WO2024092933A1 - 类团聚型多元正极材料及其制备方法、应用和锂离子电池 - Google Patents

类团聚型多元正极材料及其制备方法、应用和锂离子电池 Download PDF

Info

Publication number
WO2024092933A1
WO2024092933A1 PCT/CN2022/135490 CN2022135490W WO2024092933A1 WO 2024092933 A1 WO2024092933 A1 WO 2024092933A1 CN 2022135490 W CN2022135490 W CN 2022135490W WO 2024092933 A1 WO2024092933 A1 WO 2024092933A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
electrode material
cobalt
agglomerated
quasi
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/135490
Other languages
English (en)
French (fr)
Inventor
赵甜梦
宋顺林​
刘亚飞
陈彦彬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Easpring Material Technology Co Ltd
Original Assignee
Beijing Easpring Material Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Easpring Material Technology Co Ltd filed Critical Beijing Easpring Material Technology Co Ltd
Priority to JP2024577269A priority Critical patent/JP7788015B2/ja
Priority to EP22964229.3A priority patent/EP4531135A4/en
Priority to KR1020247043056A priority patent/KR20250017251A/ko
Publication of WO2024092933A1 publication Critical patent/WO2024092933A1/zh
Priority to US19/006,221 priority patent/US20250128962A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • C01G53/66—Complex oxides containing nickel and at least one other metal element containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
    • 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
    • C01G53/66—Complex oxides containing nickel and at least one other metal element containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
    • C01G53/68—Complex oxides containing nickel and at least one other metal element containing alkaline earth metals, e.g. SrNiO3 or SrNiO2 containing rare earths, e.g. (La1.62 Sr0.38)NiO4
    • 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
    • C01G53/70—Complex oxides containing nickel and at least one other metal element containing rare earths, e.g. LaNiO3 
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/84—Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of lithium ion batteries, and in particular to a quasi-agglomerated multi-element positive electrode material and a preparation method thereof, and a lithium ion battery.
  • High safety and long driving range are the development trends of electric vehicles.
  • power lithium batteries need to have higher energy density and better cycle stability.
  • the link with the largest market size and the highest output value is the positive electrode material, and its performance determines the battery's energy density, life, rate performance, etc.
  • the positive electrode material has become the core key material of lithium batteries.
  • Ternary materials have the characteristics of high energy density, good cycle stability and good safety.
  • the mainstream ternary materials in the market are agglomerated materials and single crystal materials.
  • Agglomerated materials have good rate performance, but slightly poor cycle performance.
  • Single crystal materials have good cycle performance, but small particle size, low production efficiency, and slightly poor rate performance.
  • a micron-scale flaky single crystal structure agglomerate of a ternary positive electrode material and a preparation method thereof which first adopts an improved chemical coprecipitation method to prepare a micron-spherical precursor composed of tightly stacked nanosheets, the D50 size of the precursor being between 6-8 ⁇ m; then the above-mentioned precursor is fully mixed with an appropriate amount of flux and lithium salt in turn; finally, two steps of high-temperature sintering are performed in a high-temperature sintering furnace to finally obtain a ternary positive electrode material of micron-scale flaky single crystal structure agglomerate.
  • the flaky single crystal structure has low compressive strength, and the agglomerates formed by the flaky structure are difficult to form regular spheres, and the primary particles are difficult to stack tightly, and the bonding force between each other is weak.
  • fracturing and slippage between primary particles are prone to occur, resulting in structural collapse and poor cycle performance; and the grain boundary gaps of the agglomerates stacked with flaky structures are large, and the grain boundaries and surfaces are not protected by a coating layer with good ductility.
  • the electrolyte can easily pass through the grain boundaries to the primary The surface of the particles causes the primary particles to be corroded by the electrolyte from the surface to the inside, resulting in a decrease in the cycle retention rate.
  • the purpose of the present invention is to overcome the problem that existing ternary positive electrode materials cannot take into account energy density, rate performance and cycle stability.
  • the first aspect of the present invention provides a quasi-agglomerated multi-element positive electrode material, wherein the multi-element positive electrode material has a structure shown in Formula I:
  • M is at least one of V, Ta, Cr, La, Al, Ce, Er, Ho, Y, Mg, Sr, Ba, Ra, Zr, Fe, Ca, Zn, B, W, Nb, Cd, Pb, Si, Mo, Cu, Sr and Ti;
  • the multi-element positive electrode material is a secondary particle formed by agglomeration of primary particles; wherein the primary particles are spherical or quasi-spherical; the average particle size DS of the primary particles is 0.9-2.4 ⁇ m; the average particle size DL of the secondary particles is 5-15 ⁇ m; and the value range of DL / DS is 5-16.
  • a second aspect of the present invention provides a method for preparing a quasi-agglomerated multi-element positive electrode material, the preparation method comprising:
  • the quasi-agglomerated positive electrode material process product is mixed with a second cobalt source for a second high-temperature sintering, and then crushed and sieved in sequence to obtain a quasi-agglomerated multi-element positive electrode material.
  • the third aspect of the present invention provides a quasi-agglomerated multi-element positive electrode material prepared by the preparation method described in the second aspect.
  • the fourth aspect of the present invention provides the use of the quasi-agglomerated multi-element positive electrode material described in the first aspect or the third aspect, or the preparation method described in the second aspect in a lithium-ion battery.
  • a fifth aspect of the present invention provides a lithium-ion battery, wherein the lithium-ion battery contains the quasi-agglomerated multi-element positive electrode material described in the first aspect or the third aspect.
  • the present invention has the following advantages:
  • the particle size of the primary particles of the agglomerated ternary positive electrode material in the prior art is usually 0.2-0.6 ⁇ m
  • the quasi-agglomerated multi-element positive electrode material provided by the present invention is a secondary particle formed by agglomeration of primary particles; wherein the primary particles are spherical or quasi-spherical, and their stacking is more compact, the binding force between each other is strong, the compaction density is high, and the secondary particles formed are also spherical or quasi-spherical.
  • the morphological characteristics of the primary particles and the secondary particles are conducive to improving the energy density and cycle performance of the battery;
  • the average particle size DS of the primary particles is 0.9-2.4 ⁇ m, which is close to the size of the single crystal ternary positive electrode material.
  • the existing agglomerated ternary positive electrode materials are easily fractured during the production of the electrode sheets, and the primary particles are easily separated due to particle expansion and contraction during the cycle, which destroys the material structure and leads to a decrease in electrical performance.
  • the agglomerated multi-element positive electrode material provided by the present invention can make up for the defects of the agglomerated material, has stronger compressive resistance, and even if the primary particles are separated from each other during fracturing and the cycle, the performance of the separated primary particles is still similar to that of the single crystal material, which can ensure the stability of the electrical performance of the positive electrode material during the cycle;
  • the average particle size DL of the secondary particles is 5-15 ⁇ m, which is close to that of the agglomerated material and larger than that of the primary particles of the single crystal material. After being made into a pole piece, the particles are more tightly bound than those of the single crystal material, and the rate performance is better. Less conductive agent and binder are required, which is beneficial to increase the proportion of active materials, and the pole piece compaction density is larger, which can improve the energy density of the battery;
  • the grain boundaries of the primary particles and the surfaces of the secondary particles are rich in Co
  • the Co molar content of the center of the primary particles is defined as K1
  • the Co molar content of the grain boundaries of the primary particles is defined as K2
  • the Co molar content of the surface of the secondary particles is defined as K3, K2-K1 ⁇ 0.5%, K3-K1 ⁇ 1.5%.
  • the primary particles of the multi-element positive electrode material of the present invention are relatively large, the grain boundary gaps between the primary particles are relatively large, and the quasi-agglomerated positive electrode material process products are coated with a cobalt-containing compound with strong ductility and then sintered at high temperature, the cobalt element can not only be coated on the surface of the secondary particles, but also can enter the interior of the secondary particles along the grain boundaries of the primary particles, and be enriched at the interface between the primary particles, so as to achieve the purpose of coating the primary particles and the secondary particles with the cobalt element at the same time.
  • the exposed surface of the primary particles is still protected by the coating layer, thereby improving the structural stability of the material, inhibiting the erosion of the electrolyte, and improving the cycle stability and safety.
  • FIG1 is a SEM image of a quasi-agglomerated multi-element positive electrode material prepared in Example 1 of the present invention
  • FIG2 is a SEM image of the positive electrode material prepared in Comparative Example 1 of the present invention.
  • FIG3 is a SEM image of the positive electrode material prepared in Comparative Example 2 of the present invention.
  • Example 4 is a cycle performance diagram of the positive electrode materials prepared in Example 1 of the present invention and Comparative Examples 1 and 2 at a 1C rate, wherein the test temperature is 45° C. and the voltage range is 3.0-4.3V.
  • first and second do not represent a sequence of precedence or a limitation on materials or operations, but are only used to distinguish materials or operations.
  • first and second in “first cobalt source” and “second cobalt source” are only used to distinguish to indicate that they are not the same cobalt source;
  • first and second in “first high-temperature sintering” and “second high-temperature sintering” are only used to distinguish to indicate that they are not the same high-temperature sintering operation.
  • the first aspect of the present invention provides a quasi-agglomerated multi-element positive electrode material, wherein the multi-element positive electrode material has a structure shown in Formula I:
  • M is at least one of V, Ta, Cr, La, Al, Ce, Er, Ho, Y, Mg, Sr, Ba, Ra, Zr, Fe, Ca, Zn, B, W, Nb, Cd, Pb, Si, Mo, Cu, Sr and Ti;
  • the multi-element positive electrode material is a secondary particle formed by agglomeration of primary particles; wherein the primary particles are spherical or quasi-spherical; the average particle size DS of the primary particles is 0.9-2.4 ⁇ m; the average particle size DL of the secondary particles is 5-15 ⁇ m; and the value range of DL / DS is 5-16.
  • the agglomerated-type multi-element positive electrode material controls the size of primary particles and secondary particles and combines the value range of DL / DS to form a quasi-agglomerated type of multi-element positive electrode material, which can have the excellent properties of single crystal materials and agglomerated materials, and can take into account the high energy density, rate performance and cycle stability of the positive electrode material.
  • the quasi-agglomerate multi-element cathode material has a spherical or quasi-spherical morphology.
