WO2023226665A1 - 一种正极材料及包括该正极材料的正极片和电池 - Google Patents

一种正极材料及包括该正极材料的正极片和电池 Download PDF

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WO2023226665A1
WO2023226665A1 PCT/CN2023/090370 CN2023090370W WO2023226665A1 WO 2023226665 A1 WO2023226665 A1 WO 2023226665A1 CN 2023090370 W CN2023090370 W CN 2023090370W WO 2023226665 A1 WO2023226665 A1 WO 2023226665A1
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cobalt oxide
lithium cobalt
phase structure
cathode
cathode material
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French (fr)
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曾家江
李素丽
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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Priority to US18/774,554 priority patent/US20240372090A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 present disclosure belongs to the field of battery technology, and specifically relates to a cathode material, a cathode sheet and a battery including the cathode material.
  • the inventor of the present disclosure has discovered through research that the currently most widely used lithium cobalt oxide cathode material has an O3 phase structure and belongs to the R-3m space group. It is the most stable of all structures and the easiest to prepare.
  • O2 phase and O4 phase are one of the various structures of lithium cobalt oxide. Because their structures are metastable, they are difficult to prepare by conventional high-temperature solid-phase sintering methods. They are usually prepared from Na-containing layered compounds through ion exchange. .
  • lithium cobalt oxide with O2 phase structure has higher capacity and magnification, but its cycle dive is serious, while lithium cobalt oxide with O3 phase structure after doping/coating modification The material cycle performance is very good.
  • the present disclosure provides a cathode material, a cathode sheet and a battery including the cathode material.
  • the cathode material has both the high capacity and high rate of lithium cobalt oxide with an O2 phase structure, and the high cycle characteristics of lithium cobalt oxide with an O3 phase structure; the cathode sheet including the cathode material has high capacity and good rate performance; including The cathode material has good battery cycle stability.
  • a cathode material includes lithium cobalt oxide with an O3 phase structure and lithium cobalt oxide with an O2 phase structure.
  • the weight content of the lithium cobalt oxide with the O3 phase structure is 60wt% to 95wt% (for example, 60wt%, 65wt%, 70wt%, 75wt %, 80wt%, 85wt%, 90wt% or 95wt%)
  • the weight of the lithium cobalt oxide with the O3 phase structure is The content is limited to the above-mentioned specific range, which can ensure good cycle stability and high structural stability of the cathode material, and is preferably 70wt% to 90wt%.
  • the weight content of the lithium cobalt oxide with the O2 phase structure is 5wt% to 40wt% (for example, 5wt%, 10wt%, 15wt%, 20wt %, 25wt%, 30wt%, 35wt% or 40wt%), limiting the weight content of the lithium cobalt oxide with the O2 phase structure within the above-mentioned specific range can ensure that the cathode material has high rate performance and high capacity performance. , preferably 10wt% to 30wt%.
  • the lithium cobalt oxide with O2 phase structure means lithium cobalt oxide containing O2 phase structure. Regardless of whether the lithium cobalt oxide with O2 phase structure has been doped or otherwise processed, the lithium cobalt oxide with O2 phase structure is It is lithium cobalt oxide with the O2 phase structure described in this disclosure.
  • the lithium cobalt oxide with the O2 phase structure includes lithium cobalt oxide with the O2 phase structure of the Me element bulk phase.
  • Me includes at least one of Al, Mg, Ti, and Mn.
  • the M element bulk phase Doping can ensure that lithium cobalt oxide with an O2 phase structure has better structural stability and better electrochemical performance at higher voltages (greater than 4.5V).
  • Me is at least one of Al, Mg, Ti, and Mn.
  • the chemical formula of the lithium cobalt oxide with O2 phase structure is Li x Na y Co 1-z Me z O 2 , where 0.85 ⁇ x ⁇ 1.3 (for example, x is 0.9, 0.92, 0.95, 0.96, 0.98, 1, 1.01, 1.02, 1.05, 1.1, 1.2 or 1.25), 0 ⁇ y ⁇ 0.03 (for example, y is 0.01, 0.02 or 0.03), 0 ⁇ z ⁇ 0.05 (for example, z is 0.001, 0.002, 0.005, 0.007, 0.01, 0.02, 0.03, 0.04 or 0.05), Me includes at least one of Al, Mg, Ti and Mn.
  • the chemical formula of the O2 phase structure lithium cobalt oxide is Li x Na y Co 1-z Me z O 2 , where 0.85 ⁇ x ⁇ 1.3 (for example, x is 0.9, 0.92, 0.95, 0.96, 0.98 , 1, 1.01, 1.02, 1.05, 1.1, 1.2 or 1.25), 0 ⁇ y ⁇ 0.03 (for example, y is 0.01, 0.02 or 0.03), 0 ⁇ z ⁇ 0.05 (for example, z is 0.001, 0.002, 0.005, 0.007 , 0.01, 0.02, 0.03, 0.04 or 0.05), Me includes at least one of Al, Mg, Ti, and Mn.
  • the chemical formula of the O2 phase structure lithium cobalt oxide is Li 1.02 Na 0.01 Co 0.96 Al 0.04 O 2 , Li 1.01 Na 0.02 Co 0.96 Al 0.035 Mg 0.005 O 2 , Li 1.0 Na 0.025 Co 0.96 Al 0.037 T i0.003 O 2 , Li 0.9 Na 0.02 Co 0.96 Al 0.038 Mn 0.002 O 2 , Li 0.95 Na 0.02 Co 0.993 Al 0.005 Mg 0.001 Ti 0.001 O 2 .
