WO2023039717A1 - 高镍正极活性材料、其制备方法、包括其的锂离子电池、电池模块、电池包和用电装置 - Google Patents

高镍正极活性材料、其制备方法、包括其的锂离子电池、电池模块、电池包和用电装置 Download PDF

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WO2023039717A1
WO2023039717A1 PCT/CN2021/118225 CN2021118225W WO2023039717A1 WO 2023039717 A1 WO2023039717 A1 WO 2023039717A1 CN 2021118225 W CN2021118225 W CN 2021118225W WO 2023039717 A1 WO2023039717 A1 WO 2023039717A1
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positive electrode
active material
electrode active
lithium
shell
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English (en)
French (fr)
Inventor
吴奇
陈强
范敬鹏
黄涛
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 KR1020227036249A priority Critical patent/KR102710205B1/ko
Priority to PCT/CN2021/118225 priority patent/WO2023039717A1/zh
Priority to EP21935452.9A priority patent/EP4177987B1/en
Priority to JP2022562376A priority patent/JP7483044B2/ja
Priority to CN202180084479.XA priority patent/CN116636047B/zh
Priority to US17/969,630 priority patent/US20230083478A1/en
Publication of WO2023039717A1 publication Critical patent/WO2023039717A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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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
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of electrochemistry, and in particular to a high-nickel positive electrode active material, a preparation method thereof, a positive electrode sheet containing the same, a lithium ion battery, a battery module, a battery pack and an electric device.
  • lithium-ion 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. Widely used in pure electric vehicles, hybrid electric vehicles and other new energy vehicles.
  • nickel-cobalt-manganese ternary positive electrode active materials are widely used due to their high gram capacity, but in the prior art, the energy density, cycle performance and safety performance of ternary lithium-ion batteries have not been comprehensively improved.
  • the higher the content of nickel atoms in the ternary positive electrode active material the more difficult it is to comprehensively improve the energy density, cycle performance, and safety performance of lithium-ion batteries containing it, which greatly limits the wider range of ternary lithium-ion batteries. application.
  • the present application is made in view of the above problems, and the purpose is to provide a high-nickel ternary positive electrode active material, so that the ternary lithium-ion battery has high energy density, good cycle performance and good safety performance.
  • the first aspect of the present application provides a high-nickel positive electrode active material with a core-shell structure, wherein,
  • the shell includes a first shell covering the core, and a second shell covering the first shell;
  • the first shell layer is a fast ion conductor composed of four elements: lithium, aluminum, silicon and oxygen;
  • the second shell layer includes an oxide of R element, and the R is selected from more than one of Al, B, Ti, P, Co, and La.
  • the shell further includes a transition layer formed between the first shell layer and the second shell layer, the transition layer including the first shell layer component and the second shell layer component
  • One or more kinds of fast ion conductors Li p R q O w are formed, wherein 1 ⁇ p ⁇ 4, 1 ⁇ q ⁇ 5, 1 ⁇ w ⁇ 12, and p, q and w are all integers.
  • the fast ion conductor of the first shell layer is Li ⁇ Al X Si Y O 4 , wherein, 0 ⁇ X ⁇ 2.4, 0 ⁇ Y ⁇ 1.8, 0.8 ⁇ 1.2, the chemical composition of aluminum element
  • the ratio of the stoichiometric coefficient X to the stoichiometric coefficient Y of the silicon element is 0.8-1.2.
  • the fast ion conductor Li p R q O w in the transition layer described in the present application is selected from LiAlO 2 , Li 3 BO 3 , Li 4 Ti 5 O 12 , Li 3 PO 4 , LiCoO 2 or LiLaO more than one of .
  • the nickel content of the high-nickel positive electrode active material in the present application is more than 80%, that is, 0.8 ⁇ x ⁇ 1, based on the total number of atoms of nickel, cobalt and manganese.
  • M in the core of the high-nickel positive electrode active material of the present application, M may be at least one of Sb, Ti, Zr, Sr, Al, and B.
  • R may be one or more of Al, La, B, Co, and Ti.
  • the mass ratio of the lithium element in the core to the lithium element in the shell is 40-1300:1.
  • M when M is selected from one or more of Al, B or Ti, R is different from M, and based on the total mass of the high nickel positive electrode active material, the M element is in the high
  • the mass content of the nickel positive electrode active material is 1000-5000ppm, optionally 3000-5000ppm.
  • R is different from M, and based on the total mass of the high-nickel positive electrode active material, the mass content of the R element is 100 ⁇ 20000ppm.
  • the mass ratio of the Si element to the R element is 0.1 ⁇ 7.0:1, optionally 0.1 ⁇ 4.4:1.
  • the total mass content of silicon and aluminum in the first shell layer is 435-13150 ppm.
  • the volume average particle diameter Dv50 of the high-nickel cathode active material of the present application is 1.5-20 ⁇ m, and the total thickness of the shell layer is 0.001-1 ⁇ m.
  • the second aspect of the present application provides a method for preparing a high-nickel positive electrode active material, which includes the following steps:
  • the high-nickel positive electrode active material has a core-shell structure
  • the shell includes a first shell covering the core, and a second shell covering the first shell;
  • the first shell layer is a fast ion conductor composed of four elements: lithium, aluminum, silicon and oxygen;
  • the second shell layer includes an oxide of the element R, and the R is selected from more than one of Al, B, Ti, P, Co, and La.
  • the preparation method of the present application has wide sources of raw materials, low cost and simple process, and is more conducive to realizing large-scale industrialization.
  • step S1 the preparation process of the high-nickel ternary precursor coated with silicon aluminum hydroxide is:
  • the mass proportion of the high-nickel ternary precursor is 16%-50%.
  • the pH of the alkaline solution is 11-13;
  • a weakly acidic gas is introduced into the solid-liquid mixture at a flow rate of 1-20 mL/min to lower the pH of the solid-liquid mixture to 8-10.
  • the reaction temperature of the hydrolysis-in-situ precipitation reaction is 20-40°C
  • the reaction time is 0.1-2h
  • the linear stirring speed is 1-6m/s.
  • step S2 assuming that the total molar weight of nickel atoms, cobalt atoms, and manganese atoms in the first intermediate is Me2, then:
  • the lithium precursor is added in an amount of 0.9 to 1.1 Me2 according to lithium atoms
  • the M precursor is added in an amount of (8 ⁇ 10 -4 to 180 ⁇ 10 -4 ) Me2 in accordance with M atoms, and the first intermediate mix.
  • step S2 the sintering temperature is 700-950° C., the sintering time is 10-20 h, and the sintering atmosphere is air or oxygen.
  • step S3 assuming that the total molar weight of nickel atoms, cobalt atoms, and manganese atoms in the second intermediate is Me3, then:
  • the R precursor is mixed with the second intermediate according to the addition amount of R atoms (16 ⁇ 10 -4 ⁇ 330 ⁇ 10 -4 ) Me3.
  • step S3 the sintering temperature is 200-700° C., the sintering time is 5-15 hours, and the sintering atmosphere is air or oxygen.
  • the third aspect of the present application provides a positive electrode sheet, including the high-nickel positive electrode active material described in the first aspect of the present application or the high-nickel positive electrode active material prepared by the preparation method of the second aspect of the present application.
  • the fourth aspect of the present application provides a lithium-ion battery, including the high-nickel positive electrode active material described in the first aspect of the present application or the high-nickel positive electrode active material prepared by the preparation method of the second aspect of the present application or the positive electrode of the third aspect of the present application piece.
  • a fifth aspect of the present application provides a battery module, including the lithium-ion battery of the fourth aspect of the present application.
  • the battery module can be prepared using methods known in the prior art for preparing battery modules.
  • the sixth aspect of the present application provides a battery pack, including one or more of the lithium-ion battery of the fourth aspect of the present application or the battery module of the fifth aspect of the present application.
  • the battery pack can be prepared using methods known in the prior art for preparing battery packs.
  • the seventh aspect of the present application provides an electric device, including one or more of the lithium-ion battery of the fourth aspect of the present application, the battery module of the fifth aspect of the present application, or the battery pack of the sixth aspect of the present application.
  • the ion battery or the battery module or the battery pack is used as a power source of the electric device or an energy storage unit of the electric device.
  • the preparation of the electric device can adopt the methods known in the prior art for the preparation of the electric device.
  • the fast ion conductor of the first shell layer especially Li ⁇ Al X SiY O 4
  • the fast ion conductor Li p R q O w of the transition layer and the second shell layer are respectively coated with the high-nickel ternary positive electrode active material.
  • the oxide of the R element in the layer obtains the high-nickel ternary positive electrode active material of the present application.
  • the high-nickel ternary positive electrode active material of the present application has a significantly reduced amount of surface lithium, and creatively transforms the surface lithium into a fast ion conductor Li ⁇ Al X Si Y O 4 , Li
  • the effective components in p R q O w can significantly improve the electrolyte decomposition and gas generation caused by surface lithium impurities, so that the high-nickel ternary lithium-ion battery has good cycle performance and safety while having high energy density performance.
  • the battery module, battery pack and electrical device of the present application include the lithium ion battery provided by the present application, and thus have at least the same advantages as the lithium ion battery.
  • FIG. 1 is a schematic structural view of a nickel-rich cathode active material according to an embodiment of the present application.
  • Fig. 2 is a volume average particle size distribution diagram of an embodiment of the present application.
  • FIG. 3 is a schematic diagram of a lithium ion battery according to an embodiment of the present application.
  • FIG. 4 is an exploded view of the lithium ion battery according to one embodiment of the present application shown in FIG. 3 .
  • FIG. 5 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 6 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 7 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 6 .
  • FIG. 8 is a schematic diagram of an electrical device 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 specified range. Ranges defined in this manner may be inclusive or exclusive and may be combined in any combination, 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 also 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.
  • the method can also include step (c), which means that step (c) can be added to the method in any order, for example, the method can include steps (a), (b) and (c), and can also include Steps (a), (c) and (b) may also include steps (c), (a) and (b) and the like.
  • 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).
  • shell layer refers to the part coated on the "core” of the high-nickel positive electrode active material, and the part can but not necessarily completely cover the “core”, using “shell” or “Shell” or “first shell” or “transition layer” or “second shell” is for convenience of description only and is not intended to limit the application.
  • the second shell layer covers the first shell layer means that the second shell layer completely or partially covers the first shell layer.
  • high nickel content means that the number of nickel atoms in the corresponding positive electrode active material accounts for more than 60% of the total number of atoms of nickel, cobalt, and manganese.
  • nickel content used herein refers to the percentage of nickel atoms in the positive electrode active material to the total number of nickel, cobalt, and manganese atoms.
  • high-nickel ternary precursor used in this application refers to a nickel-cobalt-manganese ternary material in the form of hydroxide, wherein the atomic number of nickel accounts for more than 60% based on the total atomic number of nickel-cobalt-manganese.
  • fast ionic conductor is also called a superionic conductor, sometimes also called a solid electrolyte.
  • the most basic feature that distinguishes it from general ionic conductors is that it has an ionic conductivity (0.01 ⁇ cm) comparable to that of liquid electrolytes and a low ionic conductance activation energy ( ⁇ 0.40eV) within a certain temperature range.
  • fast ion conductors that may exist in the first shell layer and the second shell layer of the present invention include LiAl 0.971 Si 1.022 O 4 , Li 3 BO 3 and the like.