  • the morphology of the quasi-agglomerate multi-element cathode material is characterized by using a scanning electron microscope (SEM).
  • the grain boundaries of the primary particles and the surfaces of the secondary particles are rich in Co
  • the Co molar content of the center of the primary particles is defined as K1
  • the Co molar content of the grain boundaries of the primary particles is defined as K2
  • the Co molar content of the surface of the secondary particles is defined as K3, wherein K2-K1 ⁇ 0.5%, preferably, K2-K1 ⁇ 1%; K3-K1 ⁇ 1.5%, preferably, K3-K1 ⁇ 3%.
  • the "center" in the center of the primary particles does not refer to the exact center, but refers to the main body other than the grain boundaries of the primary particles and the surfaces of the secondary particles.
  • the use of the above preferred implementation method is conducive to forming a uniform coating layer on the grain boundary and the surface of the secondary particles, improving the mobility of lithium ions, inhibiting electrolyte corrosion, and improving the rate and cycle performance.
  • M is at least one of Mg, W, V, Ti, La, Nb, Si, Al and B.
  • the average particle size DS of the primary particles is 1.2-1.8 ⁇ m.
  • the average particle size DL of the secondary particles is 7-13 ⁇ m.
  • the value range of DL / DS is 7-12.
  • the above preferred embodiment is used to set DS to 1.2-1.8 ⁇ m. If Ds is greater than 1.8 ⁇ m, the primary particles are too large, which will cause the material rate performance to deteriorate, and the product performance will tend to single crystal materials. If Ds is less than 1.2 ⁇ m, the primary particles are too small and the structural stability is not good, the cycle performance is deteriorated, and the product performance will tend to agglomerated materials.
  • the above preferred embodiment is used to set DL to 7-13 ⁇ m. If DL is greater than 13 ⁇ m, the secondary particles are too large, the lithium ion mobility is reduced, and the rate is deteriorated.
  • DL is less than 7 ⁇ m, the secondary particles are too small and the compaction density is low, which will lead to reduced energy density and poor cycle performance.
  • the above preferred embodiment is used to set the value range of DL / DS to 7-12. If DL / DS is greater than 12, there are too many primary particles in the secondary particles, which will form more grain boundaries, the material compressive performance will be reduced, the product performance will tend to agglomerates, and the pole pieces are prone to fracture during the manufacturing process. DL /DS If S is less than 7, there will be fewer primary particles in the secondary particles, fewer grain boundaries will be formed, the contact area between the electrolyte and the positive electrode material will be smaller, and the material capacity will be reduced.
  • the average particle size DS of the primary particles and the average particle size DL of the secondary particles are measured by scanning electron microscopy (SEM), the particle size can be obtained by any graphic analysis software or manual measurement, and the data statistical results can be obtained by any statistical software.
  • SEM scanning electron microscopy
  • the grain boundaries of the primary particles and the surfaces of the secondary particles are rich in Co.
  • the content of Co used for coating in the agglomerated multi-element positive electrode material is the same, the larger the DL / DS , the lower the Co content of the grain boundaries of the primary particles, and the higher the Co content of the surfaces of the secondary particles; the smaller the DL / DS , the higher the Co content of the grain boundaries of the primary particles, and the lower the Co content of the surfaces of the secondary particles.
  • the BET specific surface area of the quasi-agglomerated multinary cathode material is 0.1-0.4 m 2 /g, preferably 0.2-0.3 m 2 /g.
  • the BET specific surface area of the quasi-agglomerated multinary cathode material is measured by a Micromeritics Tristar 3020 surface area analyzer.
  • the half-width FWHM (104) of the characteristic peak of the XRD test (104) of the quasi-agglomerated multinary positive electrode material is in the range of 0.19-0.23, preferably 0.2-0.22.
  • the half-width FWHM (104) of the quasi-agglomerated multinary positive electrode material is obtained by testing the Smart Lab 9KW model X-ray diffractometer of Rigaku Corporation of Japan, wherein the half-width FWHM (104) specifically refers to the half-width of the (104) crystal plane of the quasi-agglomerated multinary positive electrode material.
  • the above value range indicates that the performance characterized by the XRD of the quasi-agglomerated multinary positive electrode material has the properties of a single crystal.
  • the D 50 of the quasi-agglomerated multi-element positive electrode material is 5-15 ⁇ m, preferably 7-13 ⁇ m.
  • the D 50 of the quasi-agglomerated multi-element positive electrode material is obtained by testing with a laser particle size analyzer.
  • a second aspect of the present invention provides a method for preparing a quasi-agglomerated multi-element positive electrode material, the preparation method comprising:
  • the quasi-agglomerated positive electrode material process product is mixed with a second cobalt source for a second high-temperature sintering, and then crushed and sieved in sequence to obtain a quasi-agglomerated multi-element positive electrode material.
  • the cobalt introduced by the first cobalt source is represented by Co 1
  • the cobalt introduced by the second cobalt source is represented by Co 2 , for distinction.
  • the pH value of the coprecipitation reaction is 10-13.
  • the pH value of the coprecipitation reaction is high, the primary fibers obtained are fine, the BET of the precursor is large, and it is easy to fuse during subsequent sintering, and it is easy to form a positive electrode material with larger primary particles; on the contrary, when the pH value of the coprecipitation reaction is low, the primary fibers obtained are coarse, the BET of the precursor is small, and it is not easy to fuse during subsequent sintering, and it is easy to form a positive electrode material with smaller primary particles.
  • the BET of the nickel-cobalt-manganese ternary precursor is 7-14 m 2 /g.
  • the conditions of the coprecipitation reaction further include: a temperature of 40-80° C., a time of 5-40 h, and a rotation speed of 300-900 rpm.
  • the D 50 of the nickel-cobalt-manganese ternary precursor is 5-15 ⁇ m, preferably 7-13 ⁇ m.
  • the nickel source, the first cobalt source and the manganese source are each independently selected from at least one of sulfates, chlorides, nitrates and acetates.
  • the nickel source may be selected from at least one of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate
  • the first cobalt source may be selected from at least one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate
  • the manganese source may be selected from at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
  • the mixing step comprises: passing a mixed salt solution containing the nickel source, the first cobalt source and the manganese source, the complexing agent and the precipitant into the reactor in a parallel flow manner. More preferably, the concentration of the mixed salt solution is 2-3 mol/L.
  • the mixed salt solution can be commercially available or prepared according to a conventional method in the art, and there is no particular limitation on this. Further preferably, the mixing is carried out under the protection of an inert gas.
  • the precipitant in step (1), may be a precipitant known in the art and suitable for preparing a nickel-cobalt-manganese ternary precursor, and there is no particular limitation on this, which can achieve the purpose of the present invention to a certain extent.
  • the precipitant is selected from sodium hydroxide and/or potassium hydroxide. More preferably, the precipitant is provided in the form of an aqueous precipitant solution, wherein the concentration of the aqueous precipitant solution is 5-10 mol/L.
  • the complexing agent in step (1), can be a complexing agent known in the art and suitable for preparing a nickel-cobalt-manganese ternary precursor, and there is no particular limitation on this, which can achieve the purpose of the present invention to a certain extent.
  • the complexing agent is selected from at least one of ammonia water, disodium ethylenediaminetetraacetate, ammonium nitrate, ammonium chloride and ammonium sulfate. More preferably, the complexing agent is provided in the form of a complexing agent aqueous solution, wherein the mass fraction of the complexing agent aqueous solution is 20-30%.
  • step (1) there is no particular restriction on the amount of the precipitant and the complexing agent, as long as the amount of the precipitant and the complexing agent are such that the coprecipitation reaction meets the precursor growth requirements.
  • step (1) the aging, filter pressing, washing and drying can be performed by conventional methods well known to those skilled in the art, without any particular limitation.
  • the temperature of the first high-temperature sintering is defined as T, and the value range of T satisfies Formula II:
  • C Ni is the molar percentage of nickel element in the mixture consisting of the nickel source, the first cobalt source and the manganese source; the definition and numerical range of DL can be selected with reference to the above and will not be repeated here.
  • step (2) if the temperature of the first high-temperature sintering is high, DL / DS is relatively small; if the temperature of the first high-temperature sintering is low, DL / DS is relatively large.
  • the conditions of the first high temperature sintering further include: a time of 10-30 hours, and a sintering atmosphere provided by an oxygen-containing gas.
  • the oxygen content in the oxygen-containing gas is 1-100 vol%.
  • the D 50 of the agglomerated positive electrode material process product is 5-15 ⁇ m, preferably 7-13 ⁇ m.
  • the D 50 of the nickel-cobalt-manganese ternary precursor and the D 50 of the quasi-agglomerated cathode material process product are obtained by testing with a laser particle size analyzer.
  • the amount of the lithium source satisfies, according to the stoichiometric ratio: 0.9 ⁇ [n(Li)]/[n(Ni)+n(Co 1 )+n(Mn)] ⁇ 1.1, preferably satisfies: 1.02 ⁇ [n(Li)]/[n(Ni)+n(Co 1 )+n(Mn)] ⁇ 1.06.
  • the lithium source in step (2), can be a lithium source known in the art for preparing positive electrode materials, and there is no particular limitation on this, which can achieve the purpose of the present invention to a certain extent.
  • the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, lithium oxide and lithium acetate.
  • the crushing and screening process can be carried out by conventional methods well known to those skilled in the art, without any particular limitation, as long as a quasi-agglomerated positive electrode material process product with a D50 satisfying the above requirements can be obtained.
  • the conditions of the second high temperature sintering include: a temperature of 200-1000°C, a time of 5-20 hours, and a sintering atmosphere provided by an oxygen-containing gas.
  • the oxygen content in the oxygen-containing gas is 1-100 vol%.
  • the second cobalt source is selected from at least one of cobalt oxide, cobalt hydroxide, cobalt oxyhydroxide, cobalt fluoride, cobaltous hydroxide, cobalt trioxide, cobalt carbonate and cobalt acetate, preferably at least one of cobalt oxide, cobalt hydroxide, cobaltous oxide, cobaltous hydroxide and cobaltous acetate.
  • the above preferred embodiment is conducive to achieving uniform coating and controlling surface residual alkali.
  • the amount of the second cobalt source satisfies, in terms of stoichiometric ratio: 0.005 ⁇ [n(Co 2 )]/[n(Ni)+n(Co 1 )+n(Mn)] ⁇ 0.1, preferably satisfies: 0.01 ⁇ [n(Co 2 )]/[n(Ni)+n(Co 1 )+n(Mn)] ⁇ 0.06.
  • the D 50 of the quasi-agglomerated multi-element positive electrode material is 5-15 ⁇ m, preferably 7-13 ⁇ m.
  • the crushing and screening process can be carried out by conventional methods well known to those skilled in the art, without any particular limitation, as long as a quasi-agglomerated multi-element positive electrode material with a D50 satisfying the above requirements can be obtained.
  • the mixed raw materials in step (1) further include additives.
  • the mixed raw materials in step (2) further include a dopant.
  • the mixed raw materials in step (3) also include a coating agent.
  • the additive, the dopant and the capping agent are the same or different, and are each independently selected from a compound containing M, preferably, selected from at least one of oxides, fluorides, hydroxides, oxyhydroxyls, carbonates, nitrates, sulfates and acetates containing M.
