2 , then conduct a high-temperature solid-state reaction between LiAO 2 and the oxide of B in an inert atmosphere, or conduct a high-temperature and high-pressure solvothermal reaction between LiAO 2 and the oxide of B to obtain
  • the reaction temperature in the high-temperature solid phase reaction is 400-800° C.
  • the reaction time is 4-12 hours.
  • the mixing method of the LiAO 2 and the Li 2 BO 2 is ball milling or high temperature solvothermal mixing.
  • the inert atmosphere is at least one of nitrogen, argon and helium.
  • a lithium ion battery comprising the lithium ion battery cathode material as described above.
  • the positive electrode material of the lithium ion battery of the present invention has its own pre-lithiation effect, and the Li 2 BO 2 contained in it can directly perform pre-lithiation on the negative electrode during the formation stage of the lithium ion battery, and can additionally provide lithium ions for the negative electrode SEI
  • the formation of the film can avoid the consumption of lithium ions in the main body of the positive electrode material and improve the discharge capacity of the battery;
  • the residual lithium in the positive electrode material substrate and the oxide of B are used to form an orthorhombic structure material Li 2 BO 2 , thereby reducing the residual lithium in the system;
  • the positive electrode material of the lithium ion battery of the present invention will not negatively affect the cycle and rate performance of the battery, and the pre-lithiation of the negative electrode can be realized without additional steps during the formation process of the battery.
  • Fig. 1 is the XRD figure of the lithium ion battery cathode material of embodiment 1 and comparative example 1;
  • FIG. 2 is an SEM image of the lithium-ion battery cathode material of Example 1 and Comparative Example 1.
  • FIG. 2 is an SEM image of the lithium-ion battery cathode material of Example 1 and Comparative Example 1.
  • a lithium ion battery positive electrode material the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 , the particle size D50 is 6.0 ⁇ m, LiNi in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 0.8 Co 0.1 Mn 0.1 O 2 has a hexagonal structure, and Li 2 CuO 2 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 has an orthorhombic structure.
  • the preparation method of above-mentioned lithium ion battery cathode material comprises the following steps:
  • a kind of lithium ion battery, its preparation method comprises the following steps:
  • a lithium ion battery cathode material the chemical formula is: LiNi 0.5 Co 0.2 Mn 0.3 O 2 @0.05Li 2 Cu 0.5 Ni 0.5 O 2 , the particle size D50 is 7 ⁇ m, LiNi 0.5 Co 0.2 Mn 0.3 O 2 @0.05Li 2 Cu 0.5 LiNi 0.5 Co 0.2 Mn 0.3 O 2 in Ni 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Ni 0.5 O 2 in LiNi 0.5 Co 0.2 Mn 0.3 O 2 @ 0.05Li 2 Cu 0.5 Ni 0.5 O 2 is positive Alternate crystal structure.
  • the preparation method of above-mentioned lithium ion battery cathode material comprises the following steps:
  • a kind of lithium ion battery, its preparation method comprises the following steps:
  • a lithium ion battery positive electrode material its chemical formula is: LiNi 1/3 Co 1/3 Mn 1/3 O 2 0.05Li 2 CuO 2 , particle size D50 is 13 ⁇ m, LiNi 1/3 Co 1/3 Mn 1/3 LiNi 1/3 Co 1/3 Mn 1/3 O 2 in O 2 ⁇ 0.05Li 2 CuO 2 has a hexagonal crystal structure , LiNi 1/3 Co 1/3 Mn 1/3 O 2 ⁇ 0.05Li 2 CuO 2 The Li 2 CuO 2 in is an orthorhombic crystal structure.
  • the preparation method of above-mentioned lithium ion battery cathode material comprises the following steps:
  • a kind of lithium ion battery, its preparation method comprises the following steps:
  • a lithium ion battery positive electrode material the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.05Li 2 CuO 2 , the particle size D50 is 10 ⁇ m, LiNi 0.8 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 Co 0.1 Mn 0.1 O 2 has a hexagonal crystal structure, and Li 2 CuO 2 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 has an orthorhombic crystal structure.
  • the preparation method of above-mentioned lithium ion battery cathode material comprises the following steps:
  • a kind of lithium ion battery, its preparation method comprises the following steps:
  • a lithium ion battery cathode material the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Zn 0.5 O 2 , the particle size D50 is 10 ⁇ m, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Zn 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Zn 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Zn 0.5 O 2 is positive Alternate crystal structure.
  • the preparation method of above-mentioned lithium ion battery cathode material comprises the following steps:
  • a kind of lithium ion battery, its preparation method comprises the following steps:
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • a lithium ion battery cathode material the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Mn 0.5 O 2 , the particle size D50 is 10 ⁇ m, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Mn 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Mn 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Mn 0.5 O 2 is positive Alternate crystal structure.
  • Example 5 the method for preparing the positive electrode material of the above lithium ion battery differs only in that the ZnO in step (2) in Example 5 is replaced with MnO.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • a lithium ion battery positive electrode material the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Co 0.5 O 2 , the particle size D50 is 10 ⁇ m, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Co 0.5 O 2 is a hexagonal crystal structure, and Li 2 Cu 0.5 Co 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Co 0.5 O 2 is positive Alternate crystal structure.
  • Example 5 Compared with Example 5, the above method for preparing the positive electrode material of the lithium ion battery differs only in that: ZnO in step (2) in Example 5 is replaced with Co(OH) 2 .
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • a lithium-ion battery cathode material the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Fe 0.5 O 2 , the particle size D50 is 10 ⁇ m, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Fe 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Fe 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Fe 0.5 O 2 has a positive Alternate crystal structure.
  • Example 5 Compared with Example 5, the above method for preparing the positive electrode material of the lithium ion battery differs only in that ZnO in step (2) in Example 5 is replaced with Fe(OH) 2 .
  • a lithium-ion battery cathode material the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the particle size D50 is 6.0 ⁇ m.
  • the preparation method of above-mentioned lithium ion battery cathode material comprises the following steps:
  • a kind of lithium ion battery, its preparation method comprises the following steps:
  • a lithium-ion battery cathode material the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the particle size D50 is 6.0 ⁇ m.