  • the lithium cobalt oxide with O3 phase structure means lithium cobalt oxide with O3 phase structure. Regardless of whether the lithium cobalt oxide with O3 phase structure has been doped or coated, the lithium cobalt oxide with O3 phase structure All are lithium cobalt oxides with the O3 phase structure described in this disclosure.
  • the O3 phase structure lithium cobalt oxide includes M 1 element bulk doping and M 2 a O b surface coating treatment of O3 phase structure lithium cobalt oxide, M 1 and M 2 are the same or different, independently of each other, at least one of Al, Mg, Ti, Zr, La, Y, Ce, Te, Nb, and W, such
  • the doping coating treatment can ensure that the O3 phase structure of lithium cobalt oxide has better structural stability and better electrochemical performance at higher voltages (greater than 4.5V).
  • the lithium cobalt oxide with O3 phase structure has a core-shell structure, that is, it includes a shell layer and a core.
  • the core includes a chemical formula of Li x' Co 1-z' M 1 z' O 2 materials, where 0.95 ⁇ , 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04 or 0.05)
  • the shell layer includes a material with the chemical formula M 2 a O b , wherein a and b satisfy the valence of the chemical formula State conservation, M 1 and M 2 are the same or different, and are independently at least one of Al, Mg, Ti, Zr, La, Y, Ce, Te, Nb, and W.
  • the lithium cobalt oxide with O3 phase structure has a core-shell structure, that is, it includes a shell layer and a core.
  • the core includes a material with the chemical formula LiCo 0.993 Al 0.005 Mg 0.001 Ti 0.001 O 2.
  • the shell include materials with the chemical formulas TiO 2 , WO 3 and Y 2 O 3 .
  • the lithium cobalt oxide with the O2 phase structure includes lithium cobalt oxide with the O2 phase structure of the Me element bulk phase
  • Me includes at least one of Al, Mg, Ti, Mn and the cobalt with the O3 phase structure.
  • Lithium oxide includes lithium cobalt oxide with an O3 phase structure doped with M 1 element body phase and surface-coated with M 2 a O b .
  • M 1 and M 2 are the same or different, and are independently Al, Mg, Ti, Zr, At least one of La, Y, Ce, Te, Nb, and W.
  • the weight content of the shell layer is 0.05wt% to 2wt%, such as 0.05wt%, 0.06wt%, 0.08 wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt% , 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt% or 2wt%.
  • the median particle size D50 of the O3 phase structure lithium cobalt oxide is 15.5 ⁇ m to 18 ⁇ m, such as 15.5 ⁇ m, 16 ⁇ m, 16.5 ⁇ m, 17 ⁇ m, 17.5 ⁇ m or 18 ⁇ m.
  • the median particle size D50 of the O2 phase structure lithium cobalt oxide is 7 ⁇ m to 10 ⁇ m, such as 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, 8.5 ⁇ m, 9 ⁇ m, 9.5 ⁇ m or 10 ⁇ m.
  • the median particle size D50 of the lithium cobalt oxide with the O3 phase structure is 15.5 ⁇ m to 18 ⁇ m, and/or the median particle size D50 of the lithium cobalt oxide with the O2 phase structure is 7 ⁇ m. ⁇ 10 ⁇ m.
  • the cathode material has all the characteristic peaks of the XRD pattern of lithium cobalt oxide with an O3 phase structure.
  • the positive electrode material also includes (002) characteristic peak, (102) characteristic peak, and (103) characteristic peak.
  • the range of diffraction angle 2 ⁇ of each characteristic peak is: 18.0 ⁇ 2 ⁇ (002) ⁇ 19.4, 41.2 ⁇ 2 ⁇ (102) ⁇ 42.2, 46.5 ⁇ 2 ⁇ (103) ⁇ 47.5.
  • (002) characteristic peak, (102) characteristic peak, (103) The characteristic peak is the characteristic peak of lithium cobalt oxide with O2 phase structure.
  • the median particle diameter D50 of the cathode material is 12 ⁇ m to 17 ⁇ m (for example, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m).
  • the electrochemical performance of lithium cobalt oxide with O3 phase structure is relatively stable, the cycle performance is good, and the voltage platform is relatively high.
  • its capacity is only 180mAh/g at a voltage of 4.5V, and it is charged at a voltage higher than 4.5V.
  • Lithium cobalt oxide with an O2 phase structure has higher capacity and rate performance, but its voltage platform is lower and its cycle performance is poor.
  • the inventor of the present disclosure found that when these two types of lithium cobalt oxide with different phase structures are mixed and used, the cycle performance of the battery assembled with the obtained cathode material is greatly improved, and the electrochemical capacity and rate performance of the battery can also be improved. performance.
  • specific metal elements are uniformly incorporated into the bulk structure of lithium cobalt oxide with an O3 phase structure, and specific metal oxides are coated on the surface of the lithium cobalt oxide with an O3 phase structure, which can effectively Improve the structural stability of lithium cobalt oxide with O3 phase structure under high voltage, thereby improving the cycle performance and safety performance of the battery.
  • the present disclosure also provides a positive electrode sheet, which includes the above-mentioned positive electrode material.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on at least one side surface of the positive electrode current collector.
