WO2024197866A1 - 正极活性材料、正极极片、二次电池及用电装置 - Google Patents

正极活性材料、正极极片、二次电池及用电装置 Download PDF

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Publication number
WO2024197866A1
WO2024197866A1 PCT/CN2023/085628 CN2023085628W WO2024197866A1 WO 2024197866 A1 WO2024197866 A1 WO 2024197866A1 CN 2023085628 W CN2023085628 W CN 2023085628W WO 2024197866 A1 WO2024197866 A1 WO 2024197866A1
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Prior art keywords
positive electrode
agglomerate
particle size
active material
electrode active
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PCT/CN2023/085628
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English (en)
French (fr)
Inventor
桓书星
沈重亨
陈强
吴昌栩
柳娜
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Application filed by Contemporary Amperex Technology Co Ltd filed Critical Contemporary Amperex Technology Co Ltd
Priority to EP23929449.9A priority Critical patent/EP4607609A4/en
Priority to PCT/CN2023/085628 priority patent/WO2024197866A1/zh
Priority to CN202511994276.0A priority patent/CN121709584A/zh
Priority to CN202380043315.1A priority patent/CN119256400B/zh
Publication of WO2024197866A1 publication Critical patent/WO2024197866A1/zh
Priority to US19/216,411 priority patent/US20250282643A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • 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
    • C01G53/502—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 containing lithium and cobalt
    • C01G53/504—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 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
    • C01G53/506—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 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5 with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • 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
    • C01P2006/12—Surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of secondary batteries, and in particular to a positive electrode active material, a positive electrode sheet, a secondary battery and an electrical device.
  • the present application is made in view of the above-mentioned problems, and its purpose is to provide a positive electrode active material.
  • the present application improves the compaction density of the electrode sheet and the energy density of the battery by controlling the particle size distribution and primary particle size of the material.
  • the battery has excellent rate performance to meet the use requirements of new batteries.
  • a first aspect of the present application provides a positive electrode active material, which includes an agglomerate material, wherein the chemical formula of the agglomerate material is Li a Ni x Co y M 1-xy O 2-b , wherein 0.6 ⁇ a ⁇ 1.2, 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.4, -0.1 ⁇ b ⁇ 0.1, and M includes one or more of Mn, Al, B, Zr, Sr, Y, Sb, W, Ti, Mg, Nb, and Mo; the primary particle size of the agglomerate material is 100 to 600 nm, and the particle size distribution of the agglomerate material satisfies (Dv90-Dv10)/Dv50 ⁇ 1.6.
  • the agglomerate material is controlled to have a larger particle size distribution.
  • the large and small particles in the agglomerate material cooperate with each other to fill the gaps, making the particles in the positive electrode active material more densely packed, increasing the compaction density of the pole piece, and improving the energy density of the lithium-ion battery.
  • the size of the primary particles of the agglomerate material is within an appropriate range, which shortens the migration distance of lithium ions and exposes a large number of active sites of lithium ions, thereby increasing the gram capacity of the agglomerate material, giving the battery excellent rate performance and improving the energy density of the material.
  • LiaNixCoyM1 -xyO2 0.6 ⁇ a ⁇ 1.2, 0.8 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.2, -0.1 ⁇ b ⁇ 0.1, optionally, 0.8 ⁇ a ⁇ 1.2 , 0.93 ⁇ x ⁇ 0.98 , 0 ⁇ y ⁇ 0.07, -0.1 ⁇ b ⁇ 0.1.
  • the positive electrode active material has high gram capacity and good structural stability, and can make the battery have high energy density and excellent rate performance.
  • the primary particle size of the agglomerate material is 200-500 nm.
  • the primary particle size of the agglomerate material is within a suitable range, more lithium ion reaction active sites are exposed, the gram capacity of the agglomerate material is increased, and the energy density of the battery is increased.
  • the primary particle size within a suitable range can also reduce the side reactions between the electrolyte and the material and reduce the loss of irreversible capacity.
  • the particle size Dv50 of the agglomerate material is 6-15 ⁇ m, optionally 7-13 ⁇ m.
  • the particle size Dv50 of the agglomerate material is within a suitable range, which is beneficial for the positive electrode plate to have a high compaction density and improve the energy density of the battery.
  • the agglomerate material has an appropriate Dv50 which can improve the ionic conductivity and electronic conductivity of the material, and the battery has excellent rate performance.
  • the particle size distribution of the agglomerate material measured by a particle size analysis laser diffraction method is unimodal, with the peak position of the unimodal being located at 6-15 ⁇ m, and optionally 7-13 ⁇ m.
  • the particle size distribution diagram of the agglomerate material is unimodal, and the peak position of the unimodal is within an appropriate range, which is conducive to making the positive electrode sheet have a high compaction density and improving the energy density of the battery.
  • the unimodal peak position within an appropriate range indicates that the material has a suitable particle size, which can improve the material's ionic conductivity and electronic conductivity and improve the battery's rate performance.
  • the particle size distribution of the agglomerate material satisfies 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.3.
  • the particle size distribution of the agglomerate material satisfies 1.8 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.1.
  • the particle size distribution of the agglomerate material is in a suitable range.
  • the compaction density of the electrode can be improved by the size distribution of the particle size, and the energy density of the battery can be improved.
  • the appropriate particle size distribution can reduce the presence of too large or too small particles in the material. The effect of particle size on compaction density.
  • the agglomerate material has a specific surface area of 0.5 m 2 / g to 0.9 m 2 /g.
  • the specific surface area of the aggregate material When the specific surface area of the aggregate material is within an appropriate range, the migration distance of lithium ions can be shortened and the rate performance of the battery can be improved.
  • an appropriate specific surface area can also expose more lithium ion reaction active sites, increase the gram capacity of the electrode, and increase the energy density of the battery.
  • an appropriate range of specific surface area can also reduce the side reactions between the electrolyte and the material and reduce the loss of irreversible capacity.
  • the agglomerate material includes first agglomerates and second agglomerates, the particle size Dv50 of the first agglomerates is 9-15 ⁇ m, and the particle size Dv50 of the second agglomerates is 4-8 ⁇ m.
  • the particle size Dv50 of the first agglomerate and the second agglomerate is within a suitable range, so that the agglomerate material has a suitable particle size distribution, the large and small gaps between the particles can be effectively filled, the agglomerate material is tightly packed, the compaction density of the pole piece is increased, and the energy density of the battery is increased.
  • the chemical formula of the first agglomerate is Li a1 Ni x1 Co y1 M1 1-x1- y1 O 2-b1
  • the chemical formula of the second agglomerate is Li a2 Ni x2 Co y2 M2 1-x2-y2 O 2-b2 , x 1 ⁇ x 2 ,
  • M1 and M2 independently include one or more of Mn, Al, B, Zr, Sr, Y, Sb, W, Ti, Mg, Nb and Mo.
  • the first agglomerate has a large Dv50 and relatively few lithium ion reaction active sites, and by increasing the nickel content, the purpose of high gram capacity can be achieved, thereby increasing the energy density of the battery.
  • the second agglomerate has a small particle size Dv50 and relatively many lithium ion reaction active sites, and when the nickel content is relatively low, the purpose of high gram capacity can be achieved.
  • the energy density of the battery is increased by the mutual coordination of the particle size Dv50 and the nickel content of the first agglomerate and the second agglomerate.
  • the primary particle size of the first agglomerate is larger than the primary particle size of the second agglomerate.
  • controlling the primary particle size of the first agglomerate to be larger than the primary particle size of the second agglomerate can increase the compaction density of the first agglomerate.
  • the primary particle size of the second agglomerate is relatively small, which shortens the transmission distance of lithium ions, improves the ion conductivity and electronic conductivity of the second agglomerate, and exposes more active sites for lithium ion reactions, thereby comprehensively improving the energy density and rate performance of the battery.
  • the primary particle size of the first agglomerate is 100-1000 nm
  • the primary particle size of the second agglomerate is 100-300 nm.
  • a suitable primary particle size range of the first agglomerate can increase the compaction density of the electrode and the energy density of the battery.
  • a suitable primary particle size range of the second agglomerate is beneficial to the utilization of the gram capacity of the second agglomerate and to improving the rate performance of the battery.
  • the particle size distributions of the first agglomerates and the second agglomerates satisfy (Dv90-Dv10)/Dv50 ⁇ 1.50.
  • the particle size distribution of the first agglomerates and the second agglomerates is within a suitable range, which reduces the influence of the large number of particles with larger particle sizes or small particle sizes in the material on the compaction density.
  • the particle size distribution of the first agglomerates satisfies 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.30
  • the particle size distribution of the second agglomerates satisfies 1.30 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.50.
  • the particle size distribution of the first agglomerates is within a suitable range and can provide sufficient filling space.
  • the particle size distribution of the second agglomerates is within a suitable range and can fully fill the space between the first agglomerates. The two cooperate with each other to improve the compaction density.
  • the mass ratio of the first agglomerates to the second agglomerates is 1:1-9:1.
  • the particle size Dv50 of the first agglomerate is relatively large, and the first agglomerate plays the role of a skeleton.
  • the particle size Dv50 of the second agglomerate is relatively small, and the second agglomerate plays the role of filling the gaps in the skeleton.
  • the mass ratio of the first agglomerate to the second agglomerate is within a suitable range, so that the positive electrode active material has a suitable particle size distribution, which can increase the compaction density of the pole piece and improve the energy of the battery. Quantity density.
  • the positive electrode plate has high compaction density, surface density and low elongation, which improves the gram capacity of the plate and improves the use performance and processing performance of the plate.
  • the mass content of the positive electrode active material is 95% to 99.5%, based on the total mass of the positive electrode film layer.
  • the mass content of the positive electrode active material within the above range can increase the gram capacity of the electrode sheet and improve the energy density of the battery.
  • the compaction density of the positive electrode sheet is 3.5 g/cm 3 -3.8 g/cm 3
  • the elongation of the positive electrode sheet in the longitudinal direction is 7% -8%.
  • the elongation of the pole piece in the length direction within the above range improves the flexibility of the pole piece, reduces the possibility of brittle fracture during the winding or hot pressing process of the pole piece, and improves the performance of the pole piece.
  • the coating area density of the positive electrode film layer is 21.5 mg/cm 2 -32.5 mg/cm 2 .
  • the coating surface density of the positive electrode film layer within the above range can increase the gram capacity of the electrode piece and improve the energy density of the battery.
  • the compaction density of the positive electrode sheet is 3.5 g/cm 3 -3.8 g/cm 3 .
  • the compaction density of the positive electrode plate within the above range can increase the gram capacity of the plate and improve the energy density of the battery.
  • the third aspect of the present application provides a secondary battery, comprising the positive electrode sheet of the second aspect of the present application.
  • the secondary battery comprises a lithium ion battery.
  • a fourth aspect of the present application provides an electrical device, comprising the secondary battery of the third aspect of the present application.
  • FIG1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG2 is an exploded view of the secondary battery of one embodiment of the present application shown in FIG1 ;
  • FIG3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG5 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG4 ;
  • FIG. 6 is a schematic diagram of an electric device using a secondary battery as a power source according to an embodiment of the present application.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range “ab” represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to publicly The parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the “include” and “comprising” mentioned in this application represent open-ended or closed-ended expressions.
  • the “include” and “comprising” may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: 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).
  • the compaction density, platform voltage and gram capacity of ternary materials have received extensive attention.
  • the positive electrode sheets of ternary materials generally use a compaction density of ⁇ 3.3g/ cm3 .
  • the compaction density is greater than 3.3g/ cm3 , the high nickel ternary positive electrode sheet is too compacted, which can easily cause secondary particle structure rupture or cracks. The exposed fresh interface will react with the electrolyte, accelerate the degradation of the battery cell, and reduce the battery life and safety performance.
  • the ternary positive electrode sheet is compacted too low, it will not contribute much to the improvement of battery energy density, and the energy density will be reduced, and the battery life will be reduced. Therefore, it is necessary to develop a positive active material with high compaction density and high energy density to meet the use needs of new batteries.
  • the present application provides a positive electrode active material
  • the positive electrode active material includes an agglomerate material
  • the chemical formula of the agglomerate material is Li a Ni x Co y M 1-xy O 2-b , wherein 0.6 ⁇ a ⁇ 1, 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.4, -0.1 ⁇ b ⁇ 0.1
  • M includes one or more of Mn, Al, B, Zr, Sr, Y, Sb, W, Ti, Mg, Nb, and Mo
  • the primary particle size of the agglomerate material is 100 to 600 nm
  • the particle size distribution of the agglomerate material satisfies (Dv90-Dv10)/Dv50 ⁇ 1.6.
  • agglomerate refers to an aggregate formed by the combination of primary particles under the action of interaction forces, and the particles in the agglomerate are called primary particles.
  • primary particles refers to particles before agglomeration.
  • the primary particle size can be tested by methods known in the art. As an example, after the sample is cold pressed, it is cut open using an Ar particle beam to expose the end face, and an end face image of the sample is obtained using a scanning electron microscope (SEM). The size of the primary particles of the sample is measured based on the SEM image, at least three samples are measured, at least 50 data are measured for each sample, and the number average value is taken as the primary particle size of the primary particles of the sample.
  • SEM scanning electron microscope
  • Dv90 refers to a particle size at which 90% of the volume is accumulated from the smallest particle size side in a particle size distribution based on volume of powder particles.