  • precursor of a certain element used herein can refer to the raw material, or it can refer to the raw material containing the element obtained by performing certain treatments on the initial material before obtaining the target product, and can be prepared under the conditions of the preparation method of this application The compound that undergoes further reaction to obtain the target product.
  • a "precursor” may be an oxide, a hydroxide, or a water-soluble salt of the corresponding element.
  • M represents the element aluminum
  • its precursor can be metaaluminate or aluminum hydroxide
  • the precursor of lithium element can be lithium hydroxide
  • the precursor of high nickel ternary refers to a composite hydroxide formed of five elements: nickel, cobalt, manganese, oxygen, and hydrogen.
  • the inventors of the present application found in practical work that: for nickel-cobalt-manganese ternary positive electrode active materials, increasing the lithium content in its layered structure can significantly increase the charging and discharging gram capacity of the material, and significantly increase the energy density of lithium-ion batteries.
  • increasing the lithium content in its layered structure can significantly increase the charging and discharging gram capacity of the material, and significantly increase the energy density of lithium-ion batteries.
  • the number of nickel atoms in the nickel-cobalt-manganese ternary positive electrode active material is increased to more than 60% (calculated by the total number of atoms of nickel, cobalt, and manganese)
  • the cycle performance of the corresponding lithium-ion battery is severely reduced, and the gas production inside the battery is sharp. Increase and other series of phenomena that seriously threaten the electrochemical performance and safety performance of batteries.
  • the amount of lithium impurities (such as lithium oxide, lithium carbonate) on the surface is more, so that the side reaction at the phase interface in contact with the electrolyte is serious, so that the internal gas production of the battery is seriously increased. , leading to a significant decline in battery cycle performance and safety performance.
  • the high-nickel ternary positive electrode active material can increase the energy density of the battery by increasing the nickel content, it will also greatly reduce the cycle performance and safety performance of the battery.
  • the inventors of the present application proceeded from comprehensively improving the comprehensive performance of the ternary lithium-ion battery, and developed a battery that can comprehensively improve the energy density and cycle performance of the lithium-ion battery by modifying the high-nickel ternary positive electrode active material.
  • High-nickel ternary positive electrode active material with high safety performance.
  • the application provides a high-nickel positive electrode active material, which is a core-shell structure, wherein,
  • the shell includes a first shell covering the core, and a second shell covering the first shell;
  • the first shell layer is a fast ion conductor composed of four elements: lithium, aluminum, silicon and oxygen;
  • the second shell layer includes an oxide of the element R, and the R is selected from more than one of Al, B, Ti, P, Co, and La.
  • the ratio of z to y is 2:1 to 1:2, optionally 3:2 to 2:3.
  • the ratio of y to z and y+z to x is 1:10 to 1:7, optionally 1:9 to 1: 8.
  • the fast ion conductor in the first shell layer is Li ⁇ Al X Si YO 4 , where 0 ⁇ X ⁇ 2.4, 0 ⁇ Y ⁇ 1.8, 0.8 ⁇ 1.2 , the ratio of the stoichiometric coefficient X of the aluminum element to the stoichiometric coefficient Y of the silicon element is 0.8-1.2.
  • the nickel-rich cathode active material of the present application has a core-shell structure in which a core is covered by a two-layer shell, wherein the core includes Li 1+a [ Nix Co y Mnz M b ]O 2 .
  • the coating of the continuous two-layer shell can prevent the core material from intercalating/extracting the main body of lithium ions, that is, Li 1+a [ Nix Co y Mnz M b ]O 2 , the crystallization that occurs after several charge-discharge cycles
  • the collapse of the structure can also isolate the direct contact between the nuclear material and the electrolyte, thereby reducing the corrosion of the corrosive substances in the electrolyte on the surface of the positive electrode active material, reducing the side reaction of the electrolyte on the surface of the positive electrode, and preventing gas production inside the battery.
  • the coating of the continuous double shell layer can also prevent the dissolution of transition metal elements in the core material during battery cycling and storage, and prevent the dissolution of transition metal elements from depositing on the surface of the negative electrode.
  • the coating of the continuous two-shell layer can significantly improve the amount of impurity lithium on the surface of the high-nickel cathode active material, and significantly increase the relative proportion of active lithium in the high-nickel cathode active material.
  • the coating of the continuous two-layer shell can comprehensively improve the energy density, cycle performance and safety performance of the high-nickel ternary lithium-ion battery through the effects of the above four aspects.
  • the core of the high-nickel positive electrode active material described in the present application includes Li 1+a [ Nix Co y Mnz M b ]O 2 .
  • M element When M element is doped into the nuclear material, it can form Li 1+a [ Nix Co y Mnz M b ]O 2 with other elements in the nuclear material, which improves the structural stability of the nuclear material and prevents the The structure of the core material collapses, thereby improving the cycle performance of the battery.
  • the high-nickel positive electrode active material of the present application is especially suitable for high-nickel ternary lithium-ion batteries, especially suitable for nickel content above 60%, especially suitable for nickel content above 80%.
  • the nickel content can be 60%, 80%, 90%.
  • the first shell layer is a fast ion conductor layer composed of lithium, aluminum, silicon, and oxygen
  • the fast ion conductor is Li ⁇ Al X Si Y O 4 .
  • the existence of the fast ion conductor Li ⁇ Al X Si YO 4 on the one hand, it can creatively transform the heterolithium composition on the surface of the core material into the structural lithium in Li ⁇ Al X Si YO 4 , which can effectively reduce the high-nickel ternary cathode Li ⁇ Al X Si YO 4 can significantly increase the deintercalation rate of lithium ions, thereby improving the interfacial side reactions between the material and the electrolyte, and improving the cycle performance of the battery. Improve the charge and discharge capacity and cycle performance of the battery.
  • the fast ion conductor Li ⁇ Al X Si YO 4 the molar ratio of Al atoms to Si atoms, that is, the ratio of X to Y is 0.8-1.2.
  • the ratio of X to Y it is beneficial to form a good fast ion conductor on the surface of the positive electrode material, which in turn helps to reduce the content of lithium impurities on the surface, reduce the interface side reaction of the material, and increase the lithium ion transmission rate at the same time, thereby Improve the cycle performance and safety performance of the battery.
  • the surface layer of the positive electrode material may form Al or Si with low activity, which will affect the transmission of lithium ions instead.
  • the ⁇ in the Li ⁇ Al X Si YO 4 is in the range of 0.8-1.2, may be 1, or any natural number in the range of 0.8-1.2.
  • the value of ⁇ is lower than the above range, the relative content of lithium ions in the fast ion conductor in the first shell is relatively small, and the formed fast ion conductor may have poor lithium ion transmission rate, which affects battery performance.
  • the ⁇ value is higher than the above range, too much lithium ions may lead to an increase in the amount of lithium impurities on the surface of the positive electrode material, resulting in increased interface side reactions with the electrolyte and affecting the safety performance of the battery.
  • the second shell layer includes an oxide of the element R, and the R is more than one of Al, B, Ti, P, Co, and La.
  • the setting of the second shell layer can prevent the composition loss and structural damage of the fast ion conductor Li ⁇ Al X Si YO 4 due to the immersion in the electrolyte, and can isolate the contact between the core material and the electrolyte, which is beneficial to the improvement of the high-nickel positive electrode active material.
  • the stability of the battery plays an important role, which is conducive to improving the energy density, cycle performance and safety performance of the battery.
  • the term "the oxide of the element R" herein should be particularly understood as, in addition to the oxide of the element R, when R is the element Co, it also includes the hydroxide Co(OH) 2 of the element Co.
  • the shell further includes a transition layer formed between the first shell layer and the second shell layer, the transition layer including the first shell component and the second shell component
  • One or more kinds of fast ion conductors Li p R q O w are formed, wherein 1 ⁇ p ⁇ 4, 1 ⁇ q ⁇ 5, 1 ⁇ w ⁇ 12, and p, q and w are all integers.
  • the transition layer is a transition region formed by the first shell layer and the second shell layer, and the Li p R q O w component included in the transition layer can further increase the lithium ion Deintercalation rates in high nickel cathode active materials. Therefore, in the high-nickel positive electrode active material of the present application, the gram capacity of the high-nickel positive electrode active material is greatly improved through the synergistic effect of the two fast ion conductor layers (ie, the first shell layer and the second shell layer).
  • the transition region similar to the transition layer between the first shell layer and the second shell layer may also be included between the core and the shell layer, which It may be a continuous layered structure or a discontinuous layered structure, and may have a uniform or non-uniform thickness.
  • the transition layer formed between the first shell and the second shell is a continuous layered structure, and there is a Li p R q O w composition between the first shell and the second shell This makes the connection between the two shells tighter, thereby preventing the second shell from falling off during battery use, and is also more conducive to fully improving the gram capacity of the high-nickel positive electrode active material.
  • the fast ion conductor Li p R q O w in the transition layer is selected from LiAlO 2 , Li 3 BO 3 , Li 4 Ti 5 O 12 , Li 3 PO 4 , LiCoO 2 or More than one kind of LiLaO.
  • the x is 0.8 ⁇ x ⁇ 1
  • the M is one or more of Sb, Ti, Zr, Sr, Al, B, and the R is Al, La, B , Co, Ti or more.
  • the mass ratio of the lithium element in the core layer to the lithium element in the shell layer is 40-1300:1.
  • the ratio of the mass of the lithium element in the core to the mass of the lithium element in the shell is within the above range: on the one hand, it can ensure that there is enough active lithium in the core to contribute to the high-nickel positive electrode activity The gram capacity of the material, thereby improving the energy density and cycle performance of the battery; on the other hand, it can ensure that the first shell layer, the transition layer, and the second shell layer have an appropriate amount of lithium element as an effective component to form a fast ion conductor Li ⁇ Al X Si Y O 4 , Li p R q O w ;
  • the appropriate mass ratio of the lithium element in the core to the lithium element in the shell can also effectively prevent the lithium-ion species on the surface of the high-nickel positive electrode active material generation, thereby reducing the side reactions that occur inside the battery.
  • the appropriate mass ratio of the lithium element in the core to the lithium element in the shell is conducive to improving the energy density
  • M is selected from one or more of Al, B or Ti
  • R is different from M, and based on the total mass of the high-nickel positive electrode active material, the M element is in the The mass content in the high-nickel positive electrode active material is 1000-5000ppm, optionally 3000-5000ppm.
  • the doping of M element in the core material Li 1+a [ Nix Co y Mnz M b ]O 2 can significantly improve the core material Li 1+a [Ni x
  • the structural collapse and destruction of Co y Mn z M b ]O 2 due to the repeated deintercalation of lithium ions can build a more stable channel for lithium ion transport, which is conducive to improving the gram capacity of high-nickel cathode active materials, thereby improving the performance of lithium-ion batteries. energy density and cycle performance.
  • R is different from M, and based on the total mass of the high-nickel positive electrode active material, the R The element mass content is 100-20000ppm.