  • the positive electrode active material layer includes the above-mentioned positive electrode material.
  • the positive active material layer further includes a conductive agent and a binder.
  • the mass percentage of each component in the positive active material layer is: 70wt%-99wt% (for example, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt% , 99wt%) cathode material, 0.5wt%-15wt% (for example, 0.5wt%, 1wt%, 5wt%, 10wt%, 15wt%) conductive agent, 0.5wt%-15wt% (for example, 0.5wt%, 1wt%, 5wt%, 10wt%, 15wt%) binder.
  • the mass percentage of each component in the cathode active material layer is: 80wt%-98wt% cathode material, 1wt%-10wt% conductive agent, and 1wt%-10wt% binder.
  • the mass percentage of each component in the cathode active material layer is: 90wt%-98wt% cathode material, 1wt%-5wt% conductive agent, and 1wt%-5wt% binder.
  • the mass percentage of each component in the cathode active material layer is: 90wt%-96wt% cathode material, 2wt%-5wt% conductive agent, 2wt%-5wt% binder.
  • the present disclosure also provides a battery, which includes the above-mentioned positive electrode material, or the battery includes the above-mentioned positive electrode sheet.
  • the charging cut-off voltage of the battery is greater than or equal to 4.5V.
  • the present disclosure provides a cathode material, a cathode sheet and a battery including the cathode material.
  • the present disclosure can increase the capacity of the resulting composite lithium cobalt oxide cathode material. And the rate is significantly improved while also having excellent cycle performance.
  • Figure 1 is the XRD pattern of the cathode material of Example 1, Comparative Example 1 and Comparative Example 2.
  • Figure 2 is an SEM image of the cathode material of Example 1.
  • a CR2032 button battery is used to study the electrochemical properties of the cathode material.
  • the preparation method of the button battery is as follows:
  • the positive electrode sheet uses NMP as the solvent. According to the mass ratio of 97:1.5:1.5, the positive electrode active material (the positive electrode material prepared in the examples and comparative examples), the conductive agent Super P, and the binder polyvinylidene fluoride PVDF are placed in a degassing machine. Stir evenly in the medium to prepare a slurry positive electrode slurry with a solid content of 70%, and evenly coat the positive electrode slurry on the surface of the aluminum foil. Bake it in a vacuum oven at 100°C for 12 hours, then roll and cut to obtain the positive electrode sheet. .
  • the performance testing process of the button battery produced above is as follows;
  • the test temperature is 25°C.
  • the rate performance test is first carried out.
  • the charging rate is 0.1C
  • the discharge rate is 0.1C, 0.2C, 0.5C, 1C, 2C, 5C.
  • the performance test is shown in Table 1. Then, a 50-cycle cycle performance test was performed under the conditions of a charge and discharge rate of 0.5C and a voltage range of 3.0 to 4.55V.
  • the positive active material used in this embodiment is a mixture of lithium cobalt oxide with O2 phase structure and lithium cobalt oxide with O3 phase structure.
  • the mass fraction of lithium cobalt oxide with O2 phase structure is 10%, and the mass fraction of lithium cobalt oxide with O3 phase structure is 10%.
  • the mass fraction of lithium is 90%;
  • the chemical formula of lithium cobalt oxide with O2 phase structure is Li 1.02 Na 0.01 Co 0.96 Al 0.04 O 2 , and the median particle size D50 of lithium cobalt oxide with O2 phase structure is 8.5 ⁇ m;
  • the structure of lithium cobalt oxide has a core-shell structure.
  • the core includes materials with the chemical formula Li 1.02 Na 0.01 Co 0.96 Al 0.04 O 2
  • the shell includes materials with the chemical formula TiO 2 , WO 3 and Y 2 O 3 , with an O3 phase structure.
  • the total weight of lithium cobalt oxide is used as the basis, the weight content of the shell layer is 0.1wt%, and the median particle size D50 of lithium cobalt oxide with O3 phase structure is 16.5 ⁇ m.
  • the median particle size of the cathode material is 15.5 ⁇ m, and its SEM morphology is shown in Figure 2.
  • Figure 1 shows the XRD patterns of Example 1, Comparative Example 1 and Comparative Example 2.
  • PDF#36-1007 is the standard XRD spectrum of lithium cobalt oxide with O2 phase structure
  • PDF#16-0427 is the standard XRD spectrum of lithium cobalt oxide with O3 phase structure.
  • the lithium cobalt oxide in Comparative Example 1 has an O2 phase structure
  • the lithium cobalt oxide in Comparative Example 2 has an O3 phase structure
  • the mixed cathode material of Example 1 has an O3 phase structure in the lithium cobalt oxide.
  • it also has some characteristic peaks of lithium cobalt oxide with O2 phase structure: (002) peak of 002 crystal plane, (102) peak of 102 crystal plane, and (103) peak of 103 crystal plane.
  • the angle of each characteristic peak The ranges are: 18.0 ⁇ 2 ⁇ (002) ⁇ 19.4, 41.2 ⁇ 2 ⁇ (102) ⁇ 42.2, 46.5 ⁇ 2 ⁇ (103) ⁇ 47.5. Therefore, the blended cathode material not only has the excellent cycle stability of O3 phase structure lithium cobalt oxide, but also has the high capacity and high rate performance of O2 phase structure lithium cobalt oxide.
