WO2023040357A1 - 改性的高镍三元正极材料及其制备方法，以及用电装置 - Google Patents

改性的高镍三元正极材料及其制备方法，以及用电装置 Download PDF

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WO2023040357A1
WO2023040357A1 PCT/CN2022/096550 CN2022096550W WO2023040357A1 WO 2023040357 A1 WO2023040357 A1 WO 2023040357A1 CN 2022096550 W CN2022096550 W CN 2022096550W WO 2023040357 A1 WO2023040357 A1 WO 2023040357A1
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Prior art keywords
nickel ternary
positive electrode
electrode material
containing compound
ternary positive
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English (en)
French (fr)
Inventor
吴奇
陈强
赵宇翔
范敬鹏
黄起森
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP22868734.9A priority Critical patent/EP4220767B1/en
Priority to EP25200055.9A priority patent/EP4737398A2/en
Priority to KR1020237018312A priority patent/KR102940751B1/ko
Priority to JP2023526409A priority patent/JP7617264B2/ja
Publication of WO2023040357A1 publication Critical patent/WO2023040357A1/zh
Priority to US18/325,996 priority patent/US20230395796A1/en
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    • H—ELECTRICITY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
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    • H01M10/052—Li-accumulators
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    • 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
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
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    • 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
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • 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
    • H01M4/48—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
    • H01M4/50—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
    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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 application relates to the technical field of lithium batteries, in particular to a modified high-nickel ternary positive electrode material and a preparation method thereof, a secondary battery, a battery module, a battery pack and an electrical device.
  • lithium-ion secondary batteries are widely used in various large-scale power devices, energy storage systems and various consumer products due to their excellent electrochemical performance, no memory effect, and low environmental pollution. , especially widely used in pure electric vehicles, hybrid electric vehicles and other new energy vehicles.
  • lithium-ion secondary batteries Due to the great development of lithium-ion secondary batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance.
  • high-nickel cathode active materials are considered to be the best choice to meet the requirements of high energy density.
  • nickel content With the continuous increase of nickel content, its structural stability is getting worse, which in turn affects the cycle performance and storage performance of lithium-ion secondary batteries.
  • the application provides a modified high-nickel ternary positive electrode material, aiming to make the lithium-ion secondary battery prepared by it have high capacity, improved cycle performance and storage performance.
  • the first aspect of the present application provides a modified high-nickel ternary positive electrode material, which includes an inner core and two layers of cladding layers inside and outside; the inner core contains a high-nickel ternary positive electrode material matrix, and the matrix is doped There are M1, M2 and W, wherein the M1 is one of Mo, Zr, Ti, Sb, Nb, Te, and the M2 is one of Mg, Al, Ca, Zn, Sr, doped with M1,
  • the present application at least includes the following beneficial effects:
  • ions namely M1, M2 and W
  • M1, M2 and W are synergistically doped on the matrix of the high-nickel ternary positive electrode material, which can more effectively improve the structural stability of the high-nickel ternary positive electrode material, thereby significantly improving the performance of the secondary battery.
  • Cycle performance and thermal stability; this application also doped the surface layer of the high-nickel ternary positive electrode material with Co, which can effectively reduce the content of high-valent nickel ions in the surface layer of the high-nickel ternary positive electrode material, thereby reducing the side effects of high-valent nickel ions and the electrolyte.
  • the application also uniformly coats the inner layer containing the Co compound, the outer layer containing the Al compound and the B compound to the high-nickel ternary positive electrode material, thus, it can effectively Reduce the content of impurity lithium on the surface and further effectively inhibit the interface side reaction between the high-nickel ternary positive electrode material and the electrolyte, thereby improving the capacity and rate performance of the high-nickel ternary positive electrode material, and further improving the cycle, storage and battery life of the secondary battery. safety performance.
  • the doping amount of the M1 ⁇ the doping amount of the M2 or the W.
  • the ratio of the doping amount of M1 to the sum of the doping amounts of M2 and W is 1:(0.1-2), optionally 1:(0.5-1.5).
  • the ratio of the doping amount of M1 to the sum of the doping amounts of M2 and W is controlled within the given range, it can not only ensure the high capacity of the high-nickel ternary cathode material, but also improve the structure of the material to the greatest extent. Stability, thereby further improving the cycle performance of the secondary battery.
  • the thickness d of the surface layer is 0 ⁇ d ⁇ 3 ⁇ m, optionally 0 ⁇ d ⁇ 2 ⁇ m.
  • the cycle performance of the secondary battery can be further improved.
  • the sum of the surface layer doping amount of Co and the coating amount of the Co-containing compound is 100-20000ppm, optionally 1000-13000ppm; the coating amount of the Al-containing compound is 100- 3000ppm, optionally 500-2000ppm; the coating amount of the B-containing compound is 100-2000ppm, optionally 500-1500ppm, wherein the surface layer doping amount and coating amount are relative to the corresponding elements in the compound Modified high-nickel ternary cathode material meter.
  • the cycle performance of the secondary battery can be further improved.
  • the coating amount of the Al-containing compound and the coating amount of the B-containing compound are within a given range, the cycle performance of the secondary battery can be further improved.
  • the total thickness of the inner and outer cladding layers is 0.001-1 ⁇ m.
  • the coating amount of the Al-containing compound and the coating amount of the B-containing compound meet the weight ratio of Al to B (0.5-2): 1, wherein the coating amount is based on the compound
  • the corresponding elements in are calculated relative to the modified high-nickel ternary cathode material.
  • the doping amount of W is 100-2000ppm, optionally 100-1500ppm; the doping amount of M1 is 2000-4000ppm; the doping amount of M2 is 500-2000ppm, wherein
  • the doping amounts are all calculated by corresponding elements relative to the modified high-nickel ternary positive electrode material.
  • the doping amounts of M1, M2 and W are within the given range, the structural stability of the high-nickel ternary cathode material can be further improved, thereby further improving the cycle performance and storage performance of the secondary battery.
  • the sum of the doping amount of the surface layer of Co and the coating amount of the Co-containing compound, the Al-containing compound and the B-containing compound is 1000-22000ppm, optionally 1000-15000ppm, wherein the surface layer Both the doping amount and the coating amount are calculated by the corresponding elements in the compound relative to the modified high-nickel ternary cathode material.
  • the volume particle size distribution radius of the modified high-nickel ternary positive electrode material satisfies (Dv 90 -Dv 10 )/Dv 50 ⁇ 1.1, optionally (Dv 90 -Dv 10 )/Dv 50 ⁇ 1.2.
  • the powder compacted density of the modified high-nickel ternary cathode material under a pressure of 5 tons is ⁇ 3.4g/cc, optionally ⁇ 3.5g/cc.
  • the inventors found through experiments that when the modified high-nickel ternary cathode material has a wider volume particle size distribution diameter and a higher powder compaction density, the volume energy density of the high-nickel ternary cathode material can be significantly improved.
  • the second aspect of the present application also provides a method for preparing a modified high-nickel ternary positive electrode material, including:
  • Step S1 Mix and sinter lithium salt, W-doped high-nickel ternary precursor, M1-containing compound, and M2-containing compound to obtain a high-nickel ternary positive electrode material matrix doped with M1, M2 and W, wherein the
  • the chemical formula of W-doped high-nickel ternary precursor is (Ni X Co Y Mn Z W D )(OH) 2 , where 0.65 ⁇ X ⁇ 1, 0 ⁇ Y ⁇ 0.3, 0 ⁇ Z ⁇ 0.3, 0 ⁇ D ⁇ 0.1
  • the M1 is one of Mo, Zr, Ti, Sb, Nb, Te
  • the M2 is one of Mg, Al, Ca, Zn, Sr
  • the chemical formula of the high-nickel ternary cathode material matrix is Li 1+a [Ni x Co y Mn z M1 b M2 c W d ]O 2 , where 0.65 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.3,
  • Step S2 mixing and sintering the high-nickel ternary positive electrode material matrix doped with M1, M2 and W and a Co-containing compound to obtain a high-nickel ternary positive electrode material whose surface layer is doped with Co and whose surface is coated with a Co-containing compound;
  • Step S3 Mix and sinter the high-nickel ternary anode material whose surface layer is doped with Co and whose surface is coated with a Co-containing compound, the Al-containing compound and the B-containing compound, and sintered to obtain a modified high-nickel ternary anode material.
  • the sintering temperature in step S1 is 700-950° C.
  • the sintering time is 10-20 h
  • the sintering atmosphere is air or O 2 .
  • the particle diameter of the Co-containing compound is 0.001-10 ⁇ m, optionally 0.001-1 ⁇ m.
  • the particle diameter of the Co-containing compound is within the given range, it can be uniformly coated on the surface of the high-nickel ternary positive electrode material, thereby further improving the cycle performance of the secondary battery.
  • the sintering temperature in step S2 is 500-800°C, optionally 550-750°C, the sintering time is 5-15h, optionally 5-10h, and the sintering atmosphere is air or O2 .
  • the sintering temperature in step S2 is within the given range, the Co-containing compound can be reacted with the heterolithium on the surface of the ternary positive electrode material, and the Co-containing compound can be firmly coated on the surface of the ternary positive electrode material, thereby reducing The surface is mixed with lithium and the side reaction at the interface is improved to further improve the cycle performance of the secondary battery.
  • the sintering temperature in step S3 is 200-500°C, optionally 200-400°C, the sintering time is 5-15h, optionally 5-10h, and the sintering atmosphere is air or O2 .
  • the sintering temperature in step S3 is within the given range, the Al-containing compound and the B-containing compound can be firmly coated on the surface of the ternary positive electrode material, thereby improving the interfacial reaction of the ternary positive electrode material and further improving the cycle of the secondary battery performance.
  • the third aspect of the present application provides a secondary battery, including the modified high-nickel ternary positive electrode material according to the first aspect of the present application or the modified high-nickel ternary positive electrode material prepared according to the method of the second aspect of the present application.
  • a fourth aspect of the present application provides a battery module including the secondary battery of the third aspect of the present application.
  • a fifth aspect of the present application provides a battery pack, including the battery module of the fourth aspect of the present application.
  • the sixth aspect of the present application provides an electric device, including at least one selected from the secondary battery of the third aspect of the present application, the battery module of the fourth aspect of the present application, or the battery pack of the fifth aspect of the present application. kind.
  • the battery module, battery pack, and electric device of the present application include the secondary battery of the present application, and thus have at least the same advantages as the secondary battery.
  • FIG. 1 is a SEM image of the modified high-nickel ternary cathode material prepared in Example 1-1 of the present application.
  • Fig. 2 is the first charging and discharging curve of the buckle made of the modified high-nickel ternary positive electrode material prepared in Example 1-1 of the present application.
  • Fig. 3 is a 25°C cycle comparison curve of a full battery made from the modified high-nickel ternary cathode material prepared in Comparative Example 5-1 of the present application and Example 1-1.
  • Fig. 4 is a comparison curve of storage flatulence at 70°C of a full battery made of the modified high-nickel ternary positive electrode material prepared in Comparative Example 5-1 of the present invention and Example 1-1.
  • FIG. 5 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 6 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 5 .
  • FIG. 7 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 8 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 9 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 8 .
  • Fig. 10 is a schematic diagram of an electrical device in which a secondary battery is used as a power source according to an embodiment of the present application.
  • ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • steps (a) and (b) performed in sequence
  • steps (b) and (a) performed in sequence.
  • step (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), also Steps (a), (c) and (b) may be included, and steps (c), (a) and (b) may also be included.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • This application provides a modified high-nickel ternary positive electrode material, which includes an inner core and two layers of cladding layers inside and outside.
  • the surface layer of the inner core is also doped with Co;
  • the inner coating layer is a Co-containing compound
  • the outer coating layer is an Al-containing compound and a B-containing compound.
  • the high-nickel ternary positive electrode material is doped and coated, which can improve the cycle performance and safety performance of the lithium-ion secondary battery on the premise of ensuring high capacity.
  • this application has carried out three kinds of ions (namely M1, M2 and W) synergistic doping on the high-nickel ternary cathode material, which can more effectively improve the high-nickel ternary anode material compared with single ion doping.
  • the structural stability of the positive electrode material thereby significantly improving the cycle performance and thermal stability of the secondary battery;
  • the application also doped Co to the surface layer of the high-nickel ternary positive electrode material, which can effectively reduce the surface layer of the high-nickel ternary positive electrode material.