  • Limit the mass content of the R element within a reasonable range on the one hand, it can form R oxides with a more stable physical and chemical structure, thereby effectively preventing the electrolyte from corroding the core material and the first shell layer, and reducing side reactions inside the battery; On the other hand, the existence of the second shell layer including the oxide of the R element can also effectively avoid the cracking and fragmentation of the high-nickel positive electrode active material, thereby preventing the internal thermal runaway of the battery caused by the small particles generated after the fragmentation of the nuclear material. In summary, through the above functions, limiting the mass content of the R element within a reasonable range can improve the energy density, cycle performance and safety performance of the battery.
  • the mass content of the R element is 500-15000 ppm, the improvement of the charge-discharge capacity, cycle capacity retention rate and gas production of the lithium-ion battery is more significant.
  • the mass ratio of the Si element to the R element is 0.1 ⁇ 7.0:1, optionally 0.1 ⁇ 4.4:1.
  • an appropriate mass ratio of the Si element to the R element means that the mass ratio of the first shell layer to the second shell layer is within an appropriate range. If the R element is too small and the Si element is too much, that is, the second shell coating is incomplete and the first shell coating is too thick, it may not be able to reduce the side reaction between the electrolyte and the surface of the high-nickel material, and it may also be Because the first shell layer (Si element does not contribute to the capacity) is too thick, the gram capacity of the material itself is reduced, resulting in low battery discharge capacity.
  • the R element is too small and the Si element is too much, that is, the first shell coating is incomplete and the second shell coating is too thick, it may make it impossible for the high-nickel positive electrode active material to build a complete network structure for rapidly conducting lithium ions. Thereby reducing the deintercalation rate of lithium ions, reducing the gram capacity of the high-nickel positive electrode active material, reducing the battery discharge capacity, and affecting the battery cycle performance. At the same time, it may also reduce the gram capacity of the material itself because the second shell layer (R element does not contribute to the capacity) is too thick. capacity, resulting in low battery discharge capacity.
  • the total mass content of silicon and aluminum in the first shell layer is 435-13150 ppm.
  • the total mass content of silicon element and aluminum element in the first shell layer corresponds to the amount of Li ⁇ Al X Si YO 4 in the first shell layer.
  • Coating a layer of fast ion conductor Li ⁇ Al X Si Y O 4 on the surface of the high-nickel active material can effectively improve the transmission rate of lithium ions, reduce the side reaction between the interface and the electrolyte, and improve the capacity and long-term performance;
  • the amount of coating should not be too little or too much, too little may not be effective, too much may reduce the gram capacity of the material, and may also increase the resistance of lithium ion transmission.
  • the volume average particle diameter Dv50 of the high-nickel positive electrode active material is 1.5-20 ⁇ m, and the thickness of the shell layer is 0.001-1 ⁇ m.
  • the volume average particle diameter Dv50 of the particles is too large, which will lead to an increase in lithium ion deintercalation resistance and increase the internal resistance of the battery; meanwhile, the volume average particle diameter Dv50 should not be too small. Because the particle size is too small, on the one hand, it will increase the complexity of the process and increase the production cost. On the other hand, it will also increase the contact area with the electrolyte. Once the function of the shell layer is lost, it may cause rapid deterioration of battery performance. Similarly, when the thickness of the shell layer is too large, the internal resistance of the battery will be increased and the gram capacity of the material will be reduced, but when the thickness of the shell layer is too small, it may be difficult to effectively perform the beneficial functions of the shell layer.
  • the high-nickel positive electrode active material of the present application can be a polycrystalline ternary material or a single crystal ternary material; the polycrystalline ternary material has a polycrystalline structure, and the single crystal ternary material has a single crystal structure or monocrystalline crystal structure.
  • the high-nickel positive electrode active material is a polycrystalline structure, the gram capacity contributed by the high-nickel positive electrode active material is higher; when the high-nickel ternary positive electrode active material is a single crystal structure or a single crystal structure, the corresponding lithium ion The cycle performance of the battery is better.
  • the high-nickel positive electrode active material with a single-crystal structure or a single-crystal-like structure described in this application can be controlled by controlling the particle size of the high-nickel ternary precursor between 1 and 5 ⁇ m, and by increasing the calcination of key preparation steps. The temperature is synthesized.
  • a good single crystal or similar A high-nickel cathode active material with a single crystal structure For example, in the method described in this application, a good single crystal or similar A high-nickel cathode active material with a single crystal structure.
  • high-nickel ternary positive electrode active material with polycrystalline structure or the high-nickel ternary positive electrode active material with single crystal or single crystal structure according to different application scenarios of lithium-ion batteries.
  • the application provides a method for preparing a high-nickel positive electrode active material, comprising the following steps:
  • the high-nickel positive electrode active material has a core-shell structure
  • the core includes Li 1+a [ Nix Co y Mnz M b ]O 2 , where 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.3,
  • M is Mg, Ca, Sb, Ce, Ti, Zr, Sr, Al, Zn, Mo and More than one of B;
  • the shell includes a first shell covering the core, and a second shell covering the first shell;
  • the first shell layer is a fast ion conductor composed of four elements: lithium, aluminum, silicon and oxygen;
  • the second shell layer includes an oxide of element R, and the R is selected from more than one of Al, B, Ti, P, Co, and La.
  • the preparation method of the present application has wide sources of raw materials, low cost and simple process, and is more conducive to realizing large-scale industrialization.
  • step S1 the preparation process of the high-nickel ternary precursor coated with silicon aluminum hydroxide is:
  • the above aluminum precursor can be one or more of sodium metaaluminate (NaAlO 2 ), potassium metaaluminate (KAlO 2 ), lithium metaaluminate (LiAlO 2 ), and the silicon precursor It may be one or more of sodium silicate (Na 2 O ⁇ nSiO 2 ), potassium silicate (K 2 O ⁇ nSiO 2 ), lithium silicate (Li 2 O ⁇ nSiO 2 ).
  • step (a) the solid-liquid mixture maintains a relatively high pH, which can ensure that the aluminum precursor and the silicon precursor are fully dissolved without causing excessive hydrolysis of the aluminum precursor and the silicon precursor.
  • the addition of the high-nickel ternary precursor provides a precipitation surface for the subsequent hydrolysis-in-situ precipitation reaction of the aluminum precursor and the silicon precursor.
  • step (b) lowering the pH of the solid-liquid mixture can trigger the hydrolysis-in-situ precipitation reaction of the aluminum precursor and the silicon precursor, so that the silicon-aluminum hydroxide produced by hydrolysis co-precipitates into the high-nickel trihydroxide. meta-precursor surface to obtain the first intermediate.
  • the mass proportion of the high-nickel ternary precursor is 16%-50%.
  • the pH of the alkaline solution is 11-13, which is used to prevent the hydrolysis of the aluminum precursor and the silicon precursor;
  • a weak acid gas is introduced into the solid-liquid mixture at a flow rate of 1-20 mL/min to lower the pH of the solid-liquid mixture to 8-10.
  • the weakly acidic gas is one or more of CO 2 and SO 2 .
  • the reaction temperature of the hydrolysis-in-situ precipitation reaction is 20-40°C
  • the reaction time is 0.1-2h
  • the linear stirring speed is 1-6m/s.
  • step S2 assuming that the total molar weight of nickel atoms, cobalt atoms, and manganese atoms in the first intermediate is Me2, then:
  • the lithium precursor is mixed with the first intermediate according to the addition amount of lithium atoms of 0.9 to 1.1 Me2, and the M precursor is mixed with the first intermediate according to the addition amount of M atoms of (8 ⁇ 10 -4 180 ⁇ 10 -4 ) Me2 .
  • step S2 the sintering temperature is 700-950° C., the sintering time is 10-20 hours, and the sintering atmosphere is air or oxygen.
  • step S3 assuming that the total molar weight of nickel atoms, cobalt atoms, and manganese atoms in the second intermediate is Me3, then:
  • the R precursor is mixed with the second intermediate according to the addition amount of R atoms (16 ⁇ 10 -4 ⁇ 330 ⁇ 10 -4 ) Me3.
  • the R precursor can be one or more of Al-containing oxides, hydroxides or inorganic acid salts, and the R precursor can be B-containing oxides, hydroxides Or one or more of inorganic acid salts, the R precursor can be one or more of Ti-containing oxides, hydroxides or inorganic acid salts, and the R precursor can be P-containing One or more of oxides, hydroxides or inorganic acid salts, the R precursor can be one or more of Co-containing oxides, hydroxides or inorganic acid salts, the R precursor The body can be one or more of La-containing oxides, hydroxides or inorganic acid salts.
  • the sintering temperature in step S3 is 200-700° C.
  • the sintering time is 5-15 hours
  • the sintering atmosphere is air or oxygen. It is worth noting here that the sintering temperature in step S3 is at least 500 °C lower than the sintering temperature in step S2, so that the M element in step S2 enters the core structure, and the R element in step S3 basically does not enter the core structure .
  • the present application provides a positive pole piece, and the positive pole piece includes the nickel-rich positive pole active material of the present application.
  • the positive electrode sheet includes a positive electrode collector and a positive electrode material arranged on at least one surface of the positive electrode collector.
  • the positive electrode current collector has two opposing surfaces in its own thickness direction, and the positive electrode material is disposed on any one or both of the two opposing surfaces of the positive electrode current collector.
  • the positive electrode current collector may 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 Ethylene glycol ester (PET), polybutylene terephthalate (PBT), 1,3-propane sultone (1,3-propanesultone), polyethylene (PE) and other substrates) Formed, but the application is not limited to these materials.
  • PP polypropylene
  • PET polyethylene terephthalic acid Ethylene glycol ester
  • PBT polybutylene terephthalate
  • 1,3-propane sultone 1,3-propane sultone
  • PE polyethylene
  • the positive electrode material also optionally includes a conductive agent.
  • a conductive agent there is no specific limitation on the type of conductive agent, which can be selected by those skilled in the art according to actual needs.
  • the conductive agent used for the positive electrode material may be selected from one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared according to methods known in the art.
  • the positive electrode active material, conductive agent and binder of the present application can be dispersed in a solvent (such as N-methylpyrrolidone (NMP)) to form a uniform positive electrode slurry; the positive electrode slurry is coated on the positive electrode assembly On the fluid, after drying, cold pressing and other processes, the positive electrode sheet is obtained.
  • NMP 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 may be 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 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 Ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) and other substrates), but the present application is not limited to these Material.
  • PP polypropylene
  • PET polyethylene terephthalic acid Ethylene glycol ester
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode film layer usually includes negative electrode active materials and optional binders, optional conductive agents and other optional additives, and is usually formed by coating and drying negative electrode slurry .
  • the negative electrode slurry is usually formed by dispersing the negative electrode active material and optional conductive agent and binder in a solvent and stirring evenly.
  • the solvent can be N-methylpyrrolidone (NMP) or deionized water.
  • the conductive agent may be selected from one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the negative electrode film layer may also optionally include other commonly used negative electrode active materials.
  • other commonly used negative electrode active materials artificial graphite, natural graphite, soft Carbon, hard carbon, silicon-based materials, tin-based materials and lithium titanate, etc.
  • the silicon-based material can be selected from one or more of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material can be selected from more than one of simple tin, tin oxide compounds and tin alloys.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no particular limitation on the type of electrolyte, which can be selected according to requirements.
  • the electrolyte may be selected from at least one of a solid electrolyte and a liquid electrolyte (ie, electrolyte solution).