  • the first discharge gram capacity under the cut-off voltage of 0.1C 4.5V is 184.96mAh/g, and the cycle retention rate at 0.5C 3.0 ⁇ 4.55V for 50 cycles is 90.22%.
  • the discharge rate at different rates The capacity retention rate is shown in Table 1.
  • Example 2 Other operations are the same as in Example 1, except that the mass fraction of lithium cobalt oxide with O2 phase structure is 20%, and the mass fraction of lithium cobalt oxide with O3 phase structure is 80%.
  • the first discharge gram capacity under the cut-off voltage of 0.1C 4.5V is 185.56mAh/g
  • the cycle retention rate at 0.5C 3.0 ⁇ 4.55V for 50 cycles is 89.76%.
  • the discharge rate at different rates The capacity retention rate is shown in Table 1.
  • Example 2 Other operations are the same as in Example 1, except that the mass fraction of lithium cobalt oxide with O2 phase structure is 30%, and the mass fraction of lithium cobalt oxide with O3 phase structure is 70%.
  • the first discharge gram capacity under the cut-off voltage of 0.1C 4.5V is 186.75mAh/g, and the cycle retention rate at 0.5C 3.0 ⁇ 4.55V for 50 cycles is 88.52%.
  • the discharge rate at different rates The capacity retention rate is shown in Table 1.
  • Example 1 Other operations are the same as in Example 1. The only difference is that the lithium cobalt oxide with O3 phase structure has not been bulk-doped with M1 elements and surface-coated with M 2 a O b .
  • the chemical formula of lithium cobalt oxide with O3 phase structure is Li 1.02 Na 0.01 Co 0.96 O 2 .
  • Example 2 Other operations are the same as in Example 1, except that the chemical formula of lithium cobalt oxide with O2 phase structure is Li 1.02 Na 0.01 Co 0.96 O 2 .
  • Example 2 Other operations are the same as in Example 1, except that the median particle size D50 of lithium cobalt oxide with an O2 phase structure is 5 ⁇ m.
  • Example 2 Other operations are the same as in Example 1, except that the median particle size D50 of lithium cobalt oxide with an O3 phase structure is 10 ⁇ m.
  • Example 2 Other operations are the same as in Example 1, except that the mass fraction of lithium cobalt oxide with O2 phase structure is 40%, and the mass fraction of lithium cobalt oxide with O3 phase structure is 60%.
  • the first discharge gram capacity under the cut-off voltage of 0.1C 4.5V is 191.22mAh/g, and the cycle retention rate at 0.5C 3.0 ⁇ 4.55V for 50 cycles is 54.52%.
  • the discharge rate at different rates The capacity retention rate is shown in Table 1.
  • the first discharge gram capacity under the cut-off voltage of 0.1C 4.5V is 182.41mAh/g, and the cycle capacity retention rate at 0.5C 3.0 ⁇ 4.55V for 50 cycles is 85.72%.
