WO2023108397A1 - 一种正极活性材料、电化学装置和电子装置 - Google Patents

一种正极活性材料、电化学装置和电子装置 Download PDF

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WO2023108397A1
WO2023108397A1 PCT/CN2021/137773 CN2021137773W WO2023108397A1 WO 2023108397 A1 WO2023108397 A1 WO 2023108397A1 CN 2021137773 W CN2021137773 W CN 2021137773W WO 2023108397 A1 WO2023108397 A1 WO 2023108397A1
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positive electrode
active material
electrode active
present application
core
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PCT/CN2021/137773
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English (en)
French (fr)
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彭刚
郎野
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宁德新能源科技有限公司
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Priority to CN202180018075.0A priority Critical patent/CN115280552A/zh
Priority to EP21967537.8A priority patent/EP4394944A1/en
Priority to PCT/CN2021/137773 priority patent/WO2023108397A1/zh
Publication of WO2023108397A1 publication Critical patent/WO2023108397A1/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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • 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, in particular to a positive electrode active material, an electrochemical device and an electronic device.
  • lithium-ion batteries Due to its high energy density, long cycle life and no memory effect, lithium-ion batteries are widely used in wearable devices, smart phones, drones, electric vehicles and large energy storage devices, and have become the most developed in the world today. It is a potential new green chemical power source, but it also puts forward higher requirements for the comprehensive performance of lithium-ion batteries.
  • the purpose of the present application is to provide a positive electrode active material, an electrochemical device and an electronic device, so as to improve the cycle performance and kinetic performance of the electrochemical device.
  • the first aspect of the present application provides a kind of anode active material, and it comprises matrix and the first material that exists on the surface of matrix, matrix comprises core and shell layer, and the interplanar spacing d1 of the (003) crystal plane of first material is smaller than core The interplanar spacing d2 of the (003) crystal plane.
  • the interplanar distance d1 of the (003) crystal plane of the first material is smaller, It can reduce the risk of phase transition failure of the active crystal plane providing lithium ion channels at the interface with the electrolyte, thereby improving the structural stability of the positive electrode active material surface; on the other hand, the interplanar distance d1 of the (003) crystal plane is relatively small.
  • the small first material in which lithium ions are transported, suffers less resistance and has higher lithium ion conductivity, which can reduce the interfacial charge transfer resistance of the positive electrode active material, which is conducive to simultaneously improving the cycle performance of the electrochemical device and dynamic performance.
  • the structural stability and lithium ion conductivity of the surface of the positive electrode active material can be improved, thereby improving the cycle performance of the electrochemical device under high temperature and high pressure.
  • the mole percentage of Al in the shell is X1, based on the moles of metal elements other than Li in the core, the core
  • the mole percentage of Al element in the compound is X2, which satisfies: X1>X2.
  • the first material includes Co element, based on the molar number of metal elements other than Li in the first material, the mole percentage of Co element in the first material is C1, based on the matrix except Li The number of moles of metal elements other than , the mole percentage of Co element in the matrix is C2, satisfying: C1>C2. It is more conducive to reducing the interfacial charge transfer resistance of the positive electrode active material, thereby improving the kinetic performance of the electrochemical device.
  • the total number of moles of metal elements other than Li in the nucleus is n M1
  • the number of moles of Ni elements in the nucleus is n Ni1
  • the number of moles of Co elements in the nucleus is n Co1
  • the number of moles of the Mn element in the nucleus is n Co1 .
  • the number of moles of elements is n Mn1
  • the number of moles of Al elements in the nucleus is n Al
  • the number of moles of R elements in the nucleus is n R1 , 0.5 ⁇ n Ni1 /n M1 ⁇ 1, 0 ⁇ n Co1 /n M1 ⁇ 0.2, 0 ⁇ n Mn1 /n M1 ⁇ 0.5, 0 ⁇ n Al /n M1 ⁇ 0.03, 0 ⁇ n R1 /n M1 ⁇ 0.05
  • R elements include Mg, Ti, Zr, Nb, Y, Cr, V, At least one of Ge, Mo, Fe, Cu, Zn, Ga, Ag, W, In, Sn, Pb, Sb, La, Ce, Ca or Sr.
  • the total number of moles of metal elements other than Li in the first material is n M2
  • the number of moles of the Ni element in the first material is n Ni2
  • the number of moles of the Co element in the first material is n Co2
  • the number of moles of element Z in the first material is n Z
  • the number of moles of element R in the first material is n R2 , 0 ⁇ n Ni2 /n M2 ⁇ 0.6, 0.25 ⁇ n Co2 /n M2 ⁇ 1.0 , 0 ⁇ n Z /n M2 ⁇ 0.1, 0 ⁇ n R2 /n M2 ⁇ 0.05
  • Z elements include at least one of Mn or Al
  • R elements include Mg, Ti, Zr, Nb, Y, Cr, V, At least one of Ge, Mo, Fe, Cu, Zn, Ga, Ag, W, In, Sn, Pb, Sb, La, Ce, Ca or Sr.
  • n Co2 /n M2 - n Co1 /n M1 > 0.25.
  • the area percentage of the first material is 10% to 80%.
  • the first direction is a direction for observation using a test instrument (for example, a scanning electron microscope).
  • the area percentage of the first material is within the above range, the structural stability and lithium ion conductivity of the surface of the positive electrode active material can be improved, thereby improving the cycle performance of the electrochemical device under high temperature and high pressure.
  • the area percentage of the first material is 20% to 75%.
  • the average particle diameter of the first material is 50nm to 800nm;
  • the average particle diameter of the first material is in the above range, which is conducive to improving the specific surface area of the first material, thereby facilitating the improvement of the electrochemical device. dynamic performance.
  • the shell layer has a thickness of 5 nm to 80 nm. If the thickness of the shell layer is within the above range, the structural stability of the area on the surface of the substrate not covered by the first material can be improved, thereby improving the cycle performance of the electrochemical device.
  • the specific surface area of the positive electrode active material is less than or equal to 0.65 m 2 /g.
  • the average particle diameter of the matrix is 2 ⁇ m to 11 ⁇ m.
  • the matrix includes secondary particles composed of primary particles, and the average particle size of the primary particles is 1.5 ⁇ m to 4.0 ⁇ m.
  • the second aspect of the present application provides an electrochemical device, comprising the positive electrode active material described in any embodiment of the present application.
  • the positive electrode active material provided by the present application has good structural stability and low interfacial charge transfer resistance, so the electrochemical device provided by the present application has good cycle performance and kinetic performance.
  • a third aspect of the present application provides an electronic device comprising the electrochemical device described in any embodiment of the present application.
  • the electrochemical device provided by the application has good cycle performance and power performance, so the electronic device provided by the application has a long service life and good performance.
  • the application provides a positive electrode active material, which includes a matrix and a first material present on the surface of the matrix, the matrix includes a core and a shell, and the interplanar spacing d1 of the (003) crystal plane of the first material is smaller than the (003) of the core The interplanar distance d2 of the crystal plane.
  • FIG. 1 is a schematic structural view of the positive electrode active material in some embodiments of the present application.
  • Fig. 2 is the scanning electron micrograph of the positive electrode active material in the embodiment 2-1 of the present application;
  • Example 3 is a transmission electron microscope and an energy dispersive spectrometer (EDS) analysis photo of the cross section of the positive electrode active material in Example 2-1 of the present application.
  • EDS energy dispersive spectrometer
  • a lithium-ion battery is used as an example of an electrochemical device to explain the present application, but the electrochemical device of the present application is not limited to the lithium-ion battery.
  • the first aspect of the present application provides a positive electrode active material.
  • the interplanar spacing d1 of the (003) crystal planes of a material is smaller than the interplanar spacing d2 of the (003) crystal planes of the core.
  • the inventors of the present application have found that by regulating the interplanar distance d1 of the (003) crystal plane of the first material to be smaller than the crystal interplanar distance d2 of the (003) crystal plane of the core, the activity of providing lithium ion channels can be reduced The risk of phase transition failure at the interface between the crystal face and the electrolyte, thereby improving the structural stability of the surface of the positive electrode active material; at the same time, the resistance of lithium ions to transport in the first material with a smaller interplanar distance d1 is less , can reduce the interfacial charge transfer resistance of the positive electrode active material, which is conducive to improving the cycle performance and kinetic performance of the electrochemical device at the same time, for example, reducing the impedance
  • the value of d1 could be or any range in between
  • the value of d2 can be or any range in between.
  • the mole percentage of Al in the shell is X1, based on the moles of metal elements other than Li in the core, the core
  • the mole percentage of Al element in the compound is X2, which satisfies: X1>X2.
  • the irreversible phase change and oxygen release on the surface of the layer can improve the surface structure stability of the positive electrode active material in the high delithiation state, thereby improving the cycle performance of the electrochemical device under high voltage.
  • the stability of the shell layer is high, which is conducive to enhancing the interface stability between the matrix and the first material, and reducing the interface failure caused by the interface between the matrix and the first material. The risk of lithium ion transport being hindered, thereby improving the cycle performance of electrochemical devices under high temperature and high pressure.
  • the present application has no particular limitation on the values of X1 and X2, as long as the purpose of the present application can be achieved, for example, X1 is 1.5% to 3%, and X2 is 0 to 1.5%.
  • the molar percentages X1 and X2 of the Al element in the shell or core can be obtained by analyzing and testing the cross section of the positive electrode active material particle using an energy dispersive spectrometer (EDS) in a transmission electron microscope.
  • EDS energy dispersive spectrometer
  • the first material includes Co element, based on the molar number of metal elements other than Li in the first material, the mole percentage of Co element in the first material is C1, based on the matrix except Li The number of moles of metal elements other than , the mole percentage of Co element in the matrix is C2, satisfying: C1>C2.
  • the present application has no special limitation on the content of the Co element in the matrix, as long as the purpose of the present application can be achieved, for example, based on the moles of metal elements other than Li in the first material, the mole percentage of the Co element in the first material
  • the content C1 is greater than or equal to 25%.
  • the total number of moles of metal elements other than Li in the nucleus is n M1
  • the number of moles of Ni elements in the nucleus is n Ni1
  • the number of moles of Co elements in the nucleus is n Co1
  • the number of moles of the Mn element in the nucleus is n Co1 .
  • the number of moles of elements is n Mn1
  • the number of moles of Al elements in the nucleus is n Al
  • the number of moles of R elements in the nucleus is n R1 , 0.5 ⁇ n Ni1 /n M1 ⁇ 1, 0 ⁇ n Co1 /n M1 ⁇ 0.2, 0 ⁇ n Mn1 /n M1 ⁇ 0.5, 0 ⁇ n Al /n M1 ⁇ 0.03, 0 ⁇ n R1 /n M1 ⁇ 0.05
  • R elements include Mg, Ti, Zr, Nb, Y, Cr, V, At least one of Ge, Mo, Fe, Cu, Zn, Ga, Ag, W, In, Sn, Pb, Sb, La, Ce, Ca or Sr.