  • the application uniformly coats the inner layer of the high-nickel ternary positive electrode material containing the Co compound , the outer layer containing Al compounds and B-containing compounds can effectively reduce the content of miscellaneous lithium on the surface, so that miscellaneous lithium can form Li 2 CoO 3 with Co-containing compounds, and form LiBO 2 , LiB 3 O 5 , Li 2 B 4 with B-containing compounds O 7 or their mixtures can make heterolithium into active lithium, thereby improving the capacity and rate performance of high-nickel ternary cathode materials, and the synergistic effect of the inner layer containing Co compound and the outer layer containing B compound and Al compound , can further effectively suppress the interface side reaction between the high-nickel ternary cathode material and the electrolyte, thereby further effectively improving the cycle, storage and safety performance of the secondary battery.
  • the inventors have found through in-depth research that when the modified high-nickel ternary positive electrode material of the present application satisfies the above-mentioned design conditions, if it also optionally satisfies one or more of the following conditions, it can be further improved. Performance of high nickel ternary cathode materials.
  • the doping amount of M1 is greater than or equal to the doping amount of M2 or W.
  • the ratio of the doping amount of M1 to the sum of the doping amounts of M2 and W is 1:(0.1-2), optionally 1:(0.5-1.5).
  • the ratio of the doping amount of M1 to the sum of the doping amounts of M2 and W is controlled within the given range, it can not only ensure the high capacity of the high-nickel ternary cathode material, but also improve the structure of the material to the greatest extent. Stability, thereby further improving the cycle performance of the secondary battery.
  • the M1 element has little effect on the capacity reduction of the high-nickel ternary positive electrode material, and the M2 and W elements have a greater impact on the capacity reduction. Therefore, when the ratio of the doping amount of M1 to the sum of the doping amounts of M2 and W is within the above range , the capacity of the secondary battery can be maintained or increased, and the cycle and storage performance of the secondary battery can be further improved.
  • the thickness d of the surface layer is 0 ⁇ d ⁇ 3 ⁇ m, optionally 0 ⁇ d ⁇ 2 ⁇ m.
  • the cycle performance of the battery can be further improved. Therefore, the following situation can be avoided: if the thickness d of the surface layer is too large, the matrix composition may be greatly changed, and the Ni content in the entire matrix may be reduced, thereby significantly reducing the capacity of the ternary cathode material.
  • the sum of the surface layer doping amount of Co and the coating amount of the Co-containing compound is 100-20000 ppm, optionally 1000-13000 ppm; the coating amount of the Al-containing compound is 100-20000 ppm. 3000ppm, optionally 500-2000ppm; the coating amount of the B-containing compound is 100-2000ppm, optionally 500-1500ppm, wherein the surface layer doping amount and coating amount are relative to the corresponding elements in the compound Modified high-nickel ternary cathode material meter.
  • the cycle performance of the battery can be further improved. Therefore, the following situation can be avoided: when the sum of the surface layer doping amount of Co and the coating amount of the Co-containing compound is too large, too many inactive Co compounds may remain on the surface of the high-nickel ternary positive electrode material, which will affect the material. capacity, and will affect the cycle performance of the secondary battery.
  • the cycle performance of the battery can be further improved.
  • the total thickness of the inner and outer cladding layers is 0.001-1 ⁇ m.
  • the coating amount of the Al-containing compound and the coating amount of the B-containing compound satisfy a weight ratio of Al to B of (0.5-2):1, wherein the coating amount is based on the compound
  • the corresponding elements in are calculated relative to the modified high-nickel ternary cathode material.
  • the capacity and cycle performance of the secondary battery can be further improved. Therefore, the following situation can be avoided: when the weight ratio of Al to B in the outer cladding layer is greater than 2:1, since the Al-containing compound is inactive, it may affect the ion transport kinetic activity, further affecting the capacity and cycle of the secondary battery performance.
  • the doping amount of W is 100-2000ppm, optionally 100-1500ppm; the doping amount of M1 is 2000-4000ppm; the doping amount of M2 is 500-2000ppm, wherein The doping amounts are all calculated by corresponding elements relative to the modified high-nickel ternary positive electrode material.
  • the structural stability of the high-nickel ternary positive electrode material can be further improved, thereby further improving the cycle performance and storage performance of the secondary battery.
  • the sum of the doping amount of the surface layer of Co and the coating amount of the Co-containing compound, the Al-containing compound and the B-containing compound is 1000-22000ppm, optionally 1000-15000ppm, wherein the surface layer Both the doping amount and the coating amount are calculated by the corresponding elements in the compound relative to the modified high-nickel ternary cathode material.
  • the volume particle size distribution radius of the modified high-nickel ternary positive electrode material satisfies (Dv 90 -Dv 10 )/Dv 50 ⁇ 1.1, optionally (Dv 90 -Dv 10 )/Dv 50 ⁇ 1.2.
  • the particle volume distribution particle sizes Dv 10 , Dv 50 , and Dv 90 of the modified high-nickel ternary cathode material are well-known concepts in the field.
  • Dv 10 is the particle size from the small particle size side to 10% of the cumulative volume in the volume-based particle size distribution of powder particles, and the unit is usually ⁇ m.
  • Dv 50 is the particle size at which the cumulative volume reaches 50% from the small particle size side in the volume-based particle size distribution of powder particles.
  • Dv 90 is the particle size that reaches 90% of the cumulative volume from the small particle size side in the volume-based particle size distribution of powder particles.
  • test methods for the particle volume distribution particle sizes Dv 10 , Dv 50 , and Dv 90 of the above-mentioned ternary precursors can be tested by methods known in the art.
  • the laser diffraction method for particle size distribution in GB/T 19077-2016/ISO 13320:2009 can be referred to, and the equipment Malvern 2000 can be used for measurement.
  • the powder compacted density of the modified high-nickel ternary cathode material under a pressure of 5 tons is ⁇ 3.4g/cc, optionally ⁇ 3.5g/cc.
  • the volume energy density of the high-nickel ternary cathode material can be significantly improved.
  • the present application also provides a method for preparing a modified high-nickel ternary positive electrode material, including:
  • Step S1 Mix and sinter lithium salt, W-doped high-nickel ternary precursor, M1-containing compound, and M2-containing compound to obtain a high-nickel ternary positive electrode material matrix doped with M1, M2 and W, wherein the
  • the chemical formula of W-doped high-nickel ternary precursor is (Ni X Co Y Mn Z W D )(OH) 2 , where 0.65 ⁇ X ⁇ 1, 0 ⁇ Y ⁇ 0.3, 0 ⁇ Z ⁇ 0.3, 0 ⁇ D ⁇ 0.1
  • the M1 is one of Mo, Zr, Ti, Sb, Nb, Te
  • the M2 is one of Mg, Al, Ca, Zn, Sr
  • the chemical formula of the high-nickel ternary cathode material matrix is Li 1+a [Ni x Co y Mn z M1 b M2 c W d ]O 2 , where 0.65 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.3,
  • Step S2 mixing and sintering the high-nickel ternary positive electrode material matrix doped with M1, M2, and W and a Co-containing compound to obtain a high-nickel ternary positive electrode material doped with Co on the surface and coated with a Co-containing compound on the surface;
  • Step S3 Mix and sinter the high-nickel ternary anode material whose surface layer is doped with Co and whose surface is coated with a Co-containing compound, the Al-containing compound and the B-containing compound, and sintered to obtain a modified high-nickel ternary anode material.
  • the sintering temperature is 700-950° C.
  • the sintering time is 10-20 h
  • the sintering atmosphere is air or O 2 .
  • a high-nickel ternary cathode material matrix with excellent crystal structure can be sintered, and the synergistic doping of the three elements (ie M1, M2, W) can be uniformly and effectively performed.
  • the sintering temperature in step S1 is within an appropriate temperature range, the capacity, cycle performance and storage performance of the secondary battery can be further improved.
  • lithium salts are lithium hydroxide, lithium carbonate, and lithium nitrate
  • compounds containing M1 and compounds containing M2 are oxides or carbonates of M1 and M2.
  • the synthesis method of the W-doped high-nickel ternary precursor includes:
  • the concentration of the nickel-cobalt-manganese mixed metal salt solution is 0.5-2.5 mol/L.
  • the nickel salt is one of nickel nitrate, nickel acetate and nickel sulfate
  • the cobalt salt is one of cobalt nitrate, cobalt acetate and cobalt sulfate
  • the manganese salt is one of manganese nitrate, manganese acetate and manganese sulfate
  • the tungsten-containing compound is sodium tungstate.
  • the pure water added accounts for 10-50% of the volume of the reactor.
  • the alkali solution is a sodium hydroxide solution with a concentration of 1-10 mol/L.
  • the concentration of the ammonia solution is 2-14mol/L.
  • the pH is 11.5-12.5, optionally 11.8-12.2; the ammonia concentration is 0.2-0.6mol/L, optionally 0.3-0.5mol/L; The stirring line speed is 5.0-7.0m/s; the reaction temperature is 40-75°C.
  • step (2) the flow ratio of the nickel-cobalt-manganese mixed metal salt solution doped with the W salt, the alkali solution, and the ammonia solution is 18.75:15:1.
  • the pH is 11.0-12.0, optionally 11.1-11.7; the ammonia concentration is 0.2-0.6mol/L, optionally 0.3-0.5mol/L;
  • the stirring line speed is 3.0-6.0m/s; the reaction temperature is 40-75°C.
  • step (3) the flow ratio of the W salt-doped nickel-cobalt-manganese mixed metal salt solution, alkali solution, ammonia solution, and seed crystal nucleus slurry is 18.75:15:1:2.8.
  • the volume distribution average particle diameter Dv 50 of the seed crystal nucleus slurry is 1-5 ⁇ m; the volume distribution average particle diameter Dv 50 of the W-doped high-nickel ternary precursor is 5-15 ⁇ m, 5-10 ⁇ m is optional.
  • the volume particle size distribution diameter (Dv 90 ⁇ Dv 10 )/Dv 50 of the W-doped high-nickel ternary precursor is ⁇ 1.3.
  • the bulk phase structure of the W-doped high-nickel ternary precursor synthesized by this method is uniformly doped with W element, and has a wide volume particle size distribution diameter, so that the sintered high-nickel ternary positive electrode material has a wide Excellent particle size distribution and high powder compaction density.
  • the Co-containing compound is one or more of Co 3 O 4 , Co(OH) 2 , CoO, CoOOH, cobalt acetate, cobalt oxalate, and CoCO 3 .
  • the particle diameter of the Co-containing compound is 0.001-10 ⁇ m, optionally 0.001-1 ⁇ m.
  • the particle diameter of the Co-containing compound When the particle diameter of the Co-containing compound is within the given range, it can evenly coat the surface of the high-nickel ternary positive electrode material, improve the interface side reaction between the material and the electrolyte, and further improve the cycle performance of the secondary battery.
  • the sintering temperature is 500-800°C, optionally 550-750°C, the sintering time is 5-15h, optionally 5-10h, and the sintering atmosphere is air or O2 .
  • step S2 By controlling the sintering temperature in step S2, it is possible to react the Co-containing compound with the miscellaneous lithium on the surface of the ternary positive electrode material, and to firmly coat the Co-containing compound on the surface of the ternary positive electrode material, thereby reducing the surface miscellaneous lithium and improving Interfacial side reactions further improve the cycle performance of secondary batteries.
  • the Al-containing compound is one or more of Al 2 O 3 , Al(OH) 3 , Al 2 (SO 4 ) 3 , AlCl 3 , Al(NO) 3 kind.
  • the B-containing compound is BCl 3 , B 2 (SO 4 ) 3 , B(NO 3 ) 3 , BN, B 2 O 3 , BF 3 , BBr 3 , BI 3 , H 2 BO 5 P, H 3 BO 3 , C 5 H 6 B(OH) 2 , C 3 H 9 B 3 O 6 , (C 2 H 5 O) 3 B and (C 3 H 7 O) 3 B one or more of.
  • the sintering temperature is 200-500°C, optionally 200-400°C, the sintering time is 5-15h, optionally 5-10h, and the sintering atmosphere is air or O2 .