  • the preparation method of above-mentioned lithium ion battery cathode material comprises the following steps:
  • step (2) Wash the monoalkyne substrate obtained in step (1) with water, filter and dry, then raise the temperature to 500° C. for 6 hours under nitrogen atmosphere, and obtain the positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
  • a kind of lithium ion battery, its preparation method comprises the following steps:
  • Example 1 XRD test and SEM test were performed on the positive electrode materials of lithium ion batteries in Example 1 and Comparative Example 1 respectively, wherein the results of the XRD test are shown in FIG. 1 , and the results of the SEM test are shown in FIG. 2 .
  • the residual lithium of the positive electrode material of Example 1 is significantly lower than that of Comparative Example 1, indicating that the preparation method of the lithium ion battery positive electrode material of the present invention has the effect of reducing the residual lithium of the material, and the effect of reducing the residual lithium is the same as that of the positive electrode material of the present invention.
  • the ratio 2 is equivalent to the method of washing with water.
  • the lithium ion battery positive electrode material of Example 1 has a larger improvement in the first coulombic efficiency and the first discharge capacity, indicating that the lithium ion battery positive electrode material of the present invention has the effect of pre-lithiation, and can remove residual lithium Converted into Li 2 BO 2 , and play a role in the formation process of lithium-ion batteries to supplement the Li + consumed by the formation of negative electrode SEI film, so that the first Coulombic efficiency and capacity of the battery are improved.

Abstract

The present invention discloses a lithium-ion battery positive electrode material and a preparation method therefor, and a lithium-ion battery. The chemical formula of the lithium-ion battery positive electrode material is LiAO2·xLi2BO2 or LiAO2@xLi2BO2, wherein in the chemical formula, A comprises at least one of Ni and Co, B is at least one of Ni, Co, Mn, Cu and Zn, and 0<x≤0.05. The lithium-ion battery positive electrode material can directly realize the pre-lithiation of a negative electrode without any additional processes, which is beneficial to the batch production of batteries.

Description

一种锂离子电池正极材料及其制备方法和锂离子电池A kind of positive electrode material of lithium ion battery and its preparation method and lithium ion battery 技术领域technical field
本发明属于锂离子电池技术领域，特别涉及一种锂离子电池正极材料及其制备方法和锂离子电池。The invention belongs to the technical field of lithium ion batteries, and in particular relates to a lithium ion battery cathode material, a preparation method thereof and a lithium ion battery.
背景技术Background technique
随着新能源行业的快速发展，锂离子电池作为良好的储能器件而备受关注，其中三元正极材料因具有较高的容量、较好的循环稳定性和安全性被广泛应用于动力电池中，成为近年来研究的焦点。With the rapid development of the new energy industry, lithium-ion batteries have attracted much attention as good energy storage devices. Among them, ternary cathode materials are widely used in power batteries due to their high capacity, good cycle stability and safety. has become the focus of research in recent years.
锂离子电池化成过程中负极SEI膜的形成需要消耗锂离子，而这部分的锂离子来源于正极材料，这就导致电池的库伦效率和放电容量降低。因此，许多电池厂家在电池制造过程中，在电池化成阶段需要对负极进行额外的预嵌锂，以降低对正极材料中锂离子的损耗，但这种额外预嵌锂的方法极大提高了电池生产成本和难度，不利于电池的批量化生产。The formation of the negative electrode SEI film in the formation process of lithium-ion batteries needs to consume lithium ions, and this part of lithium ions comes from the positive electrode material, which leads to a decrease in the Coulombic efficiency and discharge capacity of the battery. Therefore, in the battery manufacturing process, many battery manufacturers need to perform additional pre-intercalation of lithium on the negative electrode in the battery formation stage to reduce the loss of lithium ions in the positive electrode material, but this method of additional pre-intercalation of lithium greatly improves the battery life. Production cost and difficulty are not conducive to mass production of batteries.
发明内容Contents of the invention
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种锂离子电池正极材料及其制备方法和锂离子电池，该锂离子电池正极材料能直接对负极进行预锂化，无需额外增加工序，利于电池的批量化生产。The present invention aims to solve at least one of the technical problems existing in the prior art. For this reason, the present invention proposes a lithium ion battery positive electrode material and its preparation method and lithium ion battery. The lithium ion battery positive electrode material can directly pre-lithiate the negative electrode without additional steps, which is beneficial to the mass production of batteries.
本发明的上述技术目的是通过以下技术方案得以实现的：Above-mentioned technical purpose of the present invention is achieved through the following technical solutions:
一种锂离子电池正极材料，所述锂离子电池正极材料的化学式为LiAO 2·xLi 2BO 2或LiAO 2@xLi 2BO 2；所述化学式中A包括Ni、Co中的至少一种，所述B为Ni、Co、Mn、Cu及Zn中的至少一种，其中0＜x≤0.05。 A lithium ion battery positive electrode material, the chemical formula of the lithium ion battery positive electrode material is LiAO 2 xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 ; in the chemical formula, A includes at least one of Ni and Co, so B is at least one of Ni, Co, Mn, Cu and Zn, where 0<x≤0.05.
优选的，所述A还包括Mn或Al中的至少一种。Preferably, the A further includes at least one of Mn or Al.
优选的，所述LiAO 2·xLi 2BO 2或LiAO 2@xLi 2BO 2中A的平均价态为+3价，B的平均价态为+2价。 Preferably, the average valence state of A in the LiAO 2 ·xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 is +3, and the average valence state of B is +2.
优选的，所述LiAO 2·xLi 2BO 2或LiAO 2@xLi 2BO 2中的LiAO 2为六方晶系结构。 Preferably, LiAO 2 in the LiAO 2 · xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 has a hexagonal crystal structure.
优选的，所述LiAO 2·xLi 2BO 2或LiAO 2@xLi 2BO 2中的Li 2BO 2为正交晶系结构。 Preferably , the Li 2 BO 2 in the LiAO 2 ·xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 has an orthorhombic crystal structure.
优选的，所述LiAO 2为镍钴锰酸锂、镍钴铝酸锂及镍钴锰铝酸锂中的至少一种。 Preferably, the LiAO 2 is at least one of lithium nickel cobalt manganate, lithium nickel cobalt aluminate and lithium nickel cobalt manganese aluminate.
优选的，所述锂离子电池正极材料的粒径D50为1-13μm。Preferably, the particle size D50 of the positive electrode material of the lithium ion battery is 1-13 μm.