  • the total number of moles of metal elements other than Li in the first material is n M2
  • the number of moles of the Ni element in the first material is n Ni2
  • the number of moles of the Co element in the first material is n Co2
  • the number of moles of element Z in the first material is n Z
  • the number of moles of element R in the first material is n R2 , 0 ⁇ n Ni2 /n M2 ⁇ 0.6, 0.25 ⁇ n Co2 /n M2 ⁇ 1.0 , 0 ⁇ n Z /n M2 ⁇ 0.1, 0 ⁇ n R2 /n M2 ⁇ 0.05
  • Z elements include at least one of Mn or Al
  • R elements include Mg, Ti, Zr, Nb, Y, Cr, V, At least one of Ge, Mo, Fe, Cu, Zn, Ga, Ag, W, In, Sn, Pb, Sb, La, Ce, Ca or Sr.
  • Al and R are included in the core, which can enhance the stability of the core, and can suppress the side reaction between the positive active material and the electrolyte when the positive active material is cracked, thereby helping to improve the battery life. Cycling performance of chemical devices.
  • the core includes LiNi 0.5 Co 0.1 Mn 0.385 Al 0.012 Zr 0.002 Ti 0.001 O 2 , LiNi 0.6 Co 0.1 Mn 0.288 Al 0.012 O 2 , LiNi 0.8 Co 0.1 Mn 0.085 Al 0.012 Zr 0.003 O 2 ⁇ LiNi 0.6 Co 0.1 Mn At least one of 0.285 Al 0.012 Zr 0.002 Ti 0.001 O 2 .
  • the first material includes LiNi 0.5 Co 0.45 Mn 0.05 O 2 , LiNi 0.6 Co 0.35 Mn 0.05 O 2 , LiCoO 2 , LiNi 0.5 Co 0.45 Mn 0.04 Al 0.01 O 2 or LiNi 0.5 Co 0.45 Mn 0.038 Al 0.01 Ti 0 .001 At least one of O2 .
  • n Co2 /n M2 - n Co1 /n M1 ⁇ 0.25, preferably 0.25 ⁇ n Co2 /n M2 - n Co1 /n M1 ⁇ 0.9.
  • the value of n Co2 /n M2 ⁇ n Co1 /n M1 can be 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 or any range therebetween.
  • the area percentage of the first material is 10% to 80%.
  • the structural stability and lithium ion conductivity of the surface of the positive electrode active material can be improved, thereby improving the cycle performance of the electrochemical device under high temperature and high pressure.
  • the first material has an average particle size of 50 nm to 800 nm.
  • the average particle diameter of the first material may be 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm or any range therebetween.
  • the shell layer has a thickness of 5 nm to 80 nm.
  • the thickness of the shell layer can be 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or any range therebetween.
  • the average particle diameter of the matrix is 2 ⁇ m to 11 ⁇ m.
  • the average particle size of the matrix can be 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m or any range therebetween.
  • the specific surface area (BET) of the positive electrode active material is less than or equal to 0.65 m 2 /g, further ranging from 0.4 m 2 /g to 0.65 m 2 /g.
  • the specific surface area of the positive electrode active material may be 0.5m 2 /g, 0.55m 2 /g, 0.6m 2 /g, 0.65m 2 /g or any range therebetween.
  • the matrix includes secondary particles composed of primary particles, and the average particle size of the primary particles is 1.5 ⁇ m to 4.0 ⁇ m.
  • the average particle size of the primary particles may be 1.5 ⁇ m, 2.0 ⁇ m, 2.5 ⁇ m, 3.0 ⁇ m, 3.5 ⁇ m, 4.0 ⁇ m or any range therebetween.
  • primary particles refer to single particles observed in SEM photographs
  • secondary particles refer to structures in which multiple primary particles are aggregated or agglomerated together, and there are obvious grain boundaries between adjacent primary particles.
  • the present application has no special restrictions on the preparation method of the positive electrode active material, as long as the purpose of the present application can be achieved, for example, it may include but not limited to the following steps: mix Ni source, Co source and Mn source solution, optionally add the above-mentioned R source solution, the precursor was prepared by co-precipitation method. Then mix the precursor with the lithium source, optionally add the Al source and/or the above-mentioned R source compound, perform sintering, cooling, crushing, and sieving in an oxygen or air atmosphere to obtain an intermediate product.
  • the present application has no special limitation on the temperature and time of the primary sintering, as long as the purpose of the present application can be achieved, for example, the sintering temperature is 780°C to 1000°C, and the sintering time is 5h to 20h.
  • the first material can be prepared by a preparation method known in the art. Then mix the intermediate product with the first material, optionally add the Al source and/or the above-mentioned R source compound, and perform secondary sintering in an oxygen or air atmosphere to obtain the positive electrode active material.
  • the present application has no special limitation on the above-mentioned secondary sintering temperature and time, as long as the purpose of the present application can be achieved, for example, the sintering temperature is 500°C to 750°C, and the sintering time is 3h to 10h.
  • Al source is added in at least one of the primary sintering and secondary sintering steps.
  • the temperature and/or duration of primary sintering usually affect the size of primary particles, for example, as the temperature of primary sintering increases and/or the time prolongs, the size of primary particles in the obtained matrix is Increasing trend; as the primary sintering temperature decreases and/or the time shortens, the size of the primary particles in the resulting matrix tends to decrease.
  • the second aspect of the present application provides an electrochemical device, comprising the positive electrode active material described in any embodiment of the present application.
  • the positive electrode active material provided by the application has good structural stability and low interfacial charge transfer resistance, so the electrochemical device provided by the application has good cycle performance and kinetic performance.
  • the electrochemical device may include a positive pole piece.
  • the positive pole piece in this application is not particularly limited, as long as the purpose of this application can be achieved.
  • the positive pole piece usually includes a positive current collector.
  • the positive electrode current collector is not particularly limited, as long as the purpose of the present application can be achieved, for example, it may include but not limited to aluminum foil, aluminum alloy foil, or a composite current collector.
  • the thickness of the positive electrode collector is 8 ⁇ m to 12 ⁇ m.
  • the positive electrode material layer may be provided on one surface in the thickness direction of the positive electrode current collector, or on two surfaces in the thickness direction of the positive electrode current collector. It should be noted that the "surface” here may refer to the entire area of the positive electrode collector or a partial area of the positive electrode collector. This application is not particularly limited, as long as the purpose of this application can be achieved.
  • the positive electrode material layer includes the positive electrode active material in any of the foregoing embodiments of the application, and the positive electrode material layer may also include a positive electrode binder.
  • This application has no special restrictions on the positive electrode binder, as long as the application can be realized
  • the purpose is enough, for example, it may include but not limited to at least one of fluorine-containing resin, polypropylene resin, fiber type adhesive, rubber type adhesive or polyimide type adhesive.
  • a conductive agent may also be included in the positive electrode material layer.
  • the present application has no special limitation on the conductive agent, as long as the purpose of the application can be achieved, for example, it may include but not limited to conductive carbon black, carbon nanotubes (CNTs), At least one of carbon fiber, acetylene black, graphite, Ketjen black, graphene, metal material or conductive polymer.
  • the aforementioned carbon nanotubes may include, but are not limited to, single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
  • the aforementioned carbon fibers may include, but are not limited to, vapor grown carbon fibers (VGCF) and/or carbon nanofibers.
  • the above metal material may include but not limited to metal powder and/or metal fiber, specifically, the metal may include but not limited to at least one of copper, nickel, aluminum or silver.
  • the aforementioned conductive polymer may include but not limited to at least one of polyphenylene derivatives, polyaniline, polythiophene, polyacetylene or polypyrrole.
  • the present application has no special limitation on the content of the positive electrode active material, positive electrode binder, and conductive agent, and conventional contents in this field can be used as long as the purpose of the present application can be achieved.
  • the mass percentage of the positive electrode active material is 90% to 98%
  • the mass percentage of the positive electrode binder is 0.5% to 5%
  • the mass percentage of the conductive agent is 0.5%. to 5%.
  • the positive electrode sheet may further include a conductive layer located between the positive electrode current collector and the positive electrode material layer.
  • the present application has no particular limitation on the composition of the conductive layer, which may be a commonly used conductive layer in the field, for example, may include but not limited to the above-mentioned conductive agent and the above-mentioned positive electrode binder.
  • the electrochemical device may also include a negative electrode sheet.
  • the negative electrode sheet in this application is not particularly limited, as long as the purpose of this application can be achieved.
  • the negative electrode sheet usually includes a negative electrode collector and a negative electrode material layer.
  • the negative electrode material layer may be provided on one surface in the thickness direction of the negative electrode current collector, or on two surfaces in the thickness direction of the negative electrode current collector. It should be noted that the "surface” here may be the entire area of the negative electrode collector, or a partial area of the negative electrode collector. This application is not particularly limited, as long as the purpose of this application can be achieved.
  • the negative electrode current collector is not particularly limited, as long as the purpose of this application can be achieved, for example, it may include but not limited to copper foil, copper alloy foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam or composite Collectors, etc.
  • the thickness of the current collector of the negative electrode is 4 ⁇ m to 12 ⁇ m.
  • the negative electrode material layer includes a negative electrode active material, wherein the negative electrode active material is not particularly limited, as long as the purpose of the application can be achieved, for example, the negative electrode active material includes a carbon material that can reversibly intercalate/deintercalate lithium ions.
  • the carbon material may be a carbon material known in the art to be used as an anode active material, for example, the carbon material may include but not limited to crystalline carbon and/or amorphous carbon.
  • the above-mentioned crystalline carbon may include, but is not limited to, amorphous, plate-shaped, platelet-shaped, spherical or fibrous natural graphite or artificial graphite.
  • the aforementioned amorphous carbon may include, but is not limited to, at least one of soft carbon, hard carbon, mesophase pitch carbide, or calcined coke.
  • the negative electrode active material may include but not limited to natural graphite, artificial graphite, mesophase microcarbon spheres (MCMB), hard carbon, soft carbon, silicon, silicon oxide (SiO x , x is 1 or 2) or silicon- At least one of the carbon composites.
  • the mass ratio of silicon and carbon in the silicon-carbon composite is 1:10 to 10:1, and the Dv50 is 0.1 ⁇ m to 100 ⁇ m.
  • a conductive agent may also be included in the negative electrode material layer.
  • the conductive agent in this application, as long as the purpose of this application can be achieved, for example, it may include but not limited to the above-mentioned conductive agent.
  • the negative electrode material layer may also include a negative electrode binder.
  • the present application has no special restrictions on the negative electrode binder, as long as the purpose of the application can be achieved, for example, it may include but not limited to polyvinyl alcohol, carboxymethyl Cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, At least one of polyvinylidene fluoride, polyethylene, polypropylene, polyacrylic acid, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin or nylon.
  • the negative electrode sheet may further include a conductive layer located between the negative electrode current collector and the negative electrode material layer.
  • the present application has no particular limitation on the composition of the conductive layer, which may be a commonly used conductive layer in the field, and the conductive layer may include but not limited to the above-mentioned conductive agent and the above-mentioned negative electrode binder.