  • the Al-containing compound and the B-containing compound can be firmly coated on the surface of the ternary positive electrode material, thereby improving the interfacial reaction of the material and further improving the cycle performance of the secondary battery.
  • a secondary battery is provided.
  • a secondary battery typically includes a positive pole piece, a negative pole piece, an electrolyte, and a separator.
  • active ions are intercalated and extracted back and forth between the positive electrode and the negative electrode.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the separator is arranged between the positive pole piece and the negative pole piece, which mainly plays a role in preventing the short circuit of the positive and negative poles, and at the same time allows ions to pass through.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, and the positive electrode film layer includes the modified high-nickel ternary positive electrode material according to the first aspect of the present application.
  • the positive electrode current collector has two opposing surfaces in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposing surfaces of the positive electrode current collector.
  • the positive electrode current collector can be a metal foil or a composite current collector.
  • aluminum foil can be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene glycol ester
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode film layer may further optionally include a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode film layer may also optionally include a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the positive electrode sheet, such as positive electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, and the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposing surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposing surfaces of the negative electrode current collector.
  • the negative electrode current collector can use a metal foil or a composite current collector.
  • copper foil can be used as the metal foil.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base.
  • Composite current collectors can be formed by metal materials (copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • the negative electrode active material can be a negative electrode active material known in the art for batteries.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of simple tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials of batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further optionally include a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may also optionally include a conductive agent.
  • the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • CMC-Na sodium carboxymethylcellulose
  • the negative electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the negative electrode sheet, such as negative electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no specific limitation on the type of electrolyte, which can be selected according to requirements.
  • electrolytes can be liquid, gel or all solid.
  • the electrolyte is an electrolytic solution.
  • the electrolyte solution includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorooxalate borate, lithium difluorodifluorooxalatephosphate and lithium tetrafluorooxalatephosphate.
  • the solvent may be selected from ethylene carbonate (EC), propylene carbonate, ethyl methyl carbonate, diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate, carbonic acid Methyl propyl ester, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate , methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • DMC dimethyl carbonate
  • dipropyl carbonate carbonic acid Methyl propy
  • the electrolyte may optionally include additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performances of the battery, such as additives that improve battery overcharge performance, additives that improve high-temperature or low-temperature performance of batteries, and the like.
  • a separator is further included in the secondary battery.
  • the present application has no special limitation on the type of isolation membrane, and any known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
  • the material of the isolation film can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the separator can be a single-layer film or a multi-layer composite film, without any particular limitation. When the separator is a multilayer composite film, the materials of each layer may be the same or different, and there is no particular limitation.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer package.
  • the outer package can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard case, such as a hard plastic case, aluminum case, steel case, and the like.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft case may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 5 shows a secondary battery 5 having a square structure as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plates enclose to form an accommodating cavity.
  • the housing 51 has an opening communicating with the accommodating cavity, and the cover plate 53 can cover the opening to close the accommodating cavity.
  • the positive pole piece, the negative pole piece and the separator can be formed into an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the accommodating chamber. Electrolyte is infiltrated in the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 7 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may also include a case having a housing space in which a plurality of secondary batteries 5 are accommodated.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3 , the upper box body 2 can cover the lower box body 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electric device, which includes more than one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source of the electric device, and can also be used as an energy storage unit of the electric device.
  • the electric devices may include mobile devices (such as mobile phones, notebook computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, etc.) , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but not limited thereto.
  • a secondary battery, a battery module or a battery pack can be selected according to its use requirements.
  • FIG. 10 is an example of an electrical device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or a battery module may be used.
  • the electric device may be a mobile phone, a tablet computer, a notebook computer, and the like.
  • the electrical device is usually required to be light and thin, and a secondary battery can be used as a power source.
  • the nickel-cobalt-manganese mixed metal salt solution doped with tungsten salt, NaOH solution, and ammonia solution into the reaction kettle, wherein the flow ratio of the nickel-cobalt-manganese mixed metal salt solution doped with tungsten salt to the NaOH solution is 5 : 4, the flow ratio of NaOH solution and ammonia solution is 15:1, to keep the ammonia concentration and pH constant in the reactor, the continuous reaction synthesizes the seed crystal nucleus slurry;
  • nickel-cobalt-manganese mixed metal salt solution doped with tungsten salt a nickel-cobalt-manganese mixed metal salt solution doped with tungsten salt
  • the flow ratio with NaOH solution is 5:4
  • the flow ratio of NaOH solution and ammonia solution is 15:1
  • the flow ratio of the seed crystal nucleus slurry and the nickel-cobalt-manganese mixed metal salt solution doped with tungsten salt is 0.15, in order to keep the ammonia concentration and pH in the reactor unchanged, and continuously react to synthesize a high-nickel ternary precursor doped with tungsten in the slurry.
  • the slurry was then centrifuged at 300 rpm for 20 min, washed with deionized water, filtered, and dried at 105 °C for 10 h to obtain a tungsten-doped high-nickel ternary precursor with the molecular formula (Ni 0.8995 Co 0.05 Mn 0.05 W 0.0005 )( OH) 2 , the particle size Dv 50 is 8 ⁇ m, and the diameter of particle size volume distribution (D v90 -D v10 )/D v50 is 1.35.
  • S1 Put lithium hydroxide, the tungsten-doped high-nickel ternary precursor, TiO 2 , and Al 2 O 3 into a coulter mixer for mixing, where the molar ratio of Li to the sum of nickel, cobalt, and manganese is is 1.05, the amount of TiO 2 is 2500ppm in terms of Ti, and the amount of Al 2 O 3 is 1000ppm in terms of Al.
  • the mixed material is put into a kiln for sintering.
  • the sintering temperature is 750°C
  • the sintering time is 15h
  • the sintering atmosphere is O 2 , to obtain a high-nickel ternary cathode material matrix doped with Ti, Al and W, the molecular formula of which is Li 1.05 [Ni 0.8918 Co 0.0495 Mn 0.0495 Ti 0.005 Al 0.0037 W 0.0005 ]O 2 ;
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the nickel, cobalt and cobalt in the nickel-cobalt-manganese mixed metal salt solution , manganese molar ratio is 80:10:10, the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.7996 Co 0.09995 Mn 0.09995 W 0.0005 )(OH) 2 ; in the modified high-nickel ternary positive electrode material In the preparation of , in step S1, a high-nickel ternary cathode material matrix doped with Ti, Al and W is obtained, and its molecular formula is Li 1.05 [Ni 0.7927 Co 0.0991 Mn 0.0991 Ti 0.005 Al 0.0036 W 0.0005 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the nickel, cobalt and cobalt in the nickel-cobalt-manganese mixed metal salt solution , manganese molar ratio is 70:15:15, the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.6997 Co 0.1499 Mn 0.1499 W 0.0005 )(OH) 2 ; in the modified high-nickel ternary positive electrode material In the preparation of , in step S1, a high-nickel ternary cathode material matrix doped with Ti, Al and W is obtained, and its molecular formula is Li 1.05 [Ni 0.6936 Co 0.1486 Mn 0.1486 Ti 0.005 Al 0.0037 W 0.0005 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the modified high-nickel ternary positive electrode material, in step S1, no TiO 2 is added to obtain doped Al and W high-nickel ternary cathode material matrix, its molecular formula is Li 1.05 [Ni 0.8963 Co 0.0498 Mn 0.0498 Al 0.0036 W 0.0005 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the modified high-nickel ternary positive electrode material, in step S1, Al 2 O 3 is not added to obtain A high-nickel ternary cathode material matrix doped with Ti and W, the molecular formula of which is Li 1.05 [Ni 0.895 Co 0.0497 Mn 0.0497 Ti 0.0051 W 0.0005 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, sodium tungstate is not added, and the obtained high-nickel ternary
  • the molecular formula of the precursor is (Ni 0.90 Co 0.05 Mn 0.05 )(OH) 2 ; in the preparation of the modified high-nickel ternary positive electrode material, in step S1, a high-nickel ternary positive electrode material doped with Ti and Al is obtained matrix, its molecular formula is Li 1.05 [Ni 0.8923 Co 0.0496 Mn 0.0496 Ti 0.005 Al 0.0035 ]O 2 .
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that step S2 is not performed, and the total thickness of the inner and outer coating layers of the final product is 0.11 ⁇ m.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that step S3 is not performed, and the total thickness of the inner and outer coating layers of the final product is 0.40 ⁇ m.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that in step S3, B 2 O 3 is not added, and the total thickness of the inner and outer coating layers of the final product is 0.49 ⁇ m.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that in step S3, no Al 2 O 3 is added, and the total thickness of the inner and outer cladding layers of the final product is 0.50 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the modified high-nickel ternary positive electrode material, in step S1, TiO 2 is replaced by ZrO 2 , Al 2 O 3 was replaced by SrCO 3 , and a high- nickel ternary cathode material matrix doped with Zr , Sr and W was obtained.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the modified high-nickel ternary positive electrode material, in step S1, TiO 2 is replaced by Sb 2 O 5. Replace Al 2 O 3 with MgO to obtain a high-nickel ternary cathode material matrix doped with Sb, Mg and W, and its molecular formula is Li 1.05 [Ni 0.8941 Co 0.0497 Mn 0.0497 Sb 0.002 Mg 0.004 W 0.0005 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the modified high-nickel ternary positive electrode material, in step S1, Al 2 O 3 is replaced by ZnO , to obtain a high-nickel ternary cathode material matrix doped with Ti, Zn and W, and its molecular formula is Li 1.05 [Ni 0.8937 Co 0.0496 Mn 0.0496 Ti 0.005 Zn 0.0016 W 0.0005 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 2000ppm in terms of tungsten , the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.8991 Co 0.04995 Mn 0.04995 W 0.001 )(OH) 2 ; in the preparation of the modified high-nickel ternary positive electrode material, in step S1, TiO The amount of 2 is 2000ppm in terms of Ti, and the amount of Al 2 O 3 is 2000ppm in terms of Al, to obtain a high-nickel ternary cathode material matrix doped with Ti, Al and W, and its molecular formula is Li 1.05 [Ni 0.889 Co 0.0494 Mn 0.0494 Ti 0.004 Al 0.0072 W 0.001 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 1500ppm in terms of tungsten, The molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.8992 Co 0.05 Mn 0.05 W 0.0008 )(OH) 2 ; in the preparation of the modified high-nickel ternary cathode material, in step S1, TiO 2 The amount of Ti is 2000ppm, and the amount of Al 2 O 3 is 1500ppm in Al, to obtain a high-nickel ternary positive electrode material matrix doped with Ti, Al and W, and its molecular formula is Li 1.05 [Ni 0.8909 Co 0.0495 Mn 0.0495 Ti 0.004 Al 0.0053 W 0.0008 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 100ppm in terms of tungsten,
  • the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.8999 Co 0.05 Mn 0.05 W 0.0001 )(OH) 2 ; in the preparation of the modified high-nickel ternary cathode material, in step S1, TiO 2
  • the amount of Ti is 2000ppm, the amount of Al 2 O 3 is 1900ppm in Al, and the high-nickel ternary positive electrode material matrix doped with Ti, Al and W is obtained, and its molecular formula is Li 1.05 [Ni 0.8901 Co 0.0495 Mn 0.0495 Ti 0.004 Al 0.0068 W 0.0001 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 500ppm in terms of tungsten,
  • the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.8997 Co 0.05 Mn 0.05 W 0.0003 )(OH) 2 ; in the preparation of the modified high-nickel ternary cathode material, in step S1, TiO 2
  • the amount of Ti is 3000ppm, the amount of Al 2 O 3 is 1000ppm in Al, and the high-nickel ternary positive electrode material matrix doped with Ti, Al and W is obtained, and its molecular formula is Li 1.05 [Ni 0.8911 Co 0.0495 Mn 0.0495 Ti 0.006 Al 0.0036 W 0.0003 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 1900ppm in terms of tungsten,
  • the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.899 Co 0.05 Mn 0.05 W 0.001 )(OH) 2 ; in the preparation of the modified high-nickel ternary cathode material, in step S1, TiO 2
  • the amount of Ti is 4000ppm, and the amount of Al 2 O 3 is 500ppm in Al, to obtain a high-nickel ternary positive electrode material matrix doped with Ti, Al and W, and its molecular formula is Li 1.05 [Ni 0.8902 Co 0.0495 Mn 0.0495 Ti 0.008 Al 0.0018 W 0.001 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 100ppm in terms of tungsten,
  • the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.8999 Co 0.05 Mn 0.05 W 0.0001 )(OH) 2 ; in the preparation of the modified high-nickel ternary cathode material, in step S1, TiO 2
  • the amount of Ti is 6000ppm, the amount of Al 2 O 3 is 500ppm in Al, and the high-nickel ternary positive electrode material matrix doped with Ti, Al and W is obtained, and its molecular formula is Li 1.05 [Ni 0.8875 Co 0.0493 Mn 0.0493 Ti 0.012 Al 0.0018 W 0.0001 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 100ppm in terms of tungsten,
  • the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.8999 Co 0.05 Mn 0.05 W 0.0001 )(OH) 2 ; in the preparation of the modified high-nickel ternary cathode material, in step S1, TiO 2
  • the amount of Ti is 4000ppm, and the amount of Al 2 O 3 is 100ppm in Al, to obtain a high-nickel ternary positive electrode material matrix doped with Ti, Al and W, and its molecular formula is Li 1.05 [Ni 0.8923 Co 0.0496 Mn 0.0496 Ti 0.008 Al 0.0004 W 0.0001 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in the preparation of the tungsten-doped high-nickel ternary precursor, the amount of sodium tungstate added is 3000ppm in terms of tungsten,
  • the molecular formula of the obtained tungsten-doped high-nickel ternary precursor is (Ni 0.8984 Co 0.05 Mn 0.05 W 0.0016 )(OH) 2 ; in the preparation of the modified high-nickel ternary cathode material, in step S1, TiO 2
  • the amount of Ti is 2000ppm, and the amount of Al 2 O 3 is 3000ppm in Al, to obtain a high-nickel ternary positive electrode material matrix doped with Ti, Al and W, and its molecular formula is Li 1.05 [Ni 0.8854 Co 0.0492 Mn 0.0492 Ti 0.004 Al 0.0106 W 0.0016 ]O 2 .