  • the dopant is selected from at least one of MgO, WO 3 , TiO 2 , Nb 2 O 5 and Al 2 O 3 .
  • the coating agent is selected from at least one of V 2 O 5 , La 2 O 3 , SiO 2 and B 2 O 3 .
  • the amount of the additive satisfies: the molar fraction of the additive calculated as M element to the total molar amount of Ni, Co, and Mn is 0.01%-3%.
  • the amount of the dopant satisfies: the molar fraction of the dopant calculated as M element to the total molar amount of Ni, Co, and Mn is 0.01%-3%.
  • the coating agent is used in an amount satisfying that the molar fraction of the coating agent calculated as M element to the total molar amount of Ni, Co, and Mn is 0.01%-3%.
  • the agglomerated multi-element positive electrode material prepared by the preparation method has a structure shown in Formula I:
  • M is at least one of V, Ta, Cr, La, Al, Ce, Er, Ho, Y, Mg, Sr, Ba, Ra, Zr, Fe, Ca, Zn, B, W, Nb, Cd, Pb, Si, Mo, Cu, Sr and Ti;
  • the multi-element positive electrode material is a secondary particle formed by agglomeration of primary particles; wherein the primary particles are spherical or quasi-spherical; the average particle size DS of the primary particles is 0.9-2.4 ⁇ m; the average particle size DL of the secondary particles is 5-15 ⁇ m; and the value range of DL / DS is 5-16.
  • the third aspect of the present invention provides a quasi-agglomerated multi-element positive electrode material prepared by the preparation method described in the second aspect.
  • the fourth aspect of the present invention provides the use of the quasi-agglomerated multi-element positive electrode material described in the first aspect or the third aspect, or the preparation method described in the second aspect in a lithium-ion battery.
  • a fifth aspect of the present invention provides a lithium-ion battery, wherein the lithium-ion battery contains the quasi-agglomerated multi-element positive electrode material described in the first aspect or the third aspect.
  • room temperature refers to 25 ⁇ 2°C.
  • the electrochemical performance of the multi-element positive electrode material was tested using a 2025 button cell.
  • the preparation process of 2025 button battery is as follows:
  • pole piece The multi-element positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) were mixed with an appropriate amount of N-methylpyrrolidone (NMP) in a mass ratio of 95:3:2 to form a uniform slurry.
  • NMP N-methylpyrrolidone
  • the slurry was coated on aluminum foil and dried at 120°C for 12 hours. It was then stamped and formed using a pressure of 100MPa to form a positive electrode piece with a diameter of 12mm and a thickness of 120 ⁇ m, wherein the loading amount of the multi-element positive electrode material was 15-16mg/ cm2 .
  • the positive electrode, separator, negative electrode and electrolyte were assembled into a 2025 button cell and left to stand for 6 hours.
  • the negative electrode used a metal lithium sheet with a diameter of 17mm and a thickness of 1mm;
  • the separator used a polyethylene porous membrane (Celgard 2325) with a thickness of 25 ⁇ m;
  • the electrolyte was an equal mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) containing 1mol/L LiPF 6 .
  • the electrochemical performance of the 2025 button cell was tested using a Shenzhen Xinwell battery testing system, and the charge and discharge current density at 0.1C was 200 mA/g.
  • the charge and discharge voltage range was controlled to be 3.0-4.3V.
  • the button cell was charged and discharged at 0.1C to evaluate the initial charge and discharge specific capacity and initial charge and discharge efficiency of the multi-electrode material.
  • Cycle performance test Control the charge and discharge voltage range to 3.0-4.3V. At a constant temperature of 45°C, charge and discharge the button battery twice at 0.1C, and then charge and discharge it 80 times at 1C to evaluate the high-temperature capacity retention rate of the multi-electrode material.
  • Rate performance test Control the charge and discharge voltage range to 3.0-4.3V. At room temperature, charge and discharge the button cell twice at 0.1C, and then charge and discharge once at 0.2C, 0.33C, 0.5C and 1C, respectively.
  • the rate performance of the multi-element positive electrode material is evaluated by the ratio of the 0.1C first discharge capacity to the 1C discharge capacity.
  • the 0.1C first discharge capacity is the discharge capacity of the button cell in the first cycle
  • the 1C discharge capacity is the discharge capacity of the button cell in the sixth cycle.
  • a nickel source, a first cobalt source, a manganese source, a complexing agent and a precipitant are mixed for coprecipitation reaction to obtain a slurry; and the slurry is then aged, filtered, washed and dried in sequence to obtain a nickel-cobalt-manganese ternary precursor;
  • the nickel source is nickel sulfate;
  • the first cobalt source is cobalt sulfate;
  • the manganese source is manganese sulfate;
  • the complexing agent is provided in the form of a complexing agent aqueous solution, which is 25% by mass of ammonia water;
  • the precipitant is provided in the form of a precipitant aqueous solution, which is 8 mol/L NaOH aqueous solution;
  • the mixing step is specifically as follows: under the protection of nitrogen, the aqueous solution containing the nickel source, the first cobalt source, the manganese source, the complexing agent aqueous solution and the precipitant aqueous solution are introduced into the reaction kettle in parallel, wherein the molar ratio of Ni:Co 1 :Mn is shown in Table 1;
  • the conditions of the coprecipitation reaction include: temperature of 60°C, time of 20h, and rotation speed of 800rpm; the pH value of the coprecipitation reaction is shown in Table 1;
  • the lithium source is lithium hydroxide; the types of dopants and the molar ratios of the raw materials are shown in Table 1;
  • the conditions of the first high temperature sintering include: the time is 18 hours, the sintering atmosphere is provided by oxygen; the temperature of the first high temperature sintering is shown in Table 1; before crushing and screening, the product of the first high temperature sintering is naturally cooled to room temperature;
  • the conditions of the second high temperature sintering include: a temperature of 720° C., a time of 10 hours, and a sintering atmosphere provided by oxygen; before crushing and screening, the product of the second high temperature sintering is naturally cooled to room temperature;
  • Example 2 According to the method of Example 1, the difference is that the raw materials and process parameters used are different, as shown in Table 1, and the rest is the same as Example 1 to prepare a quasi-agglomerated multi-element positive electrode material.
  • the chemical formula composition and characteristic parameter test data of each product are shown in Table 2.
  • step (1) the pH value of the coprecipitation reaction is 11.2; in step (2), the temperature of the first high-temperature sintering is 790°C; the rest is the same as in Example 1, and a positive electrode material is prepared.
  • Table 2 The chemical formula composition and characteristic parameter test data of each product are shown in Table 2.
  • step (1) the pH value of the coprecipitation reaction is 13.2; in step (2), the temperature of the first high-temperature sintering is 970°C; the rest is the same as in Example 1, and a positive electrode material is prepared.
  • Table 2 The chemical formula composition and characteristic parameter test data of each product are shown in Table 2.
  • Example 2 The method of Example 1 is followed, except that step (3) is not performed; the rest is the same as Example 1, and the quasi-agglomerated positive electrode material process product is directly used as the positive electrode material.
  • the chemical formula composition and characteristic parameter test data of each product are shown in Table 2.
  • the present invention tests the scanning electron microscope (SEM) images of the positive electrode materials prepared in the above-mentioned embodiments and comparative examples, wherein FIG1 is a SEM image of the quasi-agglomerated multi-element positive electrode material prepared in Example 1 of the present invention; FIG2 is a SEM image of the positive electrode material prepared in Comparative Example 1 of the present invention; and FIG3 is a SEM image of the positive electrode material prepared in Comparative Example 2 of the present invention.
  • SEM scanning electron microscope
  • the primary particles in the positive electrode material obtained in Example 1 are larger than those in the agglomerated comparative example 1 and smaller than those in the single crystal comparative example 2, the gaps between the primary particles in the positive electrode material obtained in Example 1 are larger, and the secondary particles are rounded spherical.
  • the present invention tested the D 50 , BET , XRD (half peak width FWHM (104) ), average particle size DS of primary particles and average particle size DL of secondary particles of the positive electrode materials prepared in the above embodiments and comparative examples.
  • the specific test results are shown in Table 2.
  • Precursor* is the nickel-cobalt-manganese ternary precursor
  • process product** is the quasi-agglomerated positive electrode material process product
  • positive electrode material*** is the quasi-agglomerated multi-element positive electrode material prepared in the example or the positive electrode material prepared in the comparative example.
  • Precursor* refers to nickel-cobalt-manganese ternary precursor
  • process product** refers to quasi-agglomerated positive electrode material process product
  • positive electrode material*** refers to quasi-agglomerated multi-element positive electrode material.
  • the positive electrode material of comparative example 1 has a larger DL / DS , which is an agglomerated material, while comparative example 2 is a single crystal material.
  • the FWHM (104) of the agglomerated-like multi-element positive electrode material of the present invention is between the single crystal material and the agglomerated material, and is close to the single crystal material.
  • the present invention tests the Ni, Co, and Mn compositions of the center of the primary particles, the grain boundaries of the primary particles, and the surface of the secondary particles of the positive electrode materials prepared in the above embodiments and comparative examples, thereby obtaining the difference in Co content.
  • the specific test results are shown in Table 3. Among them, the Ni, Co, and Mn compositions are the average results of multi-point tests.
  • the present invention tests the electrochemical properties of the positive electrode materials prepared by the above embodiments and comparative examples, including 0.1C first discharge specific capacity, 1C discharge specific capacity, rate performance and cycle performance.
  • the specific test results are shown in Table 4; wherein, the test temperature of the discharge specific capacity at 1C rate is 25°C.
  • Example 1 202.1 187.3 0.927 95.4
  • Example 2 202.5 187.2 0.924 94.3
  • Example 3 201.5 185.7 0.922 96.1
  • Example 4 203.2 186.2 0.916 93.6
  • Example 5 218.5 201.8 0.924 91.1 Comparative Example 1 201.1 184.3 0.916 89.2 Comparative Example 2 196.8 179.5 0.912 94.6 Comparative Example 3 200.2 181.4 0.906 89.1
  • Example 2 It can be seen from Table 4 that the sintering temperature of Example 2 is lower than that of Example 1, the primary particles are smaller, the grain boundary Co is less than that of Example 1, the external Co is more, and the material circulation is poor;
  • Example 3 The sintering temperature of Example 3 is higher than that of Example 1, the primary particles are larger, the grain boundary Co is more than that of Example 1, the external Co is less, and the material capacity ratio is slightly worse;
  • Example 4 has less Co coating than Example 1, less Co at the grain boundary and surface, poor material rate and poor cycle;
  • Comparative Example 1 is an agglomerated material with small primary particles and a compact structure. Co cannot enter the secondary particles along the grain boundary. There is little Co at the grain boundary, and the material capacity ratio is poor and the cycle is poor.
  • Comparative Example 2 is a single crystal material, the primary particles are large, the primary particles are separated and independent from each other, Co is enriched on the surface of the material, and the material capacity ratio is poor;
  • Comparative Example 3 is not coated with Co, and the material rate is poor and the cycle is poor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