  • the electrochemical device can also include a separator, and the present application has no special limitation on the separator, as long as the purpose of the application can be achieved, for example, it can include but not limited to polyethylene (PE), polypropylene (PP), Polytetrafluoroethylene-based polyolefin (PO)-based separator, polyester film (such as polyethylene terephthalate (PET) film), cellulose film, polyimide film (PI), polyamide At least one of film (PA), spandex, aramid film, woven film, non-woven film (non-woven fabric), microporous film, composite film, separator paper, laminated film or spun film, preferably polyethylene or polypropylene, which have a good effect on preventing short circuits and can improve the stability of electrochemical devices through the shutdown effect.
  • PET polyethylene terephthalate
  • PI polyimide film
  • PA polyamide
  • spandex aramid film
  • woven film non-woven film (non-woven fabric)
  • the separator of the present application may have a porous structure, and the pore size is not particularly limited as long as the purpose of the present application can be achieved, for example, the pore size may be 0.01 ⁇ m to 1 ⁇ m.
  • the thickness of the isolation film is not particularly limited, as long as the purpose of the present application can be achieved, for example, the thickness may be 5 ⁇ m to 500 ⁇ m.
  • a separator may include a substrate layer and a surface treatment layer.
  • the substrate layer can be a non-woven fabric, film or composite film with a porous structure, and the material of the substrate layer can include but not limited to polyethylene, polypropylene, polyethylene terephthalate or polyimide at least one.
  • a polypropylene porous film, a polyethylene porous film, a polypropylene non-woven fabric, a polyethylene non-woven fabric, or a polypropylene-polyethylene-polypropylene porous composite film may be used.
  • at least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic material.
  • the inorganic material layer may include but not limited to inorganic particles and inorganic material layer binder, and the present application has no special limitation on inorganic particles, for example, may include but not limited to aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, At least one of tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the present application has no particular limitation on the inorganic layer binder, for example, it may include but not limited to polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, At least one of polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • polyvinylidene fluoride copolymer of vinylidene fluoride-hexafluoropropylene
  • polyamide polyacrylonitrile
  • polyacrylate polyacrylic acid
  • the polymer layer contains a polymer, and the polymer material may include but not limited to polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinyl pyrrolidone, polyvinyl ether, polyvinylidene fluoride At least one of ethylene or poly(vinylidene fluoride-hexafluoropropylene).
  • the electrochemical device may further include an electrolyte, which may include, but not limited to, one or more of a gel electrolyte, a solid electrolyte, and an electrolytic solution.
  • the electrolytic solution may include a lithium salt and a non-aqueous solvent.
  • lithium salts can be selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB or lithium difluoroborate.
  • the lithium salt comprises LiPF 6 .
  • the present application has no special limitation on the non-aqueous solvent, as long as the purpose of the present application can be achieved, for example, it may include but not limited to at least one of carbonate compounds, carboxylate compounds, ether compounds or other organic solvents.
  • the above-mentioned carbonate compound may include but not limited to at least one of chain carbonate compound, cyclic carbonate compound or fluorocarbonate compound.
  • Above-mentioned chain carbonate compound can include but not limited to dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylene propyl carbonate (EPC) or at least one of methyl ethyl carbonate (MEC).
  • the above-mentioned cyclic carbonate may include but not limited to at least one of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) or vinylethylene carbonate (VEC).
  • Fluorocarbonate compounds may include, but are not limited to, fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate Ethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2- At least one of difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, or trifluoromethylethylene carbonate.
  • FEC fluoroethylene carbonate
  • 1,2-difluoroethylene carbonate 1,1-difluoroethylene carbonate
  • carboxylate compounds may include but are not limited to methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyl At least one of lactone, decanolactone, valerolactone, mevalonolactone or caprolactone.
  • the aforementioned ether compounds may include, but are not limited to, dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxy At least one of methoxyethane, 2-methyltetrahydrofuran or tetrahydrofuran.
  • the above-mentioned other organic solvents may include but not limited to dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2- At least one of pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate or phosphoric acid ester.
  • the electrochemical device of the present application is not particularly limited, and it may include any device that undergoes an electrochemical reaction.
  • electrochemical devices may include, but are not limited to, primary batteries, secondary batteries, fuel cells, solar cells, or capacitors, among others.
  • the electrochemical device is a lithium secondary battery
  • the secondary battery may include, but not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery. More preferably, the electrochemical device is a lithium ion battery.
  • the preparation process of electrochemical devices is well known to those skilled in the art, and the present application is not particularly limited.
  • it may include but not limited to the following steps: stack the positive electrode sheet, separator and negative electrode sheet in sequence, and as required Winding, folding and other operations to obtain the electrode assembly with a winding structure, put the electrode assembly into the packaging bag, inject the electrolyte into the packaging bag and seal it, and obtain an electrochemical device; or, put the positive electrode sheet, separator and negative electrode
  • the pole pieces are stacked in order, and then the four corners of the entire laminated structure are fixed with adhesive tape to obtain the electrode assembly of the laminated structure.
  • the electrode assembly is placed in the packaging bag, and the electrolyte is injected into the packaging bag and sealed to obtain an electrochemical device.
  • overcurrent prevention elements, guide plates, etc. can also be placed in the packaging bag as needed, so as to prevent pressure rise and overcharge and discharge inside the electrochemical device.
  • a third aspect of the present application provides an electronic device comprising the electrochemical device described in any embodiment of the present application.
  • the electrochemical device provided by the application has good cycle performance and dynamic performance, so the electronic device provided by the application has a long service life and good performance.
  • the electronic device of the present application is not particularly limited, and it may be used in any electronic device known in the prior art.
  • electronic devices may include, but are not limited to, notebook computers, pen-based computers, mobile computers, e-book players, cellular phones, portable fax machines, portable copiers, portable printers, headsets, video recorders, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, automobiles, motorcycles, power-assisted bicycles, power tools, wireless Man-machines, hand-held vacuum cleaners, bicycles, lighting appliances, toys, game consoles, clocks, electric tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.
  • the lithium-ion battery is charged and discharged for the first time in an environment of 45°C, charged with a constant current at a charging current of 1.5C to a voltage of 4.35V, then charged at a constant voltage to a current of 0.05C, and then charged at a charging current of 4C Carry out constant current discharge under the discharge current until the final voltage is 2.8V, record the discharge capacity of the first cycle; then repeat the above charging and discharging cycles 1000 times, and record the discharge capacity of the 1000th cycle.
  • Cycle capacity retention (discharge capacity at the 1000th cycle/discharge capacity at the first cycle) ⁇ 100%.
  • the lithium-ion battery is subjected to the following test steps at 25°C:
  • the lithium-ion battery was fully charged to 2.8V at a current density of 0.1C, and after standing for 10min, it was disassembled in the glove box to obtain the positive pole piece; the positive pole piece was transferred to a scanning electron microscope equipped with a focused ion beam (model: FEI In the cavity of Vion Plasma FIB), the sample that can be used for transmission scanning electron microscope (STEM, model: FEI Titan3 G2 60-300) is processed, and the surface of the sample is required to be protected by Pt and processed by Ga ion beam, and the thickness of the sample should not exceed 100nm; And use the low voltage mode to clean to remove the residual surface of the sample processing.
  • EDS X-ray Energy Spectrum Analysis
  • FIG. 3 As shown in Figure 3, (a) in Figure 3 is a transmission electron micrograph of the cross section of the positive electrode active material in Example 2-1, and (b) and (c) in Figure 3 are the EDS elements of the cross section in (a) Analyzing the photos, (b) in Figure 3 is the distribution of Al elements, and (c) in Figure 3 is the distribution of Co elements. It can be seen from (b) and (c) in FIG. 3 that the contents of Al element and Co element in the shell layer 112 are greater than the contents of Al element and Co element in the core 111 .
  • the signal generated in the area above the shell layer 112 in (b) of FIG. 3 is the interference signal generated by the Pt protective layer on the sample surface.
  • EDS X-ray Energy Spectroscopy
  • Use image processing software to randomly select one positive electrode active material particle determine that the area of the positive electrode active material particle is S, and the total area of the first material particles on its surface is S1, then the area of the first material in the positive electrode active material particle accounts for The ratio is S1/S, 50 positive electrode active material particles are randomly counted, and the average value is taken as the area ratio of the first material.
  • Nickel sulfate, cobalt sulfate and manganese sulfate are mixed and added in deionized water to prepare a mixed salt solution, sodium hydroxide is added to deionized water to be prepared into an alkali solution, and ammonia water is selected as a complexing agent, and then the salt solution, the alkali solution Add the complexing agent into the reaction kettle, and add aluminum sulfate to react.
  • the reaction temperature is controlled at 25°C and the pH is 11.
  • the particle size Dv50 reaches a predetermined value of 4.5 ⁇ m, the reaction slurry is filtered, washed, and dried to obtain a precursor.
  • nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate are fed according to the molar ratio of Ni, Co, Mn, and Al being 0.5:0.1:0.385:0.012.
  • the matrix precursor and the first material LiNi 0.5 Co 0.45 Mn 0.05 O 2 to obtain a mixed material, then add it to a high-mixer and mix it evenly, then add it to a sagger and place it in a kiln under an oxygen atmosphere.
  • the mass ratio of the first material to the matrix precursor is 2:100
  • the average particle size of the first material is 200nm
  • the secondary sintering temperature is 600°C
  • the time is 6h.
  • the core in the matrix is LiNi 0.5 Co 0.1 Mn 0.385 Al 0.012 Zr 0.002 Ti 0.001 O 2 .
  • the positive electrode active material prepared above, the conductive agent acetylene black and carbon nanotubes, and the binder polyvinylidene fluoride are mixed according to a mass ratio of 96:1.2:0.8:2, N-methylpyrrolidone is added, and the mixture is mixed in a vacuum mixer Stir evenly under action to obtain positive electrode slurry, wherein the solid content of the positive electrode slurry is 70%.
  • the positive electrode slurry was evenly coated on one surface of the positive electrode current collector aluminum foil, and the aluminum foil was dried at 120° C. for 1 hour to obtain a positive electrode sheet coated with a positive electrode material layer on one side. Repeat the above steps on the other surface of the aluminum foil to obtain a positive electrode sheet coated with a positive electrode material layer on both sides. Then, after cold pressing, cutting, and slitting, the positive electrode sheet is obtained.
  • Negative electrode active material artificial graphite, binder styrene-butadiene rubber, and thickener sodium carboxymethyl cellulose are mixed according to the mass ratio of 97.4:1.2:1.4, deionized water is added, and stirred evenly under the action of a vacuum mixer to obtain the negative electrode slurry, wherein the solid content of the negative electrode slurry is 75%.
  • the negative electrode slurry was uniformly coated on one surface of the negative electrode current collector copper foil, and the copper foil was dried at 120° C. to obtain a negative electrode sheet coated with a negative electrode material layer on one side. Repeat the above steps on the other surface of the copper foil to obtain a negative electrode sheet coated with a negative electrode material layer on both sides. Then, the negative electrode sheet is obtained after cold pressing, cutting, and slitting.