优选的，当所述正极材料化学式为LiAO 2·xLi 2BO 2时，Li 2BO 2颗粒均匀分布在所述LiAO 2颗粒中；当所述正极材料化学式为LiAO 2@xLi 2BO 2时，Li 2BO 2包覆在所述LiAO 2颗粒的表面。 Preferably, when the chemical formula of the positive electrode material is LiAO 2 ·xLi 2 BO 2 , Li 2 BO 2 particles are evenly distributed in the LiAO 2 particles; when the chemical formula of the positive electrode material is LiAO 2 @xLi 2 BO 2 , Li 2 BO 2 is coated on the surface of the LiAO 2 particles.
一种如上所述锂离子电池正极材料的制备方法，包括以下步骤：A kind of preparation method of positive electrode material of lithium ion battery as mentioned above, comprises the following steps:
将含A的前驱体和锂源高温烧结得到LiAO 2，然后将LiAO 2与B的氧化物在惰性气氛下进行高温固相反应，或将LiAO 2与B的氧化物进行高温高压溶剂热反应得到所述锂离子电池正极材料LiAO 2@xLi 2BO 2； Sinter the precursor containing A and the lithium source at high temperature to obtain LiAO 2 , then conduct a high-temperature solid-state reaction between LiAO 2 and the oxide of B in an inert atmosphere, or conduct a high-temperature and high-pressure solvothermal reaction between LiAO 2 and the oxide of B to obtain The lithium-ion battery cathode material LiAO 2 @xLi 2 BO 2 ;
或or
将含A的前驱体和锂源高温烧结得到LiAO 2，将含B的前驱体和锂源高温烧结得到Li 2BO 2，然后将LiAO 2与Li 2BO 2混合得到所述锂离子电池正极材料LiAO 2·xLi 2BO 2。 Sintering the precursor containing A and the lithium source at high temperature to obtain LiAO 2 , sintering the precursor containing B and the lithium source at high temperature to obtain Li 2 BO 2 , and then mixing LiAO 2 and Li 2 BO 2 to obtain the positive electrode material of the lithium ion battery LiAO 2 ·xLi 2 BO 2 .
优选的，所述高温固相反应中反应温度为400-800℃，反应时间为4-12h。Preferably, the reaction temperature in the high-temperature solid phase reaction is 400-800° C., and the reaction time is 4-12 hours.
优选的，所述LiAO 2与所述Li 2BO 2的混合方式为球磨或高温溶剂热混合。 Preferably, the mixing method of the LiAO 2 and the Li 2 BO 2 is ball milling or high temperature solvothermal mixing.
优选的，所述惰性气氛为氮气，氩气及氦气中的至少一种。Preferably, the inert atmosphere is at least one of nitrogen, argon and helium.
一种锂离子电池，包括如上所述的锂离子电池正极材料。A lithium ion battery, comprising the lithium ion battery cathode material as described above.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明的锂离子电池正极材料自带预锂化作用，其所含的Li 2BO 2可在锂离子电池化成阶段直接对负极进行预锂化，能额外提供锂离子用于负极SEI膜的形成，可以避免消耗正极材料主体中的锂离子，提高电池的放电容量； (1) The positive electrode material of the lithium ion battery of the present invention has its own pre-lithiation effect, and the Li 2 BO 2 contained in it can directly perform pre-lithiation on the negative electrode during the formation stage of the lithium ion battery, and can additionally provide lithium ions for the negative electrode SEI The formation of the film can avoid the consumption of lithium ions in the main body of the positive electrode material and improve the discharge capacity of the battery;
(2)本发明的锂离子电池正极材料的制备方法中利用正极材料基材中的残余锂和B的氧化物形成正交晶系结构材料Li 2BO 2，从而降低体系的残余锂； (2) In the preparation method of the lithium ion battery positive electrode material of the present invention, the residual lithium in the positive electrode material substrate and the oxide of B are used to form an orthorhombic structure material Li 2 BO 2 , thereby reducing the residual lithium in the system;
(3)本发明的锂离子电池正极材料不会对电池的循环、倍率性能产生负面的影响，在电池的化成过程中无需额外增加工序即可实现对负极的预锂化。(3) The positive electrode material of the lithium ion battery of the present invention will not negatively affect the cycle and rate performance of the battery, and the pre-lithiation of the negative electrode can be realized without additional steps during the formation process of the battery.
附图说明Description of drawings
图1为实施例1及对比例1的锂离子电池正极材料的XRD图；Fig. 1 is the XRD figure of the lithium ion battery cathode material of embodiment 1 and comparative example 1;
图2为实施例1及对比例1的锂离子电池正极材料的SEM图。FIG. 2 is an SEM image of the lithium-ion battery cathode material of Example 1 and Comparative Example 1. FIG.
具体实施方式Detailed ways
下面结合具体实施例对本发明做进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1：Example 1:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.1Mn 0.1O 2@0.02Li 2CuO 2，粒度D50为6.0μm，LiNi 0.8Co 0.1Mn 0.1O 2@0.02Li 2CuO 2中的LiNi 0.8Co 0.1Mn 0.1O 2为六方晶系结构，LiNi 0.8Co 0.1Mn 0.1O 2@0.02Li 2CuO 2中的Li 2CuO 2为正交晶系结构。 A lithium ion battery positive electrode material, the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 , the particle size D50 is 6.0 μm, LiNi in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 0.8 Co 0.1 Mn 0.1 O 2 has a hexagonal structure, and Li 2 CuO 2 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 has an orthorhombic structure.
上述锂离子电池正极材料的制备方法，包括以下步骤：The preparation method of above-mentioned lithium ion battery cathode material, comprises the following steps:
(1)将前驱体Ni 0.8Co 0.1Mn 0.1(OH) 2与锂盐LiOH·H 2O按摩尔比Li/Me＝1.02的比例混合，再将混料在氧气气氛下升温至800℃保温10h，通过破碎、过筛得到LiNi 0.8Co 0.1Mn 0.1O 2； (1) Mix the precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 with the lithium salt LiOH·H 2 O at a molar ratio of Li/Me=1.02, then raise the temperature of the mixture to 800°C for 10 hours in an oxygen atmosphere , by crushing and sieving to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 ;
(2)将步骤(1)制得的LiNi 0.8Co 0.1Mn 0.1O 2与CuO按摩尔比(Ni+Co+Mn):Cu＝1:0.02进行混合，然后将混料在氮气气氛下升温至500℃保温6h，得到正极材料LiNi 0.8Co 0.1Mn 0.1O 2@0.02Li 2CuO 2。 (2) LiNi 0.8 Co 0.1 Mn 0.1 O 2 prepared in step (1) is mixed with CuO in molar ratio (Ni+Co+Mn): Cu=1:0.02, then the mixture is heated up to The temperature was kept at 500°C for 6 hours to obtain the positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 .