  • the discharge capacity retention rate is shown in Table 1.
  • lithium cobalt oxide with O2 phase structure has high capacity and high rate performance, but poor cycle performance; while lithium cobalt oxide with O3 phase structure has high capacity and rate performance.
  • the performance is not as good as that of lithium cobalt oxide with O2 phase structure, but its cycle performance is very excellent.
  • the present disclosure mixes lithium cobalt oxide with an O2 phase structure and lithium cobalt oxide with an O3 phase structure, and the resulting cathode material has excellent cycle performance, high capacity and high rate performance. This may be due to the fact that the blending of lithium cobalt oxide with O2 phase structure and lithium cobalt oxide with O3 phase structure inhibits the structural changes and capacity fading of lithium cobalt oxide under high voltage, thereby significantly improving the cycle performance of the battery.

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Abstract

本公开提供了一种正极材料及包括该正极材料的正极片和电池。本公开包括O3相结构的钴酸锂和O2相结构的钴酸锂的正极材料，具有较高容量和倍率显著提高的同时还具有优异的循环性能。

Description

一种正极材料及包括该正极材料的正极片和电池 技术领域
本公开属于电池技术领域，具体涉及一种正极材料及包括该正极材料的正极片和电池。
发明背景
近十年来，随着手机和电脑等便携式移动产品技术的不断发展，钴酸锂正极材料的开发也得到了飞速的发展，其充放电截止电压从最初的4.2V～4.3V正飞速过渡到目前的4.45V～4.48V，最后可能会达到4.5V～4.6V，甚至更高。但是，当充放电截止电压超过4.5V时，钴酸锂正极材料面临一系列不好的相变，导致电池容量衰减较快和循环急速跳水等问题。
因此，开发一种在高电压下电化学性能稳定以及更高能量密度的正极材料非常重要。
发明内容
本公开的发明人经研究发现，目前应用最广泛的钴酸锂正极材料具有O3相结构且属于R-3m空间群，是所有结构中最稳定的，也是最容易制备的。O2相和O4相作为钴酸锂多种结构的一种，因其结构是亚稳态的，常规的高温固相烧结法很难制备，通常是由含Na层状化合物通过离子交换而制备得到。其中，相对于O3相结构的钴酸锂，O2相结构的钴酸锂的容量和倍率更高，但是其循环跳水严重，而经过掺杂/包覆改性后的O3相结构的钴酸锂材料循环性能很好。
为了改善现有技术的不足，本公开提供一种正极材料及包括该正极材料的正极片和电池。所述正极材料同时具备O2相结构的钴酸锂的高容量和高倍率，以及O3相结构的钴酸锂的高循环的特点；包括该正极材料的正极片的容量高，倍率性能好；包括该正极材料的电池循环稳定性好。
为了实现以上发明目的，本公开提供如下技术方案：
一种正极材料，所述正极材料包括O3相结构的钴酸锂和O2相结构的钴酸锂。
根据一种具体的实施方式，以所述正极材料的总重量为基准，所述O3相结构的钴酸锂的重量含量为60wt％～95wt％(例如为60wt％、65wt％、70wt％、75wt％、80wt％、85wt％、90wt％或95wt％)，将所述O3相结构的钴酸锂的重 量含量限定在上述特定的范围内，可以保证所述正极材料的循环稳定性好和结构稳定性高，优选为70wt％～90wt％。
根据一种具体的实施方式，以所述正极材料的总重量为基准，所述O2相结构的钴酸锂的重量含量为5wt％～40wt％(例如为5wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％或40wt％)，将所述O2相结构的钴酸锂的重量含量限定在上述特定的范围内，可以保证所述正极材料具有高倍率性能和高容量性能，优选为10wt％～30wt％。
在本公开中，所述O2相结构的钴酸锂表示含有O2相结构的钴酸锂，无论具有O2相结构的钴酸锂是否经过掺杂或其他处理，具有O2相结构的钴酸锂均为本公开中所述的O2相结构的钴酸锂。
根据一种具体的实施方式，所述O2相结构的钴酸锂包括Me元素体相的O2相结构的钴酸锂，Me包括Al、Mg、Ti、Mn中的至少一种，M元素体相掺杂能够确保O2相结构的钴酸锂在更高电压(大于4.5V)下具有更好的结构稳定性和更好的电化学性能。
在一实例中，Me为Al、Mg、Ti、Mn中的至少一种。
根据一种具体的实施方式，所述O2相结构的钴酸锂的化学式为LixNayCo1-zMezO2，其中0.85<x<1.3(例如，x为0.9、0.92、0.95、0.96、0.98、1、1.01、1.02、1.05、1.1、1.2或1.25)，0<y≤0.03(例如，y为0.01、0.02或0.03)，0≤z≤0.05(例如，z为0.001、0.002、0.005、0.007、0.01、0.02、0.03、0.04或0.05)，Me包括Al、Mg、Ti、Mn中的至少一种。