  • a porous polyethylene film with a thickness of 7 ⁇ m was used.
  • the positive electrode sheet, separator, and negative electrode sheet prepared above in order so that the separator is placed between the positive electrode sheet and the negative electrode sheet to play the role of isolation, and the electrode assembly is obtained by winding.
  • Put the electrode assembly in an aluminum-plastic film packaging bag inject electrolyte after drying, and obtain a lithium-ion battery through processes such as vacuum packaging, standing, chemical formation, degassing, and edge trimming.
  • step (1) of ⁇ Preparation of positive electrode active material> is 0.6:0.1:0.288:0.012
  • ZrO 2 and TiO 2 are not added in step (2)
  • the molar ratio of Co+Mn+Al elements is 1.05:1, except that the core in the prepared matrix is LiNi 0.6 Co 0.1 Mn 0.288 Al 0.012 O 2 , the rest is the same as that of Example 1-1.
  • step (1) of ⁇ Preparation of positive electrode active material> is 0.8:0.1:0.085:0.012
  • no TiO 2 is added in step (2), Li, Ni+Co+Mn
  • the molar ratio of +Al to Zr is 1.05:0.997:0.003
  • the temperature of primary sintering is 830°C
  • the first material in step (3) is replaced by LiNi 0.6 Co 0.35 Mn 0.05 O 2
  • the core of the prepared matrix is LiNi 0.8 Co
  • the rest are the same as in Example 1-1.
  • step (3) of ⁇ Preparation of Positive Electrode Active Material> mix the matrix precursor, Al 2 O 3 and the first material LiNi 0.5 Co 0.45 Mn 0.05 O 2 , based on the mass of the matrix precursor, in Al 2 O 3
  • the mass percentage of Al is 0.2%, and the rest are the same as in Example 1-1.
  • FIG. 2 A scanning electron micrograph of the positive electrode active material prepared above is shown in FIG. 2 , and it can be seen from the figure that the first material is evenly distributed on the surface of the matrix.
  • Example 2-1 Except that the first material in the step (3) of ⁇ Preparation of Positive Electrode Active Material> was replaced by LiNi 0.6 Co 0.35 Mn 0.05 O 2 , the rest was the same as that of Example 2-1.
  • step (1) of ⁇ Preparation of positive electrode active material> is 0.6:0.1:0.288:0.012
  • ZrO 2 and TiO 2 are not added in step (2)
  • the molar ratio of Co+Mn+Al elements is 1.05:1, except that the core in the prepared matrix is LiNi 0.6 Co 0.1 Mn 0.288 Al 0.012 O 2 , the rest is the same as that of Example 2-1.
  • step (1) of ⁇ Preparation of Positive Electrode Active Material> is 0.6:0.1:0.285:0.012
  • the temperature of primary sintering in step (2) is 910°C
  • the core in the matrix is prepared Except for LiNi 0.6 Co 0.1 Mn 0.285 Al 0.012 Zr 0.002 Ti 0.001 O 2 , the rest are the same as in Example 2-2.
  • step (1) of ⁇ Preparation of positive electrode active material> is 0.8:0.1:0.085:0.012
  • no TiO 2 is added in step (2), Li, Ni+Co+Mn
  • the molar ratio of +Al and Zr elements is 1.05:0.997:0.003
  • the temperature of primary sintering is 830°C
  • the core of the prepared matrix is LiNi 0.8 Co 0.1 Mn 0.085 Al 0.012 Zr 0.003 O 2 , the rest is the same as that of Example 2-1.
  • Embodiment 2-11 and Embodiment 2-12 are identical to Embodiment 2-11 and Embodiment 2-12.
  • the mass percentage of Y in Y 2 O 3 is 0.1%, and the rest are the same as the implementation Example 2-6 are the same.
  • TiO is also added for sintering. Based on the quality of the matrix precursor, the mass percentage of Ti in TiO is 0.2%, and the rest are the same as those in Examples 2-6. same.
  • Example 2-15 in addition to the step (3) of ⁇ Preparation of Positive Electrode Active Material>, TiO 2 and WO 3 were added for sintering, based on the mass of the matrix precursor, the mass percentage of Ti in TiO 2 was 0.2%, Except that the mass percentage of W in WO 3 is 0.2%, the rest is the same as that of Examples 2-6.
  • step (2) of ⁇ Preparation of Positive Electrode Active Material> was adjusted to 880° C. and 930° C. so that the average particle size of the matrix is shown in Table 3, the rest was the same as that of Examples 2-6.
  • the average particle size of the first material is adjusted to 50nm, 100nm, 500nm, and 800nm in sequence, the rest is the same as that of Example 2-6.
  • Example 1-1 to Example 1-5 and Comparative Example 1-1 From Example 1-1 to Example 1-5 and Comparative Example 1-1, it can be seen that the first material is coated on the surface of the substrate in Example 1-1 to Example 1-5, and the lithium ion battery can be used under high temperature and high pressure conditions.
  • the cycle capacity retention rate is higher and the DC resistance is lower when the high-rate charge and discharge is carried out at a high rate, that is, the cycle performance and kinetic performance of the lithium-ion battery have been improved.
  • the interplanar spacing d1 of the (003) crystal plane of the first material is small, which can reduce the risk of phase transition failure of the active crystal plane providing lithium ion channels at the interface with the electrolyte, thereby Improve the structural stability of the surface of the positive electrode active material;
  • the first material with a smaller interplanar spacing d1 of the (003) crystal plane has a lower resistance to the transmission of lithium ions in it, and has a higher lithium ion conductivity
  • the efficiency can reduce the interfacial charge transfer resistance of the positive electrode active material, which is conducive to improving the cycle performance and kinetic performance of the lithium-ion battery at the same time.
  • Example 1-1 to Example 1-5 Example 2-1 to Example 2-15, it can be seen that further setting an Al-rich shell layer in the matrix can further significantly improve the performance of lithium-ion batteries under high temperature and high pressure conditions. Cycle performance when performing high rate charge and discharge.