一种类团聚型多元正极材料及其制备方法、应用和锂离子电池。类团聚型多元正极材料的化学式为Li aNi xCo yMn zM bO 2；0.9≤a≤1.1，0.5≤x＜1，0＜y＜0.5，0＜z＜0.5，0≤b＜0.05；M为V、Ta、Cr、La、Al、Ce、Er、Ho、Y、Mg、Sr、Ba、Ra、Zr、Fe、Ca、Zn、B、W、Nb、Cd、Pb、Si、Mo、Cu、Sr和Ti中的至少一种；其为由一次颗粒团聚而成的二次颗粒；一次颗粒为球形或类球形；一次颗粒的平均颗粒大小D S为0.9-2.4μm；二次颗粒的平均颗粒大小D L为5-15μm；D L/D S的取值范围为5-16。类团聚型多元正极材料能量密度高、倍率性能好、循环稳定性优良。

Description

类团聚型多元正极材料及其制备方法、应用和锂离子电池
相关申请的交叉引用
本申请要求2022年10月31日提交的中国专利申请202211352231.X的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及锂离子电池技术领域，具体涉及类团聚型多元正极材料及其制备方法和锂离子电池。
背景技术
近年来，能源及环境问题越来越受到关注，世界新能源车的发展从混合动力开始，随后逐步进入电池为主的时代，纯电动和插混成为新能源的真正政策支持主力。
高安全、长续航是电动汽车的发展趋势。为了满足电动汽车的更高需求，动力锂电池需要具有更高的能量密度和更好的循环稳定性。锂电池产业链中，市场规模最大、产值最高的环节当属正极材料，并且其性能决定了电池的能量密度、寿命、倍率性能等，正极材料成为锂电池的核心关键材料。
三元材料具有能量密度高，循环稳定性好及安全性好的特点，目前市场主流的三元材料为团聚材料和单晶材料，团聚材料倍率性能好，但循环性能略差，单晶材料循环性能好，但颗粒尺寸较小，生产效率低，并且倍率性能略差。
为了得到能量密度高、结构稳定性强的正极材料，需要通过对材料结构合理设计，同时兼顾材料的能量密度、倍率性能和循环稳定性。
相关技术公开了一种三元正极材料微米级片状单晶结构团聚体及其制备方法，其首先采用改进的化学共沉淀法制备由纳米片紧密叠成的微米球状前驱体，该前驱体的D50大小在6-8μm之间；然后把上述前驱体依次与适量的助熔剂及锂盐进行充分的混合；最后在高温烧结炉中两步高温烧结，最终得到微米级片状单晶结构团聚体的三元正极材料，其虽然能够结合单晶结构和团聚体结构两者的优势，但片状单晶结构耐压强度较低，且片状结构形成的团聚体较难形成规则球形，一次颗粒间难以紧密堆积，彼此间结合力较弱，电池极片制作过程中容易出现压裂及一次颗粒间滑移，导致结构坍塌，循环性能较差；且片状结构堆积的团聚体晶界间隙较大，晶界及表面没有延展性好的包覆层保护，电池循环过程中电解液容易通过晶界到达一次 颗粒表面，使一次颗粒由表面至内部被电解液侵蚀，导致循环保持率下降。
发明内容
本发明的目的是为了克服现有的三元正极材料无法兼顾能量密度、倍率性能和循环稳定性的问题。
为了实现上述目的，本发明第一方面提供一种类团聚型多元正极材料，所述多元正极材料具有式I所示的结构：
Li aNi xCo yMn zM bO 2      式I；
式I中，0.9≤a≤1.1，0.5≤x＜1，0＜y＜0.5，0＜z＜0.5，0≤b＜0.05；M为V、Ta、Cr、La、Al、Ce、Er、Ho、Y、Mg、Sr、Ba、Ra、Zr、Fe、Ca、Zn、B、W、Nb、Cd、Pb、Si、Mo、Cu、Sr和Ti中的至少一种；
所述多元正极材料为由一次颗粒团聚而成的二次颗粒；其中，所述一次颗粒为球形或类球形；所述一次颗粒的平均颗粒大小D S为0.9-2.4μm；所述二次颗粒的平均颗粒大小D L为5-15μm；且D L/D S的取值范围为5-16。
本发明第二方面提供一种类团聚型多元正极材料的制备方法，所述制备方法包括：
(1)将镍源、第一钴源、锰源、络合剂和沉淀剂混合进行共沉淀反应，得到浆料；然后将所述浆料依次进行陈化、压滤、洗涤、干燥，得到镍钴锰三元前驱体；
(2)将所述镍钴锰三元前驱体与锂源混合进行第一高温烧结，并依次进行破碎、过筛处理，得到类团聚型正极材料过程品；
(3)将所述类团聚型正极材料过程品与第二钴源混合进行第二高温烧结，并依次进行破碎、过筛处理，得到类团聚型多元正极材料。
本发明第三方面提供一种由第二方面所述的制备方法制得的类团聚型多元正极材料。
本发明第四方面提供第一方面或第三方面所述的类团聚型多元正极材料、或者第二方面所述的制备方法在锂离子电池中的应用。
本发明第五方面提供一种锂离子电池，所述锂离子电池含有第一方面或第三方面所述的类团聚型多元正极材料。
通过上述技术方案，本发明具有如下优势：
1、现有技术的团聚型三元正极材料的一次颗粒的颗粒大小通常为0.2-0.6μm，而本发明提供的类团聚型多元正极材料为由一次颗粒团聚而成的二次颗粒；其中，所述一次颗粒为球形 或类球形，其堆积更加紧密，彼此间结合力强，压实密度高，所形成的二次颗粒也为球形或类球形，在本发明中一次颗粒和二次颗粒的形貌特征有利于提升电池的能量密度和循环性能；所述一次颗粒的平均颗粒大小D S为0.9-2.4μm，其与单晶型三元正极材料的大小较接近。
现有的团聚型三元正极材料在极片制作过程中易被压裂，且循环过程中由于颗粒膨胀收缩，一次颗粒间易分离，破坏材料结构，导致电性能下降。而本发明提供的类团聚型多元正极材料，能够弥补团聚型材料的缺陷，抗压能力更强，且即使出现压裂及循环过程中的一次颗粒彼此分离的情况，分离后的一次颗粒性能仍然与单晶型材料相似，能够保证正极材料在循环过程中的电性能稳定；
2、本发明提供的类团聚型多元正极材料中，二次颗粒的平均颗粒大小D L为5-15μm，接近团聚型材料，且较单晶型材料的一次颗粒大，制成极片后，其较单晶型材料颗粒间结合紧密，倍率性能更好，需要更少的导电剂和粘结剂，有利于提升活性物质的比例，且极片压实密度更大，可以提升电池的能量密度；
3、本发明提供的类团聚型多元正极材料中，一次颗粒的晶界以及二次颗粒的表面富含Co，且定义所述一次颗粒的中心的Co摩尔含量为K1，所述一次颗粒的晶界的Co摩尔含量为K2，所述二次颗粒的表面的Co摩尔含量为K3，K2-K1≥0.5％，K3-K1≥1.5％。由于本发明的多元正极材料的一次颗粒较大，使得一次颗粒间晶界缝隙较大，类团聚型正极材料过程品包覆延展性较强的含钴化合物后经过高温烧结，钴元素不仅能够包覆在二次颗粒的表面，且能够沿一次颗粒晶界进入到二次颗粒内部，富集在一次颗粒之间的界面，实现一次颗粒和二次颗粒同时包覆钴元素的目的，得到的多元正极材料在极片制作及循环过程中，若二次颗粒破碎，或电解液通过晶界达到一次颗粒表面，暴露出来的一次颗粒表面仍然具有包覆层保护，从而能够提升材料的结构稳定性，抑制电解液的侵蚀，提升循环稳定性和安全性。
附图说明
图1是本发明实施例1制得的类团聚型多元正极材料的SEM图；
图2是本发明对比例1制得的正极材料的SEM图；
图3是本发明对比例2制得的正极材料的SEM图；
图4是本发明实施例1以及对比例1、对比例2制得的正极材料在1C倍率下的循环性能图，其中，测试温度为45℃，电压范围为3.0-4.3V。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
在本发明中，在没有明确说明的情况下，“第一”和“第二”均不代表先后次序，也不对各个物料或者操作起到限定作用，仅是为了区分各个物料或者操作，例如，“第一钴源”和“第二钴源”中的“第一”和“第二”仅是为了区分以表示这不是同一钴源；“第一高温烧结”和“第二高温烧结”中的“第一”和“第二”仅是为了区分以表示这不是同一高温烧结操作。
本发明第一方面提供一种类团聚型多元正极材料，所述多元正极材料具有式I所示的结构：
Li aNi xCo yMn zM bO 2     式I；
式I中，0.9≤a≤1.1，0.5≤x＜1，0＜y＜0.5，0＜z＜0.5，0≤b＜0.05；M为V、Ta、Cr、La、Al、Ce、Er、Ho、Y、Mg、Sr、Ba、Ra、Zr、Fe、Ca、Zn、B、W、Nb、Cd、Pb、Si、Mo、Cu、Sr和Ti中的至少一种；
所述多元正极材料为由一次颗粒团聚而成的二次颗粒；其中，所述一次颗粒为球形或类球形；所述一次颗粒的平均颗粒大小D S为0.9-2.4μm；所述二次颗粒的平均颗粒大小D L为5-15μm；且D L/D S的取值范围为5-16。
根据本发明的一些实施方式，所述类团聚型多元正极材料通过控制一次颗粒和二次颗粒的大小，结合D L/D S的取值范围，使得形成的多元正极材料形成类团聚型，其能够兼具单晶型材料和团聚型材料的优异性能，能够兼顾正极材料的高能量密度、倍率性能和循环稳定性。
根据本发明的一些实施方式，优选地，所述类团聚型多元正极材料具有球形或类球形的形貌。所述类团聚型多元正极材料的形貌采用扫描电子显微镜(SEM)进行表征得到。
根据本发明的一些实施方式，所述一次颗粒的晶界和所述二次颗粒的表面富含Co，且定义所述一次颗粒的中心的Co摩尔含量为K1，所述一次颗粒的晶界的Co摩尔含量为K2，所述二次颗粒的表面的Co摩尔含量为K3，其中，K2-K1≥0.5％，优选地，K2-K1≥1％；K3-K1≥1.5％，优选地，K3-K1≥3％。其中，所述一次颗粒的中心中的“中心”，不是指正中心，而是指除了一次颗粒的晶界以及二次颗粒的表面之外的其他主体部分。
采用上述优选实施方式有利于在晶界及二次颗粒表面形成均匀包覆层，提升锂离子迁移 率，且抑制电解液侵蚀，提升倍率及循环性能。
根据本发明的一些实施方式，优选地，式I中，1≤a≤1.1，0.0005≤b≤0.01。
根据本发明的一些实施方式，优选地，M为Mg、W、V、Ti、La、Nb、Si、Al和B中的至少一种。
根据本发明的一些实施方式，优选地，所述一次颗粒的平均颗粒大小D S为1.2-1.8μm。
根据本发明的一些实施方式，优选地，所述二次颗粒的平均颗粒大小D L为7-13μm。
根据本发明的一些实施方式，优选地，D L/D S的取值范围为7-12。
采用上述优选实施方式设置D S为1.2-1.8μm，若Ds大于1.8μm，则一次颗粒偏大，会导致材料倍率性能变差，产品性能会趋向单晶材料，若Ds小于1.2μm，则一次颗粒偏小结构稳定性不好，循环性能变差，产品性能会趋向团聚材料；采用上述优选实施方式设置D L为7-13μm，若D L大于13μm，则二次颗粒偏大，锂离子迁移率降低，倍率变差，若D L小于7μm，则二次颗粒偏小，压实密度低，会导致能量密度降低及循环变差；采用上述优选实施方式设置D L/D S的取值范围为7-12，若D L/D S大于12，则二次颗粒中的一次颗粒偏多，会形成较多的晶界，材料抗压性能将会有所下降，产品性能会趋向团聚体，极片在制作过程中易压裂，D L/D S小于7，则二次颗粒中的一次颗粒偏少，所形成的晶界也会偏少，电解液与正极材料接触面积较小，材料容量会有所降低。