在一实例中，所述O2相结构的钴酸锂的化学式为LixNayCo1-zMezO2，其中0.85<x<1.3(例如，x为0.9、0.92、0.95、0.96、0.98、1、1.01、1.02、1.05、1.1、1.2或1.25)，0<y≤0.03(例如，y为0.01、0.02或0.03)，0＜z≤0.05(例如，z为0.001、0.002、0.005、0.007、0.01、0.02、0.03、0.04或0.05)，Me包括Al、Mg、Ti、Mn中的至少一种。
在一实例中，所述O2相结构的钴酸锂的化学式为Li1.02Na0.01Co0.96Al0.04O2、Li1.01Na0.02Co0.96Al0.035Mg0.005O2、Li1.0Na0.025Co0.96Al0.037Ti0.003O2、Li0.9Na0.02Co0.96Al0.038Mn0.002O2、Li0.95Na0.02Co0.993Al0.005Mg0.001Ti0.001O2。
在本公开中，所述O3相结构的钴酸锂表示包括O3相结构的钴酸锂，无论具有O3相结构的钴酸锂是否经过掺杂或包覆处理，具有O3相结构的钴酸锂均为本公开中所述的O3相结构的钴酸锂。
根据一种具体的实施方式，所述O3相结构的钴酸锂包括M1元素体相掺杂和M2 aOb表面包覆处理的O3相结构的钴酸锂，M1和M2相同或不同，彼此独立地为Al、Mg、Ti、Zr、La、Y、Ce、Te、Nb、W中的至少一种，这样的 掺杂包覆处理能够确保O3相结构的钴酸锂在更高电压(大于4.5V)下具有更好的结构稳定性和更好的电化学性能。
根据一种具体的实施方式，所述O3相结构的钴酸锂具有核壳结构，即包括壳层和核芯，所述核芯包括化学式为Lix’Co1-z’M1 z’O2的材料，其中，0.95<x’<1.3(例如，x’为0.96、0.98、1、1.02、1.05、1.1、1.2或1.25)，0≤z’≤0.05(例如，z’为0.001、0.002、0.003、0.004、0.005、0.006、0.007、0.008、0.009、0.01、0.02、0.03、0.04或0.05)，所述壳层包括化学式为M2 aOb的材料，其中，a和b满足化学式的价态守恒，M1和M2相同或不同，彼此独立地为Al、Mg、Ti、Zr、La、Y、Ce、Te、Nb、W中的至少一种。
在一实例中，所述O3相结构的钴酸锂具有核壳结构，即包括壳层和核芯，所述核芯包括化学式为LiCo0.993Al0.005Mg0.001Ti0.001O2的材料，所述壳层包括化学式为TiO2、WO3和Y2O3的材料。
在一实例中，所述O2相结构的钴酸锂包括Me元素体相的O2相结构的钴酸锂，Me包括Al、Mg、Ti、Mn中的至少一种和所述O3相结构的钴酸锂包括M1元素体相掺杂和M2 aOb表面包覆处理的O3相结构的钴酸锂，M1和M2相同或不同，彼此独立地为Al、Mg、Ti、Zr、La、Y、Ce、Te、Nb、W中的至少一种。
根据一种具体的实施方式，以所述O3相结构的钴酸锂的总重量为基准，所述壳层的重量含量为0.05wt％～2wt％，例如为0.05wt％、0.06wt％、0.08wt％、0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.0wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％或2wt％。
根据一种具体的实施方式，所述O3相结构的钴酸锂的中值粒径D50为15.5μm～18μm，例如为15.5μm、16μm、16.5μm、17μm、17.5μm或18μm。
根据一种具体的实施方式，所述O2相结构的钴酸锂的中值粒径D50为7μm～10μm，例如为7μm、7.5μm、8μm、8.5μm、9μm、9.5μm或10μm。
根据一种具体的实施方式，所述O3相结构的钴酸锂的中值粒径D50为15.5μm～18μm，和/或，所述O2相结构的钴酸锂的中值粒径D50为7μm～10μm。通过O2相结构的钴酸锂和O3相结构的钴酸锂进行大小粒径的搭配，能进一步提高正极材料的压实密度，从而提高电池的能量密度。
根据一种具体的实施方式，通过X射线衍射测试，所述正极材料具备O3相结构的钴酸锂的XRD图谱的所有特征峰。所述正极材料还包括(002)特征峰、(102)特征峰、(103)特征峰，各特征峰衍射角2θ的范围分别为：18.0<2θ(002)<19.4，41.2<2θ(102)<42.2，46.5<2θ(103)<47.5。其中，(002)特征峰、(102)特征峰、(103) 特征峰为O2相结构钴酸锂的特征峰。
根据一种具体的实施方式，所述正极材料的中值粒径D50为12μm～17μm(例如，12μm、13μm、14μm、15μm、16μm、17μm)。
在本公开中，O3相结构的钴酸锂的电化学性能比较稳定，循环性能好，电压平台较高，但是其在4.5V的电压下容量仅为180mAh/g，且在高于4.5V充电截止电压下其结构容易发生破坏，循环性能变差。O2相结构的钴酸锂的容量和倍率性能较高，但是其电压平台较低，循环性能较差。本公开的发明人发现，当将这两种不同相结构的钴酸锂混合使用后，获得的正极材料组装的电池的循环性能得到大幅提升，且还可以提高电池的容量和倍率性能等电化学性能。此外，通过有效的手段将特定的金属元素均匀的掺入O3相结构的钴酸锂的体相结构中，并将特定的金属氧化物包覆在O3相结构的钴酸锂的表面，可以有效改善O3相结构的钴酸锂在高电压下的结构稳定性，从而改善电池的循环性能和安全性能。
本公开还提供一种正极片，所述正极片包括上述正极材料。
根据一种具体的实施方式，所述正极片包括正极集流体和设置在正极集流体至少一侧表面的正极活性物质层，所述正极活性物质层包括上述的正极材料。
根据一种具体的实施方式，所述正极活性物质层还包括导电剂和粘结剂。