一种锂离子电池，其制备方法包括以下步骤：A kind of lithium ion battery, its preparation method comprises the following steps:
(1)以本实施例的正极材料为正极活性物质，与导电炭黑(SP)和聚偏氟乙烯(PVDF)按重量比0.9:0.05:0.05的比例混合，加入溶剂氮-甲基吡咯烷酮(NMP)进行搅拌，匀浆后涂覆于铝箔上，干燥后得到正极片；(1) Take the positive electrode material of this embodiment as the positive electrode active material, mix it with conductive carbon black (SP) and polyvinylidene fluoride (PVDF) in a weight ratio of 0.9:0.05:0.05, add solvent nitrogen-methylpyrrolidone ( NMP) is stirred, is coated on the aluminum foil after the homogenate, obtains positive plate after drying;
(2)以上述正极片为锂离子电池正极，并以石墨为负极活性材料的负极片为负极，组装成锂离子扣式全电池。(2) Use the above-mentioned positive electrode sheet as the positive electrode of the lithium-ion battery, and use graphite as the negative electrode sheet of the negative electrode active material as the negative electrode to assemble a lithium-ion button-type full battery.
实施例2：Example 2:
一种锂离子电池正极材料，其化学式为：LiNi 0.5Co 0.2Mn 0.3O 2@0.05Li 2Cu 0.5Ni 0.5O 2，粒度D50为7μm，LiNi 0.5Co 0.2Mn 0.3O 2@0.05Li 2Cu 0.5Ni 0.5O 2中的LiNi 0.5Co 0.2Mn 0.3O 2为六方晶系结构，LiNi 0.5Co 0.2Mn 0.3O 2@0.05Li 2Cu 0.5Ni 0.5O 2中的Li 2Cu 0.5Ni 0.5O 2为正交晶系结构。 A lithium ion battery cathode material, the chemical formula is: LiNi 0.5 Co 0.2 Mn 0.3 O 2 @0.05Li 2 Cu 0.5 Ni 0.5 O 2 , the particle size D50 is 7 μm, LiNi 0.5 Co 0.2 Mn 0.3 O 2 @0.05Li 2 Cu 0.5 LiNi 0.5 Co 0.2 Mn 0.3 O 2 in Ni 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Ni 0.5 O 2 in LiNi 0.5 Co 0.2 Mn 0.3 O 2 @ 0.05Li 2 Cu 0.5 Ni 0.5 O 2 is positive Alternate crystal structure.
上述锂离子电池正极材料的制备方法，包括以下步骤：The preparation method of above-mentioned lithium ion battery cathode material, comprises the following steps:
(1)将前驱体Ni 0.5Co 0.2Mn 0.3(OH) 2与锂盐Li 2CO 3按摩尔比Li/Me＝1.05的比例混合，再将混料在氧气气氛下升温至900℃保温12h，通过破碎、过筛得到LiNi 0.5Co 0.2Mn 0.3O 2； (1) Mix the precursor Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 with the lithium salt Li 2 CO 3 at a molar ratio of Li/Me=1.05, and then raise the temperature of the mixture to 900°C for 12 hours in an oxygen atmosphere, Obtain LiNi 0.5 Co 0.2 Mn 0.3 O 2 by crushing and sieving;
(2)将步骤(1)制得的LiNi 0.5Co 0.2Mn 0.3O 2与CuO、NiO按摩尔比(Ni+Co+Mn):Cu:Ni＝1:0.025:0.025进行混合，然后将混料在氮气气氛下升温至550℃保温6h，得到正极材料LiNi 0.5Co 0.2Mn 0.3O 2@0.05Li 2Cu 0.5Ni 0.5O 2。 (2) LiNi 0.5 Co 0.2 Mn 0.3 O 2 prepared in step (1) is mixed with CuO and NiO in molar ratio (Ni+Co+Mn): Cu:Ni=1:0.025:0.025, and then the mixture The temperature was raised to 550° C. for 6 hours under a nitrogen atmosphere to obtain the positive electrode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 @0.05Li 2 Cu 0.5 Ni 0.5 O 2 .
一种锂离子电池，其制备方法包括以下步骤：A kind of lithium ion battery, its preparation method comprises the following steps:
(1)以本实施例的正极材料为正极活性物质，与SP和PVDF按重量比0.8:0.1:0.1的比例混合，加入溶剂NMP进行搅拌，匀浆后涂覆于铝箔上，干燥后得到正极片；(1) Take the positive electrode material of this example as the positive electrode active material, mix it with SP and PVDF in a weight ratio of 0.8:0.1:0.1, add the solvent NMP for stirring, coat it on aluminum foil after homogenization, and obtain the positive electrode after drying piece;
(2)以上述正极片为锂离子电池正极，并以石墨为负极活性材料的负极片为负极，组装成锂离子扣式全电池。(2) Use the above-mentioned positive electrode sheet as the positive electrode of the lithium-ion battery, and use graphite as the negative electrode sheet of the negative electrode active material as the negative electrode to assemble a lithium-ion button-type full battery.
实施例3：Example 3:
一种锂离子电池正极材料，其化学式为：LiNi 1/3Co 1/3Mn 1/3O 2·0.05Li 2CuO 2，粒度D50为13μm，LiNi 1/3Co 1/3Mn 1/3O 2·0.05Li 2CuO 2中的LiNi 1/3Co 1/3Mn 1/3O 2为六方晶系结构， LiNi 1/3Co 1/3Mn 1/3O 2·0.05Li 2CuO 2中的Li 2CuO 2为正交晶系结构。 A lithium ion battery positive electrode material, its chemical formula is: LiNi 1/3 Co 1/3 Mn 1/3 O 2 0.05Li 2 CuO 2 , particle size D50 is 13 μm, LiNi 1/3 Co 1/3 Mn 1/3 LiNi 1/3 Co 1/3 Mn 1/3 O 2 in O 2 ·0.05Li 2 CuO 2 has a hexagonal crystal structure , LiNi 1/3 Co 1/3 Mn 1/3 O 2 ·0.05Li 2 CuO 2 The Li 2 CuO 2 in is an orthorhombic crystal structure.