  • 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 (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), difluorosulfonyl Lithium amide (LiFSI), lithium bistrifluoromethanesulfonyl imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluorooxalate borate (LiDFOB), lithium difluorooxalate borate (LiBOB), lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorooxalate phosphate (LiDFOP), and lithium tetrafluorooxalate phosphate (LiTFOP).
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium perchlorate
  • the solvent may be selected from ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Dipropyl Carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Butylene Carbonate (BC), Fluoroethylene Carbonate (FEC), Methyl Formate (MF), Methyl Acetate Ester (MA), Ethyl Acetate (EA), Propyl Acetate (PA), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Methyl Butyrate (MB) , ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS) and diethyl s
  • additives may optionally be included in the electrolyte.
  • additives can include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performances of batteries, such as additives that improve battery overcharge performance, additives that improve battery high-temperature performance, and battery low-temperature performance. additives, etc.
  • the separator is arranged between the positive pole piece and the negative pole piece to play the role of isolation.
  • the present application has no particular limitation on the type of the 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 more than 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, and the positive pole piece includes the high-nickel positive electrode active material of the present application.
  • a lithium ion battery can include an outer packaging.
  • the outer package can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the lithium-ion battery can be a hard case, such as a hard plastic case, aluminum case, steel case, and the like.
  • the outer packaging of the lithium-ion battery can also be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of plastic include polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
  • FIG. 3 shows a lithium-ion battery 5 with 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 lithium-ion battery 5 can be one or more, and those skilled in the art can select according to specific needs.
  • lithium-ion batteries can be assembled into a battery module, and the number of lithium-ion 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. 5 is a battery module 4 as an example.
  • a plurality of lithium-ion batteries 5 can be arranged sequentially along the length direction of the battery module 4 .
  • the plurality of lithium ion batteries 5 can be fixed by fasteners.
  • the battery module 4 may also include a housing with an accommodating space, and a plurality of lithium-ion batteries 5 are accommodated in the accommodating space.
  • the above battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack 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 lithium-ion battery, battery module, or battery pack provided in the present application.
  • the lithium-ion battery, battery module, or battery pack can be used as a power source for the device, or as an energy storage unit for the device.
  • the device can be, but not limited to, a mobile device (such as a mobile phone, a notebook computer, etc.), an electric vehicle (such as a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • a lithium-ion battery, a battery module or a battery pack can be selected according to its use requirements.
  • Figure 8 is an example device.
  • the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • battery packs or battery modules can be employed.
  • a device may be a cell phone, tablet, laptop, or the like.
  • the device is usually required to be light and thin, and a lithium-ion battery can be used as a power source.
  • the above-mentioned high-nickel positive electrode active material, binder polyvinylidene fluoride (PVDF), conductive agent acetylene black are mixed uniformly with solvent N-methylpyrrolidone (NMP) according to the mass ratio of 94:3:3, to obtain positive electrode slurry;
  • NMP solvent N-methylpyrrolidone
  • the slurry is coated on an aluminum foil, dried, cold pressed, and cut to obtain a positive electrode sheet.
  • Negative electrode active material artificial graphite, hard carbon, conductive agent acetylene black, binder styrene-butadiene rubber (SBR), thickener carboxymethyl cellulose sodium (CMC-Na) according to mass ratio 90:5:2:2: 1 was uniformly mixed with deionized water to obtain a mixture, and the mixture was coated on a copper foil, dried, and cold-pressed to obtain the negative electrode sheet of Example 1.
  • EC:DEC:DMC was mixed according to a volume ratio of 1:1:1, and LiPF 6 was added to form an electrolyte solution, and the concentration of LiPF 6 in the electrolyte solution was 1 mol/L.
  • the positive pole piece, separator, and negative pole piece in sequence, so that the separator is between the positive and negative pole pieces to play the role of isolation, and then wind it into a square bare cell, put it into an aluminum-plastic film, inject Corresponding non-aqueous electrolyte, sealing, after standing still, hot and cold pressing, chemical formation, fixture, volume separation and other processes, the lithium-ion battery is obtained.
  • Acid-base titration method put 30 g of the high-nickel positive electrode active material of the embodiment into 100 ml of deionized water and stir for 30 min, let stand for 5 min, and then suction filter. Take 10 mL of supernatant, and titrate the above supernatant with 0.05 mol/L hydrochloric acid standard solution.
  • the pH electrode is used as the indicator electrode, and the end point is determined by means of the jump generated by the potential change, and the amount of impurity lithium on the surface of the positive electrode material Q (unit ppm) is calculated.