根据一种具体的实施方式，所述正极活性物质层中各组分的质量百分含量为：70wt％-99wt％(例如，70wt％、75wt％、80wt％、85wt％、90wt％、95wt％、99wt％)的正极材料、0.5wt％-15wt％(例如，0.5wt％、1wt％、5wt％、10wt％、15wt％)的导电剂、0.5wt％-15wt％(例如，0.5wt％、1wt％、5wt％、10wt％、15wt％)的粘结剂。
优选地，所述正极活性物质层中各组分的质量百分含量为：80wt％-98wt％的正极材料、1wt％-10wt％的导电剂、1wt％-10wt％的粘结剂。
优选地，所述正极活性物质层中各组分的质量百分含量为：90wt％-98wt％的正极材料、1wt％-5wt％的导电剂、1wt％-5wt％的粘结剂。
进一步优选地，所述正极活性物质层中各组分的质量百分含量为：90wt％-96wt％的正极材料、2wt％-5wt％的导电剂、2wt％-5wt％的粘结剂。
本公开还提供一种电池，所述电池包括上述的正极材料，或者所述电池包括上述的正极片。
根据本公开的实施方式，所述电池的充电截止电压大于等于4.5V。
本公开的有益效果：
本公开提供了一种正极材料及包括该正极材料的正极片和电池。本公开通过两种不同结构的钴酸锂进行掺混，能够使得到的复合钴酸锂正极材料的容量 和倍率显著提高的同时还具有优异的循环性能。
附图说明
图1为实施例1、对比例1和对比例2的正极材料XRD图谱。
图2为实施例1的正极材料的SEM图。
具体实施方式
下文将结合具体实施例对本公开做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本公开，而不应被解释为对本公开保护范围的限制。凡基于本公开上述内容所实现的技术均涵盖在本公开旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
下述实施例中采用CR2032型纽扣电池研究所述正极材料的电化学性能，所述纽扣电池的制备方法如下：
正极片采用NMP作为溶剂，按照质量比97:1.5:1.5，将正极活性物质(实施例和对比例制备的正极材料)、导电剂Super P、粘结剂聚偏氟乙烯PVDF，在脱泡机中搅拌均匀，配制成固含量为70％的浆料正极浆料，并将该正极浆料均匀涂覆在铝箔表面，至于100℃真空烘箱烘烤12h，然后滚压、裁切，得到正极片。
在手套箱中将该正极片和锂片负极，PP/PE/PP三层隔膜，使用1mol/L LiPF6/(EC+DEC)电解液(体积比1:1)，组装成纽扣电池进行电化学测试。
上述制得的纽扣电池的性能测试过程如下；
测试温度为25℃，在电压区间3.0～4.5V的条件下，先进行倍率性能测试，其中充电倍率为0.1C，放电倍率依次为0.1C、0.2C、0.5C、1C、2C、5C，倍率性能测试如表1所示。然后在充放电倍率为0.5C，电压区间3.0～4.55V的条件下进行50周循环性能测试。
实施例1
本实施例中所用的正极活性物质为O2相结构的钴酸锂和O3相结构的钴酸锂的混合物，O2相结构的钴酸锂所占的质量分数为10％，O3相结构的钴酸锂所占的质量分数为90％；O2相结构的钴酸锂的化学式为Li1.02Na0.01Co0.96Al0.04O2，O2相结构的钴酸锂的中值粒径D50为8.5μm；O3相结构的钴酸锂具有核壳结构，核芯包括化学式为Li1.02Na0.01Co0.96Al0.04O2的材料，壳层包括化学式为TiO2、WO3和Y2O3的材料，以O3相结构的钴酸锂的总重量为基准，壳层的重量含量为0.1wt％，O3相结构的钴酸锂的中值粒径D50为 16.5μm。
该正极材料的中值粒径为15.5μm，其SEM形貌如图2所示。
图1为实施例1、对比例1和对比例2的XRD图谱。其中PDF#36-1007为O2相结构钴酸锂的标准XRD谱图，PDF#16-0427为O3相结构钴酸锂的标准XRD谱图。
从图1中可以看出，对比例1的钴酸锂具有O2相结构，对比例2的钴酸锂具有O3相结构，掺混后的实施例1的正极材料在具有O3相结构钴酸锂所有特征的同时，还具备O2相结构钴酸锂的部分特征峰：002晶面的(002)峰、102晶面的(102)峰、103晶面的(103)峰，各特征峰的角度范围分别为：18.0<2θ(002)<19.4，41.2<2θ(102)<42.2，46.5<2θ(103)<47.5。因此，掺混后的正极材料在具有O3相结构钴酸锂优异循环稳定性的同时，还具备O2相结构钴酸锂的高容量和高倍率性能。
在纽扣电池电化学性能测试，在0.1C 4.5V截止电压下的首次放电克容量为184.96mAh/g，在0.5C 3.0～4.55V循环50圈的循环保持率为90.22％，不同倍率下的放电容量保持率如表1所示。
实施例2
其他操作同实施例1，区别仅在于O2相结构的钴酸锂所占的质量分数为20％，O3相结构的钴酸锂所占的质量分数为80％。
在纽扣电池电化学性能测试，在0.1C 4.5V截止电压下的首次放电克容量为185.56mAh/g，在0.5C 3.0～4.55V循环50圈的循环保持率为89.76％，不同倍率下的放电容量保持率如表1所示。
实施例3
其他操作同实施例1，区别仅在于O2相结构的钴酸锂所占的质量分数为30％，O3相结构的钴酸锂所占的质量分数为70％。
在纽扣电池电化学性能测试，在0.1C 4.5V截止电压下的首次放电克容量为186.75mAh/g，在0.5C 3.0～4.55V循环50圈的循环保持率为88.52％，不同倍率下的放电容量保持率如表1所示。
实施例4
其他操作同实施例1，区别仅在于O3相结构的钴酸锂未经过M1元素体相掺杂和M2 aOb表面包覆处理,O3相结构的钴酸锂的化学式为Li1.02Na0.01Co0.96O2。
实施例5
其他操作同实施例1，区别仅在于O2相结构的钴酸锂的化学式为Li1.02Na0.01Co0.96O2。
实施例6
其他操作同实施例1，区别仅在于O2相结构的钴酸锂的中值粒径D50为5μm。
实施例7
其他操作同实施例1，区别仅在于O3相结构的钴酸锂的中值粒径D50为10μm。
实施例8
其他操作同实施例1，区别仅在于O2相结构的钴酸锂所占的质量分数为40％，O3相结构的钴酸锂所占的质量分数为60％。
对比例1
其他操作同实施例1，区别仅在于O2相结构的钴酸锂所占的质量分数为100％。