上述锂离子电池正极材料的制备方法，包括以下步骤：The preparation method of above-mentioned lithium ion battery cathode material, comprises the following steps:
(1)将前驱体Ni 1/3Co 1/3Mn 1/3(OH) 2与锂盐Li 2CO 3按摩尔比Li/Me＝1.08的比例混合，再将混料在氧气气氛下升温至950℃保温14h，通过破碎、过筛得到LiNi 1/3Co 1/3Mn 1/3O 2； (1) Mix the precursor Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 with the lithium salt Li 2 CO 3 in a ratio of molar ratio Li/Me=1.08, and then raise the temperature of the mixture under an oxygen atmosphere Insulate at 950°C for 14 hours, and obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 by crushing and sieving;
(2)将CuO与LiOH·H 2O按摩尔比Li/Cu＝2:1的比例混合，再将混料在氮气气氛下升温至500℃保温4h，通过破碎、过筛得到Li 2CuO 2； (2) Mix CuO and LiOH·H 2 O at a molar ratio of Li/Cu=2:1, then raise the temperature of the mixture to 500°C for 4 hours under a nitrogen atmosphere, and obtain Li 2 CuO 2 by crushing and sieving ;
(3)将步骤(1)制得的LiNi 1/3Co 1/3Mn 1/3O 2与步骤(2)制得的Li 2CuO 2按摩尔比(Ni+Co+Mn):Cu＝1:0.05进行混合，得到正极材料LiNi 1/3Co 1/3Mn 1/3O 2·0.05Li 2CuO 2。 (3) LiNi 1/3 Co 1/3 Mn 1/3 O 2 prepared in step (1) and Li 2 CuO 2 prepared in step (2) in molar ratio (Ni+Co+Mn): Cu= 1:0.05 were mixed to obtain the positive electrode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 ·0.05Li 2 CuO 2 .
一种锂离子电池，其制备方法包括以下步骤：A kind of lithium ion battery, its preparation method comprises the following steps:
(1)以本实施例的正极材料为正极活性物质，与SP和PVDF按重量比0.8:0.15:0.05的比例混合，加入溶剂NMP进行搅拌，匀浆后涂覆于铝箔上，干燥后得到正极片；(1) Take the positive electrode material of this example as the positive electrode active material, mix it with SP and PVDF in a weight ratio of 0.8:0.15:0.05, add the solvent NMP for stirring, coat it on aluminum foil after homogenization, and obtain the positive electrode after drying piece;
(2)以上述正极片为锂离子电池正极，并以石墨为负极活性材料的负极片为负极，组装成锂离子扣式全电池。(2) Use the above-mentioned positive electrode sheet as the positive electrode of the lithium-ion battery, and use graphite as the negative electrode sheet of the negative electrode active material as the negative electrode to assemble a lithium-ion button-type full battery.
实施例4：Example 4:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.1Mn 0.1O 2@0.05Li 2CuO 2，粒度D50为10μm，LiNi 0.8Co 0.1Mn 0.1O 2@0.02Li 2CuO 2中的LiNi 0.8Co 0.1Mn 0.1O 2为六方晶系结构，LiNi 0.8Co 0.1Mn 0.1O 2@0.02Li 2CuO 2中的Li 2CuO 2为正交晶系结构。 A lithium ion battery positive electrode material, the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.05Li 2 CuO 2 , the particle size D50 is 10 μm, LiNi 0.8 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 Co 0.1 Mn 0.1 O 2 has a hexagonal crystal structure, and Li 2 CuO 2 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 has an orthorhombic crystal structure.
上述锂离子电池正极材料的制备方法，包括以下步骤：The preparation method of above-mentioned lithium ion battery cathode material, comprises the following steps:
(1)将前驱体Ni 0.8Co 0.1Mn 0.1(OH) 2与锂盐LiOH·H 2O按摩尔比Li/Me＝1.04的比例混合，再将混料在氧气气氛下升温至750℃保温12h，通过破碎、过筛得到LiNi 0.8Co 0.1Mn 0.1O 2； (1) Mix the precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 with the lithium salt LiOH·H 2 O at a molar ratio of Li/Me=1.04, then raise the temperature of the mixture to 750°C for 12 hours in an oxygen atmosphere , by crushing and sieving to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 ;
(2)将步骤(1)制得的LiNi 0.8Co 0.1Mn 0.1O 2与CuO按摩尔比(Ni+Co+Mn):Cu＝1:0.05加入到无水乙醇溶剂中混合，再转入高压反应釜中进行溶剂热反应，反应条件为200℃保温6h，过滤干燥后得到正极材料LiNi 0.8Co 0.1Mn 0.1O 2@0.02Li 2CuO 2。 (2) Add LiNi 0.8 Co 0.1 Mn 0.1 O 2 prepared in step (1) and CuO in a molar ratio (Ni+Co+Mn): Cu=1:0.05 to an anhydrous ethanol solvent and mix, then turn to high pressure The solvothermal reaction was carried out in a reaction kettle, the reaction condition was 200° C. for 6 hours, and the positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 @0.02Li 2 CuO 2 was obtained after filtration and drying.
一种锂离子电池，其制备方法包括以下步骤：A kind of lithium ion battery, its preparation method comprises the following steps:
(1)以本实施例的正极材料为正极活性物质，与导电炭黑(SP)和聚偏氟乙烯(PVDF)按重量比0.8:0.1:0.1的比例混合，加入溶剂氮-甲基吡咯烷酮(NMP)进行搅拌，匀浆后涂覆于铝箔上，干燥后得到正极片；(1) Take the positive electrode material of this embodiment as the positive electrode active material, mix it with conductive carbon black (SP) and polyvinylidene fluoride (PVDF) in a ratio of 0.8:0.1:0.1 by weight, add solvent nitrogen-methylpyrrolidone ( NMP) is stirred, is coated on the aluminum foil after the homogenate, obtains positive plate after drying;
(2)以上述正极片为锂离子电池正极，并以石墨为负极活性材料的负极片为负极，组装成锂离子扣式全电池。(2) Use the above-mentioned positive electrode sheet as the positive electrode of the lithium-ion battery, and use graphite as the negative electrode sheet of the negative electrode active material as the negative electrode to assemble a lithium-ion button-type full battery.