  • the possible reason is that by setting the Al-rich shell layer, on the one hand, it is beneficial to improve the structural stability of the area on the surface of the substrate that is not covered by the first material; The stability of the interface between the first materials reduces the risk of hindering the transmission of lithium ions between the matrix and the first material due to interface failure, thereby further improving the cycle performance of the lithium-ion battery under high temperature and high pressure.
  • Example 2-6 As can be seen from Example 2-6, Example 3-1 to Example 3-2, Example 3-6 to Example 3-9, by regulating the relative size of the average particle diameter between the substrate and the first material, The area ratio of the first material on the surface of the positive electrode active material can be regulated, and the lithium-ion battery has more excellent cycle performance when the area ratio of the first material is in the range of 20% to 65%. From Example 2-6, Example 3-3 to Example 3-5, it can be seen that as the thickness of the shell layer increases, the obtained lithium ion battery has more excellent cycle performance.

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Abstract

本申请提供了一种正极活性材料、电化学装置和电子装置，正极活性材料包括基体和存在于基体表面的第一材料，基体包括核和壳层，第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2。通过调控第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2，可以提升正极活性材料表面的结构稳定性，以及降低正极活性材料的界面电荷转移阻抗，从而有利于同时提高电化学装置的循环性能和动力学性能。

Description

一种正极活性材料、电化学装置和电子装置 技术领域
本申请涉及电化学领域，特别是涉及一种正极活性材料、电化学装置和电子装置。
背景技术
锂离子电池由于具有高能量密度、长循环寿命及无记忆效应等优点而被广泛应用于穿戴设备、智能手机、无人机、电动汽车及大型储能设备等领域，已成为当今世界最具发展潜力的新型绿色化学电源，但也对锂离子电池的综合性能提出更高的要求。
发明内容
本申请的目的在于提供一种正极活性材料、电化学装置和电子装置，以提高电化学装置的循环性能和动力学性能。
本申请的第一方面提供了一种正极活性材料，其包括基体和存在于基体表面的第一材料，基体包括核和壳层，第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2。通过调控第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2，一方面，第一材料的(003)晶面的晶面间距d1较小，可以降低提供锂离子通道的活性晶面在与电解液的交界处发生相变失效的风险，从而提升正极活性材料表面的结构稳定性；另一方面，(003)晶面的晶面间距d1较小的第一材料，锂离子在其中传输所受到的阻力较小，具有较高的锂离子电导率，能够降低正极活性材料的界面电荷转移阻抗，从而有利于同时提高电化学装置的循环性能和动力学性能。
在本申请的一些实施方案中，
Figure PCTCN2021137773-appb-000001
通过调控d1和d2的值在上述范围内，能够提升正极活性材料表面的结构稳定性和锂离子电导率，从而提高电化学装置在高温高压下的循环性能。
在本申请的一些实施方案中，基于壳层中除Li以外的金属元素的摩尔数，壳层中Al元素的摩尔百分含量为X1，基于核中除Li以外的金属元素的摩尔数，核中Al元素的摩尔百分含量为X2，满足：X1>X2。一方面，有利于提高基体表面未被第一材料覆盖区域的结构稳定性；另一方面，由于壳层的稳定性较高，有利于增强基体与第一材料之间的界面稳定性，降低由于界面失效导致基体与第一材料之间锂离子传输受阻的风险，进而提高电化学装置在高温高压下的循环性能。
在本申请的一些实施方案中，1.5％≤X1≤3％。在本申请的一些实施方案中，X2≤1.5％。
在本申请的一些实施方案中，第一材料包括Co元素，基于第一材料中除Li以外的金属元素的摩尔数，第一材料中Co元素的摩尔百分含量为C1，基于基体中除Li以外的金属元素的摩尔数，基体中Co元素的摩尔百分含量为C2，满足：C1>C2。更有利于降低正极活性材料的界面电荷转移阻抗，从而提升电化学装置的动力学性能。
在本申请的一些实施方案中，核中除Li以外的金属元素的摩尔总数为n M1，核中Ni元素的摩尔数为n Ni1，核中Co元素的的摩尔数为n Co1，核中Mn元素的的摩尔数为n Mn1，核中Al元素的的摩尔数为n Al，核中R元素的的摩尔数为n R1，0.5≤n Ni1/n M1＜1，0≤n Co1/n M1≤0.2，0≤n Mn1/n M1≤0.5，0＜n Al/n M1≤0.03，0≤n R1/n M1≤0.05，R元素包括Mg、Ti、Zr、Nb、Y、Cr、V、Ge、Mo、Fe、Cu、Zn、Ga、Ag、W、In、Sn、Pb、Sb、La、Ce、Ca或Sr中的至少一种。
在本申请的一些实施方案中，第一材料中除Li以外的金属元素的摩尔总数为n M2，第一材料中Ni元素的摩尔数为n Ni2，第一材料中Co元素的的摩尔数为n Co2，第一材料中Z元素的的摩尔数为n Z，第一材料中R元素的的摩尔数为n R2，0≤n Ni2/n M2≤0.6，0.25≤n Co2/n M2≤1.0，0≤n Z/n M2≤0.1，0≤n R2/n M2≤0.05，Z元素包括Mn或Al中的至少一种，R元素包括Mg、Ti、Zr、Nb、Y、Cr、V、Ge、Mo、Fe、Cu、Zn、Ga、Ag、W、In、Sn、Pb、Sb、La、Ce、Ca或Sr中的至少一种。
通过选择上述核和/或第一材料，有利于同时提高电化学装置的循环性能和动力学性能。
在本申请的一些实施方案中，n Co2/n M2-n Co1/n M1≥0.25。通过调控n Co2/n M2-n Co1/n M1的值在上述范围内，有利于降低正极活性材料的界面电荷转移阻抗，从而提升电化学装置的动力学性能。
在本申请的一些实施方案中，沿第一方向观察，基于正极活性材料的面积，第一材料的面积百分比为10％至80％。其中，第一方向为使用测试仪器(例如，扫描电子显微镜)进行观测的方向。第一材料的面积百分比在上述范围内，能够提升正极活性材料表面的结构稳定性和锂离子电导率，从而提高电化学装置在高温高压下的循环性能。进一步地，沿第一方向观察，基于正极活性材料的面积，第一材料的面积百分比为20％至75％。
在本申请的一些实施方案中，第一材料的平均粒径为50nm至800nm；第一材料的平均粒径在上述范围内，有利于提高第一材料的比表面积，从而有利于提高电化学装置的动力学性能。
在本申请的一些实施方案中，壳层的厚度为5nm至80nm。壳层的厚度在上述范围内， 能够提高基体表面未被第一材料覆盖区域的结构稳定性，从而有利于提高电化学装置的循环性能。
在本申请的一些实施方案中，正极活性材料的比表面积小于或等于0.65m 2/g。通过调控正极活性材料的比表面积在上述范围内，有利于降低正极活性材料表面的副反应，从而有利于提高电化学装置的循环性能。
在本申请的一些实施方案中，所述基体的平均粒径为2μm至11μm。
在本申请的一些实施方案中，基体包括由一次颗粒构成的二次颗粒，一次颗粒的平均粒径为1.5μm至4.0μm。通过调控一次颗粒的平均粒径在上述范围内，有利于提高电化学装置的动力学性能。
本申请的第二方面提供了一种电化学装置，包含本申请任一实施方案中所述的正极活性材料。本申请提供的正极活性材料具有良好的结构稳定性以及较低的界面电荷转移阻抗，从而本申请提供的电化学装置具有良好的循环性能和动力学性能。
本申请的第三方面提供了一种电子装置，包含本申请任一实施方案中所述的电化学装置。本申请提供的电化学装置具有良好的循环性能和动力性能，从而本申请提供的电子装置具有较长的使用寿命和良好的性能。
本申请提供了一种正极活性材料，其包括基体和存在于基体表面的第一材料，基体包括核和壳层，第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2。通过调控第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2，可以提升正极活性材料表面的结构稳定性以及降低正极活性材料的界面电荷转移阻抗，从而有利于同时提高电化学装置的循环性能和动力学性能。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例。
图1为本申请一些实施例中的正极活性材料的结构示意图；
图2为本申请实施例2-1中的正极活性材料的扫描电镜照片；
图3为本申请实施例2-1中正极活性材料截面的透射电镜和能谱仪(EDS)分析照片。
具体实施方式
为使本申请的目的、技术方案、及优点更加清楚明白，以下参照附图并举实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部 的实施例。基于本申请中的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本申请保护的范围。
需要说明的是，本申请的具体实施方式中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。
本申请的第一方面提供了一种正极活性材料，如图1所示，正极活性材料10包括基体11和存在于基体11表面的第一材料12，基体11包括核111和壳层112，第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2。不限于任何理论，本申请的发明人发现，通过调控第一材料的(003)晶面的晶面间距d1小于核的(003)晶面的晶面间距d2，可以降低提供锂离子通道的活性晶面在与电解液的交界处发生相变失效的风险，从而提升正极活性材料表面的结构稳定性；同时，锂离子在晶面间距d1较小的第一材料中传输所受到的阻力较小，能够降低正极活性材料的界面电荷转移阻抗，从而有利于同时提高电化学装置的循环性能和动力学性能，例如，降低电化学装置的阻抗、提高电化学装置在高温高电压下的循环容量保持率。此外，在电化学装置循环性能和动力学性能提高的同时，在高电压下电化学装置可以提供更高的可逆充放电容量，从而有利于提高电化学装置的能量密度。
在本申请的一些实施方案中，
Figure PCTCN2021137773-appb-000002
优选地，
Figure PCTCN2021137773-appb-000003
Figure PCTCN2021137773-appb-000004
例如，d1的值可以为
Figure PCTCN2021137773-appb-000005
Figure PCTCN2021137773-appb-000006
或为其间的任意范围，d2的值可以为
Figure PCTCN2021137773-appb-000007
或为其间的任意范围。通过调控d1和d2的值在上述范围内，能够提升正极活性材料表面的结构稳定性和锂离子电导率，从而提高电化学装置在高温高压下的循环性能。