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S2, the amount of CoO is 20000ppm in terms of Co, and the total thickness of the inner and outer cladding layers of the final product is 1.0 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S2, the amount of CoO is 5000ppm in terms of Co, and the total thickness of the inner and outer cladding layers of the final product is 0.32 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S2, the amount of CoO is 1000ppm in terms of Co, and the total thickness of the inner and outer cladding layers of the final product is 0.18 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S2, the amount of CoO is 100ppm in terms of Co, and the total thickness of the inner and outer cladding layers of the final product is 0.13 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S2, the amount of CoO is 25000ppm in terms of Co, and the total thickness of the inner and outer cladding layers of the final product is 1.26 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S3, the amount of Al 2 O 3 is 3000 ppm in terms of Al, and the amount of B 2 O 3 in terms of B is 2000ppm, the weight ratio of Al to B is 1.5:1, and the total thickness of the inner and outer cladding layers of the final product is 0.60 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S3, the amount of Al 2 O 3 is 2000 ppm in terms of Al, and the amount of B 2 O 3 in terms of B is 1000ppm, the weight ratio of Al to B is 2:1, and the total thickness of the inner and outer cladding layers of the final product is 0.58 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S3, the amount of Al 2 O 3 is 500 ppm in terms of Al, and the amount of B 2 O 3 in terms of B is 500ppm, the weight ratio of Al to B is 1:1, and the total thickness of the inner and outer cladding layers of the final product is 0.51 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S3, the amount of Al 2 O 3 is 750 ppm in terms of Al, and the amount of B 2 O 3 in terms of B is 1500ppm, the weight ratio of Al to B is 0.5:1, and the total thickness of the inner and outer cladding layers of the final product is 0.55 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S3, the amount of Al 2 O 3 is 100 ppm in terms of Al, and the amount of B 2 O 3 in terms of B is 100ppm, the weight ratio of Al to B is 1:1, and the total thickness of the inner and outer cladding layers of the final product is 0.46 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S3, the amount of Al 2 O 3 is 3000 ppm in terms of Al, and the amount of B 2 O 3 in terms of B is 1000ppm, the weight ratio of Al to B is 3:1, and the total thickness of the inner and outer cladding layers of the final product is 0.61 ⁇ m.
  • the preparation of the modified high-nickel ternary positive electrode material refers to Example 1-1 as a whole, the difference is that in step S2, the amount of CoO is 800ppm as Co, and in step S3 , the amount of Al2O3 is as Al
  • the amount of B 2 O 3 is 100 ppm in terms of B, the weight ratio of Al to B is 1:1, and the total thickness of the inner and outer cladding layers of the final product is 0.13 ⁇ m.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that in step S1, the sintering temperature is 700°C.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that in step S1, the sintering temperature is 950°C.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that in step S1, the sintering temperature is 650°C.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that in step S1, the sintering temperature is 1000°C.
  • Example 1-1 The preparation of the modified high-nickel ternary cathode material is generally referred to in Example 1-1, except that in step S2, the sintering temperature is 500°C.
  • Example 1-1 The preparation of the modified high-nickel ternary positive electrode material is generally referred to in Example 1-1, the difference is that in step S2, the sintering temperature is 550°C.
  • Example 1-1 The preparation of the modified high-nickel ternary cathode material is generally referred to in Example 1-1, except that in step S2, the sintering temperature is 700°C.
  • Example 1-1 The preparation of the modified high-nickel ternary cathode material is generally referred to in Example 1-1, except that in step S2, the sintering temperature is 800°C.
  • Example 1-1 The preparation of the modified high-nickel ternary cathode material is generally referred to in Example 1-1, except that in step S2, the sintering temperature is 400°C.
  • Example 1-1 The preparation of the modified high-nickel ternary cathode material is generally referred to in Example 1-1, except that in step S2, the sintering temperature is 900°C.
  • a plasma optical emission spectrometer (ICP-OES) was used, and the device model was ICAP7400 from Thermo Fisher Scientific, USA. First take 1g of sample in a beaker, add 25ml of HNO3 solution with a concentration of 25% volume ratio to the sample to dissolve the sample, and dilute it with 475ml of deionized water, then put the diluted liquid into the instrument and equipment for target element analysis. Calculate the target element content.
  • Acid-base titration method put 30g sample into 100ml pure water, stir for 30min, let it stand for 5min, filter with suction, take 10ml of supernatant, and titrate the dissolved lithium carbonate and Lithium hydroxide, using the pH electrode as the indicator electrode, determines the end point by means of the jump generated by the potential change, and calculates the amount of lithium on the surface of the positive electrode material.
  • the test method of volume distribution particle size is: refer to GB/T 19077-2016/ISO 13320:2009 particle size distribution laser diffraction method, and the equipment adopts Malvern 2000. Take a clean beaker, add an appropriate amount of the sample to be tested until the shading degree is 8%-12%, add 20ml of deionized water, and at the same time ultrasonically for 5 minutes, turn on the particle size tester and start testing.
  • the ternary positive electrode material prepared in each of the above examples and comparative examples is used as the positive electrode active material, and the conductive agent acetylene black, the binder polyvinylidene fluoride (PVDF) in the N-methyl After the pyrrolidone solvent system is fully stirred and mixed evenly, it is coated on an aluminum foil, dried, and cold-pressed to obtain a positive electrode sheet.
  • the conductive agent acetylene black the binder polyvinylidene fluoride (PVDF) in the N-methyl
  • SBR binder styrene-butadiene rubber
  • CMC thickener
  • Example 1-1 when the high-nickel ternary positive electrode material matrix is doped with M1, M2 and W elements, its surface layer is further doped with Co, and is also coated with a Co-containing compound.
  • the cladding layer and the outer cladding layer containing Al compound and B compound are used, the corresponding cycle capacity retention rate of the full battery at 25°C is higher than 94.7%, and the cycle capacity retention rate at 45°C is higher than 91.5%, while at 70°C
  • the flatulence after storage for 30 days was lower than 4.91mL/Ah.
  • Example 1-1 and Example 3-1 to Example 3-8 when the doping amount of the W is 100-2000ppm, the doping amount of the M1 is 2000-4000ppm, and the doping amount of the M2
  • the impurity amount is 500-2000ppm, and the ratio of the doping amount of M1 to the sum of the doping amounts of M2 and W is 1:(0.1-2)
  • the corresponding 0.1C buckle capacitance is higher than 222.4mAh/g
  • 1/3C full capacity is higher than 211.2mAh/g
  • 25°C cycle capacity retention rate is higher than 94.5%
  • 45°C cycle capacity retention rate is higher than 91.2%
  • the flatulence after days was lower than 5.01mL/Ah.
  • the sum of the doping amount of the Co surface layer and the coating amount of the Co-containing compound is 100-20000ppm, and the Al-containing compound
  • the coating amount of the compound is 100-3000ppm, and when the coating amount of the B-containing compound is 100-2000ppm, when the coating amount of the Al-containing compound and the coating amount of the B-containing compound meet the requirements of Al and B
  • the weight ratio is (0.5-2):1, and when the sum of the coating amount of the Co surface layer doping amount and the Co-containing compound, Al-containing compound and B-containing compound is 1000-22000ppm, the corresponding The 0.1C buckle capacity, 1/3C full capacity, 25°C and 45°C cycle capacity retention rate, and the gas performance after storage at 70°C for 30 days are all good.
  • step S1 when the sintering temperature of step S1 is 700-950°C, the 0.1C buckle capacitance, 1/3C full capacitance, 25°C and 45°C cycle capacity retention rate of the prepared ternary cathode material And the inflation performance after storage at 70°C for 30 days is good; however, if the initial firing temperature is too high or too low, the capacity, cycle and storage inflation performance of the prepared ternary cathode material will be significantly affected.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are merely examples, and within the scope of the technical solutions of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same effects are included in the technical scope of the present application.
  • various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .

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Abstract

本申请提供一种改性的高镍三元正极材料，其包含内核和内外两层包覆层，所述内核包含高镍三元正极材料基体，所述基体掺杂有M1、M2和W，其中所述M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种，掺杂M1、M2和W的高镍三元正极材料基体的化学式为Li 1+a[Ni xCo yMn zM1 bM2 cW d]O 2，其中0.65≤x<1，0≤y<0.3，0≤z<0.3，0<a<0.2，0<b<0.1，0<c<0.1，0<d<0.1，x+y+z+b+c+d＝1，可选地0.8≤x<1；所述内核的表层还掺杂有Co；所述内包覆层为含Co化合物，所述外包覆层为含Al化合物和含B化合物。本申请还涉及一种制备改性的高镍三元正极材料的方法，以及二次电池、电池模块、电池包和用电装置。

Description

改性的高镍三元正极材料及其制备方法，以及用电装置 技术领域
本申请涉及锂电池技术领域，尤其涉及一种改性的高镍三元正极材料及其制备方法、二次电池、电池模块、电池包和用电装置。
背景技术
随着新能源领域的快速发展，锂离子二次电池凭借其优良的电化学性能、无记忆效应、环境污染小等优势广泛应用于各类大型动力装置、储能系统以及各类消费类产品中，尤其广泛应用于纯电动汽车、混合电动汽车等新能源汽车领域。
由于锂离子二次电池取得了极大的发展，因此对其能量密度、循环性能和安全性能等也提出了更高的要求。而高镍正极活性材料被认为是满足高能量密度要求的最佳选择。但是随着镍含量的不断提高，其结构稳定性越来越差，进而影响锂离子二次电池的循环性能和存储性能。
因此，存在提高锂离子二次电池的容量同时确保二次电池的循环性能和存储性能的需求。
发明内容
鉴于背景技术中存在的技术问题，本申请提供一种改性的高镍三元正极材料，旨在使由其制备的锂离子二次电池在具有高容量的同时，还具有改善的循环性能和存储性能。
为了达到上述目的，本申请第一方面提供一种改性的高镍三元正极材料，包含内核和内外两层包覆层；所述内核包含高镍三元正极材料基体，所述基体掺杂有M1、M2和W，其中所述M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种，掺杂M1、M2和W的高镍三元正极材料基体的化学式为Li 1+a[Ni xCo yMn zM1 bM2 cW d]O 2，其中0.65≤x<1，0≤y<0.3，0≤z<0.3， 0<a<0.2，0<b<0.1，0<c<0.1，0<d<0.1，x+y+z+b+c+d＝1，可选地0.8≤x<1；所述内核的表层还掺杂有Co；所述内包覆层为含Co化合物，所述外包覆层为含Al化合物和含B化合物。
相对于现有技术，本申请至少包括如下所述的有益效果：
本申请对高镍三元正极材料基体进行了三种离子(即M1、M2和W)协同掺杂，能够更有效地提升高镍三元正极材料的结构稳定性，从而明显改善二次电池的循环性能和热稳定性；本申请对高镍三元正极材料的表层还掺杂了Co，能够有效降低高镍三元正极材料表层的高价镍离子含量，从而降低高价镍离子与电解液的副反应，进一步改善二次电池的循环性能与存储性能；本申请还对高镍三元正极材料均匀包覆含Co化合物的内层，含Al化合物、含B化合物的外层，由此，能够有效降低表面杂锂含量并进一步有效抑制高镍三元正极材料与电解液之间的界面副反应，从而提高高镍三元正极材料的容量和倍率性能，并进一步提高二次电池的循环、存储及安全性能。
在任意实施方式中，所述M1的掺杂量≥所述M2或所述W的掺杂量。
在任意实施方式中，所述M1的掺杂量与所述M2和W的掺杂量之和的比值为1:(0.1-2)，可选为1:(0.5-1.5)。
当M1的掺杂量与M2和W的掺杂量之和的比值控制在所给范围内时，既能保证高镍三元正极材料具有较高的容量，同时又能最大程度提升材料的结构稳定性，从而进一步改善二次电池的循环性能。
在任意实施方式中，所述表层的厚度d为0<d<3μm，可选为0<d<2μm。当表层的厚度d在所给范围内时，能够进一步改善二次电池的循环性能。
在任意实施方式中，所述Co的表层掺杂量与所述含Co化合物的包覆量之和为100-20000ppm，可选为1000-13000ppm；所述含Al化合物的包覆量为100-3000ppm，可选为500-2000ppm；所述含B化合物的包覆量为100-2000ppm，可选为500-1500ppm，其中所述表层掺杂量和包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。当Co的表层掺杂量与含Co化合物的包覆量之和在 所给范围内时，能够进一步改善二次电池的循环性能。当含Al化合物的包覆量和含B化合物的包覆量在所给范围内时，能够进一步改善二次电池的循环性能。
在任意实施方式中，所述内外包覆层的总厚度为0.001-1μm。
在任意实施方式中，所述含Al化合物的包覆量与所述含B化合物的包覆量满足Al与B的重量比为(0.5-2):1，其中所述包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。当含Al化合物的包覆量与含B化合物的包覆量满足所给关系时，能够进一步改善二次电池的容量和循环性能。
在任意实施方式中，所述W的掺杂量为100-2000ppm，可选为100-1500ppm；所述M1的掺杂量为2000-4000ppm；所述M2的掺杂量为500-2000ppm，其中所述掺杂量均以相应元素相对于改性的高镍三元正极材料计。当M1、M2和W的掺杂量在所给范围内时，能够进一步改善高镍三元正极材料的结构稳定性，从而进一步改善二次电池的循环性能和存储性能。
在任意实施方式中，所述Co的表层掺杂量以及所述含Co化合物、含Al化合物和含B化合物的包覆量之和为1000-22000ppm，可选为1000-15000ppm，其中所述表层掺杂量和包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。
在任意实施方式中，所述改性的高镍三元正极材料的体积粒度分布径距满足(Dv 90-Dv 10)/Dv 50≥1.1，可选(Dv 90-Dv 10)/Dv 50≥1.2。
在任意实施方式中，所述改性的高镍三元正极材料在5吨压力下的粉末压实密度≥3.4g/cc，可选≥3.5g/cc。
发明人通过试验发现：当改性的高镍三元正极材料具有较宽的体积粒度分布径距，具有较高的粉末压实密度，能够明显提升高镍三元正极材料的体积能量密度。
本申请的第二方面还提供一种制备改性的高镍三元正极材料的方法，包括：
步骤S1：将锂盐、掺W的高镍三元前驱体、含M1的化合物、含M2的化合物混合并烧结，得到掺杂M1、M2和W的高镍三元正 极材料基体，其中所述掺W的高镍三元前驱体的化学式为(Ni XCo YMn ZW D)(OH) 2，其中0.65≤X＜1，0≤Y＜0.3，0≤Z＜0.3，0<D<0.1，所述M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种，所述掺杂M1、M2和W的高镍三元正极材料基体的化学式为Li 1+a[Ni xCo yMn zM1 bM2 cW d]O 2，其中0.65≤x<1，0≤y<0.3，0≤z<0.3，0<a<0.2，0<b<0.1，0<c<0.1，0<d<0.1，x+y+z+b+c+d＝1，可选地0.8≤x<1；
步骤S2：将所述掺杂M1、M2和W的高镍三元正极材料基体与含Co化合物混合并烧结，得到表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料；
步骤S3：将所述表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料与含Al化合物、含B化合物混合并烧结，得到改性的高镍三元正极材料。
在任意实施方式中，在所述步骤S1中，烧结温度为700-950℃，烧结时间为10-20h，烧结气氛为空气或者O 2。当步骤S1中的烧结温度在合适的温度范围内时，能够进一步改善二次电池的容量、循环性能以及存储性能。
在任意实施方式中，所述含Co化合物颗粒直径为0.001-10μm，可选为0.001-1μm。当含Co化合物颗粒直径在所给范围内时，能够均匀包覆在高镍三元正极材料的表面，从而进一步改善二次电池的循环性能。
在任意实施方式中，在所述步骤S2中，烧结温度为500-800℃，可选为550-750℃，烧结时间为5-15h，可选为5-10h，烧结气氛为空气或者O 2。当步骤S2的烧结温度在所给范围内时，既能够使含Co化合物与三元正极材料表面的杂锂发生反应，又能将含Co化合物牢固地包覆在三元正极材料表面，从而减少表面杂锂并改善界面副反应，进一步改善二次电池的循环性能。
在任意实施方式中，在所述步骤S3中，烧结温度为200-500℃，可选为200-400℃，烧结时间为5-15h，可选为5-10h，烧结气氛为空气或者O 2。当步骤S3的烧结温度在所给范围内时，能够将含Al 化合物和含B化合物牢固地包覆在三元正极材料表面，从而改善三元正极材料的界面反应，进一步改善二次电池的循环性能。
本申请的第三方面提供一种二次电池，包括本申请第一方面的改性的高镍三元正极材料或根据本申请第二方面的方法制备的改性的高镍三元正极材料。
本申请的第四方面提供一种电池模块，包括本申请的第三方面的二次电池。
本申请的第五方面提供一种电池包，包括本申请的第四方面的电池模块。
本申请的第六方面提供一种用电装置，包括选自本申请的第三方面的二次电池、本申请的第四方面的电池模块或本申请的第五方面的电池包中的至少一种。
本申请的电池模块、电池包和用电装置包括本申请的二次电池，因而至少具有与所述二次电池相同的优势。
附图说明
图1为本申请实施例1-1制备得到的改性的高镍三元正极材料的SEM图。
图2为本申请实施例1-1制备得到的改性的高镍三元正极材料制成的扣电的首次充放电曲线。
图3为本申请对比例5-1与实施例1-1制备得到的改性的高镍三元正极材料制作成全电池的25℃循环对比曲线。
图4为本发明对比例5-1与实施例1-1制备得到的改性的高镍三元正极材料制作成全电池的70℃存储胀气对比曲线。
图5是本申请一实施方式的二次电池的示意图。
图6是图5所示的本申请一实施方式的二次电池的分解图。
图7是本申请一实施方式的电池模块的示意图。
图8是本申请一实施方式的电池包的示意图。
图9是图8所示的本申请一实施方式的电池包的分解图。
图10是本申请一实施方式的二次电池用作电源的用电装置的示 意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的改性的高镍三元正极材料及其制备方法、二次电池、电池模块、电池包和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
[改性的高镍三元正极材料]
本申请提供一种改性的高镍三元正极材料，包含内核和内外两层包覆层，
所述内核包含高镍三元正极材料基体，所述基体掺杂有M1、M2和W，其中所述M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种，掺杂M1、M2和W的高镍三元正极材料基体的化学式为Li 1+a[Ni xCo yMn zM1 bM2 cW d]O 2，其中0.65≤x<1，0≤y<0.3，0≤z<0.3，0<a<0.2，0<b<0.1，0<c<0.1，0<d<0.1，x+y+z+b+c+d＝1，可选地0.8≤x<1；
所述内核的表层还掺杂有Co；
所述内包覆层为含Co化合物，所述外包覆层为含Al化合物和含B化合物。
本申请对高镍三元正极材料进行了掺杂，并对其进行了包覆，能够在保证锂离子二次电池高容量的前提下，改善其循环性能和安全性能。
不希望限于任何理论，首先，本申请对高镍三元正极材料进行了 三种离子(即M1、M2和W)协同掺杂，相对于单离子掺杂，能够更有效地提升高镍三元正极材料的结构稳定性，从而明显提升二次电池的循环性能和热稳定性；其次，本申请对高镍三元正极材料的表层还掺杂了Co，能够有效降低高镍三元正极材料表层的高价镍离子含量，从而降低高价镍离子与电解液的副反应，进一步改善二次电池的循环性能与存储性能；最后，本申请对高镍三元正极材料均匀包覆含Co化合物的内层，含Al化合物、含B化合物的外层，能够有效降低表面杂锂含量，使杂锂与含Co化合物生成Li 2CoO 3，与含B化合物生成LiBO 2、LiB 3O 5、Li 2B 4O 7或它们的混合物，使杂锂变成活性锂，从而提高高镍三元正极材料的容量和倍率性能，同时含Co化合物的内层与含B化合物、含Al化合物的外层的协同作用，能够进一步有效抑制高镍三元正极材料与电解液之间的界面副反应，从而进一步有效提高二次电池的循环、存储及安全性能。
本发明人经深入研究发现，当本申请的改性的高镍三元正极材料在满足上述设计条件的基础上，若还可选地满足下述条件中的一个或几个时，可以进一步改善高镍三元正极材料的性能。
在一些实施方式中，所述M1的掺杂量≥所述M2或所述W的掺杂量。
在一些实施方式中，所述M1的掺杂量与所述M2和W的掺杂量之和的比值为1:(0.1-2)，可选为1:(0.5-1.5)。
当M1的掺杂量与M2和W的掺杂量之和的比值控制在所给范围内时，既能保证高镍三元正极材料具有较高的容量，同时又能最大程度提升材料的结构稳定性，从而进一步改善二次电池的循环性能。
M1元素对高镍三元正极材料的容量降低影响较小，M2和W元素对容量降低影响较大，因此当M1的掺杂量与M2和W的掺杂量之和的比值在上述范围内时，则能够保持或提高二次电池的容量，并进一步提升二次电池的循环和存储性能。
在一些实施方式中，所述表层的厚度d为0<d<3μm，可选为0<d<2μm。
当表层的厚度d在所给范围内时，能够进一步改善电池的循环性 能。因而能够避免以下情况：如果表层的厚度d过大，则可能会使基体成分发生很大变化，降低整个基体中Ni的含量，从而明显降低三元正极材料容量。
在一些实施方式中，所述Co的表层掺杂量与所述含Co化合物的包覆量之和为100-20000ppm，可选为1000-13000ppm；所述含Al化合物的包覆量为100-3000ppm，可选为500-2000ppm；所述含B化合物的包覆量为100-2000ppm，可选为500-1500ppm，其中所述表层掺杂量和包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。
当Co的表层掺杂量与含Co化合物的包覆量之和在所给范围内时，能够进一步改善电池的循环性能。因而能够避免以下情况：当Co的表层掺杂量与含Co化合物的包覆量之和过大时，可能会在高镍三元正极材料的表面残余过多的无活性的Co化合物，影响材料的容量，并会影响二次电池的循环性能。
当含Al化合物的包覆量和含B化合物的包覆量在所给范围内时，能够进一步改善电池的循环性能。
在一些实施方式中，所述内外包覆层的总厚度为0.001-1μm。
在一些实施方式中，所述含Al化合物的包覆量与所述含B化合物的包覆量满足Al与B的重量比为(0.5-2):1，其中所述包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。
当含Al化合物的包覆量与含B化合物的包覆量满足所给关系时，能够进一步改善二次电池的容量和循环性能。因而能够避免以下情况：当在外包覆层中，Al与B的重量比大于2:1时，由于含Al化合物没有活性，可能会影响离子传输动力学活性，进一步影响二次电池的容量和循环性能。
在一些实施方式中，所述W的掺杂量为100-2000ppm，可选为100-1500ppm；所述M1的掺杂量为2000-4000ppm；所述M2的掺杂量为500-2000ppm，其中所述掺杂量均以相应元素相对于改性的高镍三元正极材料计。