实施例5：Example 5:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Zn 0.5O 2，粒度D50为10μm，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Zn 0.5O 2中的LiNi 0.8Co 0.15Al 0.05O 2为六方晶系结构，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Zn 0.5O 2中的Li 2Cu 0.5Zn 0.5O 2为正交晶系结构。 A lithium ion battery cathode material, the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Zn 0.5 O 2 , the particle size D50 is 10 μm, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Zn 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Zn 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Zn 0.5 O 2 is positive Alternate crystal structure.
上述锂离子电池正极材料的制备方法，包括以下步骤：The preparation method of above-mentioned lithium ion battery cathode material, comprises the following steps:
(1)将前驱体Ni 0.8Co 0.15Al 0.05(OH) 2与锂盐LiOH·H 2O按摩尔比Li/Me＝1.02的比例混合，再将混料在氧气气氛下升温至800℃保温10h，通过破碎、过筛得到LiNi 0.8Co 0.15Al 0.05O 2； (1) Mix the precursor Ni 0.8 Co 0.15 Al 0.05 (OH) 2 with the lithium salt LiOH·H 2 O at a molar ratio of Li/Me=1.02, then raise the temperature of the mixture to 800°C for 10 hours under an oxygen atmosphere , to obtain LiNi 0.8 Co 0.15 Al 0.05 O 2 by crushing and sieving;
(2)将步骤(1)制得的LiNi 0.8Co 0.15Al 0.05O 2与CuO和ZnO按摩尔比(Ni+Co+Mn):Cu:Zn＝1:0.01:0.01进行混合，然后将混料在氮气气氛下升温至450℃保温8h，得到正极材料LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Zn 0.5O 2。 (2) LiNi 0.8 Co 0.15 Al 0.05 O 2 prepared in step (1) is mixed with CuO and ZnO in molar ratio (Ni+Co+Mn): Cu:Zn=1:0.01:0.01, and then the mixture The temperature was raised to 450° C. for 8 hours under a nitrogen atmosphere to obtain the positive electrode material LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Zn 0.5 O 2 .
一种锂离子电池，其制备方法包括以下步骤：A kind of lithium ion battery, its preparation method comprises the following steps:
(1)以本实施例的正极材料为正极活性物质，与导电炭黑(SP)和聚偏氟乙烯(PVDF)按重量比0.8:0.1:0.1的比例混合，加入溶剂氮-甲基吡咯烷酮(NMP)进行搅拌，匀浆后涂覆于铝箔上，干燥后得到正极片；(1) Take the positive electrode material of this embodiment as the positive electrode active material, mix it with conductive carbon black (SP) and polyvinylidene fluoride (PVDF) in a ratio of 0.8:0.1:0.1 by weight, add solvent nitrogen-methylpyrrolidone ( NMP) is stirred, is coated on the aluminum foil after the homogenate, obtains positive plate after drying;
(2)以上述正极片为锂离子电池正极，并以石墨为负极活性材料的负极片为负极，组装成锂离子扣式全电池。(2) Use the above-mentioned positive electrode sheet as the positive electrode of the lithium-ion battery, and use graphite as the negative electrode sheet of the negative electrode active material as the negative electrode to assemble a lithium-ion button-type full battery.
实施例6：Embodiment 6:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Mn 0.5O 2，粒度D50为10μm，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Mn 0.5O 2中的LiNi 0.8Co 0.15Al 0.05O 2为六方晶系结构，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Mn 0.5O 2中的Li 2Cu 0.5Mn 0.5O 2为正交晶系结构。 A lithium ion battery cathode material, the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Mn 0.5 O 2 , the particle size D50 is 10 μm, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Mn 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Mn 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Mn 0.5 O 2 is positive Alternate crystal structure.
上述锂离子电池正极材料的制备方法，与实施例5相比，区别仅在于：将实施例5中步骤(2)中的ZnO替换成MnO。Compared with Example 5, the method for preparing the positive electrode material of the above lithium ion battery differs only in that the ZnO in step (2) in Example 5 is replaced with MnO.
实施例7：Embodiment 7:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Co 0.5O 2，粒度D50为10μm，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Co 0.5O 2中的LiNi 0.8Co 0.15Al 0.05O 2为六方晶系结构，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Co 0.5O 2中的Li 2Cu 0.5Co 0.5O 2为正交晶系结构。 A lithium ion battery positive electrode material, the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Co 0.5 O 2 , the particle size D50 is 10 μm, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Co 0.5 O 2 is a hexagonal crystal structure, and Li 2 Cu 0.5 Co 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Co 0.5 O 2 is positive Alternate crystal structure.
上述锂离子电池正极材料的制备方法，与实施例5相比，区别仅在于：将实施例5中步骤(2)中的ZnO替换成Co(OH) 2。 Compared with Example 5, the above method for preparing the positive electrode material of the lithium ion battery differs only in that: ZnO in step (2) in Example 5 is replaced with Co(OH) 2 .
实施例8：Embodiment 8:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Fe 0.5O 2，粒度D50为10μm，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Fe 0.5O 2中的LiNi 0.8Co 0.15Al 0.05O 2为六方晶系 结构，LiNi 0.8Co 0.15Al 0.05O 2@0.02Li 2Cu 0.5Fe 0.5O 2中的Li 2Cu 0.5Fe 0.5O 2为正交晶系结构。 A lithium-ion battery cathode material, the chemical formula is: LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Fe 0.5 O 2 , the particle size D50 is 10 μm, LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 LiNi 0.8 Co 0.15 Al 0.05 O 2 in Fe 0.5 O 2 has a hexagonal crystal structure, and Li 2 Cu 0.5 Fe 0.5 O 2 in LiNi 0.8 Co 0.15 Al 0.05 O 2 @0.02Li 2 Cu 0.5 Fe 0.5 O 2 has a positive Alternate crystal structure.
与实施例5相比，区别在于：Compared with embodiment 5, the difference is:
上述锂离子电池正极材料的制备方法，与实施例5相比，区别仅在于：将实施例5中步骤(2)中的ZnO替换成Fe(OH) 2。 Compared with Example 5, the above method for preparing the positive electrode material of the lithium ion battery differs only in that ZnO in step (2) in Example 5 is replaced with Fe(OH) 2 .