  • Dv10 refers to a particle size that accounts for 10% of the cumulative volume from the smallest particle size side in the particle size distribution of powder particles based on volume.
  • Dv50 refers to the particle size distribution of powder particles based on volume, the particle size at which the volume accumulation reaches 50% from the small particle size side.
  • test methods for the above-mentioned particle volume distribution particle sizes Dv10, Dv50, and Dv90 can be tested by methods known in the art.
  • M includes Mn or Al.
  • Mn or Al can play a supporting role, providing stability during the charging and discharging process, which is beneficial to improving safety performance.
  • M includes Sb or Nb.
  • Sb or Nb can refine the grains, making the primary particle size of the material smaller, and further improving the material's gram capacity and rate performance.
  • M includes Sr.
  • Sr is a flux.
  • the flux can lower the sintering temperature and reduce the formation of rock salt phase, thereby improving the capacity and cycle life of the material and improving the cycle life of the battery.
  • the chemical formula of the aggregate material can be confirmed by testing using methods known in the art.
  • an inductively coupled plasma spectrometer ICP such as Spectroblue is used to measure the proportion of each element in the aggregate to determine the chemical formula of the aggregate material.
  • the primary particle size of the agglomerate material may be any value of 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, or a range consisting of any two values thereof.
  • the particle size distribution of the agglomerate material satisfies any one of (Dv90-Dv10)/Dv50 ⁇ 1.6, (Dv90-Dv10)/Dv50 ⁇ 1.7, (Dv90-Dv10)/Dv50 ⁇ 1.8, (Dv90-Dv10)/Dv50 ⁇ 1.9, (Dv90-Dv10)/Dv50 ⁇ 2, (Dv90-Dv10)/Dv50 ⁇ 2.1, (Dv90-Dv10)/Dv50 ⁇ 2.2, (Dv90-Dv10)/Dv50 ⁇ 2.3, and (Dv90-Dv10)/Dv50 ⁇ 2.4.
  • a is any value selected from 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 , and 1.2, or a range consisting of any two of these values.
  • x is any value of 0.6, 0.7, 0.8, 0.85, 0.9, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99 , 1, or a range consisting of any two of them.
  • y is any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.1 , 0.15, 0.2, 0.3, 0.4 , or a range consisting of any two of these values.
  • b is any value among -0.1, 0, 0.1, or a range consisting of any two values thereof.
  • the large and small particles in the agglomerate material cooperate with each other to fill the gaps, which can improve the gaps between the particles and the volume utilization rate, making the particles in the positive electrode active material more densely packed, improving the compressive resistance of the pole piece, increasing the compaction density of the pole piece, and improving the energy density of the lithium-ion battery.
  • the size of the primary particles of the agglomerate material within a suitable range, the migration distance of lithium ions is shortened.
  • the ionization and exposure of a large number of active sites of lithium ions increase the material's gram capacity, and the battery has excellent rate performance, which increases the material's energy density.
  • the close stacking of the aggregate material can also prevent the displacement of particles under high pressure in the pole piece, making the pole piece have a low elongation and improving the flexibility of the pole piece.
  • LiaNixCoyM1 -xyO2 -b in the chemical formula LiaNixCoyM1 -xyO2 -b , 0.6 ⁇ a ⁇ 1.2, 0.8 ⁇ x ⁇ 1 , 0 ⁇ y ⁇ 0.2 , and -0.1 ⁇ b ⁇ 0.1.
  • a is any value selected from 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 , and 1.2, or a range consisting of any two of these values.
  • x is any value of 0.8, 0.85 , 0.9, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1, or a range consisting of any two of these values.
  • y is any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06 , 0.07, 0.1, 0.15, 0.2, or a range consisting of any two of these values.
  • b is any value among -0.1, 0, 0.1, or a range consisting of any two values thereof.
  • LiaNixCoyM1 -xyO2 - b 0.8 ⁇ a ⁇ 1.2, 0.93 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.07 , and -0.1 ⁇ b ⁇ 0.1.
  • a is any value selected from 0.8, 0.9, 1.0 , 1.1, 1.2, or a range consisting of any two of these values.
  • x is any value of 0.93, 0.94, 0.95, 0.96, 0.97, 0.98 , or a range consisting of any two of these values.
  • y is any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06 , 0.07 , or a range consisting of any two values thereof.
  • b is any value among -0.1, 0, 0.1, or a range consisting of any two values thereof.
  • the aggregate has a high gram capacity and the battery has a high energy density.
  • the primary particle size of the agglomerate material is 200-500 nm.
  • the primary particle size of the agglomerate material is any value of 200 nm, 300 nm, 400 nm, 500 nm, or a range consisting of any two values thereof.
  • the primary particle size of the agglomerate material is within an appropriate range, exposing more lithium ion reaction active sites, increasing the gram capacity of the agglomerate material, increasing the energy density of the battery, and reducing side reactions between the electrolyte and the material, reducing the loss of irreversible capacity.
  • the particle size Dv50 of the agglomerate material is 6-15 ⁇ m. In some embodiments, the particle size Dv50 of the agglomerate material is 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, or any range consisting of any two of them.
  • the particle size Dv50 of the agglomerate material is within a suitable range, which is beneficial for the positive electrode plate to have a high compaction density and improve the energy density of the battery.
  • the agglomerate material has an appropriate Dv50 which can improve the ionic conductivity and electronic conductivity of the material and improve the rate performance of the battery.
  • the particle size Dv50 of the agglomerate material is 7-13 ⁇ m. In some embodiments, the particle size Dv50 of the agglomerate material is any value among 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, or a range consisting of any two of them.
  • the particle size Dv50 of the agglomerate material is within a suitable range, which is beneficial for the positive electrode sheet to have a high compaction density and improve the energy density of the battery.
  • the particle size distribution of the agglomerate material measured by a particle size analysis laser diffraction method is unimodal, with the peak located at 6-15 ⁇ m.
  • the single peak position is located at any value of 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, or a range consisting of any two of them.
  • the particle size distribution diagram of the agglomerate material is unimodal, and the position of the unimodal peak is within a suitable range, which is conducive to making the positive electrode sheet have a high compaction density and improving the energy density of the battery.
  • the unimodal peak position within a suitable range indicates that the material has a suitable particle size, which can improve the material's ionic conductivity and electronic conductivity and improve the battery's rate performance.
  • the single peak is located at 7-13 ⁇ m. In some embodiments, the single peak is located at any value of 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, or a range consisting of any two of them.
  • the single peak position is within a suitable range, which is beneficial for the positive electrode sheet to have a high compaction density and improve the energy density of the battery.
  • the particle size distribution of the agglomerate material satisfies 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.3. In some embodiments, the particle size distribution of the agglomerate material satisfies 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.7, 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.8, 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.9, 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.0, 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.1, 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.2, 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.3.
  • the particle size distribution of the agglomerate material is in a suitable range. On the one hand, it can improve the compaction density of the electrode and the energy density of the battery by grading the size of the particle. On the other hand, the appropriate particle size distribution can reduce the impact of the presence of too many large or too small particles in the material on the compaction density. It can also avoid the pulverization of too small particles during the cycle process, causing the deterioration of the battery cell. In addition, too many large or too small particles will also affect the preparation of the positive electrode slurry, and the slurry is prone to gel, affecting the processing performance of the slurry.
  • the particle size distribution of the agglomerate material satisfies 1.8 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.1. In some embodiments, the particle size distribution of the agglomerate material satisfies Any one of 1.8 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.9, 1.8 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.0, 1.8 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.1, 1.9 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.0, 1.9 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.1, 2.0 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.1.
  • the particle size distribution of the agglomerates is within a suitable range, and the positive electrode sheet has a suitable compaction density, thereby improving the energy density of the battery.
  • the specific surface area of the agglomerate material is 0.5 m 2 /g-0.9 m 2 /g. In some embodiments, the specific surface area of the agglomerate material can be any value of 0.5 m 2 /g, 0.6 m 2 /g, 0.7 m 2 /g, 0.8 m 2 /g, 0.9 m 2 / g , or a range consisting of any two values thereof.
  • the specific surface area can be measured by any means known in the art. As an example, reference can be made to GB/T 19587-2017 "Determination of Specific Surface Area of Solids by Gas Adsorption BET Method", which uses the TriStar II 3020 device for measurement.
  • the specific surface area of the aggregate material When the specific surface area of the aggregate material is within an appropriate range, the migration distance of lithium ions can be shortened and the rate performance of the battery can be improved.
  • an appropriate specific surface area can also expose more lithium ion reaction active sites, increase the gram capacity of the electrode, and increase the energy density of the battery.
  • an appropriate range of specific surface area can also reduce the side reactions between the electrolyte and the material and reduce the loss of irreversible capacity.
  • the agglomerate material includes first agglomerates and second agglomerates, the particle size Dv50 of the first agglomerates is 9-15 ⁇ m, and the particle size Dv50 of the second agglomerates is 4-8 ⁇ m.
  • the particle size Dv50 of the first agglomerates is any value of 9 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, or a range consisting of any two of these values.
  • the particle size Dv50 of the second agglomerates is any value of 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, or a range consisting of any two values thereof.
  • the particle size Dv50 of the first agglomerate and the second agglomerate refers to the test method for the particle size Dv50 of the agglomerate material.
  • the first agglomerate with a relatively large particle size Dv50 can be used as the skeleton of the electrode.
  • the appropriate particle size Dv50 can avoid cracks on the edge of large particles and improve the service life of the battery.
  • the second aggregate with a relatively small Dv50 can be used as a filler for the first aggregate skeleton to improve space utilization.
  • the particle size Dv50 of the first agglomerate and the second agglomerate is within a suitable range, so that the agglomerate material has a suitable particle size distribution, the large and small gaps between the particles can be effectively filled, the agglomerate material is tightly packed, the compaction density of the pole piece is increased, and the energy density of the battery is increased.
  • the chemical formula of the first aggregate is Li a1 Ni x1 Co y1 M1 1-x1- y1 O 2-b1
  • the chemical formula of the second aggregate is Li a2 Ni x2 Co y2 M2 1-x2-y2 O 2-b2 , x 1 ⁇ x 2 ,
  • M1 and M2 independently include one or more of Mn, Al, B, Zr, Sr, Y, Sb, W, Ti, Mg, Nb and Mo.
  • M1 or M2 each independently comprises Mn or Al.
  • a1 is any value of 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, or a range consisting of any two of these values.
  • x1 is any value of 0.6, 0.7, 0.8, 0.85, 0.9, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1, or a range consisting of any two of them.
  • y1 is any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.1, 0.15, 0.2, 0.3, 0.4, or a range consisting of any two values thereof.
  • b1 is any value of -0.1, 0, 0.1, or a range consisting of any two values thereof.
  • a2 is any value of 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, or a range consisting of any two of these values.
  • x2 is any value of 0.4, 0.5, 0.6, 0.7, 0.8, 0.85, 0.9, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1, or a range consisting of any two of them.
  • y2 is any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, or a range consisting of any two of them.
  • the confirmation of the chemical formula of the first aggregate and the second aggregate refers to the test method for confirmation of the chemical formula of the aggregate material.
  • the first agglomerate has a large particle size Dv50, and the first agglomerate has relatively few lithium ion reaction active sites.
  • the purpose of high gram capacity can be achieved by increasing the nickel content, thereby improving the energy density of the battery.
  • the second agglomerate has a small particle size Dv50, and the second agglomerate has relatively more lithium ion reaction active sites.
  • the nickel content is relatively low, the purpose of high gram capacity can be achieved.
  • the energy density of the battery is improved by the mutual coordination of the particle size Dv50 and the nickel content of the first agglomerate and the second agglomerate.
  • the chemical formula of the first agglomerate Li a1 Ni x1 Co y1 M1 1-x1- y1 O 2-b1 0.8 ⁇ a1 ⁇ 1.2, 0.94 ⁇ x1 ⁇ 0.98, 0 ⁇ y1 ⁇ 0.06, and -0.1 ⁇ b1 ⁇ 0.1.
  • a1 is any value of 0.8, 0.9, 1.0, 1.1, 1.2, or a range consisting of any two values thereof.
  • x1 is any value of 0.94, 0.95, 0.96, 0.97, 0.98, or a range consisting of any two values thereof.
  • y1 is any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, or a range consisting of any two values thereof.
  • b1 is any value among -0.1, 0, 0.1, or a range consisting of any two values thereof.
  • a2 is any value of 0.8, 0.9, 1.0, 1.1, 1.2, or a range consisting of any two values thereof.
  • x2 is any value of 0.93, 0.94, 0.95, 0.96, or a range consisting of any two values thereof.
  • y2 is any value of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, or a range consisting of any two values thereof.
  • b2 is any value among -0.1, 0, 0.1, or a range consisting of any two values therein.
  • the first aggregate and the second aggregate have high gram capacity, and the battery has high energy density.
  • the primary particle size of the first agglomerate is larger than the primary particle size of the second agglomerate.
  • controlling the primary particle size of the first agglomerate to be larger than the primary particle size of the second agglomerate can increase the compaction density of the first agglomerate.
  • the primary particle size of the second agglomerate is relatively small, which shortens the transmission distance of lithium ions, improves the ion conductivity and electronic conductivity of the second agglomerate, and exposes more active sites for lithium ion reactions, thereby comprehensively improving the energy density and rate performance of the battery.