在本申请的一些实施方案中，基于壳层中除Li以外的金属元素的摩尔数，壳层中Al元素的摩尔百分含量为X1，基于核中除Li以外的金属元素的摩尔数，核中Al元素的摩尔百分含量为X2，满足：X1>X2。在正极活性材料壳层中引入较多的Al元素，可以降低正极活性材料在高脱锂状态下，壳层表面二配位氧的活性，从而抑制电化学装置在高电压充放电过程中，壳层表面不可逆的相变及释氧，提高正极活性材料在高脱锂状态下的表面结构稳定性，进而改善电化学装置在高电压下的循环性能。同时，通过将Al元素富集在基体的壳层中，壳层的稳定性较高，有利于增强基体与第一材料之间的界面稳定性，降低由于界面失效导致基体与第一材料之间锂离子传输受阻的风险，进而提高电化学装置在高温 高压下的循环性能。本申请对X1和X2的值没有特别限制，只要能实现本申请的目的即可，例如，X1为1.5％至3％，X2为0至1.5％。本申请中对于壳层或核中Al元素的摩尔百分含量X1和X2，可通过对正极活性材料颗粒的截面利用透射电子显微镜中的能谱仪(EDS)进行分析测试获得。
在本申请的一些实施方案中，第一材料包括Co元素，基于第一材料中除Li以外的金属元素的摩尔数，第一材料中Co元素的摩尔百分含量为C1，基于基体中除Li以外的金属元素的摩尔数，基体中Co元素的摩尔百分含量为C2，满足：C1>C2。通过将Co元素富集在正极活性材料的第一材料中，更有利于降低正极活性材料的界面电荷转移阻抗，从而提高电化学装置的动力学性能。本申请对基体中Co元素的含量没有特别限制，只要能实现本申请的目的即可，例如，基于第一材料中除Li以外的金属元素的摩尔数，第一材料中Co元素的摩尔百分含量C1大于或等于25％。
在本申请的一些实施方案中，核中除Li以外的金属元素的摩尔总数为n M1，核中Ni元素的摩尔数为n Ni1，核中Co元素的的摩尔数为n Co1，核中Mn元素的的摩尔数为n Mn1，核中Al元素的的摩尔数为n Al，核中R元素的的摩尔数为n R1，0.5≤n Ni1/n M1＜1，0≤n Co1/n M1≤0.2，0≤n Mn1/n M1≤0.5，0＜n Al/n M1≤0.03，0≤n R1/n M1≤0.05，R元素包括Mg、Ti、Zr、Nb、Y、Cr、V、Ge、Mo、Fe、Cu、Zn、Ga、Ag、W、In、Sn、Pb、Sb、La、Ce、Ca或Sr中的至少一种。
在本申请的一些实施方案中，第一材料中除Li以外的金属元素的摩尔总数为n M2，第一材料中Ni元素的摩尔数为n Ni2，第一材料中Co元素的的摩尔数为n Co2，第一材料中Z元素的的摩尔数为n Z，第一材料中R元素的的摩尔数为n R2，0≤n Ni2/n M2≤0.6，0.25≤n Co2/n M2≤1.0，0≤n Z/n M2≤0.1，0≤n R2/n M2≤0.05，Z元素包括Mn或Al中的至少一种，R元素包括Mg、Ti、Zr、Nb、Y、Cr、V、Ge、Mo、Fe、Cu、Zn、Ga、Ag、W、In、Sn、Pb、Sb、La、Ce、Ca或Sr中的至少一种。
通过选择上述核和/或第一材料，有利于同时提高电化学装置的循环性能和动力学性能。
在本申请的一些实施方案中，核中包括Al和R，可以增强核的稳定性，在正极活性材料发生开裂时，能够抑制正极活性材料与电解液之间的副反应，从而有利于提高电化学装置的循环性能。
示例性地，核包括LiNi 0.5Co 0.1Mn 0.385Al 0.012Zr 0.002Ti 0.001O 2、LiNi 0.6Co 0.1Mn 0.288Al 0.012O 2、LiNi 0.8Co 0.1Mn 0.085Al 0.012Zr 0.003O 2、LiNi 0.6Co 0.1Mn 0.285Al 0.012Zr 0.002Ti 0.001O 2中的至少一种。
示例性地，第一材料包括LiNi 0.5Co 0.45Mn 0.05O 2、LiNi 0.6Co 0.35Mn 0.05O 2、LiCoO 2、LiNi 0.5Co 0.45Mn 0.04Al 0.01O 2或LiNi 0.5Co 0.45Mn 0.038Al 0.01Ti 0.001O 2中的至少一种。
在本申请的一些实施方案中，n Co2/n M2-n Co1/n M1≥0.25，优选为0.25≤n Co2/n M2-n Co1/n M1≤0.9。例如，n Co2/n M2-n Co1/n M1的值可以为0.25、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1或为其间的任意范围。通过调控n Co2/n M2-n Co1/n M1的值在上述范围内，有利于降低正极活性材料的界面电荷转移阻抗，从而提高电化学装置的动力学性能。
在本申请的一些实施方案中，沿第一方向观察，基于正极活性材料的面积，第一材料的面积百分比为10％至80％。第一材料的面积百分比在上述范围内，能够提升正极活性材料表面的结构稳定性和锂离子电导率，从而提高电化学装置在高温高压下的循环性能。
在本申请的一些实施方案中，第一材料的平均粒径为50nm至800nm。例如，第一材料的平均粒径可以为50nm、100nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm或为其间的任意范围。通过调控第一材料的粒径在上述范围内，有利于提高第一材料的比表面积，从而有利于提高电化学装置的动力学性能。
在本申请的一些实施方案中，壳层的厚度为5nm至80nm。例如，壳层的厚度可以为5nm、10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm或为其间的任意范围。通过调控壳层的厚度在上述范围内，能够提高基体表面未被第一材料覆盖区域的结构稳定性，从而有利于提高电化学装置的循环性性能。
在本申请的一些实施方案中，所述基体的平均粒径为2μm至11μm。例如，基体的平均粒径可以为2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm或为其间的任意范围。
在本申请的一些实施方案中，正极活性材料的比表面积(BET)小于或等于0.65m 2/g，进一步为0.4m 2/g至0.65m 2/g。例如，正极活性材料的比表面积可以为0.5m 2/g、0.55m 2/g、0.6m 2/g、0.65m 2/g或为其间的任意范围。通过调控正极活性材料的比表面积在上述范围内，有利于降低正极活性材料表面的副反应，从而有利于提高电化学装置的循环性能。
在本申请的一些实施方案中，基体包括由一次颗粒构成的二次颗粒，一次颗粒的平均粒径为1.5μm至4.0μm。例如，一次颗粒的平均粒径可以为1.5μm、2.0μm、2.5μm、3.0μm、3.5μm、4.0μm或为其间的任意范围。通过调控一次颗粒的平均粒径在上述范围内，有利于提高电化学装置的动力学性能。在本申请中，一次颗粒是指从SEM照片中观察到的单一颗粒，二次颗粒是指由多个一次颗粒聚集或团聚在一起的结构，且相邻的一次颗粒之间具 有明显晶界。
本申请对正极活性材料的制备方法没有特别限制，只要能实现本申请的目的即可，例如，可以包括但不限于以下步骤：将Ni源、Co源和Mn源混合溶液，可选地加入上述R源溶液，采用共沉淀法制备前驱体。然后将前驱体与锂源混合，可选地加入Al源和/或上述R源化合物，在氧气或空气气氛中进行一次烧结、冷却、破碎、筛分后得到中间产物。本申请对上述一次烧结的温度和时间没有特别限制，只要能实现本申请的目的即可，例如烧结温度为780℃至1000℃，烧结时间为5h至20h。第一材料可以采用本领域已知的制备方法制备得到。然后将中间产物和第一材料混合，可选地加入Al源和/或上述R源化合物，在氧气或空气气氛中进行二次烧结得到正极活性材料。本申请对上述二次烧结的温度和时间没有特别限制，只要能实现本申请的目的即可，例如烧结温度为500℃至750℃，烧结时间为3h至10h。其中，一次烧结和二次烧结步骤中的至少一者加入Al源。
在基体的制备过程中，一次烧结的温度和/或时长通常会影响一次颗粒的尺寸大小，例如，随着一次烧结的温度升高和/或时间延长，得到的基体中的一次颗粒的尺寸呈增大的趋势；随着一次烧结的温度降低和/或时间缩短，得到的基体中的一次颗粒的尺寸呈减小的趋势。
本申请的第二方面提供了一种电化学装置，包含本申请任一实施方案中所述的正极活性材料。本申请提供的正极活性材料具有良好的结构稳定性，以及较低的界面电荷转移阻抗，从而本申请提供的电化学装置具有良好的循环性能和动力学性能。
在本申请中，电化学装置可以包括正极极片，本申请中的正极极片没有特别限制，只要能实现本申请的目的即可，例如，正极极片通常包括正极集流体。在本申请中，正极集流体没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于铝箔、铝合金箔或复合集流体等。在本申请中，对正极集流体的厚度没有特别限制，只要能够实现本申请目的即可，例如厚度为8μm至12μm。在本申请中，正极材料层可以设置于正极集流体厚度方向上的一个表面上，也可以设置于正极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是正极集流体的全部区域，也可以是正极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。
在本申请中，正极材料层中包括本申请前述任一实施方案中的正极活性材料，正极材料层还可以包括正极粘结剂，本申请对正极粘结剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于含氟树脂、聚丙烯树脂、纤维型粘结剂、橡胶型粘结剂或 聚酰亚胺型粘结剂中的至少一种。
在本申请中，正极材料层中还可以包括导电剂，本申请对导电剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于导电炭黑、碳纳米管(CNTs)、碳纤维、乙炔黑、石墨、科琴黑、石墨烯、金属材料或导电聚合物中的至少一种。上述碳纳米管可以包括但不限于单壁碳纳米管和/或多壁碳纳米管。上述碳纤维可以包括但不限于气相生长碳纤维(VGCF)和/或纳米碳纤维。上述金属材料可以包括但不限于金属粉和/或金属纤维，具体地，金属可以包括但不限于铜、镍、铝或银中的至少一种。上述导电聚合物可以包括但不限于聚亚苯基衍生物、聚苯胺、聚噻吩、聚乙炔或聚吡咯中的至少一种。
本申请对正极活性材料、正极粘结剂、导电剂的含量没有特别限制，可以采用本领域的常规含量，只要能实现本申请的目的即可。例如，基于正极材料层的质量，正极活性材料的质量百分含量为90％至98％，正极粘结剂的质量百分含量为0.5％至5％，导电剂的质量百分含量为0.5％至5％。
任选地，正极极片还可以包括导电层，导电层位于正极集流体和正极材料层之间。本申请对导电层的组成没有特别限制，可以是本领域常用的导电层，例如可以包括但不限于上述导电剂和上述正极粘结剂。
在本申请中，电化学装置还可以包括负极极片，本申请中的负极极片没有特别限制，只要能实现本申请的目的即可，例如负极极片通常包括负极集流体和负极材料层。在本申请中，负极材料层可以设置于负极集流体厚度方向上的一个表面上，也可以设置于负极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是负极集流体的全部区域，也可以是负极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。
本申请中，负极集流体没有特别限制，只要能够实现本申请目的即可，例如，可以包括但不限于铜箔、铜合金箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜或复合集流体等。在本申请中，对负极的集流体的厚度没有特别限制，只要能够实现本申请目的即可，例如厚度为4μm至12μm。
本申请中，负极材料层包括负极活性材料，其中，负极活性材料没有特别限制，只要能实现本申请的目的即可，例如负极活性材料包括可逆地嵌入/脱嵌锂离子的碳材料。碳材料可以是本领域已知的用作负极活性材料的碳材料，例如，碳材料可以包括但不限于结晶碳和/或非晶碳。上述结晶碳可以包括但不限于无定形的、片形的、小片形的、球形的或纤维状的天然石墨或人造石墨。上述非晶碳可以包括但不限于软碳、硬碳、中间相沥青碳化 物或煅烧焦中的至少一种。示例性地，负极活性材料可以包括但不限于天然石墨、人造石墨、中间相微碳球(MCMB)、硬碳、软碳、硅、氧化硅(SiO x，x为1或2)或硅-碳复合物中的至少一种。其中，硅-碳复合物中硅与碳的质量比为1:10至10:1、Dv50为0.1μm至100μm。
在本申请中，负极材料层中还可以包括导电剂，本申请对导电剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于上述导电剂。
在本申请中，负极材料层中还可以包括负极粘结剂，本申请对负极粘结剂没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、聚丙烯酸、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂或尼龙中的至少一种。
任选地，负极极片还可以包括导电层，导电层位于负极集流体和负极材料层之间。本申请对导电层的组成没有特别限制，可以是本领域常用的导电层，导电层可以包括但不限于上述导电剂和上述负极粘结剂。