对比例1：Comparative example 1:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.1Mn 0.1O 2，粒度D50为6.0μm。 A lithium-ion battery cathode material, the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the particle size D50 is 6.0 μm.
上述锂离子电池正极材料的制备方法，包括以下步骤：The preparation method of above-mentioned lithium ion battery cathode material, comprises the following steps:
将前驱体Ni 0.8Co 0.1Mn 0.1(OH) 2与锂盐LiOH·H 2O按摩尔比Li/Me＝1.02的比例混合，再将混料在氧气气氛下升温至800℃保温10h，通过破碎、过筛得到LiNi 0.8Co 0.1Mn 0.1O 2。 Mix the precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 with the lithium salt LiOH·H 2 O at a molar ratio of Li/Me=1.02, then raise the temperature of the mixture to 800°C for 10 hours under an oxygen atmosphere, and then through crushing and sieving to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
一种锂离子电池，其制备方法包括以下步骤：A kind of lithium ion battery, its preparation method comprises the following steps:
(1)以本对比例的正极材料为正极活性物质，与SP和PVDF按重量比0.9:0.05:0.05的比例混合，加入溶剂NMP进行搅拌，匀浆后涂覆于铝箔上，干燥后得到正极片；(1) Take the positive electrode material of this comparative example as the positive electrode active material, mix it with SP and PVDF in a weight ratio of 0.9:0.05:0.05, add the solvent NMP to stir, coat it on aluminum foil after homogenization, and obtain the positive electrode after drying piece;
(2)以上述正极片为锂离子电池正极，并以石墨为负极活性材料的负极片为负极，组装成锂离子扣式全电池。(2) Use the above-mentioned positive electrode sheet as the positive electrode of the lithium-ion battery, and use graphite as the negative electrode sheet of the negative electrode active material as the negative electrode to assemble a lithium-ion button-type full battery.
对比例2：Comparative example 2:
一种锂离子电池正极材料，其化学式为：LiNi 0.8Co 0.1Mn 0.1O 2，粒度D50为6.0μm。 A lithium-ion battery cathode material, the chemical formula is: LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the particle size D50 is 6.0 μm.
上述锂离子电池正极材料的制备方法，包括以下步骤：The preparation method of above-mentioned lithium ion battery cathode material, comprises the following steps:
(1)将前驱体Ni 0.8Co 0.1Mn 0.1(OH) 2与锂盐LiOH·H 2O按摩尔比Li/Me＝1.02的比例混合，再将混料在氧气气氛下升温至800℃保温10h，通过破碎、过筛得到一烧基体； (1) Mix the precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 with the lithium salt LiOH·H 2 O at a molar ratio of Li/Me=1.02, then raise the temperature of the mixture to 800°C for 10 hours in an oxygen atmosphere , obtain an alkane matrix by crushing and sieving;
(2)将步骤(1)得到的一烧基体进行水洗，过滤干燥后，在氮气气氛下升温至500℃保温6h，得到正极材料LiNi 0.8Co 0.1Mn 0.1O 2。 (2) Wash the monoalkyne substrate obtained in step (1) with water, filter and dry, then raise the temperature to 500° C. for 6 hours under nitrogen atmosphere, and obtain the positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
一种锂离子电池，其制备方法包括以下步骤：A kind of lithium ion battery, its preparation method comprises the following steps:
(1)以本对比例的正极材料为正极活性物质，与SP和PVDF按重量比0.9:0.05:0.05的比例混合，加入溶剂NMP进行搅拌，匀浆后涂覆于铝箔上，干燥后得到正极片；(1) Take the positive electrode material of this comparative example as the positive electrode active material, mix it with SP and PVDF in a weight ratio of 0.9:0.05:0.05, add the solvent NMP to stir, coat it on aluminum foil after homogenization, and obtain the positive electrode after drying piece;
(2)以上述正极片为锂离子电池正极，并以石墨为负极活性材料的负极片为负极，组装成锂离子扣式全电池。(2) Use the above-mentioned positive electrode sheet as the positive electrode of the lithium-ion battery, and use graphite as the negative electrode sheet of the negative electrode active material as the negative electrode to assemble a lithium-ion button-type full battery.
试验例Test case
分别对实施例1-3及对比例1-2的锂离子电池正极材料做残余锂测试，并分别对对实施例1-3及对比例1-2的锂离子电池的首次放电容量及首次库伦效率(首效)进行测试，测试结果见表1。Respectively carry out residual lithium test to the positive electrode material of the lithium ion battery of embodiment 1-3 and comparative example 1-2, and respectively to the first discharge capacity and the first coulomb of the lithium ion battery of embodiment 1-3 and comparative example 1-2 Efficiency (first effect) is tested, and the test results are shown in Table 1.
表1：锂离子电池正极材料及锂离子电池性能测试结果Table 1: Lithium-ion battery cathode materials and performance test results of lithium-ion batteries
Figure PCTCN2022131105-appb-000001
Figure PCTCN2022131105-appb-000001
同时，分别将实施例1及对比例1的锂离子电池正极材料做XRD测试及SEM测试，其中XRD测试的结果如图1所示，SEM测试的结果如图2所示。At the same time, XRD test and SEM test were performed on the positive electrode materials of lithium ion batteries in Example 1 and Comparative Example 1 respectively, wherein the results of the XRD test are shown in FIG. 1 , and the results of the SEM test are shown in FIG. 2 .
由表1可知，实施例1正极材料的残余锂与对比例1相比显著降低，说明本发明的锂离子电池正极材料的制备方法具有降低材料残余锂的效果，且降低残余锂的效果与对比例2水洗的方法相当。As can be seen from Table 1, the residual lithium of the positive electrode material of Example 1 is significantly lower than that of Comparative Example 1, indicating that the preparation method of the lithium ion battery positive electrode material of the present invention has the effect of reducing the residual lithium of the material, and the effect of reducing the residual lithium is the same as that of the positive electrode material of the present invention. The ratio 2 is equivalent to the method of washing with water.