当M1、M2和W的掺杂量在所给范围内时，能够进一步改善高 镍三元正极材料的结构稳定性，从而进一步改善二次电池的循环性能和存储性能。
在一些实施方式中，所述Co的表层掺杂量以及所述含Co化合物、含Al化合物和含B化合物的包覆量之和为1000-22000ppm，可选为1000-15000ppm，其中所述表层掺杂量和包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。
在一些实施方式中，所述改性的高镍三元正极材料的体积粒度分布径距满足(Dv 90-Dv 10)/Dv 50≥1.1，可选(Dv 90-Dv 10)/Dv 50≥1.2。
本申请中，改性的高镍三元正极材料的颗粒体积分布粒度Dv 10、Dv 50、Dv 90为本领域的公知概念。具体地，Dv 10为粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计10％的粒径，单位通常为μm。Dv 50为粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计50％的粒径。Dv 90为粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计90％的粒径。上述三元前驱体的颗粒体积分布粒度Dv 10、Dv 50、Dv 90的测试方法可以采用本领域公知的方法进行测试。作为示例，可以参考GB/T 19077-2016/ISO 13320:2009粒度分布激光衍射法，采用设备马尔文2000进行测定。
在一些实施方式中，所述改性的高镍三元正极材料在5吨压力下的粉末压实密度≥3.4g/cc，可选≥3.5g/cc。
当改性的高镍三元正极材料具有较宽的体积粒度分布径距，具有较高的粉末压实密度，能够明显提升高镍三元正极材料的体积能量密度。
本申请还提供一种制备改性的高镍三元正极材料的方法，包括：
步骤S1：将锂盐、掺W的高镍三元前驱体、含M1的化合物、含M2的化合物混合并烧结，得到掺杂M1、M2和W的高镍三元正极材料基体，其中所述掺W的高镍三元前驱体的化学式为(Ni XCo YMn ZW D)(OH) 2，其中0.65≤X＜1，0≤Y＜0.3，0≤Z＜0.3，0<D<0.1，所述M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种，所述掺杂M1、M2和W的高镍三元正极材料基体的化学式为Li 1+a[Ni xCo yMn zM1 bM2 cW d]O 2，其中 0.65≤x<1，0≤y<0.3，0≤z<0.3，0<a<0.2，0<b<0.1，0<c<0.1，0<d<0.1，x+y+z+b+c+d＝1，可选地0.8≤x<1；
步骤S2：将所述掺杂M1、M2、W的高镍三元正极材料基体与含Co化合物混合并烧结，得到表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料；
步骤S3：将所述表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料与含Al化合物、含B化合物混合并烧结，得到改性的高镍三元正极材料。
在一些实施方式中，在所述步骤S1中，烧结温度为700-950℃，烧结时间为10-20h，烧结气氛为空气或者O 2。
在所述步骤S1中采用所述烧结工艺，能够烧结出晶体结构优良的高镍三元正极材料基体，并能均匀有效地进行三元素(即M1、M2、W)协同掺杂。特别是当步骤S1中的烧结温度在合适的温度范围内时，能够进一步改善二次电池的容量、循环性能以及存储性能。
在本申请实施例中，对锂盐、含M1的化合物和含M2的化合物的种类没有特别的限制，可以根据实际需求进行选择。例如，锂盐为氢氧化锂、碳酸锂、硝酸锂；含M1的化合物和含M2的化合物为M1和M2的氧化物或碳酸盐。
在本申请实施例中，掺W的高镍三元前驱体的合成方法包括：
(1)：使用镍盐、钴盐、锰盐和纯水配制镍钴锰混合金属盐溶液，加入含钨化合物，得到掺杂W盐的镍钴锰混合金属盐溶液；
(2)：在反应釜中加纯水作为底液，开启搅拌并保持反应温度，加入碱溶液和氨水溶液调整底液的pH值及氨浓度，将所述掺杂W盐的镍钴锰混合金属盐溶液、碱溶液、氨水溶液加入至反应釜中，维持pH值及氨浓度不变，合成晶种核浆料；
(3)：在反应釜中加入纯水作为底液，加入所述晶种核浆料，开启搅拌并保持反应温度，加入碱溶液和氨水溶液调整底液的pH值及氨浓度，将所述掺杂W盐的镍钴锰混合金属盐溶液、碱溶液、氨水溶液及所述晶种核浆料加入至反应釜中，维持pH值及氨浓度不变，得到掺W的高镍三元前驱体。
在一些实施方式中，在步骤(1)中，所述镍钴锰混合金属盐溶液的浓度为0.5-2.5mol/L。
在本申请实施例中，对镍盐、钴盐、锰盐和含钨化合物的种类没有特别的限制，可以根据实际需求进行选择。例如，镍盐为硝酸镍、醋酸镍和硫酸镍中的一种；钴盐为硝酸钴、醋酸钴和硫酸钴中的一种；锰盐为硝酸锰、醋酸锰和硫酸锰中的一种；含钨化合物为钨酸钠盐。
在一些实施方式中，在步骤(2)和(3)中，加入的纯水占反应釜体积的10-50％。
在一些实施方式中，在步骤(2)和(3)中，碱溶液为氢氧化钠溶液，其浓度为1-10mol/L。
在一些实施方式中，在步骤(2)和(3)中，氨水溶液的浓度为2-14mol/L。
在一些实施方式中，在步骤(2)中，所述pH为11.5-12.5，可选为11.8-12.2；所述氨浓度为0.2-0.6mol/L，可选为0.3-0.5mol/L；所述搅拌线速度为5.0-7.0m/s；所述反应温度为40-75℃。
在一些实施方式中，在步骤(2)中，掺杂W盐的镍钴锰混合金属盐溶液、碱溶液、氨水溶液的流量比为18.75:15:1。
在一些实施方式中，在步骤(3)中，所述pH为11.0-12.0，可选为11.1-11.7；所述氨浓度为0.2-0.6mol/L，可选为0.3-0.5mol/L；所述搅拌线速度为3.0-6.0m/s；所述反应温度为40-75℃。
在一些实施方式中，在步骤(3)中，掺杂W盐的镍钴锰混合金属盐溶液、碱溶液、氨水溶液及晶种核浆料的流量比为18.75:15:1:2.8。
在一些实施方式中，所述晶种核浆料的体积分布平均粒径Dv 50为1-5μm；所述掺W的高镍三元前驱体的体积分布平均粒径Dv 50为5-15μm，可选为5-10μm。
在一些实施方式中，所述掺W的高镍三元前驱体的体积粒度分布径距(Dv 90-Dv 10)/Dv 50≥1.3。
通过该方法合成的掺W的高镍三元前驱体的体相结构中均匀掺杂有W元素，并具有较宽的体积粒度分布径距，使烧结出的高镍三元正极材料具有较宽的粒度分布和较高的粉末压实密度。
在一些实施方式中，在步骤S2中，所述含Co化合物为Co 3O 4、Co(OH) 2、CoO、CoOOH、醋酸钴、草酸钴、CoCO 3中的一种或两种以上。
在一些实施方式中，在步骤S2中，所述含Co化合物颗粒直径为0.001-10μm，可选为0.001-1μm。
当含Co化合物颗粒直径在所给范围内时，能够均匀包覆在高镍三元正极材料的表面，改善材料与电解液之间的界面副反应，从而进一步改善二次电池的循环性能。
在一些实施方式中，在所述步骤S2中，烧结温度为500-800℃，可选为550-750℃，烧结时间为5-15h，可选为5-10h，烧结气氛为空气或者O 2。
通过控制步骤S2的烧结温度，既能够使含Co化合物与三元正极材料表面的杂锂发生反应，又能将含Co化合物牢固地包覆在三元正极材料表面，从而减少表面杂锂并改善界面副反应，进一步改善二次电池的循环性能。
在一些实施方式中，在所述步骤S3中，含Al化合物为Al 2O 3、Al(OH) 3、Al 2(SO 4) 3、AlCl 3、Al(NO) 3中的一种或多种。
在一些实施方式中，在所述步骤S3中，含B化合物为BCl 3、B 2(SO 4) 3、B(NO 3) 3、BN、B 2O 3、BF 3、BBr 3、BI 3、H 2BO 5P、H 3BO 3、C 5H 6B(OH) 2、C 3H 9B 3O 6、(C 2H 5O) 3B及(C 3H 7O) 3B中的一种或多种。
在一些实施方式中，在所述步骤S3中，烧结温度为200-500℃，可选为200-400℃，烧结时间为5-15h，可选为5-10h，烧结气氛为空气或者O 2。
通过控制步骤S3的烧结温度，能够将含Al化合物和含B化合物牢固地包覆在三元正极材料表面，从而改善材料的界面反应，进一步改善二次电池的循环性能。
另外，以下适当参照附图对本申请的二次电池、电池模块、电池包和用电装置进行说明。
本申请的一个实施方式中，提供一种二次电池。
通常情况下，二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
[正极极片]
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，所述正极膜层包括本申请第一方面的改性的高镍三元正极材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，所述正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，所述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料； 将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基体至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，所述电解质采用电解液。所述电解液包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯(EC)、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性 和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图5是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图6，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图7是作为一个示例的电池模块4。参照图7，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多 个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可以根据电池包的应用和容量进行选择。
图8和图9是作为一个示例的电池包1。参照图8和图9，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的一种以上。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图10是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的用电装置可以是手机、平板电脑、笔记本电脑等。该用电装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具 体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1-1
[掺钨的高镍三元前驱体的制备]
(1)：使用硫酸镍、硫酸钴、硫酸锰和纯水按照镍、钴、锰摩尔比为90:5:5配制浓度为2mol/L的镍钴锰混合金属盐溶液，加入钨酸钠盐，加入的量以钨计为1000ppm，得到掺杂钨盐的镍钴锰混合金属盐溶液；
(2)：在100L的反应釜中加入20L的纯水，开启搅拌，搅拌速度为6m/s，保持45℃的恒温，加入5mol/L的NaOH溶液至反应釜中pH为12.0，加入9mol/L的氨水溶液至反应釜中氨浓度为0.4mol/L。将所述掺杂钨盐的镍钴锰混合金属盐溶液、NaOH溶液、氨水溶液加入至反应釜中，其中所述掺杂钨盐的镍钴锰混合金属盐溶液与NaOH溶液的流量比为5:4，NaOH溶液与氨水溶液的流量比为15:1，以保持反应釜中氨浓度及pH不变，连续反应合成出晶种核浆料；
(3)：在另一个100L的反应釜中加入20L的纯水，加入2kg的所述晶种核浆料，开启搅拌，搅拌速度为5m/s，保持50℃的恒温，加入5mol/L的NaOH溶液至反应釜中pH为11.5，加入9mol/L的氨水溶液至反应釜中氨浓度为0.3mol/L。将所述掺杂钨盐的镍钴锰混合金属盐溶液、NaOH溶液和氨水溶液及所述晶种核浆料加入至反应釜中，其中所述掺杂钨盐的镍钴锰混合金属盐溶液与NaOH溶液的流量比为5:4，NaOH溶液与氨水溶液的流量比为15:1，所述晶种核浆料与所述掺杂钨盐的镍钴锰混合金属盐溶液的流量比为0.15，以保持反应釜中氨浓度及pH不变，连续反应合成出浆料掺钨的高镍三元前驱体。然后将浆料在300rpm下离心20min，用去离子水洗涤，过滤，在105℃下干燥10h，得到掺钨的高镍三元前驱体，其分子式为(Ni 0.8995Co 0.05Mn 0.05W 0.0005)(OH) 2，粒度Dv 50为8μm，粒度体积分布径 距(D v90-D v10)/D v50为1.35。
[改性的高镍三元正极材料的制备]
S1：将氢氧化锂、所述掺钨的高镍三元前驱体、TiO 2、Al 2O 3放入犁刀混料机中进行混合，其中Li与镍钴锰三者之和的摩尔比为1.05，TiO 2的量以Ti计为2500ppm，Al 2O 3的量以Al计为1000ppm，将混合物料放入窑炉中进行烧结，烧结温度为750℃，烧结时间为15h，烧结气氛为O 2，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8918Co 0.0495Mn 0.0495Ti 0.005Al 0.0037W 0.0005]O 2；
S2：将所述掺杂Ti、Al和W的高镍三元正极材料基体与CoO放入犁刀混料机中进行混合，其中CoO的量以Co计为13000ppm，将混合物料放入窑炉中进行烧结，烧结温度为600℃，烧结时间为5h，烧结气氛为O 2，得到表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料；
S3：将所述表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料与Al 2O 3、B 2O 3放入犁刀混料机中进行混合，其中Al 2O 3的量以Al计为1000ppm，B 2O 3的量以B计为1000ppm，Al与B的重量比为1:1，将混合物料放入窑炉中进行烧结，烧结温度为250℃，烧结时间为6h，烧结气氛为O 2，得到改性的高镍三元正极材料产品，所述产品的内外包覆层的总厚度为0.54μm。
实施例1-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，所述镍钴锰混合金属盐溶液中镍、钴、锰摩尔比为80:10:10，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.7996Co 0.09995Mn 0.09995W 0.0005)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.7927Co 0.0991Mn 0.0991Ti 0.005Al 0.0036W 0.0005]O 2。
实施例1-3