根据本发明的一些实施方式，所述一次颗粒的平均颗粒大小D S与所述二次颗粒的平均颗粒大小D L通过扫描电子显微镜(SEM)测得，颗粒大小可以由任意图形分析软件或人工测量获得，并由任意统计软件获得数据统计结果。
根据本发明的一些实施方式，所述一次颗粒的晶界和所述二次颗粒的表面富含Co。优选地，当所述类团聚型多元正极材料中用于包覆Co的含量相同时，D L/D S越大，所述一次颗粒的晶界的Co含量越低，所述二次颗粒的表面的Co含量越高；D L/D S越小，所述一次颗粒的晶界的Co含量越高，所述二次颗粒的表面的Co含量越低。
根据本发明的一些实施方式，优选地，所述类团聚型多元正极材料的BET比表面积为0.1-0.4m 2/g，优选为0.2-0.3m 2/g。所述类团聚型多元正极材料的BET比表面积通过Micromeritics公司的Tristar 3020型号的比表面仪测试得到。
根据本发明的一些实施方式，优选地，所述类团聚型多元正极材料XRD测试(104)特征峰的半峰宽FWHM (104)的取值范围为0.19-0.23，优选为0.2-0.22。所述类团聚型多元正极材料的半峰宽FWHM (104)通过日本理学公司的Smart Lab 9KW型号的X射线衍射仪测试得到， 其中，半峰宽FWHM (104)具体是指所述类团聚型多元正极材料的(104)晶面的半峰宽，上述取值范围表明所述类团聚型多元正极材料的XRD所表征的性能具备单晶的性质。
根据本发明的一些实施方式，优选地，所述类团聚型多元正极材料的D 50为5-15μm，优选为7-13μm。所述类团聚型多元正极材料的D 50通过激光粒度仪测试得到。
本发明第二方面提供一种类团聚型多元正极材料的制备方法，所述制备方法包括：
(1)将镍源、第一钴源、锰源、络合剂和沉淀剂混合进行共沉淀反应，得到浆料；然后将所述浆料依次进行陈化、压滤、洗涤、干燥，得到镍钴锰三元前驱体；
(2)将所述镍钴锰三元前驱体与锂源混合进行第一高温烧结，并依次进行破碎、过筛处理，得到类团聚型正极材料过程品；
(3)将所述类团聚型正极材料过程品与第二钴源混合进行第二高温烧结，并依次进行破碎、过筛处理，得到类团聚型多元正极材料。
此处需要说明的是，在本发明中，第一钴源引入的钴用Co 1表示，第二钴源引入的钴用Co 2表示，以示区分。
根据本发明的一些实施方式，步骤(1)中，所述共沉淀反应的pH值为10-13。所述共沉淀反应的pH值高，则得到的一次纤维细，前驱体的BET大，后续烧结时易融合，易形成一次颗粒较大的正极材料；相反，所述共沉淀反应的pH值低，则得到的一次纤维粗，前驱体的BET小，后续烧结时不易融合，易形成一次颗粒较小的正极材料。
根据本发明的一些实施方式，优选地，步骤(1)中，所述镍钴锰三元前驱体的BET为7-14m 2/g。
根据本发明的一些实施方式，优选地，步骤(1)中，所述共沉淀反应的条件还包括：温度为40-80℃，时间为5-40h，转速为300-900rpm。
根据本发明的一些实施方式，优选地，步骤(1)中，所述镍钴锰三元前驱体的D 50为5-15μm，优选为7-13μm。
根据本发明的一些实施方式，优选地，步骤(1)中，所述镍源、所述第一钴源和所述锰源各自独立地选自硫酸盐、氯化盐、硝酸盐和醋酸盐中的至少一种，例如，所述镍源可以选自硫酸镍、氯化镍、硝酸镍和醋酸镍中的至少一种；所述第一钴源可以选自硫酸钴、氯化钴、硝酸钴和醋酸钴中的至少一种；所述锰源可以选自硫酸锰、氯化锰、硝酸锰和醋酸锰中的至少一种。
根据本发明的一些实施方式，优选地，步骤(1)中，所述混合的步骤包括：将含有所述 镍源、所述第一钴源和所述锰源的混合盐水溶液、所述络合剂和沉淀剂以并流的方式通入反应釜。更优选地，所述混合盐水溶液的浓度为2-3mol/L。所述混合盐水溶液可以商购得到，也可以按照本领域的常规方法配制得到，对此没有特别的限制。进一步优选地，所述混合在惰性气体的保护下进行。
根据本发明的一些实施方式，步骤(1)中，所述沉淀剂可以为本领域所公知的适用于制备镍钴锰三元前驱体的沉淀剂，对此没有特别的限制，其均能在一定程度上实现本发明的发明目的。优选地，所述沉淀剂选自氢氧化钠和/或氢氧化钾。更优选地，所述沉淀剂以沉淀剂水溶液的形式提供，其中，所述沉淀剂水溶液的浓度为5-10mol/L。
根据本发明的一些实施方式，步骤(1)中，所述络合剂可以为本领域所公知的适用于制备镍钴锰三元前驱体的络合剂，对此没有特别的限制，其均能在一定程度上实现本发明的发明目的。优选地，所述络合剂选自氨水、乙二胺四乙酸二钠、硝酸铵、氯化铵和硫酸铵中的至少一种。更优选地，所述络合剂以络合剂水溶液的形式提供，其中，所述络合剂水溶液的质量分数为20-30％。
根据本发明的一些实施方式，步骤(1)中，对所述沉淀剂和所述络合剂的用量没有特别的限制，只要沉淀剂的用量和络合剂的用量使得共沉淀反应满足前驱体生长要求即可。
根据本发明的一些实施方式，步骤(1)中，所述陈化、压滤、洗涤、干燥可以采用本领域技术人员熟知的常规方法进行，对此没有特别的限制。
根据本发明的一些实施方式，优选地，步骤(2)中，定义所述第一高温烧结的温度为T，且T的取值范围满足式II：
Figure PCTCN2022135490-appb-000001
优选T的取值范围满足式III：
Figure PCTCN2022135490-appb-000002
其中，C Ni为由所述镍源、所述第一钴源和所述锰源组成的混合物中镍元素的摩尔百分比；D L的定义和数值范围可参照上文进行选用，在此不再赘述。
根据本发明的一些实施方式，优选地，步骤(2)中，所述第一高温烧结的温度高，则D L/D S偏小；所述第一高温烧结的温度低，则D L/D S偏大。
根据本发明的一些实施方式，优选地，步骤(2)中，所述第一高温烧结的条件还包括：时间为10-30h，烧结气氛由含氧气体提供。优选地，所述含氧气体中的氧气含量为1-100vol％。
根据本发明的一些实施方式，优选地，步骤(2)中，所述类团聚型正极材料过程品的 D 50为5-15μm，优选为7-13μm。
根据本发明的一些实施方式，所述镍钴锰三元前驱体的D 50与所述类团聚型正极材料过程品的D 50通过激光粒度仪测试得到。
根据本发明的一些实施方式，优选地，步骤(2)中，按照化学计量比计，所述锂源的用量满足：0.9≤[n(Li)]/[n(Ni)+n(Co 1)+n(Mn)]≤1.1，优选满足：1.02≤[n(Li)]/[n(Ni)+n(Co 1)+n(Mn)]≤1.06。
根据本发明的一些实施方式，步骤(2)中，所述锂源可以为本领域所公知的适用于制备正极材料的锂源，对此没有特别的限制，其均能在一定程度上实现本发明的发明目的。优选地，所述锂源选自碳酸锂、氢氧化锂、氧化锂和醋酸锂中的至少一种。
根据本发明的一些实施方式，步骤(2)中，所述破碎、过筛处理可以采用本领域技术人员熟知的常规方法进行，对此没有特别的限制，只要能够得到D 50满足上述要求的类团聚型正极材料过程品即可。
根据本发明的一些实施方式，优选地，步骤(3)中，所述第二高温烧结的条件包括：温度为200-1000℃，时间为5-20h，烧结气氛由含氧气体提供。优选地，所述含氧气体中的氧气含量为1-100vol％。
根据本发明的一些实施方式，优选地，步骤(3)中，所述第二钴源选自氧化钴、氢氧化钴、羟基氧化钴、氟化钴、氢氧化亚钴、四氧化三钴、碳酸钴和醋酸钴中的至少一种，优选为氧化钴、氢氧化钴、四氧化三钴、羟基氧化钴和氢氧化亚钴中的至少一种。采用上述优选实施方式有利于实现均匀包覆并控制表面残碱。
根据本发明的一些实施方式，优选地，步骤(3)中，按照化学计量比计，所述第二钴源的用量满足：0.005≤[n(Co 2)]/[n(Ni)+n(Co 1)+n(Mn)]≤0.1，优选满足：0.01≤[n(Co 2)]/[n(Ni)+n(Co 1)+n(Mn)]≤0.06。
根据本发明的一些实施方式，所述第一钴源与所述第二钴源的用量使得所述类团聚型多元正极材料中的Co的总含量满足：n(Ni)：n(Co)：n(Mn)＝x：y：z，其中，n(Co)＝n(Co 1)+n(Co 2)，x、y、z的取值可参照上文进行定义和选用，在此不再赘述。
根据本发明的一些实施方式，优选地，步骤(3)中，所述类团聚型多元正极材料的D 50为5-15μm，优选为7-13μm。
根据本发明的一些实施方式，步骤(3)中，所述破碎、过筛处理可以采用本领域技术人员熟知的常规方法进行，对此没有特别的限制，只要能够得到D 50满足上述要求的类团聚型多 元正极材料即可。
根据本发明的一些实施方式，优选地，步骤(1)中所述混合的原料还包括添加剂。
根据本发明的一些实施方式，优选地，步骤(2)中所述混合的原料还包括掺杂剂。
根据本发明的一些实施方式，优选地，步骤(3)中所述混合的原料还包括包覆剂。
根据本发明的一些实施方式，所述添加剂、所述掺杂剂和所述包覆剂相同或不同，各自独立地选自含有M的化合物，优选地，选自含有M的氧化物、氟化物、氢氧化物、羟基氧化物、碳酸盐、硝酸盐、硫酸盐和醋酸盐中的至少一种。
根据本发明的一些实施方式，优选地，所述掺杂剂选自MgO、WO 3、TiO 2、Nb 2O 5和Al 2O 3中的至少一种。
根据本发明的一些实施方式，优选地，所述包覆剂选自V 2O 5、La 2O 3、SiO 2和B 2O 3中的至少一种。
根据本发明的一些实施方式，优选地，所述添加剂的用量满足：以M元素计的所述添加剂占Ni、Co、Mn总摩尔量的摩尔分数为0.01％-3％。
根据本发明的一些实施方式，优选地，所述掺杂剂的用量满足：以M元素计的所述掺杂剂占Ni、Co、Mn总摩尔量的摩尔分数为0.01％-3％。
根据本发明的一些实施方式，优选地，所述包覆剂的用量满足：以M元素计的所述包覆剂占Ni、Co、Mn总摩尔量的摩尔分数为0.01％-3％。
根据本发明的一些实施方式，所述添加剂、所述掺杂剂和所述包覆剂的总用量使得得到的多元正极材料中，n(Ni)：n(Co)：n(Mn)：n(M)＝x：y：z：b，其中，x、y、z、b的取值可参照上文进行定义和选用，在此不再赘述。
根据本发明的一些实施方式，所述制备方法制得的类团聚型多元正极材料具有式I所示的结构：