  • a plasma optical emission spectrometer (ICP-OES) was used, and the device model was ICAP7400 from Thermo Fisher Scientific, USA. First weigh 1g sample in a beaker, add 25ml HNO3 solution with a mass fraction of 25% to the sample to dissolve the sample, and dilute it with 475ml deionized water, then put the diluted liquid into the instrument and equipment for target element analysis, after calculation Get the target element content.
  • ICP-OES plasma optical emission spectrometer
  • the Dv50 value is the volume average particle diameter of the particle.
  • sample preparation glue a jelly formed by dispersing PVDF into NMP, the mass content of PVDF is 8%
  • sample powder the weight of the powder is about 5 times that of the glue
  • the prepared sample was cut into a size of 6 mm ⁇ 6 mm with scissors, fixed on the sample stage, and put into an ion polisher (model: IB-19500CP) for cutting. Put the cut sample into the American FEI Tecnai G2 transmission electron microscope equipment for shell thickness test, and then the particle shell thickness can be tested.
  • the lithium-ion battery of the embodiment was placed in an oven at 25° C. for 5 minutes, and then a charge and discharge test was performed.
  • a charge and discharge process is as follows: 1/3C constant current discharge to 2.8V, stand still for 5 minutes, continue to charge with 1/3C constant current to 4.25V, then charge at 4.25V constant voltage to current ⁇ 0.05mA, stand still for 5 minutes , and then discharged to 2.8V at a constant current of 1/3C, the discharge capacity at this time is the initial discharge capacity described in this application.
  • the battery performance measurement method of the comparative example is the same as that of the example.
  • Example 1 and Examples 34-35 in Table 8 shows that when the volume average particle size Dv50 of the high-nickel positive electrode active material is 1.5-20 ⁇ m and the shell thickness is 0.001-1 ⁇ m, the amount of lithium impurities on the surface of the positive electrode and lithium ions The amount of flatulence inside the battery is improved, and the lithium-ion battery has good discharge capacity, safety performance, and cycle performance.
  • 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 exhibit 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

本申请提供一种高镍三元正极活性材料，其包括核Li1+a[NixCoyMnzMb]O2，以及第一壳层的快离子导体LiαAlXSiYO4、第二壳层的R元素的氧化物和形成于第一壳层和第二壳层之间的过渡层LipRqOw。本申请的高镍三元正极活性材料具有显著减少的表面杂锂量，并创造性地将表面杂锂转变成加速核材中锂离子嵌入/脱出的快离子导体LiαAlXSiYO4、LipRqOw中的有效组分，显著改善因表面杂锂导致的电解液分解产气，使高镍三元锂离子电池在具有高能量密度的同时，还兼具良好的循环性能和安全性能。

Description

高镍正极活性材料、其制备方法、包括其的锂离子电池、电池模块、电池包和用电装置 技术领域
本申请涉及电化学领域，尤其涉及一种高镍正极活性材料、其制备方法、包含其的正极极片、锂离子电池、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。
相比于磷酸铁锂材料，镍钴锰三元正极活性材料凭借其高克容量得到广泛应用，但是现有技术中，三元锂离子电池能量密度与其循环性能、安全性能一直无法得到综合提升。特别地，三元正极活性材料中镍原子含量越高，包含其的锂离子电池能量密度与循环性能、安全性能的综合提升难度更大，这极大限制了三元锂离子电池更大范围的应用。
因此，设计出一款兼具高能量密度、良好的循环性能以及良好的安全性能的锂离子电池是非常困难的。
发明内容
本申请是鉴于上述课题而进行的，目的在于提供一种高镍三元正极活性材料，使三元锂离子电池兼具高能量密度、良好的循环性能以及良好的安全性能。
本申请第一方面提供一种核壳结构的高镍正极活性材料，其中，
所述核包括Li 1+a[Ni xCo yMn zM b]O 2，其中0.6≤x＜1，0＜y＜0.3， 0＜z＜0.3，0＜a＜0.2，0＜b＜0.2，x+y+z+b＝1，M为Mg、Ca、Sb、Ce、Ti、Zr、Sr、Al、Zn、Mo及B中的一种以上；
所述壳包括包覆所述核的第一壳层，以及包覆所述第一壳层的第二壳层；其中，
所述第一壳层为由锂、铝、硅、氧四种元素组成的快离子导体；
所述第二壳层包括R元素的氧化物，所述R选自Al、B、Ti、P、Co、La中的一种以上。
在任意实施方式中，所述壳还包括形成于第一壳层和第二壳层之间的过渡层，所述过渡层包括所述第一壳层组分和所述第二壳层组分形成的一种或多种快离子导体Li pR qO w，其中1≤p≤4，1≤q≤5，1≤w≤12，并且p、q和w均为整数。
在任意实施方式中，所述第一壳层的快离子导体为Li αAl XSi YO 4，其中，0＜X＜2.4，0＜Y＜1.8，0.8≤α≤1.2，铝元素的化学计量系数X与硅元素的化学计量系数Y之比为0.8～1.2。
在任意实施方式中，本申请所述过渡层中的快离子导体Li pR qO w选自LiAlO 2、Li 3BO 3、Li 4Ti 5O 12、Li 3PO 4、LiCoO 2或LiLaO中的一种以上。
在任意实施方式中，本申请中的高镍正极活性材料的镍含量为80％以上，即0.8≤x＜1，基于镍钴锰总原子数计。
在任意实施方式中，本申请的高镍正极活性材料的核中，M可以为Sb、Ti、Zr、Sr、Al、B中的一种以上。
在任意实施方式中，本申请的高镍正极活性材料中，R可以为Al、La、B、Co、Ti中的一种以上。
在任意实施方式中，本申请高镍正极活性材料，所述核中的锂元素与壳层中的锂元素的质量之比为40～1300∶1。
在任意实施方式中，当M选自Al、B或Ti中的一种或多种时，R与M不同，并且基于所述高镍正极活性材料总质量计，所述M元素在所述高镍正极活性材料中的质量含量为1000～5000ppm，可选为3000～5000ppm。
在任意实施方式中，当M选自Al、B或Ti中的一种或多种时， R与M不同，并且基于所述高镍正极活性材料总质量计，所述R元素质量含量为100～20000ppm。
在任意实施方式中，在所述高镍正极活性材料中，所述Si元素的质量与所述R元素的质量之比为0.1～7.0∶1，可选为0.1～4.4∶1。
在任意实施方式中，基于所述高镍正极活性材料的总质量计，所述第一壳层中硅元素与铝元素的总质量含量为435～13150ppm。
在任意实施方式中，本申请高镍正极活性材料的体积平均粒径Dv50为1.5～20μm，所述壳层的总厚度为0.001～1μm。
本申请第二方面提供一种高镍正极活性材料的制备方法，其包括如下步骤：
S1：提供包覆有硅铝氢氧化物的高镍三元前驱体，得到第一中间体；
S2：将所述第一中间体与M前驱体、锂前驱体混合，烧结后得到第二中间体；
S3：将所述第二中间体与R前驱体混合，烧结后得到所述高镍正极活性材料；
其中，所述高镍正极活性材料为核壳结构，
所述核包括Li 1+a[Ni xCo yMn zM b]O 2，其中0.6≤x＜1，0＜y＜0.3，0＜z＜0.3，0＜a＜0.2，0＜b＜0.2，x+y+z+b＝1，M为Mg、Ca、Sb、Ce、Ti、Zr、Sr、Al、Zn、Mo及B中的一种以上；
所述壳包括包覆所述核的第一壳层，以及包覆所述第一壳层的第二壳层；其中，
所述第一壳层为由锂、铝、硅、氧四种元素组成的快离子导体；
所述第二壳层包括元素R的氧化物，所述R选自Al、B、Ti、P、Co、La中的一种以上。
本申请的制备方法，原料来源广泛、成本低，工艺简洁，更有利于实现大规模工业化。
在任意实施方式中，在步骤S1中，所述包覆有硅铝氢氧化物的高镍三元前驱体的制备过程为：
(a)将铝前驱体、硅前驱体完全溶于碱性溶液，而后加入高镍 三元前驱体，得到固液混合物；
(b)降低所述固液混合物的pH，引发铝前驱体和硅前驱体发生水解-原位沉淀反应，得到包覆有硅铝氢氧化物的高镍三元前驱体。
在任意实施方式中，在所述步骤(a)中，将所述铝前驱体和所述硅前驱体按照铝∶硅＝0.8～1.2∶1的摩尔比加入到所述碱性溶液中。
在任意实施方式中，在所述步骤(a)中，基于所述固液混合物的总质量计，所述高镍三元前驱体的质量占比为16％～50％。
在任意实施方式中，在所述步骤(a)中，所述碱性溶液的pH为11～13；
在所述步骤(b)中，按照1～20mL/min的流速向所述固液混合物中通入弱酸性气体，使所述固液混合物的pH降低为8～10。
在任意实施方式中，在所述步骤(b)中，所述水解-原位沉淀反应的反应温度为20～40℃，反应时间为0.1～2h，搅拌线速度为1～6m/s。
在任意实施方式中，在步骤S2中，设所述第一中间体中镍原子、钴原子、锰原子的总摩尔量为Me2，则：
所述锂前驱体按照锂原子为0.9～1.1Me2的加入量、所述M前驱体按照M原子为(8×10 -4～180×10 -4)Me2的加入量与所述第一中间体混合。
在任意实施方式中，在步骤S2中，烧结温度为700～950℃，烧结时间为10～20h，烧结气氛为空气或氧气。
在任意实施方式中，在步骤S3中，设所述第二中间体中镍原子、钴原子、锰原子的总摩尔量为Me3，则：
所述R前驱体按照R原子为(16×10 -4～330×10 -4)Me3的加入量与所述第二中间体混合。
在任意实施方式中，在步骤S3中，烧结温度为200～700℃，烧结时间为5～15h，烧结气氛为空气或氧气。
本申请第三方面提供一种正极极片，包括本申请第一方面所述的高镍正极活性材料或本申请第二方面制备方法制备的高镍正极活性材料。
本申请第四方面提供一种锂离子电池，包括本申请第一方面所述 的高镍正极活性材料或本申请第二方面制备方法制备的高镍正极活性材料或本申请第三方面的正极极片。
本申请第五方面提供一种电池模块，包括本申请第四方面的锂离子电池。电池模块的制备可以采用现有技术已知的用于制备电池模块的方法。
本申请第六方面提供一种电池包，包括本申请第四方面的锂离子电池或本申请第五方面的电池模块中的一种以上。电池包的制备可以采用现有技术已知的用于制备电池包的方法。
本申请第七方面提供一种用电装置，包括本申请第四方面的锂离子电池、本申请第五方面的电池模块、或本申请第六方面的电池包中的一种以上，所述锂离子电池或所述电池模组或所述电池包用作所述用电装置的电源或所述用电装置的能量存储单元。用电装置的制备可以采用现有技术已知的用于制备用电装置的方法。
[有益效果]
本申请通过对高镍三元正极活性材料分别包覆第一壳层的快离子导体、特别是Li αAl XSi YO 4，过渡层的快离子导体Li pR qO w和第二壳层的R元素的氧化物，得到了本申请的高镍三元正极活性材料。本申请的高镍三元正极活性材料具有显著减少的表面杂锂量，并创造性地将表面杂锂转变成加速核中锂离子嵌入/脱出的快离子导体Li αAl XSi YO 4、Li pR qO w中的有效组分，显著改善因表面杂锂导致的电解液分解产气，使高镍三元锂离子电池在具有高能量密度的同时，还兼具良好的循环性能和安全性能。
本申请的电池模块、电池包和用电装置包括本申请提供的锂离子电池，因而至少具有与所述锂离子电池相同的优势。
附图说明
图1是本申请一实施方式的高镍正极活性材料的结构示意图。
图2是本申请一实施方式的体积平均粒径分布图。