在本申请中，电化学装置还可以包括隔离膜，本申请对隔离膜没有特别限制，只要能够实现本申请目的即可，例如可以包括但不限于聚乙烯(PE)、聚丙烯(PP)、聚四氟乙烯为主的聚烯烃(PO)类隔离膜、聚酯膜(例如聚对苯二甲酸二乙酯(PET)膜)、纤维素膜、聚酰亚胺膜(PI)、聚酰胺膜(PA)、氨纶、芳纶膜、织造膜、非织造膜(无纺布)、微孔膜、复合膜、隔膜纸、碾压膜或纺丝膜中的至少一种，优选为聚乙烯或聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善电化学装置的稳定性。本申请的隔离膜可以具有多孔结构，孔径的尺寸没有特别限制，只要能实现本申请的目的即可，例如，孔径的尺寸可以为0.01μm至1μm。在本申请中，隔离膜的厚度没有特别限制，只要能实现本申请的目的即可，例如厚度可以为5μm至500μm。
例如，隔离膜可以包括基材层和表面处理层。基材层可以为具有多孔结构的无纺布、膜或复合膜，基材层的材料可以包括但不限于聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯或聚酰亚胺中的至少一种。任选地，可以使用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。任选地，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。
无机物层可以包括但不限于无机颗粒和无机物层粘结剂，本申请对无机颗粒没有特别 限制，例如，可以包括但不限于氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。本申请对无机物层粘结剂没有特别限制，例如，可以包括但不限于聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。聚合物层中包含聚合物，聚合物的材料可以包括但不限于聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)中的至少一种。
在本申请中，电化学装置还可以包括电解质，电解质可以包括但不限于凝胶电解质、固态电解质和电解液中的一种或多种。其中，电解液可以包括锂盐和非水溶剂。
本申请对锂盐没有特别限制，只要能实现本申请的目的即可，例如可以包括但不限于锂盐可以选自LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiSiF 6、LiBOB或者二氟硼酸锂中的至少一种。优选地，锂盐包括LiPF 6。
本申请对非水溶剂没有特别限制，只要能实现本申请的目的即可，例如可以包括但不限于碳酸酯化合物、羧酸酯化合物、醚化合物或其它有机溶剂中的至少一种。上述碳酸酯化合物可以包括但不限于链状碳酸酯化合物、环状碳酸酯化合物或氟代碳酸酯化合物中的至少一种。上述链状碳酸酯化合物可以包括但不限于碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)或碳酸甲乙酯(MEC)中的至少一种。上述环状碳酸酯可以包括但不限于碳酸乙烯酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)或碳酸乙烯基亚乙酯(VEC)中的至少一种。氟代碳酸酯化合物可以包括但不限于氟代碳酸乙烯酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯或碳酸三氟甲基亚乙酯中的至少一种。上述羧酸酯化合物可以包括但不限于甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯或己内酯中的至少一种。上述醚化合物可以包括但不限于二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃或四氢呋喃中的至少一种。上述其它有机溶剂可以包括但不限于二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰 胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯或磷酸酯中的至少一种。
本申请的电化学装置没有特别限制，其可以包括发生电化学反应的任何装置。在一些实施方案中，电化学装置可以包括但不限于：一次电池、二次电池、燃料电池、太阳能电池或电容等。优选地，电化学装置为锂二次电池，二次电池可以包括但不限于锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池等。更优选地，电化学装置为锂离子电池。
电化学装置的制备过程为本领域技术人员所熟知的，本申请没有特别的限制，例如，可以包括但不限于以下步骤：将正极极片、隔离膜和负极极片按顺序堆叠，并根据需要将其卷绕、折叠等操作得到卷绕结构的电极组件，将电极组件放入包装袋内，将电解液注入包装袋并封口，得到电化学装置；或者，将正极极片、隔离膜和负极极片按顺序堆叠，然后用胶带将整个叠片结构的四个角固定好得到叠片结构的电极组件，将电极组件置入包装袋内，将电解液注入包装袋并封口，得到电化学装置。此外，也可以根据需要将防过电流元件、导板等置于包装袋中，从而防止电化学装置内部的压力上升、过充放电。
本申请的第三方面提供了一种电子装置，包含本申请任一实施方案中所述的电化学装置。本申请提供的电化学装置具有良好的循环性能和动力学性能，从而本申请提供的电子装置具有较长的使用寿命和良好的使用性能。
本申请的电子装置没有特别限定，其可以是用于现有技术中已知的任何电子装置。在一些实施例中，电子装置可以包括但不限于笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、动力工具、无人机、手持吸尘器、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
实施例
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。另外，只要无特别说明，“份”、“％”为质量基准。
测试方法和设备：
循环容量保持率测试：
将锂离子电池在45℃的环境中，进行第一次充电和放电，在1.5C的充电电流下进行恒流充电至电压为4.35V，然后恒压充电至电流为0.05C，然后在4C的放电电流下进行恒流放电，直到最终电压为2.8V，记录首次循环的放电容量；而后重复进行1000次上述的充电和放电循环，记录第1000次循环的放电容量。循环容量保持率＝(第1000次循环的放电容量/首次循环的放电容量)×100％。
每个实施例和对比例中制备的锂离子电池各取4个进行测试，取平均值为最终结果。
直流阻抗(DCR)测试：
将锂离子电池在25℃环境下进行如下测试步骤：
(1)静置5min；(2)0.5C恒流放电至2.8V；(3)静置5min；(4)1.5C恒流充电至电压为4.25V，恒压充电至电流为0.05C；(5)静置20min；(6)0.5C恒流放电至2.8V(所测实际放电容量为C实)；(7)静置5min；(8)调节炉温至25℃；(9)静置60min；(10)1.5C恒流充电至电压为4.25V，恒压充电至电流为0.05C；(11)调节炉温至25℃；(12)静置60min；(13)0.1C恒流放电10s(0.1s取点)；(14)1C恒流放电360s(0.1s取点)；(15)静置120min(30s取点)；(16)循环步骤(13)至步骤(15)，直至电压＜2.7V；；(17)静置5min。
步骤(14)为调节SOC，放一次电SOC降低10％，0.1C放电10s放电末端电压标记为V1，临近步骤1C实放电360s放电1s末端电压标记为V2，DCR＝(V1-V2)/(1C-0.1C)。
(003)晶面的晶面间距和元素含量的测试：
将锂离子电池在0.1C的电流密度下满放至2.8V，并且静置10min后在手套箱内拆解获得正极极片；将正极极片转移至配备聚焦离子束的扫描电镜(型号：FEI Vion Plasma FIB)腔体内，加工得到可用于透射扫描电镜(STEM，型号：FEI Titan3 G2 60-300)分析的样品，要求样品表面用Pt保护，并且用Ga离子束加工，样品厚度不超过100nm；并且用低电压模式进行清洗，除去样品加工的残留表面。将样品在STEM下观察，在合适的倍率下，拍摄第一材料以及基体中核部分的晶格条纹照片，利用图像处理软件测量第一材料中n条晶格条纹之间的距离为D1以及核中n条晶格条纹之间的距离为D2，则第一材料的(003)晶面的晶面间距d1＝D1/(n-1)，核的(003)晶面的晶面间距d2＝D2/(n-1)。
同时，在合适的倍率下利用X射线能谱分析(EDS)功能进行数据采集，直接在核、壳层、第一材料处通过EDS能谱进行点扫描，获得正极活性材料中第一材料、核以及壳层的元素含量。采集至少3处不同位置，取平均值作为最终结果。
如图3所示，图3中的(a)为实施例2-1中的正极活性材料截面的透射电镜照片，图3中的(b)和(c)为(a)中截面的EDS元素分析照片，图3中的(b)为Al元素的分 布，图3中的(c)为Co元素的分布。从图3中的(b)和(c)可以看出，壳层112中Al元素和Co元素的含量均大于核111中Al元素和Co元素的含量。其中，在图3的(b)中壳层112上方区域产生的信号为样品表面Pt保护层产生的干扰信号。
壳层厚度测试：
将样品在STEM下观察，在合适的倍率下，利用X射线能谱分析(EDS)功能进行数据采集，根据Al元素浓度差异，确定核与壳层界面，使用图像处理软件测量从基体表面至该界面处的距离，随机取基体表面10处进行测量，取平均值作为最终结果。
第一材料和基体平均粒径、第一材料面积占比的测试：
取正极活性材料在扫描电子显微镜(SEM)下观察，以观测方向为第一方向，在合适的倍率下拍摄SEM照片，使用图像处理软件，随机统计基体表面50个第一材料颗粒的最长直径，取其平均值作为第一材料的平均粒径；随机统计50个基体颗粒的最长直径，取其平均值作为基体的平均粒径。
使用图像处理软件，随机选择1个正极活性材料颗粒，确定该正极活性材料颗粒的面积为S，其表面的第一材料颗粒的总面积为S1，则该正极活性材料颗粒中第一材料面积占比为S1/S，随机统计50个正极活性材料颗粒，取其平均值作为第一材料的面积占比。
实施例1-1
<正极活性材料的制备>
(1)将硫酸镍、硫酸钴和硫酸锰混合加入去离子水中配制成混合盐溶液，将氢氧化钠加入去离子水中配制成碱溶液，选择氨水作为络合剂，然后将盐溶液、碱溶液和络合剂加入反应釜中，并加入硫酸铝进行反应。控制反应温度为25℃、pH为11，当粒度Dv50达到预定值4.5μm后，将反应浆料过滤、洗涤、干燥得到前驱体。其中，硫酸镍、硫酸钴、硫酸锰和硫酸铝按照Ni、Co、Mn、Al元素摩尔比为0.5:0.1:0.385:0.012加料。
(2)将LiOH·H 2O、前驱体、ZrO 2和TiO 2按照Li、Ni+Co+Mn+Al、Zr、Ti元素摩尔比为1.05:0.997:0.002:0.001混合后加入高混机中混合均匀，然后加入到匣钵中置于窑炉中在氧气气氛下进行一次烧结，然后机械破碎、气流粉碎以及分级得到基体前驱体。其中，一次烧结的温度为930℃、时间为12h。
(3)将基体前驱体和第一材料LiNi 0.5Co 0.45Mn 0.05O 2混合后得到混合物料，然后加入高混机中混合均匀后加入到匣钵中置于窑炉中在氧气气氛下进行二次烧结，然后机械制粉分级、除磁、筛粉后得到正极活性材料。其中，第一材料与基体前驱体的质量比为2:100，第一材料的平均粒径为200nm；二次烧结温度为600℃，时间为6h。其中，基体中核为 LiNi 0.5Co 0.1Mn 0.385Al 0.012Zr 0.002Ti 0.001O 2。
<正极极片的制备>
将上述制备得到的正极活性材料、导电剂乙炔黑和碳纳米管、粘结剂聚偏二氟乙烯按照质量比为96:1.2:0.8:2进行混合，加入N-甲基吡咯烷酮，在真空搅拌机作用下搅拌均匀，获得正极浆料，其中正极浆料的固含量为70％。将正极浆料均匀涂覆于正极集流体铝箔的一个表面上，将铝箔在120℃下烘干处理1h，得到单面涂覆有正极材料层的正极极片。在铝箔的另一个表面上重复以上步骤，即得到双面涂覆有正极材料层的正极极片。然后经过冷压、裁片、分切后，得到正极极片。
<负极极片的制备>
将负极活性材料人造石墨、粘结剂丁苯橡胶、增稠剂羧甲基纤维素钠按照质量比为97.4:1.2:1.4进行混合，加入去离子水，在真空搅拌机作用下搅拌均匀，获得负极浆料，其中负极浆料的固含量为75％。将负极浆料均匀涂覆于负极集流体铜箔的一个表面上，将铜箔在120℃下烘干，得到单面涂覆有负极材料层的负极极片。在铜箔的另一个表面上重复以上步骤，即得到双面涂覆有负极材料层的负极极片。然后经过冷压、裁片、分切后得到负极极片。
<电解液的制备>
在干燥的氩气气氛手套箱中，将碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯按照质量比为1:1:1混合得到有机溶剂，然后向有机溶剂中加入锂盐LiPF 6溶解并混合均匀，得到电解液。其中，LiPF 6在电解液中的质量浓度为12.5％。
<隔离膜的制备>
采用厚度为7μm的多孔聚乙烯薄膜。
<锂离子电池的制备>
将上述制备得到的正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正极极片和负极极片中间以起到隔离的作用，卷绕得到电极组件。将电极组件置于铝塑膜包装袋中，干燥后注入电解液，经过真空封装、静置、化成、脱气、切边等工序得到锂离子电池。
实施例1-2
除了将<正极活性材料的制备>的步骤(3)中的第一材料替换为LiNi 0.6Co 0.35Mn 0.05O 2以外，其余与实施例1-1相同。