在纽扣电池电化学性能测试，在0.1C 4.5V截止电压下的首次放电克容量为191.22mAh/g，在0.5C 3.0～4.55V循环50圈的循环保持率为54.52％，不同倍率下的放电容量保持率如表1所示。
对比例2
其他操作同实施例1，区别仅在于O3相结构的钴酸锂所占的质量分数为100％。
在纽扣电池电化学性能测试，在0.1C 4.5V截止电压下的首次放电克容量为182.41mAh/g，在0.5C 3.0～4.55V循环50圈的循环容量保持率为85.72％，不同倍率下的放电容量保持率如表1所示。
表1实施例和对比例的纽扣电池的倍率性能测试结果

从表1中实施例和对比例的具体测试结果可以看出，O2相结构的钴酸锂具有高容量和高倍率性能，但循环性能不好；而O3相结构的钴酸锂虽然容量和倍率性能没有O2相结构的钴酸锂好，但是其循环性能非常优异。本公开将O2相结构的钴酸锂和O3相结构的钴酸锂混合使用后，得到的正极材料具有优异的循环性能，同时具备高容量和高倍率性能。这可能是由于在高电压下O2相结构的钴酸锂和O3相结构的钴酸锂共混后会抑制钴酸锂结构的变化和容量衰减，从而显著提高电池的循环性能。
以上，对本公开的实施方式进行了说明。但是，本公开不限定于上述实施方式。凡在本公开的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。

Claims (14)

  1. 一种正极材料，其特征在于，所述正极材料包括O3相结构的钴酸锂和O2相结构的钴酸锂。
  2. 根据权利要1所述的正极材料，其特征在于，以所述正极材料的总重量为基准，所述O3相结构的钴酸锂的重量含量为60wt％～95wt％，优选为70wt％～90wt％；
    和/或，所述正极材料的总重量为基准，所述O2相结构的钴酸锂的重量含量为5wt％～40wt％，优选为10wt％～30wt％。
  3. 根据权利要1或2所述的正极材料，其特征在于，所述O2相结构的钴酸锂包括Me元素体相的O2相结构的钴酸锂，Me包括Al、Mg、Ti、Mn中的至少一种，和/或，所述O3相结构的钴酸锂包括M1元素体相掺杂和M2 aOb表面包覆处理的O3相结构的钴酸锂，M1和M2相同或不同，彼此独立地为Al、Mg、Ti、Zr、La、Y、Ce、Te、Nb、W中的至少一种。
  4. 根据权利要1-3任一项所述的正极材料，其特征在于，所述O2相结构的钴酸锂的化学式为LixNayCo1-zMezO2，其中0.95<x<1.3，0<y≤0.03，0≤z≤0.05，Me为Al、Mg、Ti、Mn中的至少一种，和/或，所述O3相结构的钴酸锂具有核壳结构，即包括壳层和核芯，核芯包括化学式为Lix’Co1-z’M1 z’O2的材料，壳层包括化学式为M2 aOb的材料；其中，0.85<x’<1.3，0≤z’≤0.05，a和b满足化学式的价态守恒，M1和M2相同或不同，彼此独立地为Al、Mg、Ti、Zr、La、Y、Ce、Te、Nb、W中的至少一种；
    优选地，所述O2相结构的钴酸锂的化学式中0＜z≤0.05。
  5. 根据权利要求1-4任一项所述的正极材料，其特征在于，所述O2相结构的钴酸锂的化学式为Li1.02Na0.01Co0.96Al0.04O2、Li1.01Na0.02Co0.96Al0.035Mg0.005O2、Li1.0Na0.025Co0.96Al0.037Ti0.003O2、Li0.9Na0.02Co0.96Al0.038Mn0.002O2、Li0.95Na0.02Co0.993Al0.005Mg0.001Ti0.001O2，和/或，所述O3相结构的钴酸锂具有核壳结构，即包括壳层和核芯，所述核芯包括化学式为LiCo0.993Al0.005Mg0.001Ti0.001O2的材料，所述壳层包括化学式为TiO2、WO3和Y2O3的材料。
  6. 根据权利要求4或5所述的正极材料，其特征在于，以所述O3相结构的钴酸锂的总重量为基准，所述壳层的重量含量为0.05wt％～2wt％。
  7. 根据权利要1-6任一项所述的正极材料，其特征在于，所述O3相结构的钴酸锂的中值粒径D50为15.5μm～18μm，和/或，所述O2相结构的钴酸锂的中值粒径D50为7μm～10μm。
  8. 根据权利要1-7任一项所述的正极材料，其特征在于，通过X射线衍射测 试，所述正极材料具备O3相结构的钴酸锂的XRD图谱的所有特征峰，所述正极材料还包括(002)特征峰、(102)特征峰、(103)特征峰，各特征峰衍射角2θ的范围分别为：18.0<2θ(002)<19.4，41.2<2θ(102)<42.2，46.5<2θ(103)<47.5。
  9. 根据权利要1-8任一项所述的正极材料，其特征在于，所述正极材料的中值粒径D50为12μm～17μm。
  10. 一种正极片，所述正极片包括权利要求1-9任一项所述的正极材料。
  11. 根据权利要求10所述的正极片，其特征在于，所述正极片包括正极集流体和设置在正极集流体至少一侧表面的正极活性物质层，所述正极活性物质层包括所述的正极材料。
  12. 根据权利要求10或11所述的正极片，其特征在于，所述正极活性物质层还包括导电剂和粘结剂，所述正极活性物质层中各组分的质量百分含量为：70wt％-99wt％的正极材料、0.5wt％-15wt％的导电剂、0.5wt％-15wt％的粘结剂；
    优选地，所述正极活性物质层中各组分的质量百分含量为：80wt％-98wt％的正极材料、1wt％-10wt％的导电剂、1wt％-10wt％的粘结剂；
    优选地，所述正极活性物质层中各组分的质量百分含量为：90wt％-98wt％的正极材料、1wt％-5wt％的导电剂、1wt％-5wt％的粘结剂；
    优选地，所述正极活性物质层中各组分的质量百分含量为：90wt％-96wt％的正极材料、2wt％-5wt％的导电剂、2wt％-5wt％的粘结剂。
  13. 一种电池，其特征在于，所述电池包括权利要求1-9任一项所述的正极材料，或者所述电池包括权利要求10-12任一项所述的正极片。
  14. 根据权利要求13所述的电池，其特征在于，所述电池的充电截止电压大于等于4.5V。
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