同时实施例1的锂离子电池正极材料相比对比例1在首次库伦效率和首次放电容量上有较大的提升，说明本发明的锂离子电池正极材料具有预锂化的效果，能将残余锂转化为Li 2BO 2，并发挥在锂离子电池化成过程中，补充负极SEI膜形成消耗的Li +，使得电池首次库伦效率和容量提高。 Simultaneously, compared with comparative example 1, the lithium ion battery positive electrode material of Example 1 has a larger improvement in the first coulombic efficiency and the first discharge capacity, indicating that the lithium ion battery positive electrode material of the present invention has the effect of pre-lithiation, and can remove residual lithium Converted into Li 2 BO 2 , and play a role in the formation process of lithium-ion batteries to supplement the Li + consumed by the formation of negative electrode SEI film, so that the first Coulombic efficiency and capacity of the battery are improved.
此外，由图1可知实施例1的LiNi 0.8Co 0.1Mn 0.1O 2在加入CuO后进行二次烧结形成了Li 2CuO 2，对比图2可知，实施例1的锂离子电池正极材料的扫描电镜图中显示形成了部分尺寸较大的单晶一次颗粒，并且均匀散布在锂离子电池正极材料中，说明实施例1的锂离子电池正极材料中生成了Li 2CuO 2。 In addition, it can be seen from Figure 1 that the LiNi 0.8 Co 0.1 Mn 0.1 O 2 of Example 1 was sintered after the addition of CuO to form Li 2 CuO 2 , and compared with Figure 2, it can be seen that the scanning electron microscope of the positive electrode material of the lithium ion battery in Example 1 The figure shows that some large-sized single crystal primary particles are formed and evenly dispersed in the positive electrode material of the lithium ion battery, indicating that Li 2 CuO 2 is generated in the positive electrode material of the lithium ion battery in Example 1.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

  1. 一种锂离子电池正极材料，其特征在于，所述锂离子电池正极材料的化学式为LiAO 2·xLi 2BO 2或LiAO 2@xLi 2BO 2；所述化学式中A包括Ni、Co中的至少一种，所述B为Ni、Co、Mn、Cu及Zn中的至少一种，其中0＜x≤0.05。 A lithium ion battery positive electrode material, characterized in that the chemical formula of the lithium ion battery positive electrode material is LiAO 2 xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 ; in the chemical formula, A includes at least Ni and Co One, the B is at least one of Ni, Co, Mn, Cu and Zn, wherein 0<x≤0.05.
  2. 根据权利要求1所述的一种锂离子电池正极材料，其特征在于，所述A还包括Mn或Al中的至少一种。A lithium ion battery positive electrode material according to claim 1, wherein said A further comprises at least one of Mn or Al.
  3. 根据权利要求1所述的一种锂离子电池正极材料，其特征在于，所述LiAO 2·xLi 2BO 2或LiAO 2@xLi 2BO 2中的LiAO 2为六方晶系结构。 The anode material for a lithium ion battery according to claim 1 , wherein the LiAO 2 in the LiAO 2 ·xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 has a hexagonal crystal structure.
  4. 根据权利要求1所述的一种锂离子电池正极材料，其特征在于，所述LiAO 2·xLi 2BO 2或LiAO 2@xLi 2BO 2中的Li 2BO 2为正交晶系结构。 The anode material for a lithium ion battery according to claim 1, characterized in that Li 2 BO 2 in said LiAO 2 ·xLi 2 BO 2 or LiAO 2 @xLi 2 BO 2 has an orthorhombic crystal structure.
  5. 根据权利要求1所述的一种锂离子电池正极材料，其特征在于，所述LiAO 2为镍钴锰酸锂、镍钴铝酸锂及镍钴锰铝酸锂中的至少一种。 The anode material for a lithium ion battery according to claim 1, wherein the LiAO is at least one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide and lithium nickel cobalt manganese aluminum oxide.
  6. 根据权利要求1所述的一种锂离子电池正极材料，其特征在于，所述锂离子电池正极材料的粒径D50为1-13μm。The anode material for a lithium ion battery according to claim 1, wherein the particle diameter D50 of the anode material for a lithium ion battery is 1-13 μm.
  7. 一种如权利要求1至6任一项所述锂离子电池正极材料的制备方法，其特征在于，包括以下步骤：A preparation method for lithium-ion battery cathode material according to any one of claims 1 to 6, characterized in that it comprises the following steps:
    将含A的前驱体和锂源进行高温烧结得到LiAO 2，然后将LiAO 2与B的氧化物在惰性气氛下进行高温固相反应，或将LiAO 2与B的氧化物进行高温高压溶剂热反应得到所述锂离子电池正极材料LiAO 2@xLi 2BO 2； The precursor containing A and the lithium source are sintered at high temperature to obtain LiAO 2 , and then LiAO 2 is subjected to high-temperature solid-state reaction with B oxide under an inert atmosphere, or LiAO 2 is subjected to high-temperature and high-pressure solvothermal reaction with B oxide Obtaining the lithium ion battery cathode material LiAO 2 @xLi 2 BO 2 ;
    或or
    将含A的前驱体和锂源高温烧结得到LiAO 2，将含B的前驱体和锂源在高温烧结得到Li 2BO 2，然后将LiAO 2与Li 2BO 2混合得到所述锂离子电池正极材料LiAO 2·xLi 2BO 2。 Sintering the precursor containing A and the lithium source at high temperature to obtain LiAO 2 , sintering the precursor containing B and the lithium source at high temperature to obtain Li 2 BO 2 , and then mixing LiAO 2 and Li 2 BO 2 to obtain the positive electrode of the lithium ion battery Material LiAO 2 ·xLi 2 BO 2 .
  8. 根据权利要求7所述的一种锂离子电池正极材料的制备方法，其特征在于，所述高温固相反应中反应温度为400-800℃，反应时间为4-12h。The preparation method of a lithium-ion battery cathode material according to claim 7, characterized in that the reaction temperature in the high-temperature solid-state reaction is 400-800°C, and the reaction time is 4-12h.
  9. 根据权利要求7所述的一种锂离子电池正极材料的制备方法，其特征在于，所述LiAO 2与所述Li 2BO 2的混合方式为球磨或高温溶剂热混合。 The preparation method of a lithium ion battery positive electrode material according to claim 7, characterized in that, the mixing method of the LiAO 2 and the Li 2 BO 2 is ball milling or high temperature solvothermal mixing.
  10. 一种锂离子电池，其特征在于，包括权利要求1至6任一项所述的锂离子电池正极材料。A lithium ion battery, characterized in that it comprises the lithium ion battery cathode material according to any one of claims 1 to 6.
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