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，所述镍钴锰混合金属盐溶液 中镍、钴、锰摩尔比为70:15:15，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.6997Co 0.1499Mn 0.1499W 0.0005)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.6936Co 0.1486Mn 0.1486Ti 0.005Al 0.0037W 0.0005]O 2。
对比例1-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在改性的高镍三元正极材料的制备中，在步骤S1中，不加入TiO 2，得到掺杂Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8963Co 0.0498Mn 0.0498Al 0.0036W 0.0005]O 2。
对比例1-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在改性的高镍三元正极材料的制备中，在步骤S1中，不加入Al 2O 3，得到掺杂Ti和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.895Co 0.0497Mn 0.0497Ti 0.0051W 0.0005]O 2。
对比例1-3
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，不加入钨酸钠盐，得到的高镍三元前驱体的分子式为(Ni 0.90Co 0.05Mn 0.05)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，得到掺杂Ti和Al的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8923Co 0.0496Mn 0.0496Ti 0.005Al 0.0035]O 2。
对比例1-4
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，不进行步骤S2，并且最终产品的内外包覆层的总厚度为0.11μm。
对比例1-5
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，不进行步骤S3，并且最终产品的内外包覆层的总厚度为0.40μm。
对比例1-6
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，不加入B 2O 3，并且最终产品的内外包覆层的总厚 度为0.49μm。
对比例1-7
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，不加入Al 2O 3，并且最终产品的内外包覆层的总厚度为0.50μm。
实施例2-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在改性的高镍三元正极材料的制备中，在步骤S1中，将TiO 2更换为ZrO 2，将Al 2O 3更换为SrCO 3，得到掺杂Zr、Sr和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8961Co 0.0498Mn 0.0498Zr 0.0027Sr 0.0011W 0.0005]O 2。
实施例2-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在改性的高镍三元正极材料的制备中，在步骤S1中，将TiO 2更换为Sb 2O 5，将Al 2O 3更换为MgO，得到掺杂Sb、Mg和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8941Co 0.0497Mn 0.0497Sb 0.002Mg 0.004W 0.0005]O 2。
实施例2-3
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在改性的高镍三元正极材料的制备中，在步骤S1中，将Al 2O 3更换为ZnO，得到掺杂Ti、Zn和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8937Co 0.0496Mn 0.0496Ti 0.005Zn 0.0016W 0.0005]O 2。
实施例3-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入的钨酸钠盐的量以钨计为2000ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.8991Co 0.04995Mn 0.04995W 0.001)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为2000ppm，Al 2O 3的量以Al计为2000ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.889Co 0.0494Mn 0.0494Ti 0.004Al 0.0072W 0.001]O 2。
实施例3-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入钨酸钠盐的量以钨计为1500ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.8992Co 0.05Mn 0.05W 0.0008)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为2000ppm，Al 2O 3的量以Al计为1500ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8909Co 0.0495Mn 0.0495Ti 0.004Al 0.0053W 0.0008]O 2。
实施例3-3
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入钨酸钠盐的量以钨计为100ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.8999Co 0.05Mn 0.05W 0.0001)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为2000ppm，Al 2O 3的量以Al计为1900ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8901Co 0.0495Mn 0.0495Ti 0.004Al 0.0068W 0.0001]O 2。
实施例3-4
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入钨酸钠盐的量以钨计为500ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.8997Co 0.05Mn 0.05W 0.0003)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为3000ppm，Al 2O 3的量以Al计为1000ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8911Co 0.0495Mn 0.0495Ti 0.006Al 0.0036W 0.0003]O 2。
实施例3-5
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入钨酸钠盐的量以钨计为1900ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.899Co 0.05Mn 0.05W 0.001)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为4000ppm，Al 2O 3的量以Al 计为500ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8902Co 0.0495Mn 0.0495Ti 0.008Al 0.0018W 0.001]O 2。
实施例3-6
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入钨酸钠盐的量以钨计为100ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.8999Co 0.05Mn 0.05W 0.0001)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为6000ppm，Al 2O 3的量以Al计为500ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8875Co 0.0493Mn 0.0493Ti 0.012Al 0.0018W 0.0001]O 2。
实施例3-7
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入钨酸钠盐的量以钨计为100ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.8999Co 0.05Mn 0.05W 0.0001)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为4000ppm，Al 2O 3的量以Al计为100ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8923Co 0.0496Mn 0.0496Ti 0.008Al 0.0004W 0.0001]O 2。
实施例3-8
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在掺钨的高镍三元前驱体的制备中，加入钨酸钠盐的量以钨计为3000ppm，得到的掺钨的高镍三元前驱体的分子式为(Ni 0.8984Co 0.05Mn 0.05W 0.0016)(OH) 2；在改性的高镍三元正极材料的制备中，在步骤S1中，TiO 2的量以Ti计为2000ppm，Al 2O 3的量以Al计为3000ppm，得到掺杂Ti、Al和W的高镍三元正极材料基体，其分子式为Li 1.05[Ni 0.8854Co 0.0492Mn 0.0492Ti 0.004Al 0.0106W 0.0016]O 2。
实施例4-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，CoO的量以Co计为20000ppm，并且最终产品的内外包覆层的总厚度为1.0μm。
实施例4-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，CoO的量以Co计为5000ppm，并且最终产品的内外包覆层的总厚度为0.32μm。
实施例4-3
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，CoO的量以Co计为1000ppm，并且最终产品的内外包覆层的总厚度为0.18μm。
实施例4-4
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，CoO的量以Co计为100ppm，并且最终产品的内外包覆层的总厚度为0.13μm。
实施例4-5
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，CoO的量以Co计为25000ppm，并且最终产品的内外包覆层的总厚度为1.26μm。
实施例4-6
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，Al 2O 3的量以Al计为3000ppm，B 2O 3的量以B计为2000ppm，Al与B的重量比为1.5:1，并且最终产品的内外包覆层的总厚度为0.60μm。
实施例4-7
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，Al 2O 3的量以Al计为2000ppm，B 2O 3的量以B计为1000ppm，Al与B的重量比为2:1，并且最终产品的内外包覆层的总厚度为0.58μm。
实施例4-8
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，Al 2O 3的量以Al计为500ppm，B 2O 3的量以B计为500ppm，Al与B的重量比为1:1，并且最终产品的内外包覆层的 总厚度为0.51μm。
实施例4-9
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，Al 2O 3的量以Al计为750ppm，B 2O 3的量以B计为1500ppm，Al与B的重量比为0.5:1，并且最终产品的内外包覆层的总厚度为0.55μm。
实施例4-10
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，Al 2O 3的量以Al计为100ppm，B 2O 3的量以B计为100ppm，Al与B的重量比为1:1，并且最终产品的内外包覆层的总厚度为0.46μm。
实施例4-11
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S3中，Al 2O 3的量以Al计为3000ppm，B 2O 3的量以B计为1000ppm，Al与B的重量比为3:1，并且最终产品的内外包覆层的总厚度为0.61μm。
实施例4-12
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，CoO的量以Co计为800ppm，在步骤S3中，Al 2O 3的量以Al计为100ppm，B 2O 3的量以B计为100ppm，Al与B的重量比为1:1，并且最终产品的内外包覆层的总厚度为0.13μm。
实施例5-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S1中，烧结温度为700℃。
实施例5-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S1中，烧结温度为950℃。
对比例5-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S1中，烧结温度为650℃。
对比例5-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S1中，烧结温度为1000℃。
实施例6-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，烧结温度为500℃。
实施例6-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，烧结温度为550℃。
实施例6-3
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，烧结温度为700℃。
实施例6-4
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，烧结温度为800℃。