Li aNi xCo yMn zM bO 2      式I；
式I中，0.9≤a≤1.1，0.5≤x＜1，0＜y＜0.5，0＜z＜0.5，0≤b＜0.05；M为V、Ta、Cr、La、Al、Ce、Er、Ho、Y、Mg、Sr、Ba、Ra、Zr、Fe、Ca、Zn、B、W、Nb、Cd、Pb、Si、Mo、Cu、Sr和Ti中的至少一种；
所述多元正极材料为由一次颗粒团聚而成的二次颗粒；其中，所述一次颗粒为球形或类球形；所述一次颗粒的平均颗粒大小D S为0.9-2.4μm；所述二次颗粒的平均颗粒大小D L为5-15μm；且D L/D S的取值范围为5-16。
本发明第三方面提供一种由第二方面所述的制备方法制得的类团聚型多元正极材料。
本发明第四方面提供第一方面或第三方面所述的类团聚型多元正极材料，或者第二方面所述的制备方法在锂离子电池中的应用。
本发明第五方面提供一种锂离子电池，所述锂离子电池含有第一方面或第三方面所述的类团聚型多元正极材料。
以下将通过实施例对本发明进行详细描述。以下实施例和对比例中，在没有特别说明的情况下，所有原料均为市售品。
在没有特别说明的情况下，室温是指25±2℃。
以下实施例和对比例中，相关参数通过以下方法测试得到：
(1)形貌测试：通过日本日立HITACHI公司的S-4800型号的扫描电子显微镜测试得到的；
(2)BET测试：通过Micromeritics公司的Tristar 3020型号的比表面仪测试得到的；
(3)XRD测试：通过日本理学公司的Smart Lab 9KW型号的X射线衍射仪测试得到的；
(4)D 50粒度测试：通过Marvern公司的Hydro 2000mu型号的激光粒度仪测试得到的；
(5)电化学性能测试：
以下实施例和对比例中，多元正极材料的电化学性能采用2025型扣式电池进行测试。
2025型扣式电池的制备过程具体如下：
极片制备：将多元正极材料、乙炔黑和聚偏二氟乙烯(PVDF)按照95：3：2的质量比与适量的N-甲基吡咯烷酮(NMP)充分混合形成均匀的浆料，将浆料涂覆在铝箔上于120℃干燥12h后，使用100MPa的压力将其冲压成型，制成直径为12mm、厚度为120μm的正极极片，其中，所述多元正极材料的负载量为15-16mg/cm 2。
电池组装：在水含量与氧含量均小于5ppm的充有氩气的气手套箱内，将正极极片、隔膜、负极极片以及电解液组装成2025型扣式电池后，静置6h。其中，负极极片使用直径为17mm、厚度为1mm的金属锂片；隔膜使用厚度为25μm的聚乙烯多孔膜(Celgard 2325)；电解液为含1mol/L LiPF 6的碳酸乙烯酯(EC)和碳酸二乙酯(DEC)的等量混合液。
电化学性能测试：
以下实施例和对比例中，采用深圳新威尔电池测试系统对2025型扣式电池进行电化学性能测试，0.1C的充放电电流密度为200mA/g。
控制充放电电压区间为3.0-4.3V，在室温下，将扣式电池在0.1C下进行充放电测试，评 估多元正极材料的首次充放电比容量和首次充放电效率。
循环性能测试：控制充放电电压区间为3.0-4.3V，在恒温45℃下，将扣式电池在0.1C下充放电循环2次，然后在1C下充放电循环80次，评估多元正极材料的高温容量保持率。
倍率性能测试：控制充放电电压区间为3.0-4.3V，在室温下，将扣式电池在0.1C下充放电循环2次，然后在0.2C、0.33C、0.5C和1C下分别充放电循环1次，以0.1C首次放电比容量与1C放电比容量的比值评估多元正极材料的倍率性能。其中，0.1C首次放电比容量为扣式电池第1周循环的放电比容量，1C放电比容量为扣式电池第6周循环的放电比容量。
实施例1
(1)将镍源、第一钴源、锰源、络合剂和沉淀剂混合进行共沉淀反应，得到浆料；再将该浆料依次进行陈化、压滤、洗涤、干燥，得到镍钴锰三元前驱体；其中：
镍源为硫酸镍；第一钴源为硫酸钴；锰源为硫酸锰；络合剂以络合剂水溶液的形式提供，其为质量分数为25％的氨水；沉淀剂以沉淀剂水溶液的形式提供，其为8mol/L的NaOH水溶液；
混合的步骤具体为：在氮气的保护下，将含有上述镍源、第一钴源、锰源的水溶液、络合剂水溶液和沉淀剂水溶液以并流的方式通入反应釜中，其中，Ni：Co 1：Mn的摩尔比见表1；
共沉淀反应的条件包括：温度为60℃，时间为20h，转速为800rpm；共沉淀反应的pH值见表1；
得到的镍钴锰三元前驱体的化学式组成、BET和D 50见表2。
(2)将镍钴锰三元前驱体与锂源和掺杂剂混合进行第一高温烧结，并依次进行破碎、过筛处理，得到类团聚型正极材料过程品；其中：
锂源为氢氧化锂；掺杂剂的种类和各原料的用量摩尔比见表1；
第一高温烧结的条件包括：时间为18h，烧结气氛由氧气提供；第一高温烧结的温度见表1；进行破碎、过筛处理前，将第一高温烧结的产物自然冷却至室温；
得到的类团聚型正极材料过程品的化学式组成和D 50见表2。
(3)将类团聚型正极材料过程品与第二钴源混合进行第二高温烧结，并依次进行破碎、过筛处理，得到类团聚型多元正极材料；其中：
第二钴源的种类和各原料的用量摩尔比见表1；
第二高温烧结的条件包括：温度为720℃，时间为10h，烧结气氛由氧气提供；进行破碎、 过筛处理前，将第二高温烧结的产物自然冷却至室温；
得到的类团聚型多元正极材料的化学式组成和D 50见表2。
实施例2-5
按照实施例1的方法，不同的是，采用的原料和工艺参数不同，具体如表1所示，其余均与实施例1相同，制备得到类团聚型多元正极材料。其中，各产物的化学式组成和特性参数测试数据见表2。
对比例1
按照实施例1的方法，不同的是，步骤(1)中，共沉淀反应的pH值为11.2；步骤(2)中，第一高温烧结的温度为790℃；其余均与实施例1相同，制备得到正极材料。其中，各产物的化学式组成和特性参数测试数据见表2。
对比例2
按照实施例1的方法，不同的是，步骤(1)中，共沉淀反应的pH值为13.2；步骤(2)中，第一高温烧结的温度为970℃；其余均与实施例1相同，制备得到正极材料。其中，各产物的化学式组成和特性参数测试数据见表2。
对比例3
按照实施例1的方法，不同的是，不进行步骤(3)；其余均与实施例1相同，直接将类团聚型正极材料过程品作为正极材料。其中，各产物的化学式组成和特性参数测试数据见表2。
表1
Figure PCTCN2022135490-appb-000003
Figure PCTCN2022135490-appb-000004
注：各元素的比例以摩尔比计
测试例
(1)形貌测试
本发明测试了上述实施例和对比例制备得到的正极材料的扫描电子显微镜(SEM)图像，其中，图1是本发明实施例1制得的类团聚型多元正极材料的SEM图；图2是本发明对比例1制得的正极材料的SEM图；图3是本发明对比例2制得的正极材料的SEM图。从图中可以看出实施例1得到的正极材料中的一次颗粒较团聚型对比例1大，较单晶型对比例2小，实施例1得到的正极材料中的一次颗粒间缝隙较大，二次颗粒为圆润球形。
(2)物性测试
本发明测试了上述实施例和对比例制备得到的正极材料的D 50、BET、XRD(半峰宽FWHM (104))、一次颗粒的平均颗粒大小D S和二次颗粒的平均颗粒大小D L，具体测试结果如表2所示。
表2
Figure PCTCN2022135490-appb-000005
Figure PCTCN2022135490-appb-000006
注：前驱体*即为镍钴锰三元前驱体；过程品**即为类团聚型正极材料过程品；正极材料***即为实施例制得的类团聚型多元正极材料或对比例制得的正极材料。
表2(续)
Figure PCTCN2022135490-appb-000007
注：前驱体*即为镍钴锰三元前驱体；过程品**即为类团聚型正极材料过程品；正极材料***即为类团聚型多元正极材料。
通过表1和表2的结果可以看出，类团聚型多元正极材料的制备过程中，升高一次烧结温度，正极材料的FWHM (104)变小，温度升高一次颗粒的平均尺寸增大，当一次颗粒长到一定尺寸时会彼此分离，成为独立的颗粒。
对比例1的正极材料的D L/D S较大，为团聚型材料，对比例2为单晶型材料，本发明的类团聚型多元正极材料的FWHM (104)在单晶型材料与团聚型材料之间，接近单晶型材料。
(3)组成测试
本发明测试了上述实施例和对比例制备得到的正极材料的一次颗粒的中心，一次颗粒的晶界及二次颗粒的表面的Ni、Co、Mn组成，从而得到Co含量差异，具体测试结果如表3所示。其中，Ni、Co、Mn组成为多点测试的平均结果。
表3(Ni、Co、Mn的总含量以100摩尔％计)
Figure PCTCN2022135490-appb-000008
通过表3可以看出，正极材料中的一次颗粒大，则一次颗粒间的晶界较大，进入晶界的Co较多，一次颗粒小，则Co不易进入晶界，大多包覆在材料二次颗粒表面。
(4)电化学性能测试
本发明测试了上述实施例和对比例制备得到的正极材料的电化学性能，包括0.1C首次放电比容量、1C放电比容量、倍率性能以及循环性能，具体测试结果如表4所示；其中，1C倍率下的放电比容量的测试温度为25℃。
表4
项目 首次放电比容量 放电比容量 倍率性能 容量保持率
单位 0.1C/mAh/g 1.0C/mAh/g 1.0C/0.1C 45℃循环80次/％
实施例1 202.1 187.3 0.927 95.4
实施例2 202.5 187.2 0.924 94.3
实施例3 201.5 185.7 0.922 96.1
实施例4 203.2 186.2 0.916 93.6
实施例5 218.5 201.8 0.924 91.1
对比例1 201.1 184.3 0.916 89.2
对比例2 196.8 179.5 0.912 94.6
对比例3 200.2 181.4 0.906 89.1
通过表4可以看出，实施例2比实施例1的烧结温度低，一次颗粒小，晶界Co较实施例1少，外部Co较多，材料循环较差；
实施例3比实施例1烧结温度高，一次颗粒大，晶界Co较实施例1多，外部Co较少，材料容量倍率略差；
实施例4比实施例1包覆Co少，晶界及表面Co较少，材料倍率差，循环差；
对比例1为团聚型材料，一次颗粒小，结构紧密，Co不能够延晶界进入到二次颗粒内部，晶界Co很少，材料容量倍率差，循环差；
对比例2为单晶型材料，一次颗粒大，一次颗粒彼此分离独立，Co富集在材料表面，材料容量倍率差；
对比例3没有包覆Co，材料倍率差，循环差。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (12)