图3是本申请一实施方式的锂离子电池的示意图。
图4是图3所示的本申请一实施方式的锂离子电池的分解图。
图5是本申请一实施方式的电池模块的示意图。
图6是本申请一实施方式的电池包的示意图。
图7是图6所示的本申请一实施方式的电池包的分解图。
图8是本申请一实施方式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 锂离子电池
51 壳体
52 电极组件
53 顶盖组件
6 核
7 第一壳层
8 过渡层
9 第二壳层
具体实施方式
以下，适当地参照附图详细说明本申请具体公开的高镍正极活性材料、其制备方法、包括其的锂离子电池、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定范围的边界。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，则理解为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，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。
本申请中使用的术语“以上”、“以下”包含本数，例如“一种以上”是指一种或多种，“A和B中的一种以上”是指“A”、“B”或“A和B”。
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)。
需要说明的是，术语“壳层”是指包覆在高镍正极活性材料的“核”上的部分，所述部分可以但并不一定完全包覆所述“核”，使用“壳”或者“壳层”或者“第一壳层”或者“过渡层”或者“第二壳层”只是为了便于描述，并不意图限制本申请。类似地，“第二壳层包覆第一壳层”是指第二壳层完全包覆或部分包覆第一壳层。
术语“高镍含量”是指对应的正极活性材料中镍原子数占镍钴锰总原子数的60％以上。类似地，本文中使用的术语“镍含量”是指正极活性材料中镍原子数占镍钴锰总原子数的百分比。本申请中使用的术语“高镍三元前驱体”是指氢氧化物形式的镍钴锰三元材料，其中基于镍钴锰的总原子数计，镍的原子数占比在60％以上。
术语“快离子导体(fast ionic conductor)”又称超离子导体，有时也称作固体电解质。它区别于一般离子导体的最基本特征是在一定的温度范围内具有能与液体电解质相比拟的离子电导率(0.01Ω·cm)和低的离子电导激活能(≤0.40eV)。例如，作为示例，在本发明第一壳层和第二壳层中可能存在的快离子导体包括LiAl 0.971Si 1.022O 4、Li 3BO 3等。
本文中使用的术语某种元素的“前驱体”可以指原材料，也可以指在获得目标产物前，对初始材料进行一定的处理而获得的包含所述元素，并且可在本申请制备方法的条件下发生进一步反应而获得目标产物的化合物。例如，“前驱体”可以是相应元素的氧化物、氢氧化物或可溶于水中的盐。作为示例，例如，当M表示元素铝时，其前驱体可以为偏铝酸盐，也可以为氢氧化铝；又如，锂元素的前驱体可以为氢氧化锂；又如，高镍三元前驱体是指由镍、钴、锰、氧、氢五种元素形成的复合氢氧化物。
本申请发明人实际作业中发现：对于镍钴锰三元正极活性材料，提高其层状结构中锂的含量，能够显著提高材料的充放电克容量，对锂离子电池能量密度提高显著。但是，当镍钴锰三元正极活性材料中镍原子数提高到60％(以镍、钴、锰总原子数计)以上时，对应的锂离子电池出现循环性能严重下降、电池内部产气量急剧增加等系列严 重威胁电池电化学性能和安全性能的现象。
经过发明人大量研究发现，上述高镍三元正极活性材料具有上述不良效应的原因如下：第一，随着锂离子的数次嵌入/脱出，相比于低镍三元正极活性材料，高镍三元正极活性材料，其微观层状结构更容易发生晶格畸变，层状结构更容易坍塌，从而使其失去脱嵌锂离子的能力，最终使得锂离子电池的能量密度和循环性能严重下降。第二，对于高镍三元正极活性材料，其表面杂锂(例如，氧化锂、碳酸锂)量更多，使其与电解液接触的相界面处副反应严重，从而电池内部产气量严重增加，导致电池循环性能和安全性能显著下降。
由此，高镍三元正极活性材料尽管能够通过提高镍含量提高电池能量密度，但是也相应会大幅降低电池的循环性能和安全性能。
本申请发明人面对上述研究课题，从综合提高三元锂离子电池的综合性能出发，通过对高镍三元正极活性材料改性，开发出一种能够综合提高锂离子电池能量密度、循环性能和安全性能的高镍三元正极活性材料。
[高镍三元正极活性材料]
本申请提供一种高镍正极活性材料，其为核壳结构，其中，
所述核包括Li 1+a[Ni xCo yMn zM b]O 2，其中0.6≤x＜1，0＜y＜0.3，0＜z＜0.3，0＜a＜0.2，0＜b＜0.2，x+y+z+b＝1，M为Mg、Ca、Sb、Ce、Ti、Zr、Sr、Al、Zn、Mo及B中的一种以上；
所述壳包括包覆所述核的第一壳层，以及包覆所述第一壳层的第二壳层；其中，
所述第一壳层为由锂、铝、硅、氧四种元素组成的快离子导体；
所述第二壳层包括元素R的氧化物，所述R选自Al、B、Ti、P、Co、La中的一种以上。
在一些实施方式中，可选地，在本申请正极活性材料的核中，z与y的比值为2∶1至1∶2，可选为3∶2至2∶3。
在一些实施方式中，可选地，在本申请正极活性材料的核中，y与z的和y+z与x的比值为1∶10至1∶7，可选为1∶9至1∶8。
在一些实施方式中，可选地，所述第一壳层中的快离子导体为 Li αAl XSi YO 4，其中，0＜X＜2.4，0＜Y＜1.8，0.8≤α≤1.2，铝元素的化学计量系数X与硅元素的化学计量系数Y之比为0.8～1.2。
本申请的高镍正极活性材料具有二层壳层包覆核的核壳结构，其中核包括Li 1+a[Ni xCo yMn zM b]O 2。连续二层壳层的包覆一方面能够防止核材嵌入/脱出锂离子的主体，即Li 1+a[Ni xCo yMn zM b]O 2，在数次充放电循环后发生的晶体结构坍塌，另一方面也能够隔绝核材与电解液的直接接触，进而减少电解液中腐蚀性物质对正极活性材料表面的腐蚀，减少电解液在正极表面的副反应，防止电池内部产气。除此之外，连续二壳层的包覆还能够防止核材的过渡金属元素在电池循环和存储过程中的溶出现象，防止溶出的过渡金属元素在负极表面沉积。最后但同等重要的是，连续二壳层的包覆能够显著改善高镍正极活性物质材料表面的杂锂量，显著增加高镍正极活性物质材料中活性锂的相对占比。总之，连续二层壳层的包覆通过上述四方面的作用，能够使高镍三元锂离子电池的能量密度、循环性能和安全性能得到综合提高。
进一步地，本申请所述高镍正极活性材料的核包括Li 1+a[Ni xCo yMn zM b]O 2。M元素掺杂到核材中，能够与核材中的其他元素形成Li 1+a[Ni xCo yMn zM b]O 2，提高核材的结构稳定性，防止在多次充放电循环中核材的结构坍塌，进而提高电池的循环性能。
值得一提的是，本申请的高镍正极活性材料尤其适用于高镍三元锂离子电池，尤其适用于镍含量在60％以上的范围，尤其适用于镍含量在80％以上范围。可选地，镍含量可以为60％、80％、90％。
值得一提的是，当M为Sb、Ti、Zr、Sr、Al、B中的一种以上时，锂离子电池的充放电容量、循环容量保持率和对产气量的改善更为显著。
进一步地，第一壳层为由锂、铝、硅、氧四种元素组成的快离子导体层，例如，快离子导体为Li αAl XSi YO 4。快离子导体Li αAl XSi YO 4的存在：一方面能够创造性地将核材表面的杂锂成分转变为Li αAl XSi YO 4中的结构锂，能够有效减少高镍三元正极活性材料的杂锂量，进而改善该材料与电解液之间的界面副反应，提高电池的循环性能；另一方面，Li αAl XSi YO 4能够显著提高锂离子的脱嵌速率，进 而提高电池的充放电容量和循环性能。
值得一提的是，对于快离子导体Li αAl XSi YO 4，Al原子与Si原子的摩尔比，即X与Y的比值为0.8～1.2。当X与Y的比值在上述范围内时，有利于在正极材料表面形成良好的快离子导体，进而有助于减少表面杂锂含量，减少材料的界面副反应，同时提升锂离子传输速率，从而改善电池的循环性能和安全性能。值得注意的是，当Al或Si的含量过多，也即X与Y的比值偏离上述范围时，正极材料表层可能会形成Al或Si的低活性的物质，反而会影响锂离子的传输。
值得一提的是，所述Li αAl XSi YO 4的中的α在0.8～1.2范围内，可选为1，也可以为0.8～1.2范围内的任何自然数。当α数值低于上述范围时，第一壳层中快离子导体的锂离子相对含量相对较少，形成的快离子导体传输锂离子的速率可能较差，影响电池性能。当α数值高于上述范围时，过多的锂离子可能会导致正极材料表面上的杂锂数量增多，导致与电解液的界面副反应增多，影响电池的安全性能。
进一步地，第二壳层包括元素R的氧化物，所述R为Al、B、Ti、P、Co、La中的一种以上。第二壳层的设置，能够防止快离子导体Li αAl XSi YO 4因电解液浸泡导致的成分流失和结构破坏，并且能够隔绝核材与电解液的接触，对提高高镍正极活性材料的稳定性具有重要作用，有利于提高电池能量密度、循环性能以及安全性能。
需要说明的是，当R为Co元素时，如果制备第二壳层时的烧结温度较低，例如200℃，则还可能存在Co元素的氢氧化物Co(OH)2，这同样应当涵盖在本发明的范围内。因此，本文中的术语“元素R的氧化物”应特别地理解为，除元素R的氧化物以外，当R为Co元素时，还包括Co元素的氢氧化物Co(OH) 2。
值得一提的是，当R为Al、La、B、Co、Ti中的一种以上时，锂离子电池的充放电容量、循环容量保持率和对产气量的改善更为显著。
在一些实施方式中，所述壳还包括形成于第一壳层和第二壳层之间的过渡层，所述过渡层包括所述第一壳层组分和所述第二壳层组分形成的一种或多种快离子导体Li pR qO w，其中1≤p≤4，1≤q≤5，1≤w≤12， 并且p、q和w均为整数。
在本申请的高镍正极活性材料的壳层中，过渡层是由第一壳层和第二壳层形成的过渡区域，过渡层中包括的Li pR qO w组分能够进一步提高锂离子在高镍正极活性材料中的脱嵌速率。因此，本申请的高镍正极活性材料中，通过两层快离子导体层(即第一壳层和第二壳层)的协同增效作用，极大提高了高镍正极活性材料克容量。
值得一提的是，本申请的高镍正极活性材料中，所述核和所述壳层之间也可以包括类似于第一壳层和第二壳层之间的过渡层的过渡区域，其可以为连续的层状结构，也可以为不连续的层状结构，并且可以具有均匀或不均匀的厚度。
值得一提的是，形成于第一壳层和第二壳层之间的过渡层为连续的层状结构，第一壳层与第二壳层之间因具有Li pR qO w组分而使两个壳层之间的连接更紧密，进而防止电池使用过程中第二壳层脱落，同时也更有利于充分提高高镍正极活性材料克容量。
在一些实施方式中，可选地，所述过渡层中的快离子导体Li pR qO w选自LiAlO 2、Li 3BO 3、Li 4Ti 5O 12、Li 3PO 4、LiCoO 2或LiLaO中的一种以上。
在一些实施方式中，可选地，所述x为0.8≤x＜1，所述M为Sb、Ti、Zr、Sr、Al、B中的一种以上，所述R为Al、La、B、Co、Ti中的一种以上。
在一些实施方式中，可选地，本申请高镍正极活性材料，核层中的锂元素与壳层中的锂元素的质量之比为40～1300∶1。
本申请的高镍正极活性材料，核中锂元素的质量与壳中锂元素的质量之比位于上述范围内：一方面，能够确保核中存在足够多的活性锂，用于贡献高镍正极活性材料的克容量，从而提高电池能量密度和循环性能；另一方面，能够确保第一壳层、过渡层、第二壳层中具有合适量的锂元素作为有效组分，用于形成快离子导体Li αAl XSi YO 4、Li pR qO w；除此之外，核中锂元素的质量与壳中锂元素的合适质量比，还能够有效防止高镍正极活性材料表面杂锂物质的产生，从而减少电池内部发生的副反应。总之，通过上述三方面的作用，核中锂元素的 质量与壳中锂元素合适的质量比，有利于提高电池能量密度、循环性能以及安全性能(主要体现在电池内部产气量的改善)。
在一些实施方式中，可选地，当M选自Al、B或Ti中的一种或多种时，R与M不同，并且基于所述高镍正极活性材料总质量计，M元素在所述高镍正极活性材料中的质量含量为1000～5000ppm，可选为3000～5000ppm。
相比于低镍含量的三元正极活性材料，核材Li 1+a[Ni xCo yMn zM b]O 2中M元素的掺杂，能够显著改善核材Li 1+a[Ni xCo yMn zM b]O 2因锂离子的反复脱嵌而造成的结构坍塌和破坏，为锂离子传输构建更稳定的通道，有利于提高高镍正极活性材料克容量，从而提高锂离子电池的能量密度和循环性能。
在一些实施方式中，可选地，当M选自Al、B或Ti中的一种或多种时，R与M不同，并且基于所述高镍正极活性材料的总质量计，所述R元素质量含量为100～20000ppm。
将R元素的质量含量限定在合理范围内：一方面，能够形成物化结构更稳定的R的氧化物，从而有效阻隔电解液对核材和第一壳层的腐蚀，减少电池内部的副反应；另一方面，包括R元素的氧化物的第二壳层的存在，也能够有效避免高镍正极活性材料的开裂和破碎，进而防止核材破碎后产生的小颗粒引发的电池内部热失控。综上，通过上述作用，将R元素的质量含量限定在合理范围内，能够提高电池的能量密度、循环性能和安全性能。
进一步地，当R元素质量含量为500～15000ppm时，锂离子电池的充放电容量、循环容量保持率和对产气量的改善更为显著。
在一些实施方式中，可选地，在高镍正极活性材料中，所述Si元素的质量与所述R元素的质量之比为0.1～7.0∶1，可选为0.1～4.4∶1。
高镍正极活性材料中，Si元素与R元素合适的质量比，意味着第一壳层与第二壳层的质量比位于合适范围内。R元素过少Si元素过多，即第二壳层包覆不完整而第一壳层包覆过厚，则可能起不到减少电解液与高镍材料表面的副反应的作用，同时还可能因为第一壳层 (Si元素不贡献容量)过厚而降低材料本身克容量，导致电池放电容量低。相反，R元素过少Si元素过多，即第一壳层包覆不完整而第二壳层包覆过厚，则可能使高镍正极活性材料无法构建完整的快速传导锂离子的网络结构，从而降低锂离子的脱嵌速率，降低高镍正极活性材料克容量，降低电池放电容量，影响电池循环性能，同时还可能因为第二壳层(R元素不贡献容量)过厚而降低材料本身克容量，导致电池放电容量低。