实施例1-3
除了将<正极活性材料的制备>的步骤(3)中的第一材料替换为LiCoO 2以外，其余与实施例1-1相同。
实施例1-4
除了<正极活性材料的制备>的步骤(1)中Ni、Co、Mn、Al元素摩尔比为0.6:0.1:0.288:0.012，步骤(2)中不加ZrO 2和TiO 2，Li、Ni+Co+Mn+Al元素摩尔比为1.05:1，制备得到基体中核为LiNi 0.6Co 0.1Mn 0.288Al 0.012O 2以外，其余与实施例1-1相同。
实施例1-5
除了<正极活性材料的制备>的步骤(1)中Ni、Co、Mn、Al元素摩尔比为0.8:0.1:0.085:0.012，步骤(2)中不加TiO 2，Li、Ni+Co+Mn+Al、Zr元素摩尔比为1.05:0.997:0.003，一次烧结的温度为830℃，步骤(3)中的第一材料替换为LiNi 0.6Co 0.35Mn 0.05O 2，制备得到基体中核为LiNi 0.8Co 0.1Mn 0.085Al 0.012Zr 0.003O 2以外，其余与实施例1-1相同。
实施例2-1
除了<正极活性材料的制备>的步骤(3)中，将基体前驱体、Al 2O 3和第一材料LiNi 0.5Co 0.45Mn 0.05O 2混合，基于基体前驱体的质量，Al 2O 3中的Al的质量百分含量为0.2％，其余与实施例1-1相同。
上述制备得到的正极活性材料的扫描电镜照片如图2所示，从图中可以看出第一材料均匀分布在基体的表面。
实施例2-2
除了将<正极活性材料的制备>的步骤(3)中的第一材料替换为LiNi 0.6Co 0.35Mn 0.05O 2以外，其余与实施例2-1相同。
实施例2-3
除了将<正极活性材料的制备>的步骤(3)中的第一材料替换为LiCoO 2以外，其余与实施例2-1相同。
实施例2-4
除了<正极活性材料的制备>的步骤(1)中Ni、Co、Mn、Al元素摩尔比为0.6:0.1:0.288:0.012，步骤(2)中不加ZrO 2和TiO 2，Li、Ni+Co+Mn+Al元素摩尔比为1.05:1，制备得到基体中核为LiNi 0.6Co 0.1Mn 0.288Al 0.012O 2以外，其余与实施例2-1相同。
实施例2-5
除了<正极活性材料的制备>的步骤(1)中Ni、Co、Mn、Al元素摩尔比为0.6:0.1:0.285:0.012，步骤(2)中一次烧结的温度为910℃，制备得到基体中核为LiNi 0.6Co 0.1Mn 0.285Al 0.012Zr 0.002Ti 0.001O 2以外，其余与实施例2-2相同。
实施例2-6
除了将<正极活性材料的制备>的步骤(3)中的第一材料替换为LiNi 0.5Co 0.45Mn 0.05O 2以外，其余与实施例2-5相同。
实施例2-7至实施例2-9
除了将<正极活性材料的制备>的步骤(3)中的第一材料依次替换为LiNi 0.5Co 0.45Mn 0.04Al 0.01O 2、LiNi 0.5Co 0.45Mn 0.039Al 0.01Ti 0.001O 2、LiCoO 2以外，其余与实施例2-6相同。
实施例2-10
除了<正极活性材料的制备>的步骤(1)中Ni、Co、Mn、Al元素摩尔比为0.8:0.1:0.085:0.012，步骤(2)中不加TiO 2，Li、Ni+Co+Mn+Al、Zr元素摩尔比为1.05:0.997:0.003，一次烧结的温度为830℃，制备得到基体中核为LiNi 0.8Co 0.1Mn 0.085Al 0.012Zr 0.003O 2以外，其余与实施例2-1相同。
实施例2-11和实施例2-12
除了将<正极活性材料的制备>的步骤(3)中的第一材料依次替换为LiNi 0.6Co 0.35Mn 0.05O 2、LiCoO 2以外，其余与实施例2-10相同。
实施例2-13
除了<正极活性材料的制备>的步骤(3)中还加入Y 2O 3进行烧结，基于基体前驱体的质量，Y 2O 3中的Y的质量百分含量为0.1％以外，其余与实施例2-6相同。
实施例2-14
除了<正极活性材料的制备>的步骤(3)中还加入TiO 2进行烧结，基于基体前驱体的质量，TiO 2中的Ti的质量百分含量为0.2％以外，其余与实施例2-6相同。
实施例2-15除了<正极活性材料的制备>的步骤(3)中还加入TiO 2和WO 3进行烧结，基于基体前驱体的质量，TiO 2中的Ti的质量百分含量为0.2％，WO 3中的W的质量百分含量为0.2％以外，其余与实施例2-6相同。
实施例3-1和实施例3-2
除了<正极活性材料的制备>的步骤(2)中一次烧结的温度依次调整为880℃、930℃ 使得基体的平均粒径如表3所示以外，其余与实施例2-6相同。
实施例3-3至实施例3-5
除了<正极活性材料的制备>的步骤(3)中Al的质量百分含量依次调整为0.02％、0.4％、0.8％使得壳层的厚度如表3所示以外，其余与实施例2-6相同。
实施例3-6至实施例3-9
除了<正极活性材料的制备>的步骤(3)中第一材料的平均粒径依次调整为50nm、100nm、500nm、800nm以外，其余与实施例2-6相同。
对比例1-1
除了<正极活性材料的制备>的步骤(3)中不加第一材料以外，其余与实施例2-6相同。
各实施例和对比例的制备参数及性能如表1至表3所示。
表1
Figure PCTCN2021137773-appb-000008
Figure PCTCN2021137773-appb-000009
注：表1中的“/”表示不存在对应参数或物质。
表2
Figure PCTCN2021137773-appb-000010
从实施例1-1至实施例1-5、对比例1-1可以看出，在基体表面包覆第一材料的实施例1-1至实施例1-5，锂离子电池在高温高压条件下进行高倍率充放电时的循环容量保持率更高、直流阻抗更低，也即锂离子电池的循环性能和动力学性能均得到了提高。可能的原因在于，一方面，第一材料的(003)晶面的晶面间距d1较小，可以降低提供锂离子通道的活性晶面在与电解液的交界处发生相变失效的风险，从而提升正极活性材料表面的结构稳定性；另一方面，(003)晶面的晶面间距d1较小的第一材料，锂离子在其中传输所受到的阻力较小，具有较高的锂离子电导率，能够降低正极活性材料的界面电荷转移阻抗，从而有利于同时提高锂离子电池的循环性能和动力学性能。
从实施例1-1至实施例1-5、实施例2-1至实施例2-15可以看出，在基体中进一步设置富Al壳层，能够进一步显著提高锂离子电池在高温高压条件下进行高倍率充放电时的的循环性能。可能的原因在于，通过设置富Al壳层，一方面，有利于提高基体表面未被第一材料覆盖区域的结构稳定性；另一方面，由于壳层的稳定性较高，有利于增强基体与第一材料之间的界面稳定性，降低由于界面失效导致基体与第一材料之间锂离子传输受阻的风险，从而进一步提高锂离子电池在高温高压下的循环性能。
表3
Figure PCTCN2021137773-appb-000011
从实施例2-6、实施例3-1至实施例3-2、实施例3-6至实施例3-9可以看出，通过调控基体和第一材料之间平均粒径的相对大小，可对第一材料在正极活性材料表面的面积占比进行调控，第一材料面积占比在20％至65％范围内锂离子电池具有更加优异的循环性能。从实施例2-6、实施例3-3至实施例3-5可以看出，随着壳层厚度的增大，得到的锂离子电池具有更加优异的循环性能。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (11)

  1. 一种正极活性材料，其包括基体和存在于所述基体表面的第一材料，所述基体包括核和壳层，所述第一材料的(003)晶面的晶面间距d1小于所述核的(003)晶面的晶面间距d2。
  2. 根据权利要求1所述的正极活性材料，其中，
    Figure PCTCN2021137773-appb-100001
    Figure PCTCN2021137773-appb-100002
  3. 根据权利要求1所述的正极活性材料，其中，基于所述壳层中除Li以外的金属元素的摩尔数，所述壳层中Al元素的摩尔百分含量为X1，基于所述核中除Li以外的金属元素的摩尔数，所述核中Al元素的摩尔百分含量为X2，满足：X1>X2。
  4. 根据权利要求3所述的正极活性材料，其中，1.5％≤X1≤3％，和/或X2≤1.5％
  5. 根据权利要求1所述的正极活性材料，其中，所述第一材料包括Co元素，基于所述第一材料中除Li以外的金属元素的摩尔数，所述第一材料中Co元素的摩尔百分含量为C1，基于所述基体中除Li以外的金属元素的摩尔数，所述基体中Co元素的摩尔百分含量为C2，满足：C1>C2。
  6. 根据权利要求1所述的正极活性材料，其满足以下条件的至少一者：
    (a)所述核中除Li以外的金属元素的摩尔总数为n M1，所述核中Ni元素的摩尔数为n Ni1，所述核中Co元素的的摩尔数为n Co1，所述核中Mn元素的的摩尔数为n Mn1，所述核中Al元素的的摩尔数为n Al，所述核中R元素的的摩尔数为n R1，0.5≤n Ni1/n M1＜1，0≤n Co1/n M1≤0.2，0≤n Mn1/n M1≤0.5，0＜n Al/n M1≤0.03，0≤n R1/n M1≤0.05，所述R元素包括Mg、Ti、Zr、Nb、Y、Cr、V、Ge、Mo、Fe、Cu、Zn、Ga、Ag、W、In、Sn、Pb、Sb、La、Ce、Ca或Sr中的至少一种；
    (b)所述第一材料中除Li以外的金属元素的摩尔总数为n M2，所述第一材料中Ni元素的摩尔数为n Ni2，所述第一材料中Co元素的的摩尔数为n Co2，所述第一材料中Z元素的的摩尔数为n Z，所述第一材料中R元素的的摩尔数为n R2，0≤n Ni2/n M2≤0.6，0.25≤n Co2/n M2≤1.0，0≤n Z/n M2≤0.1，0≤n R2/n M2≤0.05，所述Z元素包括Mn或Al中的至少一种，所述R元素包括Mg、Ti、Zr、Nb、Y、Cr、V、Ge、Mo、Fe、Cu、Zn、Ga、Ag、W、In、Sn、Pb、Sb、La、Ce、Ca或Sr中的至少一种。
  7. 根据权利要求6所述的正极活性材料，其中，n Co2/n M2-n Co1/n M1≥0.25。
  8. 根据权利要求1所述的正极活性材料，其满足以下条件的至少一者：
    (c)沿第一方向观察，基于所述正极活性材料的面积，所述第一材料的面积百分比为10％至80％；
    (d)所述第一材料的平均粒径为50nm至800nm；
    (e)所述壳层的厚度为5nm至80nm；
    (f)所述基体的平均粒径为2μm至11μm。
  9. 根据权利要求1所述的正极活性材料，所述正极活性材料的比表面积小于或等于0.65m 2/g。
  10. 一种电化学装置，其包括权利要求1至9中任一项所述的正极活性材料。
  11. 一种电子装置，其包括权利要求10所述的电化学装置。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100578448B1 (ko) * 2004-11-04 2006-05-10 한규승 자가혼합 공융법을 이용한 고출력 리튬2차전지용 양극활물질인 나노미립자 리튬/코발트 산화물의 제조방법
CN102088084A (zh) * 2009-12-03 2011-06-08 剩沅科技股份有限公司 一种锂电池复合电极活性材料及其制备方法
CN103985857A (zh) * 2014-05-19 2014-08-13 青岛乾运高科新材料股份有限公司 一种混合锂电池正极材料及其制备方法
CN108832089A (zh) * 2018-06-08 2018-11-16 中南大学 一种二硫化钼包覆镍钴锰酸锂复合材料及其制备方法和应用
CN110247031A (zh) * 2019-05-24 2019-09-17 乳源东阳光磁性材料有限公司 一种钴酸锂包覆高镍三元正极材料及其制备方法
CN111628149A (zh) * 2020-06-02 2020-09-04 格林美股份有限公司 一种梯度掺杂的高镍三元正极材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100578448B1 (ko) * 2004-11-04 2006-05-10 한규승 자가혼합 공융법을 이용한 고출력 리튬2차전지용 양극활물질인 나노미립자 리튬/코발트 산화물의 제조방법
CN102088084A (zh) * 2009-12-03 2011-06-08 剩沅科技股份有限公司 一种锂电池复合电极活性材料及其制备方法
CN103985857A (zh) * 2014-05-19 2014-08-13 青岛乾运高科新材料股份有限公司 一种混合锂电池正极材料及其制备方法
CN108832089A (zh) * 2018-06-08 2018-11-16 中南大学 一种二硫化钼包覆镍钴锰酸锂复合材料及其制备方法和应用
CN110247031A (zh) * 2019-05-24 2019-09-17 乳源东阳光磁性材料有限公司 一种钴酸锂包覆高镍三元正极材料及其制备方法
CN111628149A (zh) * 2020-06-02 2020-09-04 格林美股份有限公司 一种梯度掺杂的高镍三元正极材料及其制备方法

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