  • the primary particle size of the first agglomerate is 100-1000 nm
  • the primary particle size of the second agglomerate is 100-300 nm.
  • the primary particle size of the first agglomerate is any value of 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or a range consisting of any two values thereof.
  • the primary particle size of the second agglomerate is any value of 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, or a range consisting of any two values thereof.
  • the test method of primary particle size of the first agglomerate and the second agglomerate refers to the test method of primary particle size of agglomerate material.
  • a suitable primary particle size range of the first agglomerate can increase the compaction density of the electrode and the energy density of the battery.
  • a suitable primary particle size range of the second agglomerate is beneficial to the utilization of the gram capacity of the second agglomerate and to improving the rate performance of the battery.
  • the particle size distributions of the first agglomerates and the second agglomerates satisfy (Dv90-Dv10)/Dv50 ⁇ 1.50.
  • the particle size distribution of the first agglomerate satisfies (Dv90-Dv10)/Dv50 ⁇ 0.4, (Dv90-Dv10)/Dv50 ⁇ 0.5, (Dv90-Dv10)/Dv50 ⁇ 0.6, (Dv90-Dv10)/Dv50 ⁇ 0.7, (Dv90-Dv10)/Dv50 ⁇ 0.8, (Dv90-Dv10)/Dv50 ⁇ 0.9, (Dv90-Dv10)/Dv50 ⁇ 0.10, (Dv90-Dv10)/Dv50 ⁇ 0.11, (Dv90-Dv10)/Dv50 ⁇ 0.12, (Dv90-Dv10)/Dv50 ⁇ 0.13, (Dv90-Dv10)/Dv50 ⁇ 0.14, (Dv90-Dv10)/Dv50 ⁇ 0.15 Any one of 0 ⁇ 0.9, (Dv90-Dv10)/Dv50 ⁇ 1.0, (Dv90-Dv10)/Dv50 ⁇ 1.1, (Dv90-Dv10)/Dv50 ⁇ 1.2
  • the particle size distribution of the second agglomerate satisfies (Dv90-Dv10)/Dv50 ⁇ 0.4, (Dv90-Dv10)/Dv50 ⁇ 0.5, (Dv90-Dv10)/Dv50 ⁇ 0.6, (Dv90-Dv10)/Dv50 ⁇ 0.7, (Dv90-Dv10)/Dv50 ⁇ 0.8, (Dv90-Dv10)/Dv50 ⁇ 0.9, (Dv90-Dv10)/Dv50 ⁇ 0.10, (Dv90-Dv10)/Dv50 ⁇ 0.11, (Dv90-Dv10)/Dv50 ⁇ 0.12, (Dv90-Dv10)/Dv50 ⁇ 0.13, (Dv90-Dv10)/Dv50 ⁇ 0.14, (Dv90-Dv10)/Dv50 ⁇ 0.15 Any one of 0 ⁇ 0.9, (Dv90-Dv10)/Dv50 ⁇ 1.0, (Dv90-Dv10)/Dv50 ⁇ 1.1, (Dv90-Dv10)/Dv50 ⁇ 1.2
  • the particle size distribution of the first agglomerate and the second agglomerate refers to the test method for agglomerate materials.
  • the particle size distribution of the first agglomerate and the second agglomerate is within a suitable range, which reduces the influence of the presence of larger particles or smaller particles in the material on the compaction density, so that the battery has a high compaction density and a high energy density.
  • the particle size distribution of the first agglomerates satisfies 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.30
  • the particle size distribution of the second agglomerates satisfies 1.30 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.50.
  • the particle size distribution of the first agglomerate satisfies 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 0.6, 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 0.7, 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 0.8, 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 0.9, 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.0, 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.1, 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.2, 0.50 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.3, 0.6 ⁇ (Dv90-Dv10) /Dv50 ⁇ 0.7, 0.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 0.8, 0.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 0.9, 0.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.0, 0.6 ⁇ (Dv90-Dv10)/Dv50 ⁇
  • the particle size distribution of the second agglomerates satisfies 1.30 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.50.
  • the particle size distribution of the second agglomerates satisfies any one of 1.30 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.40, 1.30 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.5, and 1.40 ⁇ (Dv90-Dv10)/Dv50 ⁇ 1.50.
  • the particle size distribution of the first agglomerates is within a suitable range, which can provide sufficient filling space.
  • the particle size distribution of the second agglomerates is within a suitable range, which can fully fill the space between the first agglomerates. The cooperation between the two can improve the compaction density and the energy density of the battery.
  • the mass ratio of the first agglomerates to the second agglomerates is 1:1-9:1.
  • the mass ratio of the first agglomerate to the second agglomerate is any value of 1:1, 2:1, 3:1, 4:1, 5:1, 5:1, 7:1, 8:1, 9:1, or a range consisting of any two values thereof.
  • the particle size Dv50 of the first agglomerate is relatively large, and the first agglomerate plays the role of a skeleton.
  • the particle size Dv50 of the second agglomerate is relatively small, and the second agglomerate plays the role of filling the gaps in the skeleton.
  • the mass ratio of the first agglomerate to the second agglomerate is within a suitable range, so that the positive electrode active material has a suitable particle size distribution, which can increase the compaction density of the pole piece and the energy density of the battery.
  • the mechanical strength of the small-sized second agglomerate is relatively low, and it is easier to break under the action of the pressure roller.
  • the first agglomerate and the second agglomerate with a suitable mass ratio can improve the structural stability of the material and improve the safety performance of the battery.
  • the gram capacity of the positive electrode active material is 230-245 mAh/g.
  • the gram capacity of the positive electrode active material can be tested by any means known in the art.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer formed on at least a portion of the surface of the positive electrode current collector, and the positive electrode film layer includes a positive electrode active material in some embodiments.
  • the positive electrode plate has high compaction density, surface density and low elongation, which improves the gram capacity of the plate and improves the use performance and processing performance of the plate.
  • the mass content of the positive electrode active material is 95% to 99.5%, based on the total mass of the positive electrode film layer. In some embodiments, based on the total mass of the positive electrode film layer, the mass content of the positive electrode active material is any value of 95%, 96%, 97%, 98%, 99%, 99.5%, or a range consisting of any two values thereof.
  • the mass content of the positive electrode active material within the above range can increase the gram capacity of the electrode sheet and improve the energy density of the battery.
  • the longitudinal extension of the positive electrode sheet is 7% to 8%. In some embodiments, the longitudinal extension of the positive electrode sheet is any value of 7%, 7.5%, 8%, or a range consisting of any two of these values.
  • the elongation of the positive electrode sheet in the longitudinal direction can be tested by any means known in the art. As an example, take the positive electrode sheet before cold pressing, cut off a length of 1m, mark the two end points, adjust the pressure to the target compaction density, and after cold pressing, take the distance between the two end points of the positive electrode sheet and record it as L.
  • the elongation of the sheet is (L-1)/1*100%.
  • the elongation of the pole piece in the length direction within the above range improves the flexibility of the pole piece, reduces the possibility of brittle fracture during the winding or hot pressing process of the pole piece, and improves the performance of the pole piece.
  • the coating area density of the positive electrode film layer is 21.5 mg/cm 2 - In some embodiments, the coating area density of the positive electrode film layer is any value of 21.5 mg/cm 2 , 24 mg/cm 2 , 26 mg/cm 2 , 28 mg/cm 2 , 30 mg/cm 2 , 32 mg/cm 2 , 32.5 mg/cm 2 , or a range consisting of any two of these values.
  • the coating area density of the positive electrode film layer is tested by any means known in the art.
  • the coating area density of the positive electrode film layer is determined by measuring the coating weight (g) of the positive electrode film layer on one side and the coating area (cm 2 ) of the positive electrode film layer on one side (the number of collection points is greater than 14).
  • the coating area density of the positive electrode film layer the coating weight (g) of the positive electrode film layer on one side / the coating area (cm 2 ) of the positive electrode film layer.
  • the coating surface density of the positive electrode film layer within the above range can increase the gram capacity of the electrode piece and improve the energy density of the battery.
  • the compaction density of the positive electrode sheet is 3.5 g/cm 3 -3.8 g/cm 3. In some embodiments, the compaction density of the positive electrode sheet is any value of 3.5 g/cm 3 , 3.6 g/cm 3 , 3.7 g/cm 3 , 3.8 g/cm 3 , or a range consisting of any two of these values.
  • the compaction density of the positive electrode sheet can be tested by any means known in the art.
  • the compaction density PD of the positive electrode sheet is determined by measuring the surface density (g/cm 2 ) and thickness (cm) of the positive electrode film layer on one side (the number of collection points is greater than 14).
  • the compaction density PD of the positive electrode sheet surface density (g/cm 2 ) of the positive electrode film layer on one side / thickness (cm) of the positive electrode film layer on one side.
  • the compaction density of the positive electrode plate within the above range can increase the gram capacity of the plate and improve the energy density of the battery.
  • the positive electrode active material layer may further include a conductive agent to improve the conductivity of the positive electrode.
  • the conductive agent may be selected from one or more of Super P, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphite, graphene and carbon nanofibers.
  • the positive electrode active material layer may further include a binder to firmly bind the positive electrode active material and the optional conductive agent to the positive electrode current collector.
  • the binder may be selected from at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer (EVA), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), sodium alginate (SA), polymethacrylic acid (PMA) and carboxymethyl chitosan (CMCS).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • EVA ethylene-vinyl acetate copolymer
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • SA sodium al
  • the positive electrode current collector can be made of conductive carbon sheet, metal foil, carbon-coated metal foil,
  • the conductive carbon material of the conductive carbon sheet can be selected from one or more of Super P, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphite, graphene and carbon nanofibers.
  • the metal material of the metal foil, carbon-coated metal foil and porous metal plate is independently selected from at least one of copper, aluminum, nickel and stainless steel.
  • the composite current collector can be a composite current collector formed by a composite of a metal foil and a polymer base film.
  • the positive electrode sheet can be prepared in the following manner: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, wherein the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • a metal foil a copper foil may be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material may adopt the negative electrode active material for batteries known in the art.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, etc.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries may also be used. These negative electrode active materials may be used alone, or two or more may be combined. Suitable for use.
  • the negative electrode film layer may further include a binder.
  • the binder may be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may further include a conductive agent, which may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • a conductive agent which may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).
  • a thickener eg, sodium carboxymethyl cellulose (CMC-Na)
  • the negative electrode sheet can be prepared in the following manner: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive electrode and the negative electrode.
  • the present application has no specific restrictions on the type of electrolyte, which can be selected according to needs.
  • the electrolyte can be liquid, gel or all-solid.
  • the electrolyte is an electrolyte solution, which includes an electrolyte salt and a solvent.
  • the electrolyte salt can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate, and lithium tetrafluorooxalatophosphate.
  • the solvent can be selected from ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, At least one of ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may further include additives, such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • additives such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the secondary battery further includes a separator.
  • the present application has no particular limitation on the type of separator, and any known porous separator with good chemical stability and mechanical stability can be selected.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer can be the same or different, without particular limitation.
  • the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
  • the secondary battery may include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
  • the energy density of the secondary battery is 360-510 Wh/kg.
  • the energy density of the secondary battery is any value of 360Wh/kg, 380Wh/kg, 400Wh/kg, 420Wh/kg, 440Wh/kg, 460Wh/kg, 480Wh/kg, 500Wh/kg, 510Wh/kg, or a range consisting of any two of them.
  • the energy density of the secondary battery is tested by any means known in the art.
  • the battery cell is left at 25° C. for 2 hours to ensure that the temperature of the battery cell is 25° C.
  • charge the battery cell at 0.1C to the charge cut-off voltage and then continue to charge at the charge cut-off voltage until the current reaches 0.05C and the charge is cut off (where C represents the rated capacity of the battery cell).
  • C represents the rated capacity of the battery cell.
  • C represents the rated capacity of the battery cell.
  • C represents the rated capacity of the battery cell.
  • Battery cell weight measurement Place the battery cell on an electronic balance until the weight is stable, and read the battery cell weight value M0.
  • Battery cell discharge energy E0/battery cell weight M0 is the energy density of the battery cell.
  • FIG. 1 is a secondary battery 5 of a square structure as an example
  • FIG. 2 is an exploded view of the secondary battery 5 .
  • the outer package may include a shell 51 and a cover plate 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate are enclosed to form a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the isolation membrane can form an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the non-Newtonian fluid electrolyte composition is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries may be assembled into a battery module.
  • the number of secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG3 is a battery module 3 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 3. Of course, they may also be arranged in any other manner. Further, the plurality of secondary batteries 5 may be fixed by fasteners.
  • the battery module 3 may further include a housing having a receiving space, and the plurality of secondary batteries 5 are received in the receiving space.
  • the battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the pack may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • FIG4 and FIG5 are battery packs 1 as an example.
  • 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, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • an electric device comprising at least one of a secondary battery of any embodiment, a battery module of any embodiment, or a battery pack of any embodiment.
  • the electrical device includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source for the electrical device, or as an energy storage unit for the electrical device.
  • the electrical device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • Fig. 6 is an example of an electric device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module may be used.
  • a device may be a mobile phone, a tablet computer, a notebook computer, etc. Such a device is usually required to be thin and light, and a secondary battery may be used as a power source.