在一些实施方式中，可选地，基于所述高镍正极活性材料的总质量计，所述第一壳层的硅元素与铝元素总质量含量为435～13150ppm。
所述第一壳层的硅元素与铝元素总质量含量与第一壳层中Li αAl XSi YO 4的量相对应。在高镍活性材料表面包覆一层快离子导体Li αAl XSi YO 4，能有效改善锂离子的传输速率，并能够减少界面与电解液之间的副反应，改善容量及长期性能；但包覆量不宜过少或过多，过少可能起不到作用，过多则可能降低材料克容量，还可能增大锂离子传输阻力。
在一些实施方式中，可选地，所述高镍正极活性材料的体积平均粒径Dv50为1.5～20μm，所述壳层厚度为0.001～1μm。在本申请的高镍正极活性材料中，颗粒的体积平均粒径Dv50过大，会导致锂离子脱嵌阻力增大，造成电池内阻增大；同时，体积平均粒径Dv50也不宜过小，因为过小的粒径一方面增大工艺复杂程度，增加生产成本，另一方面也会增加与电解液的接触面积，一旦壳层功能丧失，将可能造成电池性能急速恶化。类似地，壳层厚度过大时，会增大电池内阻，降低材料克容量，但当壳层厚度过小时，可能难以有效发挥壳层的有益功能。
本申请的高镍正极活性材料，可以为多晶三元材料，也可以为单晶三元材料；所述多晶三元材料具有多晶结构，所述单晶三元材料具有单晶结构或类单晶结构。当所述高镍正极活性材料为多晶结构时，高镍正极活性材料贡献的克容量更高，当所述高镍三元正极活性材料为单晶结构或类单晶结构时，对应锂离子电池的循环性能更优。
在一些实施方式中，本申请所述的单晶结构或类单晶结构的高镍 正极活性材料能够通过控制高镍三元前驱体粒度在1～5μm之间，并通过提高关键制备步骤的焙烧温度合成出来。
例如，在本申请所述的方法中，通过将S2步骤的烧结温度由700℃提升至950℃，将S1步骤中的前驱体Dv50粒度由9μm调整为3μm即可合成出良好的单晶或类单晶结构的高镍正极活性材料。
本领域技术人员可以根据锂离子电池的不同应用场景，选用本申请多晶结构的高镍三元正极活性材料，或具有单晶或类单晶结构的高镍三元正极活性材料。
本申请提供一种高镍正极活性材料的制备方法，包括如下步骤：
S1：提供包覆有硅铝氢氧化物的高镍三元前驱体，得到第一中间体；
S2：将所述第一中间体与M前驱体、锂前驱体混合，烧结后得到第二中间体；
S3：将所述第二中间体与R前驱体混合，烧结后得到所述高镍正极活性材料；
其中，所述高镍正极活性材料为核壳结构，
所述核包括Li 1+a[Ni xCo yMn zM b]O 2，其中0.6≤x＜1，0＜y＜0.3，
0＜z＜0.3，0＜a＜0.2，0＜b＜0.2，x+y+z+b＝1，M为Mg、Ca、Sb、Ce、Ti、Zr、Sr、Al、Zn、Mo及B中的一种以上；
所述壳包括包覆所述核的第一壳层，以及包覆所述第一壳层的第二壳层；其中，
所述第一壳层为由锂、铝、硅、氧四种元素组成的快离子导体；
所述第二壳层包括元素R的氧化物，所述R选自Al、B、Ti、P、Co、La中的一种以上。
本申请制备方法，原料来源广泛、成本低，工艺简洁，更有利于实现大规模工业化。
在一些实施方式中，可选地，在步骤S1中，所述包覆有硅铝氢氧化物的高镍三元前驱体的制备过程为：
(a)将铝前驱体、硅前驱体完全溶于碱性溶液，而后加入高镍三元前驱体，得到固液混合物；
(b)降低所述固液混合物的pH，引发铝前驱体和硅前驱体发生水解-原位沉淀反应，得到包覆有硅铝氢氧化物的高镍三元前驱体。
在步骤(a)中，上述铝前驱体可以为偏铝酸钠(NaAlO 2)、偏铝酸钾(KAlO 2)、偏铝酸锂(LiAlO 2)中的一种或多种，硅前驱体可以为硅酸钠(Na 2O·nSiO 2)、硅酸钾(K 2O·nSiO 2)、硅酸锂(Li 2O·nSiO 2)中的一种或多种。
在步骤(a)中，固液混合物保持相对较高pH，能够保证铝前驱体、硅前驱体充分溶解，又不至于引发铝前驱体、硅前驱体的过度水解。高镍三元前驱体的加入为后续铝前驱体和硅前驱体发生水解-原位沉淀反应提供沉淀表面。
进一步地，在步骤(b)中，降低固液混合物的pH，能够引发铝前驱体和硅前驱体发生水解-原位沉淀反应，从而使水解产生的硅铝氢氧化物共沉淀到高镍三元前驱体表面，得到第一中间体。
进一步地，在步骤(a)中，将所述铝前驱体和所述硅前驱体按照铝∶硅＝0.8～1.2∶1的摩尔比加入到所述碱性溶液中。
进一步地，在所述步骤(a)中，基于所述固液混合物的总质量计，所述高镍三元前驱体的质量占比为16％～50％。
进一步地，在所述步骤(a)中，所述碱性溶液的pH为11～13，用于防止铝前驱体和硅前驱体水解；
进一步地，按照1～20mL/min的流速向所述固液混合物中通入弱酸性气体，使所述固液混合物的pH降低为8～10。
在一些实施方式中，可选地，所述弱酸性气体为CO 2、SO 2中的一种或多种。
进一步地，在所述步骤(b)中，所述水解-原位沉淀反应的反应温度为20～40℃，反应时间为0.1～2h，搅拌线速度为1～6m/s。
在一些实施方式中，可选地，在步骤S2中，设所述第一中间体中镍原子、钴原子、锰原子的总摩尔量为Me2，则：
所述锂前驱体按照锂原子为0.9～1.1Me2的加入量、所述M前驱体按照M原子为(8×10 -4180×10 -4)Me2的加入量与所述第一中间体混合。
进一步地，在步骤S2中，烧结温度为700～950℃，烧结时间为10～20h，烧结气氛为空气或氧气。
在一些实施方式中，可选地，在步骤S3中，设所述第二中间体中镍原子、钴原子、锰原子的总摩尔量为Me3，则：
所述R前驱体按照R原子为(16×10 -4～330×10 -4)Me3的加入量与所述第二中间体混合。
在一些实施方式中，所述R前驱体可以为含Al的氧化物、氢氧化物或无机酸盐中的一种或几种，所述R前驱体可以为含B的氧化物、氢氧化物或无机酸盐中的一种或几种，所述R前驱体可以为含Ti的氧化物、氢氧化物或无机酸盐中的一种或几种，所述R前驱体可以为含P的氧化物、氢氧化物或无机酸盐中的一种或几种，所述R前驱体可以为含Co的氧化物、氢氧化物或无机酸盐中的一种或几种，所述R前驱体可以为含La的氧化物、氢氧化物或无机酸盐中的一种或几种。
在一些实施方式中，可选地，在步骤S3中，烧结温度为200～700℃，烧结时间为5～15h，烧结气氛为空气或氧气。这里值得注意的是，步骤S3的烧结温度至少比步骤S2中的烧结温度低500℃，以使步骤S2中的M元素进入核结构中，而步骤S3中的R元素基本不会进入核结构中。
[正极极片]
本申请提供一种正极极片，所述正极极片包括本申请的高镍正极活性材料。
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，正极材料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。
本申请的锂离子电池中，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)、1，3-丙烷磺酸内酯(1，3-propanesultone)、聚乙烯(PE)等的基材)上而形成，但本申请并不限定于这些材料。
所述正极材料还可选地包括导电剂。但对导电剂的种类不做具体限制，本领域技术人员可以根据实际需求进行选择。作为示例，用于正极材料的导电剂可以选自超导碳、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一种以上。
本申请中可按照本领域已知的方法制备正极极片。作为示例，可以将本申请的正极活性材料、导电剂和粘结剂分散于溶剂(例如N-甲基吡咯烷酮(NMP))中，形成均匀的正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，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。
本申请的锂离子电池中，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(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，但本申请并不限定于这些材料。
本申请的负极极片中，所述负极膜层通常包含负极活性材料以及可选的粘结剂、可选的导电剂和其他可选助剂，通常是由负极浆料涂布干燥而成的。负极浆料通常是将负极活性材料以及可选的导电剂和粘结剂等分散于溶剂中并搅拌均匀而形成的。溶剂可以是N-甲基吡咯烷酮(NMP)或去离子水。
作为示例，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一种以上。
本申请的负极极片中，所述负极膜层除了包括负极活性材料外，还可选地包括其它常用负极活性材料，例如，作为其它常用负极活性材料，可列举出人造石墨、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一种以上。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的一种以上。
[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特别的限制，可根据需求进行选择。例如，电解质可选自固态电解质及液态电解质(即电解液)中的至少一种。
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(LiPF 6)、四氟硼酸锂(LiBF 4)、高氯酸锂(LiClO 4)、六氟砷酸锂(LiAsF 6)、双氟磺酰亚胺锂(LiFSI)、双三氟甲磺酰亚胺锂(LiTFSI)、三氟甲磺酸锂(LiTFS)、二氟草酸硼酸锂(LiDFOB)、二草酸硼酸锂(LiBOB)、二氟磷酸锂(LiPO 2F 2)、二氟二草酸磷酸锂(LiDFOP)及四氟草酸磷酸锂(LiTFOP)中的一种以上。
在一些实施方式中，溶剂可选自碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸亚丁酯(BC)、氟代碳酸亚乙酯(FEC)、甲酸甲酯(MF)、乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸甲酯(MP)、丙酸乙酯(EP)、丙酸丙酯(PP)、丁酸甲酯(MB)、丁酸乙酯(EB)、1，4-丁内酯(GBL)、环丁砜(SF)、二甲砜(MSM)、甲乙砜(EMS)及二乙砜(ESE)中的一种以上。
在一些实施方式中，所述电解液中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，也可以包括正极成膜添加剂，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、改善电池高温性能的添加剂、以及改善电池低温性能的添加剂等。
[隔离膜]
采用电解液的锂离子电池、以及一些采用固态电解质的锂离子电池中，还包括隔离膜。隔离膜设置在正极极片和负极极片之间，起到隔离的作用。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一种以上。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。
[锂离子电池]
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，所述正极极片包括本申请的高镍正极活性材料。
在一些实施方式中，锂离子电池可包括外包装。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，锂离子电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。锂离子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(PP)、聚对苯二甲酸丁二醇酯(PBT)以及聚丁二酸丁二醇酯(PBS)等。
本申请对锂离子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3是作为一个示例的方形结构的锂离子电池5。
在一些实施方式中，参照图4，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。锂离子电池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需求进行选择。
[电池模块]
在一些实施方式中，锂离子电池可以组装成电池模块，电池模块所含锂离子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5是作为一个示例的电池模块4。参照图5，在电池模块4中，多个锂离子电池5可以沿电池模块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锂离子电池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，多个锂离子电池5容纳于该容纳空间。
[电池包]
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6和图7是作为一个示例的电池包1。参照图6和图7，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。
[用电装置]
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锂离子电池、电池模块、或电池包中的一种以上。所述锂离子电池、电池模块、或电池包可以用作所述装置的电源，也可以用作所述装置的能量存储单元。所述装置可以但不限于是移动设备(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。
作为所述用电装置，可以根据其使用需求来选择锂离子电池、电池模块或电池包。
图8是作为一个示例的装置。该装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该装置对锂离子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。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用锂离子电池作为电源。
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，均为本领域通常使用的可以通过市购获得的常规产品。本申请实施例中各成分的含量，如果没有特别说明，均以质量计。
实施例1
【高镍三元正极活性材料的制备】
S1，第一中间体的制备：称取13.02g偏铝酸钠(以NaAlO 2计)、19.37g硅酸钠(以Na 2O·SiO 2计)溶于2L的pH＝12.2的NaOH水溶液中，再加入953.00g的Dv50中值粒径为9.0μm的高镍三元前驱体(Ni 0.9Co 0.05Mn 0.05)(OH) 2，开启搅拌，搅拌期间以10mL/min的流速通入CO 2气体，在30℃下以3m/s的线速度连续搅拌2h，停止搅拌后，经抽滤、干燥、过筛，得到包覆有硅铝氢氧化物的高镍三元前驱体，即第一中间体；
S2，第二中间体的制备：将980.62g第一中间体、472g氢氧化锂(以LiOH·H 2O计)、8.33g氧化钛(以TiO 2计)混合均匀，在700℃、氧气气氛下烧结20h，得到第二中间体；
S3，得到目标产物：将1000g的第二中间体、3.18g氧化硼(以B 2O 3计)混合均匀，在200℃、氧气气氛下烧结5h，得到实施例1的高镍正极活性材料。
其他实施例和对比例的高镍正极活性材料的具体制备参数参见表A～表H。
实施例和对比例的高镍活性材料的产品参数以及锂离子电池性能参数参见表1～表8。
【正极极片】
将上述高镍正极活性材料、粘结剂聚偏氟乙烯(PVDF)、导电剂乙炔黑按照94∶3∶3的质量比与溶剂N-甲基吡咯烷酮(NMP)混合均匀，得到正极浆料；将此浆料涂覆于铝箔上，烘干、冷压、分切后，得到正极极片。
【负极极片】
将负极活性材料人造石墨、硬碳、导电剂乙炔黑、粘接剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC-Na)按照质量比90∶5∶2∶2∶1与去离子水混合均匀得到混合物，将所述混合物涂覆于铜箔上烘干、冷压，得到实施例1的负极极片。
【电解液】
将EC∶DEC∶DMC按照1∶1∶1的体积比混合，加入LiPF 6形成电解液，在所述电解液中，LiPF 6的浓度为1mol/L。
【隔离膜】
聚丙烯隔离膜。
【锂离子电池的制备】
将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，再卷绕成方形的裸电芯后，装入铝塑膜，注入相应的非水电解液、封口，经静置、热冷压、化成、夹具、分容等工序后，得到锂离子电池。
【高镍正极活性材料相关参数测试】
1、表面杂锂量测试
酸碱滴定法：将30g实施例的高镍正极活性材料放入100ml去离子水中并搅拌30min，静置5min后抽滤。取10mL上清液，用0.05mol/L的盐酸标准溶液滴定上述上清液。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，并计算正极材料表面杂锂量Q(单位ppm)。具体公式为Q＝V2×C×6.94×n×100/(m×1000)×100000，其中C为盐酸标准溶液浓度(单位mol/L)；V2为开始滴定到第二个 滴定终点所消耗的盐酸标准溶液的总体积(单位mL)；n为V2与V1比值，V1为滴定后10mL上清液与V2的体积总和；m为样品的质量(单位g)。
2、高镍正极活性物质中各元素含量测试
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质量分数为25％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。
3、核中的锂元素与壳层中的锂元素的质量分布测试
联合采用IB-19500CP离子抛光仪和EPMA(电子探针微量分析，Electron Probe Microanalysis)设备。清洗制样用工具，将制样用胶(PVDF分散到NMP中形成的胶状物，PVDF质量含量为8％)与样品粉末混合(粉末重量约为胶的5倍)均匀后涂到铜箔上，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)中进行切割，得到核结构与层结构分界明显的切面图；
结合切面图，再通过EPMA测试，对核与壳层中分别取3个点进行锂元素分析测试，最后取平均值得出核与壳层中锂元素的质量百分含量，EPMA的详细操作流程参见标准NF A92-801-4-2006(NF A92-801-4-2006，高级工业陶瓷，陶瓷涂层的试验方法，第4部分：使用电探针微量分析法(EPMA)测量化学成分)。
4、体积平均粒径Dv50测试
取一洁净烧杯，加入适量待测样品，超声120W/5min确保样品完全分散。测试仪器为美国马尔文2000。样品倒入进样塔后随溶液循环到测试光路系统，颗粒在激光束的照射下，通过接受和测量散向光的能量分布就可以得出颗粒的粒度分布特征(遮光度：8-12％)。根据测试数据绘制粒径体积分布图(如附图2，为实施例1的高镍活性材料的粒径体积分布图)。从该分布图中得到：占总体积50％的颗粒直径大于某Dv50值，另有占总体积50％的颗粒直径小于此Dv50值， 则此Dv50值为颗粒的体积平均粒径。
5、壳层厚度测试
联合采用IB-19500CP离子抛光仪和美国FEI Tecnai G2透射电子显微镜设备。清洗制样用工具，将制样用胶(PVDF分散到NMP中形成的胶状物，PVDF质量含量为8％)与样品粉末混合(粉末重量约为胶的5倍)均匀后涂到铜箔上，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)中进行切割。将切割好的样品放入美国FEI Tecnai G2透射电子显微镜设备中进行壳层厚度测试，即可测试出颗粒壳层厚度。
对比例的上述相关参数测定方法与实施例相同。
【电池性能测试】
1、初始放电容量
将实施例的锂离子电池置于25℃烘箱中，静置5min，然后进行充放电测试。一次充放电过程如下：1/3C电流恒流放电到2.8V，静置5min，继续以1/3C恒流充电至4.25V，然后在4.25V下恒压充电至电流≤0.05mA，静置5min，然后再以1/3C恒流放电至2.8V，此时的放电容量即为本申请所述的初始放电容量。
2、循环容量保持率
在25℃下，对所有实施例和对比例的锂离子电池进行充放电测试。一个充放电循环过程如下：1C电流恒流充电到4.25V，然后在4.25V下恒压充电至电流≤0.05mA，静置5min，然后以1C电流恒流放电到2.8V，记录此时电池容量为C1，以上为电池的一个充放电循环。按照上述过程循环300圈，记录此时电池的容量C300。则循环容量保持率＝C300/C1×100％。
表1-表8中的循环容量保持率均是在循环300圈后测得的。
3、70℃胀气性能测试
在70℃下，对100％SOC(荷电状态，State of Charge)的电池(标称容量2.25Ah)用排水法测试单个电池的初始体积为V0，取出 电池并放入到70℃的存储炉存储48h，冷却至室温后再次用排水法测试电池体积为V1，重复以上步骤，存储20天后，用排水法测试电池体积为V10，则胀气量＝(V10-V0)/2.25。
表1-表8中的胀气量均是在储存20天后测得的。
对比例的电池性能测定方法与实施例相同。
Figure PCTCN2021118225-appb-000001
Figure PCTCN2021118225-appb-000002
Figure PCTCN2021118225-appb-000003
Figure PCTCN2021118225-appb-000004
Figure PCTCN2021118225-appb-000005
Figure PCTCN2021118225-appb-000006
Figure PCTCN2021118225-appb-000007
Figure PCTCN2021118225-appb-000008
Figure PCTCN2021118225-appb-000009
Figure PCTCN2021118225-appb-000010
Figure PCTCN2021118225-appb-000011
Figure PCTCN2021118225-appb-000012
综合分析表8中实施例1以及实施例34-35可知，当高镍正极活性材料的体积平均粒径Dv50在1.5～20μm，壳层厚度在0.001～1μm时，正极表面杂锂量和锂离子电池内部胀气量得到改善，锂离子电池具有良好的放电容量、安全性能、循环性能。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为例示，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 (17)

  1. 一种核壳结构的高镍正极活性材料，其中，
    所述核包括Li 1+a[Ni xCo yMn zM b]O 2，其中0.6≤x<1，0<y<0.3，0<z<0.3，0<a<0.2，0<b<0.2，x+y+z+b＝1，M为Mg、Ca、Sb、Ce、Ti、Zr、Sr、Al、Zn、Mo及B中的一种以上；
    所述壳包括包覆所述核的第一壳层，以及包覆所述第一壳层的第二壳层；其中，
    所述第一壳层为由锂、铝、硅、氧四种元素组成的快离子导体；
    所述第二壳层包括元素R的氧化物，所述R选自Al、B、Ti、P、Co、La中的一种以上。
  2. 根据权利要求1所述的高镍正极活性材料，其中，
    所述壳还包括形成于第一壳层和第二壳层之间的过渡层，所述过渡层包括所述第一壳层组分和所述第二壳层组分形成的一种或多种快离子导体Li pR qO w，其中1≤p≤4，1≤q≤5，1≤w≤12，并且p、q和w均为整数。
  3. 根据权利要求1或2所述的高镍正极活性材料，其中，
    所述第一壳层的快离子导体为Li αAl XSi YO 4，其中，0<X<2.4，0<Y<1.8，0.8≤α≤1.2，铝元素的化学计量系数X与硅元素的化学计量系数Y之比为0.8～1.2。
  4. 根据权利要求1-3中任一项所述的高镍正极活性材料，其中，
    所述过渡层中的快离子导体Li pR qO w选自LiAlO 2、Li 3BO 3、Li 4Ti 5O 12、Li 3PO 4、LiCoO 2或LiLaO中的一种以上。
  5. 根据权利要求1-4中任一项所述的高镍正极活性材料，其中，
    所述x为0.8≤x<1，所述M为Sb、Ti、Zr、Sr、Al、B中的一种以上，所述R为Al、La、B、Co、Ti中的一种以上。
  6. 根据权利要求1-5中任一项所述的高镍正极活性材料，其中，
    所述核中的锂元素与所述壳层中的锂元素的质量之比为40～1300：1。
  7. 根据权利要求1-6中任一项所述的高镍正极活性材料，其中，
    当M选自Al、B或Ti中的一种或多种时，R与M不同，并且基于所述高镍正极活性材料总质量计，所述M元素在所述高镍正极活性材料中的质量含量为1000～5000ppm，可选为3000～5000ppm。
  8. 根据权利要求1-7中任一项所述的高镍正极活性材料，其中，
    当M选自Al、B或Ti中的一种或多种时，R与M不同，并且基于所述高镍正极活性材料的总质量计，所述R元素质量含量为100～20000ppm。
  9. 根据权利要求1-8中任一项所述的高镍正极活性材料，其中，
    在所述高镍正极活性材料中，所述Si元素的质量与所述R元素的质量之比为0.1～7.0：1，可选为0.1～4.4：1。
  10. 根据权利要求1-9中任一项所述的高镍正极活性材料，其中，
    基于所述高镍正极活性材料的总质量计，所述第一壳层中硅元素与铝元素的总质量含量为435～13150ppm。
  11. 根据权利要求1-10中任一项所述的高镍正极活性材料，其中，所述高镍正极活性材料的体积平均粒径Dv50为1.5～20μm，所述壳层的总厚度为0.001～1μm。
  12. 一种高镍正极活性材料的制备方法，其包括如下步骤：
    S1：提供包覆有硅铝氢氧化物的高镍三元前驱体，得到第一中间体；
    S2：将所述第一中间体与M前驱体、锂前驱体混合，烧结后得到第二中间体；
    S3：将所述第二中间体与R前驱体混合，烧结后得到所述高镍正极活性材料；
    其中，所述高镍正极活性材料为核壳结构，
    所述核包括Li 1+a[Ni xCo yMn zM b]O 2，其中0.6≤x<1，0<y<0.3，0<z<0.3，0<a<0.2，0<b<0.2，x+y+z+b＝1，M为Mg、Ca、Sb、Ce、Ti、Zr、Sr、Al、Zn、Mo及B中的一种以上；
    所述壳包括包覆所述核的第一壳层，以及包覆所述第一壳层的第二壳层；其中，
    所述第一壳层为由锂、铝、硅、氧四种元素组成的快离子导体；
    所述第二壳层包括元素R的氧化物，所述R选自Al、B、Ti、P、Co、La中的一种以上。
  13. 根据权利要求12所述的制备方法，其中，
    在步骤S1中，所述包覆有硅铝氢氧化物的高镍三元前驱体的制备过程为：
    (a)将铝前驱体、硅前驱体完全溶于碱性溶液，而后加入高镍三元前驱体，得到固液混合物；
    (b)降低所述固液混合物的pH，引发铝前驱体和硅前驱体发生水解-原位沉淀反应，得到包覆有硅铝氢氧化物的高镍三元前驱体。
  14. 一种锂离子电池，包括权利要求1-11中任一项所述的高镍正极活性材料或根据权利要求12或13所述的制备方法制备的高镍正极活性材料。
  15. 一种电池模块，包括权利要求14所述的锂离子电池。
  16. 一种电池包，包括权利要求14所述的锂离子电池或权利要求15所述的电池模块中的一种以上。
  17. 一种用电装置，
    包括权利要求14所述的锂离子电池、权利要求15所述的电池模块或权利要求16所述的电池包中的一种以上，所述锂离子电池或所述电池模组或所述电池包用作所述用电装置的电源或所述用电装置的能量存储单元。
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