对比例6-1
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，烧结温度为400℃。
对比例6-2
改性的高镍三元正极材料的制备整体上参照实施例1-1，区别在于，在步骤S2中，烧结温度为900℃。
测试方法
1.掺W的高镍三元前驱体以及掺杂M1、M2和W的高镍三元正极材料基体的测定
采用等离子体发射光谱仪(ICP-OES)，设备型号为美国Thermo Fisher Scientific公司ICAP7400。首先称取1g样品于烧杯中，向样品中加入25ml浓度为25％体积比的HNO 3溶液将样品溶解，并用475ml去离子水进行稀释，然后将稀释液体放入仪器设备进行目标元素分析，经计算得到目标元素含量。
2.Co掺杂厚度
将制样用胶(将PVDF分散到N-甲基吡咯烷酮中，PVDF含量约为8％)与样品粉末混合均匀(粉末重量约为胶的5倍)后涂到铜箔上，60℃烘干30min。用剪刀将制备的样品剪成6mm*6mm大小，固定在样品台上，放入离子抛光仪(型号：IB-19500CP)中，调节样品边缘平行于对中线X轴，Y轴位置40-60μm，进行切割。切割完后，采用英国牛津仪器集团的X-Max型能谱仪(EDS)结合德国ZEISS的Sigma-02-33型扫描电子显微镜(SEM)，在被切制样上选取合适的颗粒切面，沿颗粒直径方向进行Co元素含量线性扫描，测量Co含量相比颗粒内核开始增加的位点距离颗粒中心位置的距离为L1，则Co掺杂厚度为(颗粒半径R-L1)μm。
3.表面杂锂量
酸碱滴定法：将30g样品放入100ml纯水中，搅拌30min后静置5min，抽滤，取10ml上清液，用0.05mol/L的盐酸标准溶液滴定正极材料中溶解下来的碳酸锂及氢氧化锂，以pH电极为指示电极，借助于电位变化产生的突跃来确定终点，计算正极材料表面杂锂量。
4.体积分布粒度
体积分布粒度的测试方法为：参考GB/T 19077-2016/ISO 13320:2009粒度分布激光衍射法，设备采用马尔文2000。取洁净烧杯，加入待测样品适量至遮光度8％-12％，加入20ml去离子水，同时外超声5min，开启粒度测试仪开始测试。
5. 5吨压力下的粉末压实密度
压实密度测试方法包括，在特定模具中通过5吨的压力压实样品得到厚度，通过ρ c＝m/V＝m/(S*H)计算压实密度，其中m为物料重量，S为粉末面积，H为粉末高度。
6.制备扣式电池：
将上述各实施例和对比例中制备的三元正极材料、PVDF、导电碳以重量比90:5:5加入N-甲基吡咯烷酮中，在干燥房中搅拌制成浆料，在铝箔上涂敷上述浆料，干燥、冷压制成正极极片，采用锂片作为负极，电解液为1mol/L的LiPF 6/(EC+DEC+DMC)(体积比为1:1:1)， 在扣电箱中组装成扣式电池。
扣电初始克容量测试方法：
在2.8-4.3V下，按照0.1C充电至4.3V，然后在4.3V下恒压充电至电流≤0.05mA，静置2min，此时的充电容量记为C 0，然后按照0.1C放电至2.8V，此时的放电容量为初始克容量，记为D 0。
7.制备全电池：
将上述各实施例和对比例中制备的三元正极材料作为正极活性物质，与导电剂乙炔黑、粘结剂聚偏二氟乙烯(PVDF)按重量比94:3:3在N-甲基吡咯烷酮溶剂体系中充分搅拌混合均匀后，涂覆于铝箔上烘干、冷压，得到正极极片。将负极活性物质人造石墨、硬碳，导电剂乙炔黑，粘结剂丁苯橡胶(SBR)，增稠剂碳甲基纤维素钠(CMC)按照重量比90:5:2:2:1在去离子水溶剂体系中充分搅拌混合均匀后，涂覆于铜箔上烘干、冷压，得到负极极片。以聚乙烯多孔聚合薄膜作为隔离膜。将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正负极片中间起到隔离的作用，并卷绕得到裸电芯。将裸电芯置于外包装中，注入配好的基础电解液，即1mol/L的LiPF 6/(EC+EMC+DMC)(体积比为1:1:1)，并封装，得到全电池。
全电初始克容量测试方法：
在25℃恒温环境下，静置5min，按照1/3C放电至2.8V，静置5min，按照1/3C充电至4.25V，然后在4.25V下恒压充电至电流≤0.05mA，静置5min，此时的充电容量记为C 0，然后按照1/3C放电至2.8V，此时的放电容量为初始克容量，记为D 0。
全电25/45℃循环性能测试：
在25℃或者45℃的恒温环境下，在2.8-4.25V下，按照1C充电至4.25V，然后在4.25V下恒压充电至电流≤0.05mA，静置5min，然后按照1C放电至2.8V，容量记为D 0，重复前面过程，记录容量D n(n＝0,1,2……)，计算300次循环容量保持率：(D 300-D 0)/D 0*100％。
8.全电70℃胀气测试：
70℃100％SOC(剩余容量)存储，在存储前后及过程中测量电芯OCV(开路电压)，IMP(阻抗)，体积(排水法测试)，存储结 束测试电芯残余容量和可逆容量，每48h出炉，静置1h后测试OCV、IMP，冷却至室温后用排水法测试电芯体积，存储30天结束测试，或者体积膨胀超过50％停止存储，保护电压范围：2.7-4.3V，标称容量2.25Ah。
按照上述过程分别测试上述实施例和对比例，具体数值参见表1-表6。
Figure PCTCN2022096550-appb-000001
Figure PCTCN2022096550-appb-000002
Figure PCTCN2022096550-appb-000003
Figure PCTCN2022096550-appb-000004
Figure PCTCN2022096550-appb-000005
Figure PCTCN2022096550-appb-000006
根据表1可知，所有实施例对应的全电池的25℃和45℃循环容量保持率均显著高于对比例，同时，所有实施例在70℃下存储30天后的胀气均低于所有对比例。此外，在相同的三元正极材料基体的情况下，实施例的0.1C扣电容量和1/3C全电容量也显著优于所有对比例。
综合比较实施例1-1至实施例1-3，当高镍三元正极材料基体中掺杂有M1、M2和W元素，其表层进一步掺杂Co，并且还包覆有含Co化合物内包覆层以及含Al化合物和含B化合物的外包覆层时，所对应的全电池25℃循环容量保持率都高于94.7％，45℃循环容量保持率都高于91.5％，而在70℃下存储30天后的胀气均低于4.91mL/Ah。
综合比较实施例1-1和实施例2-1至实施例2-3，当M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种时，所对应的0.1C扣电容量、1/3C全电容量、25℃和45℃循环容量保持率以及在70℃下存储30天后的胀气性能均良好。
综合比较实施例1-1和实施例3-1至实施例3-8，当所述W的掺杂量为100-2000ppm，所述M1的掺杂量为2000-4000ppm，所述M2的掺杂量为500-2000ppm，且所述M1的掺杂量与所述M2和W的掺杂量之和的比值为1:(0.1-2)时，所对应的0.1C扣电容量均高于222.4mAh/g，1/3C全电容量均高于211.2mAh/g，25℃循环容量保持率都高于94.5％，45℃循环容量保持率都高于91.2％，而在70℃下存储30天后的胀气均低于5.01mL/Ah。进一步地，当所述M1的掺杂量与所述M2和W的掺杂量之和的比值为1:(0.5-1.5)时，所对应的0.1C扣电容量、1/3C全电容量、25℃和45℃循环容量保持率以及在70℃下存储30天后的胀气性能得到进一步改善。
综合比较实施例1-1和实施例4-1至实施例4-12，在所述Co的表层掺杂量与所述含Co化合物的包覆量之和为100-20000ppm，所述含Al化合物的包覆量为100-3000ppm，所述含B化合物时的包覆量为100-2000ppm时，当所述含Al化合物的包覆量与所述含B化合物的包覆量满足Al与B的重量比为(0.5-2):1，且当所述Co的表层掺杂量以及所述含Co化合物、含Al化合物和含B化合物的包覆量 之和为1000-22000ppm时，所对应的0.1C扣电容量、1/3C全电容量、25℃和45℃循环容量保持率以及在70℃下存储30天后的胀气性能均良好。进一步地，当所述Co的表层掺杂量以及所述含Co化合物、含Al化合物和含B化合物的包覆量之和为1000-15000ppm时，所对应的0.1C扣电容量、1/3C全电容量、25℃和45℃循环容量保持率得到进一步改善。
根据表5可知，当步骤S1的烧结温度为700-950℃时，所制备的三元正极材料所对应的0.1C扣电容量、1/3C全电容量、25℃和45℃循环容量保持率以及在70℃下存储30天后的胀气性能良好；而初烧温度过高或者过低，均会明显影响所制备的三元正极材料的容量、循环及存储涨气性能。
根据表6可知，当步骤S2的烧结温度为500-800℃时，所制备的三元正极材料所对应的0.1C扣电容量、1/3C全电容量、25℃和45℃循环容量保持率以及在70℃下存储30天后的胀气性能良好；当步骤S2中温度过高时，Co会基本全部掺杂进入颗粒中，使整个颗粒成分发生很大变化，降低整个材料颗粒中镍的含量，从而明显降低材料容量，同时由于表面包覆的含Co化合物很少，会影响电池的循环及存储性能；当步骤S2中的温度过低时，含Co化合物基本上全部包覆在颗粒的表面，并没有较好地与颗粒表面的杂锂发生反应，导致杂锂较高，同时含Co化合物没有与杂锂反应，使含Co化合物没有活性，使整个材料的容量偏低，并影响电池的循环及存储性能。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (20)

  1. 一种改性的高镍三元正极材料，其特征在于，包含内核和内外两层包覆层，
    所述内核包含高镍三元正极材料基体，所述基体掺杂有M1、M2和W，其中所述M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种，掺杂M1、M2和W的高镍三元正极材料基体的化学式为Li 1+a[Ni xCo yMn zM1 bM2 cW d]O 2，其中0.65≤x<1，0≤y<0.3，0≤z<0.3，0<a<0.2，0<b<0.1，0<c<0.1，0<d<0.1，x+y+z+b+c+d＝1，可选地0.8≤x<1；
    所述内核的表层还掺杂有Co；
    所述内包覆层为含Co化合物，所述外包覆层为含Al化合物和含B化合物。
  2. 根据权利要求1所述的改性的高镍三元正极材料，其特征在于，所述M1的掺杂量≥所述M2或所述W的掺杂量。
  3. 根据权利要求1或2所述的改性的高镍三元正极材料，其特征在于，所述M1的掺杂量与所述M2和W的掺杂量之和的比值为1:(0.1-2)，可选为1:(0.5-1.5)。
  4. 根据权利要求1至3中任一项所述的改性的高镍三元正极材料，其特征在于，所述表层的厚度d为0<d<3μm，可选为0<d<2μm。
  5. 根据权利要求1至4中任一项所述的改性的高镍三元正极材料，其特征在于，所述Co的表层掺杂量与所述含Co化合物的包覆量之和为100-20000ppm，可选为1000-13000ppm；所述含Al化合物的包覆量为100-3000ppm，可选为500-2000ppm；所述含B化合物的包覆量为100-2000ppm，可选为500-1500ppm，其中所述表层掺杂量和包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。
  6. 根据权利要求1至5中任一项所述的改性的高镍三元正极材料，其特征在于，所述内外包覆层的总厚度为0.001-1μm。
  7. 根据权利要求1至6中任一项所述的改性的高镍三元正极材料，其特征在于所述含Al化合物的包覆量与所述含B化合物的包覆 量满足Al与B的重量比为(0.5-2):1，其中所述包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。
  8. 根据权利要求1至7中任一项所述的改性的高镍三元正极材料，其特征在于，所述W的掺杂量为100-2000ppm，可选为100-1500ppm；所述M1的掺杂量为2000-4000ppm；所述M2的掺杂量为500-2000ppm，其中所述掺杂量均以相应元素相对于改性的高镍三元正极材料计。
  9. 根据权利要求1至8中任一项所述的改性的高镍三元正极材料，其特征在于，所述Co的表层掺杂量以及所述含Co化合物、含Al化合物和含B化合物的包覆量之和为1000-22000ppm，可选为1000-15000ppm，其中所述表层掺杂量和包覆量均以化合物中的相应元素相对于改性的高镍三元正极材料计。
  10. 根据权利要求1至9中任一项所述的改性的高镍三元正极材料，其特征在于，其体积粒度分布径距满足(Dv 90-Dv 10)/Dv 50≥1.1，可选(Dv 90-Dv 10)/Dv 50≥1.2。
  11. 根据权利要求1至10中任一项所述的改性的高镍三元正极材料，其特征在于，其在5吨压力下的粉末压实密度≥3.4g/cc，可选≥3.5g/cc。
  12. 一种制备改性的高镍三元正极材料的方法，其特征在于，包括：
    步骤S1：将锂盐、掺W的高镍三元前驱体、含M1的化合物、含M2的化合物混合并烧结，得到掺杂M1、M2和W的高镍三元正极材料基体，其中所述掺W的高镍三元前驱体的化学式为(Ni XCo YMn ZW D)(OH) 2，其中0.65≤X＜1，0≤Y＜0.3，0≤Z＜0.3，0<D<0.1，所述M1为Mo、Zr、Ti、Sb、Nb、Te中的一种，所述M2为Mg、Al、Ca、Zn、Sr中的一种，所述掺杂M1、M2和W的高镍三元正极材料基体的化学式为Li 1+a[Ni xCo yMn zM1 bM2 cW d]O 2，其中0.65≤x<1，0≤y<0.3，0≤z<0.3，0<a<0.2，0<b<0.1，0<c<0.1，0<d<0.1，x+y+z+b+c+d＝1，可选地0.8≤x<1；
    步骤S2：将所述掺杂M1、M2和W的高镍三元正极材料基体与 含Co化合物混合并烧结，得到表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料；
    步骤S3：将所述表层掺杂Co、表面包覆含Co化合物的高镍三元正极材料与含Al化合物、含B化合物混合并烧结，得到改性的高镍三元正极材料。
  13. 根据权利要求12所述的方法，其特征在于，在所述步骤S1中，烧结温度为700-950℃，烧结时间为10-20h，烧结气氛为空气或者O 2。
  14. 根据权利要求12或13所述的方法，其特征在于，所述含Co化合物颗粒直径为0.001-10μm，可选为0.001-1μm。
  15. 根据权利要求12至14中任一项所述的方法，其特征在于，在所述步骤S2中，烧结温度为500-800℃，可选为550-750℃，烧结时间为5-15h，可选为5-10h，烧结气氛为空气或者O 2。
  16. 根据权利要求12至15中任一项所述的方法，其特征在于，在所述步骤S3中，烧结温度为200-500℃，可选为200-400℃，烧结时间为5-15h，可选为5-10h，烧结气氛为空气或者O 2。
  17. 一种二次电池，其包括根据权利要求1至11中任一项所述的改性的高镍三元正极材料或根据权利要求12至16中任一项所述的方法制备的改性的高镍三元正极材料。
  18. 一种电池模块，包括根据权利要求17所述的二次电池。
  19. 一种电池包，包括根据权利要求18所述的电池模块。
  20. 一种用电装置，包括根据权利要求17所述的二次电池、根据权利要求18所述的电池模块、或根据权利要求19所述的电池包中的至少一种。
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