  • First agglomerate lithium hydroxide and Ni 0.94 Co 0.05 Mn 0.01 (OH) 2 were placed in a mixer, mixed evenly, and sintered at 750° C. in an oxygen atmosphere for 20 h to obtain the first agglomerate, wherein the molar ratio of lithium hydroxide and Ni 0.94 Co 0.05 Mn 0.01 (OH) 2 was 1.04:1.
  • Second agglomerate lithium hydroxide and Ni 0.93 Co 0.05 Mn 0.02 (OH) 2 are placed in a mixer, mixed evenly, and sintered at 800° C. in an oxygen atmosphere for 20 h to obtain a second agglomerate, wherein the molar ratio of lithium hydroxide and Ni 0.93 Co 0.05 Mn 0.02 (OH) 2 is 1.05:1.
  • the first agglomerate and the second agglomerate are mixed in a mass ratio of 7:3 to form an agglomerate material.
  • the agglomerate material prepared in Example 1 was put into a 5L stirring tank, and the conductive agent acetylene black (SP) and the binder polyvinylidene fluoride (PVDF) were added for premixing for 30 minutes, and then the solvent N-methylpyrrolidone (NMP) was added and stirred rapidly under vacuum to form a slurry.
  • SP conductive agent acetylene black
  • PVDF binder polyvinylidene fluoride
  • NMP solvent N-methylpyrrolidone
  • the mass ratio of agglomerate material: acetylene black: polyvinylidene fluoride 96:2:2, and the solid content of the slurry was 70%.
  • the slurry was evenly and double-sidedly coated on a positive electrode current collector with a thickness of 12 ⁇ m, and then dried, cold pressed, and cut to obtain a positive electrode sheet.
  • the negative electrode active material artificial graphite, hard carbon, conductive agent acetylene black, binder styrene butadiene rubber (SBR), and thickener sodium carbon methyl cellulose (CMC) are fully stirred and mixed in a deionized water solvent system in a weight ratio of 90:5:2:2:1, and then coated on a copper foil, dried, and cold pressed to obtain a negative electrode sheet.
  • the negative electrode active material graphite and silicon carbon material, carbon black (SP), styrene butadiene rubber (SBR), and carboxymethyl fiber (CMC) are dissolved in a solvent deionized water at a weight ratio of 90:4:4:2, and a uniformly dispersed negative electrode slurry is obtained by stirring.
  • the negative electrode slurry is evenly coated on The surface of the negative electrode current collector copper foil is dried, cold pressed and cut to obtain the negative electrode sheet. Based on the total mass of graphite and silicon-carbon materials, the mass of silicon-carbon materials accounts for 30%.
  • Polypropylene film is used as the isolation film.
  • the positive electrode sheet, isolation film, and negative electrode sheet of Example 1 are stacked in order, so that the isolation film is placed between the positive and negative electrode sheets to play an isolating role, and then wound to obtain a bare battery cell, the electrode ears are welded to the bare battery cell, and the bare battery cell is placed in an aluminum shell and baked at 80°C to remove water, and then the electrolyte is injected and sealed to obtain an uncharged battery.
  • the uncharged battery is then subjected to the processes of standing, hot and cold pressing, formation, shaping, capacity testing, etc., to obtain the lithium-ion battery product of Example 1.
  • ICP inductively coupled plasma spectrometer
  • SEM test After the sample is cold pressed, it is cut open using an Ar particle beam to expose the end face, and the end face image of the sample is obtained using a scanning electron microscope (SEM). The size of the primary particles of the sample is measured based on the SEM image, at least three samples are measured, and at least 50 data are measured for each sample, and the number average value is taken as the primary particle size of the primary particles of the sample.
  • SEM scanning electron microscope
  • volume distribution particle sizes Dv10, Dv50, and Dv90 are well-known concepts in the art. Specifically, Dv10 is the particle size that reaches 10% of the cumulative volume from the small particle size side in the particle size distribution of powder particles based on volume, and the unit is usually ⁇ m. Dv50 is the particle size that reaches 50% of the cumulative volume from the small particle size side in the particle size distribution of powder particles based on volume. Dv90 is the particle size that reaches 90% of the cumulative volume from the small particle size side in the particle size distribution of powder particles based on volume.
  • test methods for the particle volume distribution particle sizes Dv10, Dv50 and Dv90 can be tested by methods known in the art.
  • the BET test method for specific surface area can be tested by methods known in the art. As an example, reference can be made to GB/T 19587-2017 "Determination of specific surface area of solid substances by gas adsorption BET method", and the test can be performed using the TriStar II 3020 equipment.
  • Capacity test of battery cells Let the battery cells stand at 25°C for 2h, and ensure that the temperature of the battery cells is 25°C. At 25°C, charge the battery cells at 0.1C to the charge cut-off voltage, and continue to charge at the charge cut-off voltage at a constant voltage until the current reaches 0.05C and the charge is cut off (where C represents the rated capacity of the battery cells). Let the battery cells stand at 25°C for 1h. At 25°C, discharge the battery cells at 0.1C to the discharge cut-off voltage, and record the total discharge capacity C0 released by the battery cells. The total discharge energy is E0.
  • Battery cell weight measurement Place the battery cell on an electronic balance until the weight is stable, and read the battery cell weight value M0.
  • Battery cell discharge energy E0/battery cell weight M0 is the energy density of the battery cell.
  • the batteries of the embodiments and comparative examples were prepared according to the above method, and various performance parameters were measured. The results are shown in Tables 1, 2 and 3 below.
  • the positive electrode active materials in Examples 1 to 20 include aggregate materials, and the chemical formulas of the aggregate materials are LiNi 0.937 Co 0.05 Mn 0.013 O 2 , LiNi 0.9375 Co 0.04 Mn 0.0225 O 2 , LiNi 0.9375 Co 0.0475 Mn 0.015 O 2 , LiNi 0.948 Co 0.042 Mn 0.01 O 2 , LiNi 0.95 Co 0.033 Mn 0.017 O 2 , LiNi 0.959 Co 0.039 Mn 0.002 O 2 , LiNi 0.96 Co 0.02 Mn 0.02 O 2 ,
  • LiNi 0.967 Co 0.02 Mn 0.013 O 2 LiNi 0.967 Co 0.0255 Mn 0.0075 O 2 , LiNi 0.95 Co 0.037 Mn 0.013 O 2 , LiNi 0.953 Co 0.033 Mn 0.014 O 2 , LiNi 0.96 Co 0.
  • the primary particle size of the agglomerate material is 100-600 nm, and the agglomerate The particle size distribution of the material satisfies (Dv90-Dv10)/Dv50 ⁇ 1.6.
  • the primary particle size of the agglomerate material is 200-500 nm, which can further improve the energy density of the battery.
  • the particle size Dv50 of the agglomerate material is 6-15 ⁇ m
  • the pole piece has a high compaction density and a low elongation
  • the battery has a high energy density and excellent rate performance
  • the electrochemical performance of the battery is comprehensively improved.
  • the particle size Dv50 of the agglomerate material is 7-13 ⁇ m, which can further improve the energy density of the battery, and the battery has excellent rate performance.
  • the particle size distribution of the agglomerate material determined by the particle size analysis laser diffraction method is unimodal with a peak position of 6-15 ⁇ m
  • the pole piece has a high surface density and a low elongation
  • the battery has a high energy density and excellent rate performance
  • the electrochemical performance of the battery is comprehensively improved.
  • the particle size distribution of the agglomerate material satisfies 1.6 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.3
  • the pole piece has a high surface density and low elongation
  • the battery has a high energy density and excellent rate performance
  • the electrochemical performance of the battery is comprehensively improved.
  • Example 4 From the comparison between Example 4 and Example 5, it can be seen that the particle size distribution of the agglomerate material satisfies 1.8 ⁇ (Dv90-Dv10)/Dv50 ⁇ 2.1, which can further improve the energy density of the battery.
  • the specific surface area of the aggregate material is 0.5 m 2 /g-0.9 m 2 /g
  • the electrode has a high surface density and a low elongation
  • the battery has a high energy density and excellent rate performance
  • the electrochemical performance of the battery is comprehensively improved.
  • the coating area density of the positive electrode film layer is 21.5 mg/cm 2 -32.5 mg/cm 2
  • the pole piece has a high area density
  • the battery has a high energy density.
  • the compaction density of the positive electrode plate is 3.5 g/cm 3 -3.8 g/cm 3 , the plate has a high compaction density, and the battery has a high energy density.

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Abstract

本申请提供了一种正极活性材料，该正极活性材料包括团聚体材料，团聚体材料的化学式为LiaNixCoyM1-x-yO2-b，其中0.6≤a≤1.2，0.6≤x≤1，0≤y≤0.4，-0.1≤b≤0.1，M包括Mn、Al、B、Zr、Sr、Y、Sb、W、Ti、Mg、Nb、Mo中的一种或者多种；团聚体材料的一次颗粒粒径为100～600nm，团聚体材料的粒径分布满足(Dv90-Dv10)/Dv50≥1.6，该正极活性材料可以提高极片的压实密度，提高电池的能量密度，满足高能量密度电池的需求。

Description

正极活性材料、正极极片、二次电池及用电装置 技术领域
本申请涉及二次电池技术领域，尤其涉及一种正极活性材料、正极极片、二次电池和用电装置。
背景技术
自二次电池商业化后，因其具有能量密度高、电池电压高、循环寿命长和无记忆效应等优点，不仅迅速成为能量存储装置运用于生活的各个领域中，并且引起了专家研究者们的广泛兴趣。随着电子电气设备的发展，特别是电动汽车的迅速发展，使得现有的二次电池在能量密度和倍率性能不能满足使用需求，因此寻找和制备具有高能量密度的材料是迫在眉睫的问题。
发明内容
本申请是鉴于上述课题而进行的，其目的在于提供一种正极活性材料，本申请通过控制材料的粒度分布和一次颗粒粒径，提高极片的压实密度，提高电池的能量密度，同时电池具有优异的倍率性能，满足新型电池的使用需求。
本申请的第一方面提供一种正极活性材料，正极活性材料包括团聚体材料，团聚体材料的化学式为LiaNixCoyM1-x-yO2-b，其中0.6≤a≤1.2，0.6≤x≤1，0≤y≤0.4，-0.1≤b≤0.1，M包括Mn、Al、B、Zr、Sr、Y、Sb、W、Ti、Mg、Nb、Mo中的一种或者多种；团聚体材料的一次颗粒粒径为100～600nm，团聚体材料的粒径分布满足(Dv90-Dv10)/Dv50≥1.6。
控制团聚体材料具有较大的粒径分布，团聚体材料中的大小颗粒相互配合填充缝隙，使得正极活性材料中的颗粒堆积更加致密，提高极片的压实密度，提升锂离子电池的能量密度，同时通过控制 团聚体材料的一次颗粒的大小在合适范围内，缩短锂离子的迁移距离，并且暴露大量的锂离子的活性位点，提升团聚体材料的克容量，电池具有优异的倍率性能，提高材料的能量密度。
在任意实施方式中，化学式LiaNixCoyM1-x-yO2中，0.6≤a≤1.2，0.8≤x≤1，0≤y≤0.2，-0.1≤b≤0.1，可选地，0.8≤a≤1.2，0.93≤x≤0.98，0≤y≤0.07，-0.1≤b≤0.1。
该正极活性材料具有高的克容量和良好的结构稳定性，能使电池具有高的能量密度和优异的倍率性能。
在任意实施方式中，团聚体材料的一次颗粒粒径为200-500nm。
团聚体材料的一次颗粒粒径在合适范围内，暴露出多的锂离子反应活性位点，提高团聚体材料的克容量，提高电池的能量密度，合适范围的一次颗粒粒径还能减少电解液与材料之间的副反应，减少不可逆容量的损失。
在任意实施方式中，团聚体材料的粒径Dv50为6-15μm，可选为7-13μm。
团聚体材料的粒径Dv50在合适范围内，有利于使正极极片具有高的压实密度，提高电池的能量密度，同时团聚体材料具有适当的Dv50能提高材料的导离子性和导电子性，电池具有优异的倍率性能。
在任意实施方式中，通过粒度分析激光衍射法测定团聚体材料的粒径分布图为单峰状，单峰峰位位于6-15μm，可选为7-13μm。
团聚体材料的粒径分布图为单峰状，且单峰峰位在合适范围内，有利于使正极极片具有高的压实密度，提高电池的能量密度，同时合适范围内的单峰峰位，表明材料具有合适的粒径，能提高材料的导离子性和导电子性，改善电池的倍率性能。
在任意实施方式中，团聚体材料的粒径分布满足1.6≤(Dv90-Dv10)/Dv50≤2.3，可选地，所述团聚体材料的粒径分布满足1.8≤(Dv90-Dv10)/Dv50≤2.1。
团聚体材料的粒径分布在合适范围的，一方面可以通过大小粒径级配，提高极片的压实密度，提高电池的能量密度，另一方面，合适的粒径分布，减少材料中存在多的过大粒径颗粒或过小粒径颗 粒对压实密度的影响。
在任意实施方式中，团聚体材料的比表面积为0.5m2/g-0.9m2/g。
团聚体材料的比表面积在合适范围内，缩短锂离子迁移距离，改善电池的倍率性能，另外合适的比表面积也可以暴露出多的锂离子反应活性位点，提高极片的克容量，提高电池的能量密度，同时合适范围的比表面积，还能减少电解液与材料之间的副反应，减少不可逆容量的损失。
在任意实施方式中，团聚体材料包括第一团聚体和第二团聚体，第一团聚体的粒径Dv50为9-15μm，第二团聚体的粒径Dv50为4-8μm。
第一团聚体和第二团聚体的粒径Dv50在合适范围内，使得团聚体材料具有合适的粒径分布，颗粒间的大大小小的间隙能够得到有效填充，团聚体材料紧密推积，提高极片的压实密度，提高电池的能量密度。
在任意实施方式中，第一团聚体的化学式为Lia1Nix1Coy1M11-x1- y1O2-b1，第二团聚体的化学式为Lia2Nix2Coy2M21-x2-y2O2-b2，x1≥x2，
其中0.6≤a1≤1.2，0.6≤x1≤1，0≤y1≤0.4，-0.1≤b1≤0.1，0.6≤a2≤1.2，0.4≤x2≤1，0≤y2≤0.6，-0.1≤b2≤0.1，M1、M2各自独立地包括Mn、Al、B、Zr、Sr、Y、Sb、W、Ti、Mg、Nb、Mo中的一种或者多种。
第一团聚体具有大的Dv50，第一团聚体具有相对少的锂离子反应活性位点，而通过提高镍含量可以达到高克容量的目的，提高电池的能量密度。第二团聚体具有小的粒径Dv50，第二团聚体具有相对多的锂离子反应活性位点，在镍含量相对低的情况下，就能达到高克容量的目的。通过第一团聚体和第二团聚体的粒径Dv50和镍含量的相互配合，提高电池的能量密度。
在任意实施方式中，第一团聚体的化学式Lia1Nix1Coy1M11-x1- y1O2-b1中，0.8≤a1≤1.2，0.94≤x1≤0.98，0≤y1≤0.06，-0.1≤b1≤0.1。
在任意实施方式中，第二团聚体的化学式Lia2Nix2Coy2M21-x2- y2O2-b2中，0.8≤a2≤1.2，0.93≤x2≤0.96，0≤y2≤0.07，-0.1≤b2≤0.1。
在任意实施方式中，第一团聚体的一次颗粒粒径大于第二团聚体的一次颗粒粒径。
在第一团聚体的粒径Dv50大于第二团聚体的粒径Dv50前提下，控制第一团聚体的一次颗粒粒径大于第二团聚体的一次颗粒粒径，可以提高第一团聚体的压实密度，同时第二团聚体的一次颗粒粒径相对小，缩短锂离子的传输距离，提高第二团聚的导离子性和导电子性，同时暴露出更多的锂离子反应的活性位点，综合提高电池的能量密度和倍率性能。
在任意实施方式中，第一团聚体的一次颗粒粒径为100-1000nm，第二团聚体的一次颗粒粒径为100-300nm。
合适的第一团聚体的一次颗粒粒径范围可以提高极片的压实密度，提高电池的能量密度，同时合适的第二团聚体的一次颗粒粒径范围，有利于第二团聚体的克容量的发挥，有利于改善电池的倍率性能。
在任意实施方式中，第一团聚体和第二团聚体的粒径分布满足(Dv90-Dv10)/Dv50≤1.50。
第一团聚体和第二团聚体的粒径分布在合适范围内，减少材料中存在多的较大粒径的颗粒或较小粒径的颗粒对压实密度的影响。
在任意实施方式中，第一团聚体的粒径分布满足0.50≤(Dv90-Dv10)/Dv50≤1.30，第二团聚体的粒径分布满足1.30≤(Dv90-Dv10)/Dv50≤1.50。
第一团聚体的粒径分布在合适范围内，可以提供充分的填充空间，第二团聚体的粒径分布在合适范围内，可以充分填充第一团聚体之间的空间，两者的相互配合，提高压实密度。
在任意实施方式中，第一团聚体与第二团聚体的质量比为1:1-9:1。
第一团聚体的粒径Dv50相对大，第一团聚体起到骨架作用，第二团聚体的粒径Dv50相对小，第二团聚体起到填充骨架间隙的作用。第一团聚体与第二团聚体的质量比在合适范围内，使得正极活性材料具有合适的粒度分布，可以提高极片的压实密度，提高电池的能 量密度。
本申请的第二方面提供一种正极极片，包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，正极膜层包括第一方面的正极活性材料。
该正极极片具有高的压实密度、面密度和低的延展率，提高极片的克容量，提高极片的使用性能和加工性能。
在任意实施方式中，正极活性材料的质量含量为95％～99.5％，基于正极膜层的总质量计。
在上述范围内的正极活性材料的质量含量，可以提高极片的克容量，提高电池的能量密度。
在任意实施方式中，当正极极片的压实密度为3.5g/cm3-3.8g/cm3时，正极极片的长度方向延展率为7％～8％。
在上述范围内的极片的长度方向延展率，提高极片的柔韧性，减少在极片卷绕或者热压过程中出现脆断的可能性，提高极片的使用性能。
在任意实施方式中，正极膜层的涂布面密度为21.5mg/cm2-32.5mg/cm2。
在上述范围内的正极膜层的涂布面密度，可以提高极片的克容量，提高电池的能量密度。
在任意实施方式中，正极极片的压实密度为3.5g/cm3-3.8g/cm3。
在上述范围内的正极极片的压实密度，可以提高极片的克容量，提高电池的能量密度。
本申请的第三方面提供一种二次电池，包括本申请第二方面的正极极片。
在任意实施方式中，二次电池包括锂离子电池。
本申请的第四方面提供一种用电装置，包括本申请第三方面的二次电池。
附图说明
图1是本申请一实施方式的二次电池的示意图；
图2是图1所示的本申请一实施方式的二次电池的分解图；
图3是本申请一实施方式的电池模块的示意图；
图4是本申请一实施方式的电池包的示意图；
图5是图4所示的本申请一实施方式的电池包的分解图；
图6是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53盖板。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的粘结剂、制备方法、电极、电池及用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开 了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
三元材料的压实密度、平台电压和克容量受到广泛的关注，三元材料的正极极片一般使用压实密度≤3.3g/cm3，当使用压实密度＞3.3g/cm3时，高镍三元正极极片使用压实过大则易造成二次颗粒结构破裂或裂纹，裸露的新鲜界面会与电解液发生副反应，加速电芯的劣化，降低电池使用寿命和安全性能；而当三元正极片使用压实过低，则对电池能量密度提升贡献不大，能量密度降低，电池续航里程下降。因此需要开发一种高压实密度，且能量密度高的正极活性材料，以满足新型电池的使用需要。
[正极活性材料]
基于此，本申请提供一种正极活性材料，正极活性材料包括团聚体材料，团聚体材料的化学式为LiaNixCoyM1-x-yO2-b，其中0.6≤a≤1，0.6≤x≤1，0≤y≤0.4，-0.1≤b≤0.1，M包括Mn、Al、B、Zr、Sr、Y、Sb、W、Ti、Mg、Nb、Mo中的一种或者多种；团聚体材料的一次颗粒粒径为100～600nm，团聚体材料的粒径分布满足(Dv90-Dv10)/Dv50≥1.6。
在本文中，术语“团聚体”是指一次颗粒在相互作用力的作用下结合形成的聚集体，团聚体内的颗粒称为一次颗粒。
在本文中，术语“一次颗粒”是指未团聚之前的颗粒。
一次颗粒粒径可以采用本领域公知的方法进行测试。作为示例，将样品冷压处理后，利用Ar粒子束将样品切开，暴露出端面，通过扫描电子显微镜(SEM)获取样品的端面图片。根据SEM图片测量样品一次颗粒粒子的尺寸，至少测量三个样品，每个样品至少测量50个数据，取数均平均值作为样品的一次粒子的一次颗粒粒径。
在本文中，术语“Dv90”是指粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计90％的粒径。
在本文中，术语“Dv10”是指粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计10％的粒径。
在本文中，术语“Dv50”是指粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计50％的粒径
上述颗粒体积分布粒度Dv10、Dv50、Dv90的测试方法可以采用本领域公知的方法进行测试。作为示例，可以参考GB/T 19077-2016/ISO 13320:2009粒度分布激光衍射法，采用设备马尔文3000进行测定。
在一些实施方式中，M包括Mn或Al。
Mn或Al可以起到支撑的作用，提供充放电过程中的稳定性，有利于改善安全性能。
在一些实施方式中，M包括Sb或Nb。
Sb或Nb可以起到细化晶粒的作用，使材料一次颗粒粒径更小，进一步提升材料克容量和倍率性能。
在一些实施方式中，M包括Sr。
Sr是助熔剂，在制备得到合适粒径大小的前提下，助熔剂可以降低烧结温度，同时减少岩盐相的生成，使材料的容量和循环寿命都有一定提升，改善电池的循环寿命。
团聚体材料化学式的确认可以采用本领域公知的方法进行测试。作为示例，采用电感耦合等离子体光谱仪ICP(例如Spectroblue型)测定团聚体中各元素在材料中所占的比例，确定团聚体材料的化学式。
在一些实施方式中，团聚体材料的一次颗粒粒径可以为100nm、200nm、300nm、400nm、500nm、600nm中的任意值或其中任意两值组成的范围。
在一些实施方式中，团聚体材料的粒径分布满足(Dv90-Dv10)/Dv50≥1.6、(Dv90-Dv10)/Dv50≥1.7、(Dv90-Dv10)/Dv50≥1.8、(Dv90-Dv10)/Dv50≥1.9、(Dv90-Dv10)/Dv50≥2、(Dv90-Dv10)/Dv50≥2.1、(Dv90-Dv10)/Dv50≥2.2、(Dv90-Dv10)/Dv50≥2.3、(Dv90-Dv10)/Dv50≥2.4中的任意一种。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，a为0.6、0.7、0.8、0.9、1.0、1.1、1.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，x为0.6、0.7、0.8、0.85、0.9、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，y为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.1、0.15、0.2、0.3、0.4中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，b为-0.1、0、0.1中的任意值或其中任意两值组成的范围。
通过控制团聚体材料具有较大的粒径分布，团聚体材料中的大小颗粒相互配合填充缝隙，能够提高颗粒间的空隙和体积利用率，使得正极活性材料中的颗粒堆积更加致密，提高极片的抗压能力，提高极片的压实密度，提升锂离子电池的能量密度，同时通过控制团聚体材料的一次颗粒的大小在合适范围内，缩短锂离子的迁移距 离，并且暴露大量的锂离子的活性位点，提升材料的克容量，电池具有优异的倍率性能，提高材料的能量密度。另外团聚体材料的紧密堆积也可以避免极片产生高压下的颗粒位移，使得极片具有低的延展率，改善极片的柔韧性。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，0.6≤a≤1.2，0.8≤x≤1，0≤y≤0.2，-0.1≤b≤0.1。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，a为0.6、0.7、0.8、0.9、1.0、1.1、1.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，x为0.8、0.85、0.9、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，y为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.1、0.15、0.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，b为-0.1、0、0.1中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，0.8≤a≤1.2，0.93≤x≤0.98，0≤y≤0.07，-0.1≤b≤0.1。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，a为0.8、0.9、1.0、1.1、1.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，x为0.93、0.94、0.95、0.96、0.97、0.98中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，y为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式LiaNixCoyM1-x-yO2-b中，b为-0.1、0、0.1中的任意值或其中任意两值组成的范围。
在上述范围内的化学式，团聚体具有高的克容量，电池具有高的能量密度。
在一些实施方式中，团聚体材料的一次颗粒粒径为200-500nm。
在一些实施方式中，团聚体材料的一次颗粒粒径为200nm、300nm、400nm、500nm中的任意值或其中任意两值组成的范围。
团聚体材料的一次颗粒粒径在合适范围内，暴露出多的锂离子反应活性位点，提高团聚体材料的克容量，提高电池的能量密度，还能减少电解液与材料之间的副反应，减少不可逆容量的损失。
在一些实施方式中，团聚体材料的粒径Dv50为6-15μm。在一些实施方式中，团聚体材料的粒径Dv50为6μm、7μm、8μm、9μm10μm、11μm、12μm、13μm、14μm、15μm中的任意值或其中任意两值组成的范围。
团聚体材料的粒径Dv50在合适范围内，有利于使正极极片具有高的压实密度，提高电池的能量密度，同时团聚体材料具有适当的Dv50能提高材料的导离子性和导电子性，改善电池的倍率性能。
在一些实施方式中，团聚体材料的粒径Dv50为7-13μm。在一些实施方式中，团聚体材料的粒径Dv50为7μm、8μm、9μm 10μm、11μm、12μm、13μm中的任意值或其中任意两值组成的范围。
团聚体材料的粒径Dv50在合适范围内，有利于使正极极片具有高的压实密度，提高电池的能量密度。
在一些实施方式中，通过粒度分析激光衍射法测定团聚体材料的粒径分布图为单峰状，单峰峰位位于6-15μm。
在本文中，参考GB/T 19077-2016/ISO 13320:2009粒度分布激光衍射法，采用设备马尔文3000进行测定，得到基于体积分布的粒度分布图，从粒度分度图测得单峰峰位。
在一些实施方式中，单峰峰位位于6μm、7μm、8μm、9μm10μm、11μm、12μm、13μm、14μm、15μm中的任意值或其中任意两值组成的范围。
团聚体材料的粒径分布图为单峰状，且单峰峰位在合适范围内，有利于使正极极片具有高的压实密度，提高电池的能量密度，同时合适范围内的单峰峰位，表明材料具有合适的粒径，能提高材料的导离子性和导电子性，改善电池的倍率性能。
在一些实施方式中，单峰峰位位于7-13μm。在一些实施方式中，单峰峰位位于7μm、8μm、9μm、10μm、11μm、12μm、13μm中的任意值或其中任意两值组成的范围。
单峰峰位在合适范围内，有利于使正极极片具有高的压实密度，提高电池的能量密度。
在一些实施方式中，团聚体材料的粒径分布满足1.6≤(Dv90-Dv10)/Dv50≤2.3。在一些实施方式中，团聚体材料的粒径分布满足1.6≤(Dv90-Dv10)/Dv50≤1.7、1.6≤(Dv90-Dv10)/Dv50≤1.8、1.6≤(Dv90-Dv10)/Dv50≤1.9、1.6≤(Dv90-Dv10)/Dv50≤2.0、1.6≤(Dv90-Dv10)/Dv50≤2.1、1.6≤(Dv90-Dv10)/Dv50≤2.2、1.6≤(Dv90-Dv10)/Dv50≤2.3、1.7≤(Dv90-Dv10)/Dv50≤1.8、1.7≤(Dv90-Dv10)/Dv50≤1.9、1.7≤(Dv90-Dv10)/Dv50≤2.0、1.7≤(Dv90-Dv10)/Dv50≤2.1、1.7≤(Dv90-Dv10)/Dv50≤2.2、1.7≤(Dv90-Dv10)/Dv50≤2.3、1.8≤(Dv90-Dv10)/Dv50≤1.9、1.8≤(Dv90-Dv10)/Dv50≤2.0、1.8≤(Dv90-Dv10)/Dv50≤2.1、1.8≤(Dv90-Dv10)/Dv50≤2.2、1.8≤(Dv90-Dv10)/Dv50≤2.3、1.9≤(Dv90-Dv10)/Dv50≤2.0、1.9≤(Dv90-Dv10)/Dv50≤2.1、1.9≤(Dv90-Dv10)/Dv50≤2.2、1.9≤(Dv90-Dv10)/Dv50≤2.3、2.0≤(Dv90-Dv10)/Dv50≤2.1、2.0≤(Dv90-Dv10)/Dv50≤2.2、2.0≤(Dv90-Dv10)/Dv50≤2.3、2.1≤(Dv90-Dv10)/Dv50≤2.2、2.1≤(Dv90-Dv10)/Dv50≤2.3、2.2≤(Dv90-Dv10)/Dv50≤2.3中的任意一种。
团聚体材料的粒径分布在合适范围的，一方面可以通过大小粒径级配，提高极片的压实密度，提高电池的能量密度，另一方面，合适的粒径分布，减少材料中存在多的过大粒径颗粒或过小粒径颗粒对压实密度的影响，也可以避免过小粒径的颗粒在循环过程的粉化，造成电芯的恶化，另外多的过大粒径颗粒或过小粒径颗粒也会影响正极浆料的制备，浆料容易出现凝胶，影响浆料的加工性能。
在一些实施方式中，团聚体材料的粒径分布满足1.8≤(Dv90-Dv10)/Dv50≤2.1。在一些实施方式中，团聚体材料的粒径分布满足 1.8≤(Dv90-Dv10)/Dv50≤1.9、1.8≤(Dv90-Dv10)/Dv50≤2.0、1.8≤(Dv90-Dv10)/Dv50≤2.1、1.9≤(Dv90-Dv10)/Dv50≤2.0、1.9≤(Dv90-Dv10)/Dv50≤2.1、2.0≤(Dv90-Dv10)/Dv50≤2.1中的任意一种。
团聚体的粒径分布在合适范围内，正极极片具有合适的压实密度，提高电池的能量密度。
在一些实施方式中，团聚体材料的比表面积为0.5m2/g-0.9m2/g。在一些实施方式中，团聚体材料的比表面积可以为0.5m2/g、0.6m2/g、0.7m2/g、0.8m2/g、0.9m2/g中的任意值或其中任意两值组成的范围。
比表面积的测试方法可以采用本领域公知的任意手段进行测试。作为示例，可以参考GB/T 19587-2017《气体吸附BET法测定固态物质比表面积》，采用设备TriStar II 3020进行测定。
团聚体材料的比表面积在合适范围内，缩短锂离子迁移距离，改善电池的倍率性能，另外合适的比表面积也可以暴露出多的锂离子反应活性位点，提高极片的克容量，提高电池的能量密度，同时合适范围的比表面积，还能减少电解液与材料之间的副反应，减少不可逆容量的损失。
在一些实施方式中，团聚体材料包括第一团聚体和第二团聚体，第一团聚体的粒径Dv50为9-15μm，第二团聚体的粒径Dv50为4-8μm。
在一些实施方式中，第一团聚体的粒径Dv50为9μm、11μm、12μm、13μm、14μm、15μm中的任意值或其中任意两值组成的范围。
在一些实施方式中，第二团聚体的粒径Dv50为4μm、5μm、6μm、7μm、8μm中的任意值或其中任意两值组成的范围。
第一团聚体和第二团聚体的粒径Dv50参考团聚体材料的粒径Dv50的测试方法。
粒径Dv50相对大的第一团聚体可以作为极片的骨架，合适的粒径Dv50可以避免大颗粒边缘出现裂纹，提高电池的使用寿命；粒径 Dv50相对小的第二团聚体可以作为第一团聚体骨架的填充物，提高空间利用率。
第一团聚体和第二团聚体的粒径Dv50在合适范围内，使得团聚体材料具有合适的粒径分布，颗粒间的大大小小的间隙能够得到有效填充，团聚体材料紧密推积，提高极片的压实密度，提高电池的能量密度。
在一些实施方式中，第一团聚体的化学式为Lia1Nix1Coy1M11-x1- y1O2-b1，第二团聚体的化学式为Lia2Nix2Coy2M21-x2-y2O2-b2，x1≥x2，
其中0.6≤a1≤1.2，0.6≤x1≤1，0≤y1≤0.4，-0.1≤b1≤0.1，0.6≤a2≤1.2，0.4≤x2≤1，0≤y2≤0.6，-0.1≤b2≤0.1，M1、M2各自独立地包括Mn、Al、B、Zr、Sr、Y、Sb、W、Ti、Mg、Nb、Mo中的一种或者多种。
在一些实施方式中，M1或M2各自独立地包含Mn或Al。
在一些实施方式中，化学式Lia1Nix1Coy1M11-x1-y1O2-b1中，a1为0.6、0.7、0.8、0.9、1.0、1.1、1.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式Lia1Nix1CoyM11-x1-y1O2-b1中，x1为0.6、0.7、0.8、0.85、0.9、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式Lia1Nix1Coy1M11-x1-y1O2-b1中，y1为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.1、0.15、0.2、0.3、0.4中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式Lia1Nix1Coy1M11-x1-y1O2-b1中，b1为-0.1、0、0.1中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式Lia2Nix2Coy2M21-x2-y2O2-b2中，a2为0.6、0.7、0.8、0.9、1.0、1.1、1.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式Lia2Nix2Coy2M21-x2-y2O2-b2中，x2为0.4、0.5、0.6、0.7、0.8、0.85、0.9、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式Lia2Nix2Coy2M21-x2-y2O2-b2中，y2为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.1、0.15、0.2、0.3、0.4、0.5、0.6中的任意值或其中任意两值组成的范围。
在一些实施方式中，化学式Lia2Nix2Coy2M11-x2-y2O2-b2中，b2为
-0.1、0、0.1中的任意值或其中任意两值组成的范围。
第一团聚体和第二团聚体的化学式的确认参考团聚体材料的化学式的确认的测试方法。
第一团聚体具有大的粒径Dv50，第一团聚体具有相对少的锂离子反应活性位点，可以通过提高镍含量可以达到高克容量的目的，提高电池的能量密度。第二团聚体具有小的粒径Dv50，第二团聚体具有相对多的锂离子反应活性位点，在镍含量相对低的情况下，就能达到高克容量的目的。通过第一团聚体和第二团聚体的粒径Dv50和镍含量的相互配合，提高电池的能量密度。
在一些实施方式中，第一团聚体的化学式Lia1Nix1Coy1M11-x1- y1O2-b1中，0.8≤a1≤1.2，0.94≤x1≤0.98，0≤y1≤0.06，-0.1≤b1≤0.1。
在一些实施方式中，a1为0.8、0.9、1.0、1.1、1.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，x1为0.94、0.95、0.96、0.97、0.98中的任意值或其中任意两值组成的范围。
在一些实施方式中，y1为0、0.01、0.02、0.03、0.04、0.05、0.06中的任意值或其中任意两值组成的范围。
在一些实施方式中，b1为-0.1、0、0.1中的任意值或其中任意两值组成的范围。
在一些实施方式中，第二团聚体的化学式Lia2Nix2Coy2M21-x2- y2O2-b2中，0.8≤a2≤1.2，0.93≤x2≤0.96，0≤y2≤0.07，-0.1≤b2≤0.1。
在一些实施方式中，a2为0.8、0.9、1.0、1.1、1.2中的任意值或其中任意两值组成的范围。
在一些实施方式中，x2为0.93、0.94、0.95、0.96中的任意值或其中任意两值组成的范围。
在一些实施方式中，y2为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07中的任意值或其中任意两值组成的范围。
在一些实施方式中，b2为-0.1、0、0.1中的任意值或其中任意两值组成的范围。
第一团聚体、第二团聚体的化学式在上述范围内，第一团聚体和第二团聚体具有高的克容量，电池具有高的能量密度。
在一些实施方式中，第一团聚体的一次颗粒粒径大于第二团聚体的一次颗粒粒径。
在第一团聚体的粒径Dv50大于第二团聚体的粒径Dv50前提下，控制第一团聚体的一次颗粒粒径大于第二团聚体的一次颗粒粒径，可以提高第一团聚体的压实密度，同时第二团聚体的一次颗粒粒径相对小，缩短锂离子的传输距离，提高第二团聚的导离子性和导电子性，同时暴露出更多的锂离子反应的活性位点，综合提高电池的能量密度和倍率性能。
在一些实施方式中，第一团聚体的一次颗粒粒径为100-1000nm，第二团聚体的一次颗粒粒径为100-300nm。
在一些实施方式中，第一团聚体的一次颗粒粒径为100nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm、900nm、1000nm中的任意值或其中任意两值组成的范围。
在一些实施方式中，第二团聚体的一次颗粒粒径为100nm、150nm、200nm、250nm、300nm中的任意值或其中任意两值组成的范围。
第一团聚体和第二团聚体的一次颗粒粒径的测试参考团聚体材料的一次颗粒粒径的测试方法。
合适的第一团聚体的一次颗粒粒径范围可以提高极片的压实密度，提高电池的能量密度，同时合适的第二团聚体的一次颗粒粒径范围，有利于第二团聚体的克容量的发挥，有利于改善电池的倍率性能。
在一些实施方式中，第一团聚体和第二团聚体的粒径分布满足(Dv90-Dv10)/Dv50≤1.50。
在一些实施方式中，第一团聚体的粒径分布满足(Dv90-Dv10)/Dv50≤0.4、(Dv90-Dv10)/Dv50≤0.5、(Dv90-Dv10)/Dv50≤0.6、(Dv90-Dv10)/Dv50≤0.7、(Dv90-Dv10)/Dv50≤0.8、(Dv90-Dv10)/Dv50≤0.9、(Dv90-Dv10)/Dv50≤1.0、(Dv90-Dv10)/Dv50≤1.1、(Dv90-Dv10)/Dv50≤1.2、(Dv90-Dv10)/Dv50≤1.3、(Dv90-Dv10)/Dv50≤0.4、0.6≤(Dv90-Dv10)/Dv50≤1.5中的任意一种。
在一些实施方式中，第二团聚体的粒径分布满足(Dv90-Dv10)/Dv50≤0.4、(Dv90-Dv10)/Dv50≤0.5、(Dv90-Dv10)/Dv50≤0.6、(Dv90-Dv10)/Dv50≤0.7、(Dv90-Dv10)/Dv50≤0.8、(Dv90-Dv10)/Dv50≤0.9、(Dv90-Dv10)/Dv50≤1.0、(Dv90-Dv10)/Dv50≤1.1、(Dv90-Dv10)/Dv50≤1.2、(Dv90-Dv10)/Dv50≤1.3、(Dv90-Dv10)/Dv50≤0.4、0.6≤(Dv90-Dv10)/Dv50≤1.5中的任意一种。
第一团聚体和第二团聚体的粒径分布参考团聚体材料的测试方法。
第一团聚体和第二团聚体的粒径分布在合适范围内，减少材料中存在多的较大粒径的颗粒或较小粒径的颗粒对压实密度的影响，电池具有高的压实密度，电池具有高的能量密度。
在一些实施方式中，第一团聚体的粒径分布满足0.50≤(Dv90-Dv10)/Dv50≤1.30，第二团聚体的粒径分布满足1.30≤(Dv90-Dv10)/Dv50≤1.50。
在一些实施方式中，第一团聚体的粒径分布满足0.50≤(Dv90-Dv10)/Dv50≤0.6、0.50≤(Dv90-Dv10)/Dv50≤0.7、0.50≤(Dv90-Dv10)/Dv50≤0.8、0.50≤(Dv90-Dv10)/Dv50≤0.9、0.50≤(Dv90-Dv10)/Dv50≤1.0、0.50≤(Dv90-Dv10)/Dv50≤1.1、0.50≤(Dv90-Dv10)/Dv50≤1.2、0.50≤(Dv90-Dv10)/Dv50≤1.3、0.6≤(Dv90-Dv10)/Dv50≤0.7、0.6≤(Dv90-Dv10)/Dv50≤0.8、0.6≤(Dv90-Dv10)/Dv50≤0.9、0.6≤(Dv90-Dv10)/Dv50≤1.0、0.6≤(Dv90-Dv10)/Dv50≤1.1、0.6≤(Dv90-Dv10)/Dv50≤1.2、0.6≤(Dv90-Dv10)/Dv50≤1.3、0.7≤(Dv90-Dv10)/Dv50≤0.8、0.7≤(Dv90-Dv10)/Dv50≤0.9、0.7≤(Dv90-Dv10)/Dv50≤1.0、0.7≤(Dv90- Dv10)/Dv50≤1.1、0.7≤(Dv90-Dv10)/Dv50≤1.2、0.7≤(Dv90-Dv10)/Dv50≤1.3、0.8≤(Dv90-Dv10)/Dv50≤0.9、0.8≤(Dv90-Dv10)/Dv50≤1.0、0.8≤(Dv90-Dv10)/Dv50≤1.1、0.8≤(Dv90-Dv10)/Dv50≤1.2、0.8≤(Dv90-Dv10)/Dv50≤1.3、0.9≤(Dv90-Dv10)/Dv50≤1.0、0.9≤(Dv90-Dv10)/Dv50≤1.1、0.9≤(Dv90-Dv10)/Dv50≤1.2、0.9≤(Dv90-Dv10)/Dv50≤1.3、1≤(Dv90-Dv10)/Dv50≤1.1、1≤(Dv90-Dv10)/Dv50≤1.2、1≤(Dv90-Dv10)/Dv50≤1.3、1.1≤(Dv90-Dv10)/Dv50≤1.2、1.1≤(Dv90-Dv10)/Dv50≤1.3、1.2≤(Dv90-Dv10)/Dv50≤1.3中的任意一种。
一些实施方式中，第二团聚体的粒径分布满足1.30≤(Dv90-Dv10)/Dv50≤1.50。
在一些实施方式中，第二团聚体的粒径分布满足1.30≤(Dv90-Dv10)/Dv50≤1.40、1.30≤(Dv90-Dv10)/Dv50≤1.5、1.40≤(Dv90-Dv10)/Dv50≤1.50中的任意一种。
第一团聚体的粒径分布在合适范围内，可以提供充分的填充空间，第二团聚体的粒径分布在合适范围内，可以充分填充第一团聚体之间的空间，两者的相互配合，提高压实密度，提高电池的能量密度。
在一些实施方式中，第一团聚体与第二团聚体的质量比为1:1-9:1。
在一些实施方式中，第一团聚体与第二团聚体的质量比为1:1、2:1、3:1、4:1、5:1、5:1、7:1、8:1、9:1中的任意值或其中任意两值组成的范围。
第一团聚体的粒径Dv50相对大，第一团聚体起到骨架作用，第二团聚体的粒径Dv50相对小，第二团聚体起到填充骨架间隙的作用。第一团聚体与第二团聚体的质量比在合适范围内，使得正极活性材料具有合适的粒度分布，可以提高极片的压实密度，提高电池的能量密度。同时小尺寸的第二团聚体的力学强度相对低，在压辊的作用下，更易破碎，合适质量比的第一团聚体与第二团聚体可以提高材料的结构稳定性，提高电池的安全性能。
在一些实施方式中，正极活性材料的克容量为230-245mAh/g。
正极活性材料中的克容量可以采用本领域公知的任意手段进行测试。作为示例，将二次电池以0.33C恒流放电至2.8V，静置30min；以0.33C恒流充电至4.25V而后以0.05C恒压直至电压稳定，静置30min；以0.33C恒流放电至2.8V，此时读取放电容量，计算二次电池的首次放电容量与正极活性材料的质量比，记为正极活性材料的克容量，其中1C＝230mAh。
[正极极片]
正极极片包括正极集流体及形成于正极集流体的至少部分表面上的正极膜层，正极膜层包括一些实施方式中的正极活性材料。
该正极极片具有高的压实密度、面密度和低的延展率，提高极片的克容量，提高极片的使用性能和加工性能。
在一些实施方式中，正极活性材料的质量含量为95％～99.5％，基于正极膜层的总质量计。在一些实施方式中，基于正极膜层的总质量计，正极活性材料的质量含量为95％、96％、97％、98％、99％、99.5％中的任意值或其中任意两值组成的范围。
在上述范围内的正极活性材料的质量含量，可以提高极片的克容量，提高电池的能量密度。
在一些实施方式中，当正极极片的压实密度为3.5g/cm3-3.8g/cm3时，正极极片的长度方向延展率为7％～8％。在一些实施方式中，正极极片的长度方向延展率为7％、7.5％、8％中的任意值或其中任意两值组成的范围。
正极极片长度方向延展率可以采用本领域公知的任意手段进行测试。作为示例，取冷压前的正极极片，截取1m长度，在两端点处做好标记，调节压力至目标压实密度，冷压后，取正极极片测试两端点的距离记录为L，极片的延展率为(L-1)/1*100％。
在上述范围内的极片的长度方向延展率，提高极片的柔韧性，减少在极片卷绕或者热压过程中出现脆断的可能性，提高极片的使用性能。
在一些实施方式中，正极膜层的涂布面密度为21.5mg/cm2- 32.5mg/cm2。在一些实施方式中，正极膜层的涂布面密度为21.5mg/cm2、24mg/cm2、26mg/cm2、28mg/cm2、30mg/cm2、32mg/cm2、32.5mg/cm2中的任意值或其中任意两值组成的范围。
正极膜层的涂布面密度采用本领域公知的任意手段进行测试。作为示例，正极膜层的涂布面密度是通过测量单侧的正极膜层的涂布重量(g)和单侧正极膜层的涂布面积(cm2)(采集点数＞14)确定的。具体的，正极膜层的涂布面密度＝单侧的正极膜层的涂布重量(g)/正极膜层的涂布面积(cm2)。
在上述范围内的正极膜层的涂布面密度，可以提高极片的克容量，提高电池的能量密度。
在一些实施方式中，正极极片的压实密度为3.5g/cm3-3.8g/cm3。在一些实施方式中，正极极片的压实密度为3.5g/cm3、3.6g/cm3、3.7g/cm3、3.8g/cm3中的任意值或其中任意两值组成的范围。
正极极片的压实密度可以采用本领域公知的任意手段进行测试。作为示例，正极极片的压实密度PD是通过测量单侧的正极膜层的面密度(g/cm2)和单侧正极膜层厚度(cm)(采集点数＞14)确定的。具体的，正极极片的压实密度PD＝单侧的正极膜层面密度(g/cm2)/正极膜层厚度(cm)。
在上述范围内的正极极片的压实密度，可以提高极片的克容量，提高电池的能量密度。
正极活性材料层还可以包括导电剂，以改善正极的导电性能。导电剂可选为Super P、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨、石墨烯及碳纳米纤维中的一种或几种。
正极活性材料层还可以包括粘结剂，以将正极活性材料和可选的导电剂牢固地粘结在正极集流体上。粘结剂可选为聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚丙烯酸(PAA)、聚乙烯醇(PVA)、乙烯-醋酸乙烯酯共聚物(EVA)、丁苯橡胶(SBR)、羧甲基纤维素(CMC)、海藻酸钠(SA)、聚甲基丙烯酸(PMA)及羧甲基壳聚糖(CMCS)中的至少一种。
正极集流体可以采用导电碳片、金属箔材、涂炭金属箔材、多 孔金属板或复合集流体。导电碳片的导电碳材质可选为Super P、炭黑、科琴黑、碳点、碳纳米管、石墨、石墨烯及碳纳米纤维中的一种或几种，金属箔材、涂炭金属箔材和多孔金属板的金属材质各自独立地选自铜、铝、镍及不锈钢中的至少一种，复合集流体可以为金属箔材与高分子基膜复合形成的复合集流体。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组 合使用。
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，所述电解质采用电解液。所述电解液包括电解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、 丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
[二次电池]
在一些实施方式中，二次电池的能量密度为360-510Wh/kg。
在一些实施方式中，二次电池的能量密度为360Wh/kg、380Wh/kg、400Wh/kg、420Wh/kg、440Wh/kg、460Wh/kg、480Wh/kg、500Wh/kg、510Wh/kg中的任意值或其中任意两值组成的范围。
二次电池的能量密度采用本领域公知的任意手段进行测试。作为示例，将电池单体在25℃静置2h，确保电池单体的温度为25℃。 在25℃下，以0.1C将电池单体充电至充电截止电压后，继续以该充电截止电压进行恒压充电，直至电流为0.05C，充电截止(其中，C表示电池单体额定容量)。将电池单体在25℃静置1h。在25℃下，以0.1C将电池单体放电至放电截止电压，记录电池单体放出的总放电容量C0，总放电能量为E0。
电池单体重量测量：将电池单体放置在电子天平上至重量稳定，读取电池单体重量数值M0。
能量密度计算：电池单体放电能量E0/电池单体重量M0即为电池单体的能量密度。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的二次电池5，图2是二次电池5的分解图。
在一些实施方式中，参照图2，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能够盖设于开口，以封闭容纳腔。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封装于容纳腔内。非牛顿流体电解质组合物浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块3。参照图3，在电池模块3中，多个二次电池5可以是沿电池模块3的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块3还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池 包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图4和图5是作为一个示例的电池包1。参照图4和图5，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]
本申请的一个实施方式中，提供一种用电装置，包括任意实施方式的二次电池、任意实施方式的电池模块或任意实施方式的电池包中的至少一种。
用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。二次电池、电池模块、或电池包可以用作用电装置的电源，也可以用作用电装置的能量存储单元。用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或 者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
1)团聚体材料的制备
第一团聚体：将氢氧化锂，Ni0.94Co0.05Mn0.01(OH)2置于混料机中混合均匀并在氧气气氛中750℃烧结20h得到第一团聚体，其中投入的氢氧化锂，Ni0.94Co0.05Mn0.01(OH)2的摩尔比1.04：1。
第二团聚体：将氢氧化锂，Ni0.93Co0.05Mn0.02(OH)2置于混料机中混合均匀并在氧气气氛中800℃烧结20h得到第二团聚体，其中投入的氢氧化锂，Ni0.93Co0.05Mn0.02(OH)2的摩尔比1.05：1。
将第一团聚体和第二团聚体按照7:3的质量比例混合作为团聚体材料。
2)正极极片的制备
将实施例1制备的团聚体材料投5L搅拌罐中，加入导电剂乙炔黑(SP)与粘结剂聚偏氟乙烯(PVDF)进行30min的预混合，然后加入溶剂N-甲基吡咯烷酮(NMP)在抽真空环境下进行快速搅拌，形成浆料。其中，团聚体材料：乙炔黑：聚偏氟乙烯的质量比＝96：2：2，浆料的固含量为70％。将浆料均匀、双面涂覆于厚度为12μm的正极集流体上，之后经过烘干、冷压、分切，得到正极极片。
3)负极极片的制备
将负极活性物质人造石墨、硬碳，导电剂乙炔黑，粘结剂丁苯橡胶(SBR)，增稠剂碳甲基纤维素钠(CMC)按照重量比90:5:2:2:1在去离子水溶剂体系中充分搅拌混合均匀后，涂覆于铜箔上烘干、冷压，得到负极极片。
将负极活性材料石墨与硅碳材料、炭黑(SP)、丁苯橡胶(SBR)、羧甲基纤维(CMC)按照重量比为90:4:4:2溶于溶剂去离子水中，经搅拌得到分散均匀的负极浆料，将负极浆料均匀地涂在 负极集流体铜箔的表面，经过干燥、冷压、裁切，得到负极极片。基于石墨和硅碳材料的总质量计，硅碳材料的质量占比为30％。
4)隔膜
以聚丙烯膜作为隔离膜。
5)电解液的制备
在氩气气氛手套箱中(H2O<0.1ppm，O2<0.1ppm)，将有机溶剂碳酸乙烯酯(EC)/碳酸甲乙酯(EMC)按照体积比3/7混合均匀，加入LiPF6锂盐溶解于有机溶剂中，搅拌均匀，使得LiPF6锂盐的质量含量为12.5％，得到实施例1的电解液。
6)电池的制备
将实施例1的正极极片、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，然后卷绕得到裸电芯，给裸电芯焊接极耳，并将裸电芯装入铝壳中，并在80℃下烘烤除水，随即注入电解液并封口，得到不带电的电池。
不带电的电池再依次经过静置、热冷压、化成、整形、容量测试等工序，获得实施例1的锂离子电池产品。
实施例2～实施例20、对比例1～3中制备参数与实施例1基本相同，具体参数见表1和表2。
二、测试方法
1、正极活性材料的表征
1)团聚体材料、第一团聚体、第二团聚体的化学式确认
采用电感耦合等离子体光谱仪ICP(例如Spectroblue型)测定样品中各元素在材料中所占的比例，确定样品的化学式。
2)团聚体材料、第一团聚体、第二团聚体的一次颗粒粒径
采用SEM测试：将样品冷压处理后，利用Ar粒子束将样品切开，暴露出端面，通过扫描电子显微镜(SEM)获取样品的端面图片。根据SEM图片测量样品一次颗粒粒子的尺寸，至少测量三个样品，每个样品至少测量50个数据，取数均平均值作为样品的一次粒子的一次颗粒粒径。
3)团聚体材料、第一团聚体、第二团聚体的DV50和(Dv90- Dv10)/Dv50
体积分布粒度Dv10、Dv50、Dv90为本领域的公知概念。具体地，Dv10为粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计10％的粒径，单位通常为μm。Dv50为粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计50％的粒径。Dv90为粉体颗粒以体积为基准的粒度分布中，从小粒径侧起、达到体积累计90％的粒径。
上述颗粒体积分布粒度Dv10、Dv50、Dv90的测试方法可以采用本领域公知的方法进行测试。作为示例，可以参考GB/T 19077-2016/ISO 13320:2009粒度分布激光衍射法，采用设备马尔文3000进行测定。
4)粒径分布图的单峰峰位
参考GB/T 19077-2016/ISO 13320:2009粒度分布激光衍射法，采用设备马尔文3000进行测定，得到基于体积分布的粒度分布图，从粒度分度图测得单峰峰位。
5)团聚体材料的比表面积
比表面积BET的测试方法可以采用本领域公知的方法进行测试。作为示例，可以参考GB/T 19587-2017《气体吸附BET法测定固态物质比表面积》，采用设备TriStar II 3020进行测定。
2、正极极片
1)正极膜层的涂布面密度
正极膜层的涂布面密度是通过测量单侧的正极膜层的涂布重量(g)和单侧正极膜层的涂布面积(cm2)(采集点数＞14)确定的。具体的，正极膜层的涂布面密度＝单侧的正极膜层的涂布重量(g)/正极膜层的涂布面积(cm2)。
2)正极极片的压实密度
正极极片的压实密度PD是通过测量单侧的正极膜层的面密度(g/cm2)和单侧正极膜层厚度(cm)(采集点数＞14)确定的。具体的，正极极片的压实密度PD＝单侧的正极膜层面密度(g/cm2)/正极膜层厚度(cm)。
3)正极极片的长度方向延展率
取冷压前的正极极片，截取1m长度，在两端点处做好标记，调节压力至目标压实密度，冷压后，取正极极片测试两端点的距离记录为L，极片的延展率为(L-1)/1*100％。
3、电池
1)电池的质量能量密度
电池单体的容量测试：将电池单体在25℃静置2h，确保电池单体的温度为25℃。在25℃下，以0.1C将电池单体充电至充电截止电压后，继续以该充电截止电压进行恒压充电，直至电流为0.05C，充电截止(其中，C表示电池单体额定容量)。将电池单体在25℃静置1h。在25℃下，以0.1C将电池单体放电至放电截止电压，记录电池单体放出的总放电容量C0，总放电能量为E0。
电池单体重量测量：将电池单体放置在电子天平上至重量稳定，读取电池单体重量数值M0。
能量密度计算：电池单体放电能量E0/电池单体重量M0即为电池单体的能量密度。
2)电池在40％SOC时以4.5C的放电时间
将电池单体以0.33C恒流放电至2.8V，静置30min；以0.33C恒流充电至4.25V而后以0.05C恒压直至电压稳定，静置30min；以0.33C恒流放电至2.8V，此时读取初始容量C0，静置30min；以0.33C恒流充电至4.25V而后以0.05C恒压直至电压稳定，静置30min；以0.33C恒流放电至0.4C0Ah(40％)SOC静置60min；4.5C恒流放电至2.8V，记录放电时间。
三、各实施例、对比例测试结果分析
按照上述方法分别制备各实施例和对比例的电池，并测量各项性能参数，结果见下表1、表2和表3。
表1



表3

根据上述结果，实施例1～20中的正极活性材料，正极活性材料包括团聚体材料，团聚体材料的化学式为LiNi0.937Co0.05Mn0.013O2、LiNi0.9375Co0.04Mn0.0225O2、LiNi0.9375Co0.0475Mn0.015O2、LiNi0.948Co0.042Mn0.01O2、LiNi0.95Co0.033Mn0.017O2、LiNi0.959Co0.039Mn0.002O2、LiNi0.96Co0.02Mn0.02O2、
LiNi0.967Co0.02Mn0.013O2、LiNi0.967Co0.0255Mn0.0075O2、LiNi0.95Co0.037Mn0.013O2、LiNi0.953Co0.033Mn0.014O2、LiNi0.96Co0.033Mn0.007O2、LiNi0.951Co0.029Mn0.02O2、LiNi0.936Co0.046Mn0.018O2、LiNi0.94Co0.04Mn0.02O2、LiNi0.94Co0.05Mn0.01O2、LiNi0.942Co0.044Mn0.014O2、LiNi0.945Co0.0325Mn0.0225O2、LiNi0.954Co0.04Mn0.006O2或LiNi0.955Co0.0275Mn0.0175O2，团聚体材料的一次颗粒粒径为100～600nm，团聚体材料的粒径分布满足(Dv90-Dv10)/Dv50≥1.6。
从实施例1～20与对比例1～3对比可见，团聚体材料的一次颗粒粒径为100-600nm，且团聚体材料的粒径分布满足(Dv90-Dv10)/Dv50≥1.6，可以提高极片的压实密度，提高电池的能量密度，且电池具有优异的倍率性能，满足新型电池的使用需求。
从实施例8-10与实施例6-7对比可见，团聚体材料的一次颗粒粒径为200-500nm，可以进一步提高电池的能量密度。
从实施例1～20中可见，团聚体材料的粒径Dv50为6-15μm，极片具有高的压实密度和低的延展率，电池具有高的能量密度和优异的倍率性能，综合改善电池的电化学性能。
从实施例12、14～16、18～20与实施例11、13、17对比可见，团聚体材料的粒径Dv50为7-13μm，可以进一步提高电池的能量密度，同时电池具有优异的倍率性能。
从实施例1～20中可见，通过粒度分析激光衍射法测定所述团聚体材料的粒径分布图为单峰状，单峰峰位位于6-15μm，极片具有高的面密度和低的延展率，电池具有高的能量密度和优异的倍率性能，综合改善电池的电化学性能。
从实施例12、14～16、18～20与实施例11、13、17对比可见，通过粒度分析激光衍射法测定所述团聚体材料的粒径分布图为单峰状，单峰峰位位于7-13μm，可以进一步提高电池的能量密度，同时电池具有优异的倍率性能。
从实施例1～20中可见，团聚体材料的粒径分布满足1.6≤(Dv90-Dv10)/Dv50≤2.3，极片具有高的面密度和低的延展率，电池具有高的能量密度和优异的倍率性能，综合改善电池的电化学性能。
从实施例4与实施例5对比可见，团聚体材料的粒径分布满足1.8≤(Dv90-Dv10)/Dv50≤2.1，可以进一步提高电池的能量密度。
从实施例1～20可见，团聚体材料的比表面积为0.5m2/g-0.9m2/g，可以极片具有高的面密度和低的延展率，电池具有高的能量密度和优异的倍率性能，综合改善电池的电化学性能。
从实施例1～20可知，正极极片的长度方向延展率为7％～8％，极片具有低的延展率，改善极片的加工性能。
从实施例1～20可知，正极膜层的涂布面密度为21.5mg/cm2-32.5mg/cm2，极片具有高的面密度，电池具有高的能量密度。
从实施例1～20可知，正极极片的压实密度为3.5g/cm3-3.8g/cm3，极片具有高的压实密度，电池具有高的能量密度。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (24)

  1. 一种正极活性材料，其特征在于，所述正极活性材料包括团聚体材料，所述团聚体材料的化学式为LiaNixCoyM1-x-yO2，其中0.6≤a≤1.2，0.6≤x≤1，0≤y≤0.4，-0.1≤b≤0.1，M包括Mn、Al、B、Zr、Sr、Y、Sb、W、Ti、Mg、Nb、Mo中的一种或者多种；所述团聚体材料的一次颗粒粒径为100～600nm，所述团聚体材料的粒径分布满足(Dv90-Dv10)/Dv50≥1.6。
  2. 根据权利要求1所述的正极活性材料，其特征在于，所述化学式LiaNixCoyM1-x-yO2-b中，0.6≤a≤1.2，0.8≤x≤1，0≤y≤0.2，-0.1≤b≤0.1，可选地，0.8≤a≤1.2，0.93≤x≤0.98，0≤y≤0.07，-0.1≤b≤0.1。
  3. 根据权利要求1或2所述的正极活性材料，其特征在于，所述团聚体材料的一次颗粒粒径为200-500nm。
  4. 根据权利要求1-3任一项所述的正极活性材料，其特征在于，所述团聚体材料的粒径Dv50为6-15μm，可选为7-13μm。
  5. 根据权利要求1-4任一项所述的正极活性材料，其特征在于，通过粒度分析激光衍射法测定所述团聚体材料的粒径分布图为单峰状，单峰峰位位于6-15μm，可选为7-13μm。
  6. 根据权利要求1-5任一项所述的正极活性材料，其特征在于，所述团聚体材料的粒径分布满足1.6≤(Dv90-Dv10)/Dv50≤2.3，可选地，所述团聚体材料的粒径分布满足1.8≤(Dv90-Dv10)/Dv50≤2.1。
  7. 根据权利要求1-6任一项所述的正极活性材料，其特征在于， 所述团聚体材料的比表面积为0.5-0.9m2/g。
  8. 根据权利要求1-7任一项所述的正极活性材料，其特征在于，所述团聚体材料包括第一团聚体和第二团聚体，所述第一团聚体的粒径Dv50为9-15μm，所述第二团聚体的粒径Dv50为4-8μm。
  9. 根据权利要求8所述的正极活性材料，其特征在于，所述第一团聚体的化学式为Lia1Nix1Coy1M11-x1-y1O2-b1，所述第二团聚体的化学式为Lia2Nix2Coy2M21-x2-y2O2-b2，x1≥x2，
    其中0.6≤a1≤1.2，0.6≤x1≤1，0≤y1≤0.4，-0.1≤b1≤0.1，0.6≤a2≤1.2，0.4≤x2≤1，0≤y2≤0.6，-0.1≤b2≤0.1，M1、M2各自独立地包括Mn、Al、B、Zr、Sr、Y、Sb、W、Ti、Mg、Nb、Mo中的一种或者多种。
  10. 根据权利要求9所述的正极活性材料，其特征在于，所述第一团聚体的化学式Lia1Nix1Coy1M11-x1-y1O2-b1中，0.8≤a1≤1.2，0.94≤x1≤0.98，0≤y1≤0.06，-0.1≤b1≤0.1。
  11. 根据权利要求9或10所述的正极活性材料，其特征在于，所述第二团聚体的化学式Lia2Nix2Coy2M21-x2-y2O2-b2中，0.8≤a2≤1.2，0.93≤x2≤0.96，0≤y2≤0.07，-0.1≤b2≤0.1。
  12. 根据权利要求8-11中任一项所述的正极活性材料，其特征在于，所述第一团聚体的一次颗粒粒径大于所述第二团聚体的一次颗粒粒径。
  13. 根据权利要求8-12任一项所述的正极活性材料，其特征在于，所述第一团聚体的一次颗粒粒径为100-1000nm，第二团聚体的一次颗粒粒径为100-300nm。
  14. 根据权利要求8-13任一项所述的正极活性材料，其特征在于，所述第一团聚体和第二团聚体的粒径分布满足(Dv90-Dv10)/Dv50≤1.50。
  15. 根据权利要求8-14任一项所述的正极活性材料，其特征在于，所述第一团聚体的粒径分布满足0.50≤(Dv90-Dv10)/Dv50≤1.30，所述第二团聚体的粒径分布满足1.30≤(Dv90-Dv10)/Dv50≤1.50。
  16. 根据权利要求8-15任一项所述的正极活性材料，其特征在于，所述第一团聚体与所述第二团聚体的质量比为1:1-9:1。
  17. 一种正极极片，包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，所述正极膜层包括权利要求1-16任一项所述的正极活性材料。
  18. 根据权利要求17所述的正极极片，其特征在于，所述正极活性材料的质量含量为95％～99.5％，基于所述正极膜层的总质量计。
  19. 根据权利要求17或18所述的正极极片，其特征在于，所述正极极片的压实密度为3.5g/cm3-3.8g/cm3时，所述正极极片的长度方向延展率为7％～8％。
  20. 根据权利要求17-19任一项所述的正极极片，其特征在于，所述正极膜层的涂布面密度为21.5mg/cm2-32.5mg/cm2。
  21. 根据权利要求17-20任一项所述的正极极片，其特征在于，所述正极极片的压实密度为3.5g/cm3-3.8g/cm3。
  22. 一种二次电池，其特征在于，包括正极极片，所述正极极片为权利要求16-21任一项所述的正极极片。
  23. 根据权利要求22所述的二次电池，其特征在于，所述二次电池包括锂离子电池。
  24. 一种用电装置，其特征在于，包括权利要求22或23所述的二次电池。
PCT/CN2023/085628 2023-03-31 2023-03-31 正极活性材料、正极极片、二次电池及用电装置 Ceased WO2024197866A1 (zh)

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