  1. 一种类团聚型多元正极材料，其特征在于，所述多元正极材料具有式I所示的结构：
    Li aNi xCo yMn zM bO 2  式I；
    式I中，0.9≤a≤1.1，0.5≤x＜1，0＜y＜0.5，0＜z＜0.5，0≤b＜0.05；M为V、Ta、Cr、La、Al、Ce、Er、Ho、Y、Mg、Sr、Ba、Ra、Zr、Fe、Ca、Zn、B、W、Nb、Cd、Pb、Si、Mo、Cu、Sr和Ti中的至少一种；
    所述多元正极材料为由一次颗粒团聚而成的二次颗粒；其中，所述一次颗粒为球形或类球形；所述一次颗粒的平均颗粒大小D S为0.9-2.4μm；所述二次颗粒的平均颗粒大小D L为5-15μm；且D L/D S的取值范围为5-16。
  2. 根据权利要求1所述的类团聚型多元正极材料，所述一次颗粒的晶界和所述二次颗粒的表面富含Co，且定义所述一次颗粒的中心的Co摩尔含量为K1，所述一次颗粒的晶界的Co摩尔含量为K2，所述二次颗粒的表面的Co摩尔含量为K3，其中，K2-K1≥0.5％，优选地，K2-K1≥1％；K3-K1≥1.5％，优选地，K3-K1≥3％。
  3. 根据权利要求1或2所述的类团聚型多元正极材料，其中，式I中，1≤a≤1.1，0.0005≤b≤0.01；
    和/或，M为Mg、W、V、Ti、La、Nb、Si、Al和B中的至少一种；
    和/或，所述一次颗粒的平均颗粒大小D S为1.2-1.8μm；
    和/或，所述二次颗粒的平均颗粒大小D L为7-13μm；
    和/或，D L/D S的取值范围为7-12。
  4. 根据权利要求1或2所述的类团聚型多元正极材料，其中，所述类团聚型多元正极材料的BET比表面积为0.1-0.4m 2/g，优选为0.2-0.3m 2/g；
    和/或，所述类团聚型多元正极材料XRD测试(104)特征峰的半峰宽FWHM (104)的取值范围为0.19-0.23，优选为0.2-0.22；
    和/或，所述类团聚型多元正极材料的D 50为5-15μm，优选为7-13μm。
  5. 一种类团聚型多元正极材料的制备方法，其特征在于，所述制备方法包括：
    (1)将镍源、第一钴源、锰源、络合剂和沉淀剂混合进行共沉淀反应，得到浆料；然后将所述浆料依次进行陈化、压滤、洗涤、干燥，得到镍钴锰三元前驱体；
    (2)将所述镍钴锰三元前驱体与锂源混合进行第一高温烧结，并依次进行破碎、过筛处理，得到类团聚型正极材料过程品；
    (3)将所述类团聚型正极材料过程品与第二钴源混合进行第二高温烧结，并依次进行破碎、过筛处理，得到类团聚型多元正极材料。
  6. 根据权利要求5所述的制备方法，其中，步骤(1)中，所述共沉淀反应的pH值为10-13；
    和/或，所述共沉淀反应的温度为40-80℃，时间为5-40h，转速为300-900rpm；
    和/或，所述镍钴锰三元前驱体的BET比表面积为7-14m 2/g；
    和/或，所述镍钴锰三元前驱体的D 50为5-15μm，优选为7-13μm。
  7. 根据权利要求5所述的制备方法，其中，步骤(2)中，定义所述第一高温烧结的温度为T，且T的取值范围满足式II：
    Figure PCTCN2022135490-appb-100001
    优选T的取值范围满足式III：
    Figure PCTCN2022135490-appb-100002
    其中，C Ni为由所述镍源、所述第一钴源和所述锰源组成的混合物中镍元素的摩尔百分比；
    和/或，所述第一高温烧结的时间为10-30h，烧结气氛由含氧气体提供；
    和/或，所述类团聚型正极材料过程品的D 50为5-15μm，优选为7-13μm；
    和/或，按照化学计量比计，所述锂源的用量满足：0.9≤[n(Li)]/[n(Ni)+n(Co 1)+n(Mn)]≤1.1，优选满足：1.02≤[n(Li)]/[n(Ni)+n(Co 1)+n(Mn)]≤1.06。
  8. 根据权利要求5-7中任意一项所述的制备方法，其中，步骤(3)中，所述第二高温烧结的条件包括：温度为200-1000℃，时间为5-20h，烧结气氛由含氧气体提供；
    和/或，所述第二钴源选自氧化钴、氢氧化钴、羟基氧化钴、氟化钴、氢氧化亚钴、四氧化三钴、碳酸钴和醋酸钴中的至少一种，优选为氧化钴、氢氧化钴、四氧化三钴、羟基氧化钴和氢氧化亚钴中的至少一种；
    和/或，按照化学计量比计，所述第二钴源的用量满足：
    0.005≤[n(Co 2)]/[n(Ni)+n(Co 1)+n(Mn)]≤0.1，优选满足：0.01≤[n(Co 2)]/[n(Ni)+n(Co 1)+n(Mn)]≤0.06。
  9. 根据权利要求5-8中任意一项所述的制备方法，其中，步骤(1)中所述混合的原料还包括添加剂；和/或，步骤(2)中所述混合的原料还包括掺杂剂；和/或，步骤(3)中所述混合的原料还包括包覆剂；
    其中，所述添加剂、所述掺杂剂和所述包覆剂相同或不同，各自独立地选自含有M的化合物，优选地，选自含有M的氧化物、氟化物、氢氧化物、羟基氧化物、碳酸盐、硝酸盐、硫酸盐和醋酸盐中的至少一种；
    优选地，所述掺杂剂选自MgO、WO 3、TiO 2、Nb 2O 5和Al 2O 3中的至少一种；和/或，所述包覆剂选自V 2O 5、La 2O 3、SiO 2和B 2O 3中的至少一种。
  10. 一种由权利要求5-9中任意一项所述的制备方法制得的类团聚型多元正极材料。
  11. 权利要求1-4或10中任意一项所述的类团聚型多元正极材料，或者权利要求5-9所述的制备方法在锂离子电池中的应用。
  12. 一种锂离子电池，其特征在于，所述锂离子电池含有权利要求1-4或10中任意一项所述的类团聚型多元正极材料。
PCT/CN2022/135490 2022-10-31 2022-11-30 类团聚型多元正极材料及其制备方法、应用和锂离子电池 Ceased WO2024092933A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2024577269A JP7788015B2 (ja) 2022-10-31 2022-11-30 類凝集状多元系正極材料及びその製造方法、使用並びにリチウムイオン電池
EP22964229.3A EP4531135A4 (en) 2022-10-31 2022-11-30 Multi-element agglomerated positive electrode material, its preparation process, its use, and lithium-ion battery
KR1020247043056A KR20250017251A (ko) 2022-10-31 2022-11-30 응집-유사형 다원계 양극재 및 그 제조방법, 응용, 리튬이온 배터리
US19/006,221 US20250128962A1 (en) 2022-10-31 2024-12-31 Agglomeration-like multi-element cathode material, preparation method therefor, and lithium-ion battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211352231.X 2022-10-31
CN202211352231.XA CN116111081B (zh) 2022-10-31 2022-10-31 类团聚型多元正极材料及其制备方法、应用和锂离子电池

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US19/006,221 Continuation US20250128962A1 (en) 2022-10-31 2024-12-31 Agglomeration-like multi-element cathode material, preparation method therefor, and lithium-ion battery

Publications (1)

Publication Number Publication Date
WO2024092933A1 true WO2024092933A1 (zh) 2024-05-10

Family

ID=86260476

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/135490 Ceased WO2024092933A1 (zh) 2022-10-31 2022-11-30 类团聚型多元正极材料及其制备方法、应用和锂离子电池

Country Status (6)

Country Link
US (1) US20250128962A1 (zh)
EP (1) EP4531135A4 (zh)
JP (1) JP7788015B2 (zh)
KR (1) KR20250017251A (zh)
CN (1) CN116111081B (zh)
WO (1) WO2024092933A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116947117B (zh) * 2023-07-07 2025-11-14 三一技术装备有限公司 制备正极材料的方法、正极材料、正极片和电池
CN117613210B (zh) * 2023-10-25 2024-09-13 北京当升材料科技股份有限公司 多元正极材料及其制备方法、正极极片、锂离子电池
CN117712371B (zh) * 2023-12-29 2025-12-09 宁波容百新能源科技股份有限公司 一种高镍正极材料及其制备方法和应用
CN119542413B (zh) * 2024-09-30 2026-04-07 宁波容百新能源科技股份有限公司 一种高镍正极材料及其制备方法和应用
CN119447287A (zh) * 2025-01-07 2025-02-14 宁波容百新能源科技股份有限公司 一种正极材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1581543A (zh) * 2003-08-15 2005-02-16 比亚迪股份有限公司 非水二次电池用正极活性材料、其制备方法以及使用该材料的非水二次电池
JP2008130287A (ja) * 2006-11-17 2008-06-05 Matsushita Battery Industrial Co Ltd 非水電解質二次電池用正極活物質の製造方法および非水電解質二次電池
CN103296249A (zh) * 2013-06-19 2013-09-11 宁德新能源科技有限公司 掺杂改性锂镍钴锰、制备方法及锂离子电池
CN111370677A (zh) * 2020-03-24 2020-07-03 江门市科恒实业股份有限公司 一种高电压类团聚态钴酸锂材料及其制备方法与应用
CN112750999A (zh) * 2020-12-28 2021-05-04 北京当升材料科技股份有限公司 正极材料及其制备方法和锂离子电池

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012113823A (ja) * 2010-11-19 2012-06-14 Nippon Chem Ind Co Ltd リチウム二次電池用正極活物質、その製造方法及びリチウム二次電池
JP6072688B2 (ja) 2011-07-28 2017-02-01 三洋電機株式会社 非水電解質二次電池及び非水電解質二次電池の製造方法
KR101785262B1 (ko) 2013-07-08 2017-10-16 삼성에스디아이 주식회사 양극 활물질, 그 제조방법, 이를 채용한 양극 및 리튬이차전지
CN105185962B (zh) * 2015-08-31 2018-06-29 宁波容百新能源科技股份有限公司 一种高镍正极材料及其制备方法和锂离子电池
CN108206281B (zh) * 2016-12-20 2020-06-19 比亚迪股份有限公司 一种三元材料及其制备方法以及电池浆料和正极与锂电池
KR102698846B1 (ko) 2017-11-22 2024-08-26 주식회사 엘지에너지솔루션 리튬 이차전지용 양극활물질 및 그 제조방법
US20220166007A1 (en) 2019-03-29 2022-05-26 Panasonic Intellectual Property Management Co., Ltd. Non-aqueous electrolyte secondary battery
US20230348294A1 (en) * 2020-11-10 2023-11-02 Lg Energy Solution, Ltd. Positive Electrode Active Material for Lithium Secondary Battery, Method for Preparing the Same and Lithium Secondary Battery Comprising the Same
KR102660455B1 (ko) 2021-01-15 2024-04-23 주식회사 엘지에너지솔루션 리튬 이차 전지용 양극 활물질, 그 제조방법, 이를 포함하는 양극 및 리튬 이차 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1581543A (zh) * 2003-08-15 2005-02-16 比亚迪股份有限公司 非水二次电池用正极活性材料、其制备方法以及使用该材料的非水二次电池
JP2008130287A (ja) * 2006-11-17 2008-06-05 Matsushita Battery Industrial Co Ltd 非水電解質二次電池用正極活物質の製造方法および非水電解質二次電池
CN103296249A (zh) * 2013-06-19 2013-09-11 宁德新能源科技有限公司 掺杂改性锂镍钴锰、制备方法及锂离子电池
CN111370677A (zh) * 2020-03-24 2020-07-03 江门市科恒实业股份有限公司 一种高电压类团聚态钴酸锂材料及其制备方法与应用
CN112750999A (zh) * 2020-12-28 2021-05-04 北京当升材料科技股份有限公司 正极材料及其制备方法和锂离子电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4531135A4 *

Also Published As

Publication number Publication date
US20250128962A1 (en) 2025-04-24
KR20250017251A (ko) 2025-02-04
JP2025524787A (ja) 2025-08-01
CN116111081A (zh) 2023-05-12
EP4531135A4 (en) 2026-01-07
CN116111081B (zh) 2025-09-19
JP7788015B2 (ja) 2025-12-17
EP4531135A1 (en) 2025-04-02

Similar Documents

Publication Publication Date Title
CN110931768B (zh) 一种高镍类单晶锂离子电池正极材料及制备方法
CN102763247B (zh) 锂离子电池用正极活性物质、锂离子电池用正极以及锂离子电池
JP6089433B2 (ja) Ｌｉ−Ｎｉ複合酸化物粒子粉末及びその製造方法、並びに非水電解質二次電池
CN102754254B (zh) 锂离子电池用正极活性物质、锂离子电池用正极及锂离子电池
JP7788015B2 (ja) 類凝集状多元系正極材料及びその製造方法、使用並びにリチウムイオン電池
CN101652883B (zh) 非水电解液二次电池用锰酸锂及其制造方法、以及非水电解液二次电池
CN116190560B (zh) 一种正极片和电池
JP2011096650A (ja) 正極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池
WO2024109564A1 (zh) 一种高容量长循环的低钴单晶正极材料及其制备方法
CN114956211B (zh) 一种锰镍铜前驱体、钠离子电池正极材料及其制备方法
CN114824196A (zh) 一种高功率长循环镍钴锰三元正极材料及其制备方法
WO2014063407A1 (zh) 改性高能量密度锂离子电池正极材料及其制备方法
CN115084506A (zh) 大粒径单晶三元正极材料及其制备方法和应用
CN115663139B (zh) 镍钴锰多元正极材料及其制备方法与应用、锂离子电池
CN115863604A (zh) 一种正极材料及包括该正极材料的正极片和电池
CN116565188A (zh) 正极材料前驱体及其制备方法、正极材料及其制备方法
JP7622934B2 (ja) リチウム複合酸化物及びその製造方法
CN114477311B (zh) 钴复合氢氧化物及其制备方法、锂离子电池正极材料和锂离子电池
CN116504950A (zh) 一种超高价金属离子修饰改性镍铁锰酸钠正极材料及其制备方法
CN117525386A (zh) 高镍正极材料及其制备方法和应用
WO2026002261A1 (zh) 羟基氧化钴及其制备方法、正极材料、电池和涉电设备
CN112952056A (zh) 一种富锂锰基复合正极材料及其制备方法和应用
CN116947122B (zh) 一种表面掺钴超高镍单晶三元正极材料及其制备方法和锂离子电池
CN117012963A (zh) 纳米正极材料及其制备方法、锂离子电池
CN115036509A (zh) 一种固态电池用正极材料及其制备方法与应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22964229

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2022964229

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20247043056

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020247043056

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2024577269

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 2022964229

Country of ref document: EP

Effective date: 20241223

WWP Wipo information: published in national office

Ref document number: 1020247043056

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2022964229

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE