WO2023155366A1 - Ternary positive electrode precursor material, method for preparing same, and ternary positive electrode material - Google Patents

Ternary positive electrode precursor material, method for preparing same, and ternary positive electrode material Download PDF

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WO2023155366A1
WO2023155366A1 PCT/CN2022/104342 CN2022104342W WO2023155366A1 WO 2023155366 A1 WO2023155366 A1 WO 2023155366A1 CN 2022104342 W CN2022104342 W CN 2022104342W WO 2023155366 A1 WO2023155366 A1 WO 2023155366A1
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positive electrode
ternary
precursor material
ternary positive
electrode precursor
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刘会基
傅有焘
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湖南力合厚浦科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—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
    • C01P2004/60—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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C01P2006/11—Powder tap 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
    • C01P2006/40—Electric properties
    • 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 battery materials, in particular to a ternary positive electrode precursor material, a preparation method and a ternary positive electrode material.
  • New energy vehicles refer to the use of unconventional vehicle fuels as power sources (or the use of conventional vehicle fuels, the use of new vehicle power devices), integrated vehicle power control and advanced technology in driving, the formation of advanced technical principles, with Automobiles with new technology and new structure.
  • the demand for power batteries is increasing, and they are also facing greater challenges, especially the stricter conditions for the performance of cathode materials.
  • the precursor product of the ternary cathode material is based on nickel salt, cobalt salt, and manganese salt, and the ratio of nickel, cobalt, and manganese can be adjusted according to actual needs.
  • most of the public ternary positive electrode material precursor products are hydroxides.
  • the mainstream preparation technology is: dissolving nickel salt, manganese salt, and cobalt salt to form a mixed solution, mixing with ammonia water and lye, and complexing the ammonia water Function, the co-precipitation of lye, after the formation of crystal nuclei, the crystals continue to grow through agglomeration, and the ternary positive electrode hydroxide precursor is obtained.
  • the preparation process of the ternary positive electrode hydroxide precursor is often difficult to control, which easily affects the stability of the product; in addition, because the ternary positive electrode precursor hydroxide itself is a secondary ball, the structure of the prepared ternary positive electrode material Poor stability and low density are prone to breakage during the rolling process of the pole piece, resulting in poor cycle stability and low energy density of the battery.
  • One of the purposes of the embodiments of the present application is to provide a ternary positive electrode precursor material and its preparation method, as well as a ternary positive electrode material, aiming at solving the problem of poor structural stability and low density of the ternary positive electrode hydroxide precursor. Affect the technical issues such as cycle stability and energy density of ternary cathode materials.
  • a ternary positive electrode precursor material in a first aspect, includes a ternary oxide precursor with a general chemical formula of Ni (1-yz) Co y Mn z O x , wherein, 1 ⁇ x ⁇ 1.2, 0.03 ⁇ y ⁇ 0.1, 0.2 ⁇ z ⁇ 0.35.
  • a method for preparing a ternary positive electrode precursor material comprising the following steps:
  • the mixed solution is atomized and calcined to obtain a ternary positive electrode precursor material.
  • a ternary positive electrode material is provided, the ternary positive electrode material is obtained by sintering a lithium source and a ternary positive electrode precursor material, wherein the ternary positive electrode precursor material includes the above-mentioned ternary positive electrode precursor material.
  • the beneficial effect of the ternary positive electrode precursor material provided by the embodiment of the present application is that: on the one hand, the precursor exists in the form of oxides. Compared with the traditional hydroxide precursors, the content of nickel, cobalt and manganese main metals in the oxide precursors Higher, when sintering into a ternary cathode material, the unit loading amount is increased, thereby increasing the output when sintering into a ternary cathode material, and reducing the manufacturing cost of the ternary cathode material.
  • the proportion of cobalt is only 0.03 ⁇ y ⁇ 0.1, and the low cobalt content is beneficial to increase the nickel content in the ternary cathode material Furthermore, the actual energy density of the ternary cathode material is increased. If the cobalt content is too high, the actual capacity of the material will be reduced, and if the cobalt content is too low, the structural stability of the material will be reduced.
  • the ratio of manganese is 0.2 ⁇ z ⁇ 0.35, which effectively ensures the stability and safety of the crystal structure of the ternary oxide precursor.
  • the proportion of nickel is 0.55 ⁇ 1-yz ⁇ 0.77, which makes the ternary positive electrode precursor material a high-nickel material, which improves the volume energy density of the ternary positive electrode material, and if the nickel content is too low, the gram capacity of the material is reduced , if the nickel content is too high, it will lead to mixed discharge of lithium and nickel, which will easily lead to lithium precipitation.
  • the ternary positive electrode precursor material of the present application by adjusting the proportion of each main metal element in the ternary oxide precursor, makes the ternary positive electrode precursor material have better structural stability at the same time, thereby improving the corresponding three-component Cycling stability and gram capacity of primary cathode materials.
  • the ternary oxide precursor provided by this application can be crystallized once
  • the preparation not only shortens the preparation time and improves the preparation efficiency, but also is more conducive to improving the structural stability of the precursor material, increasing the density of the precursor material, improving the controllability of the particle size, and refining the particle size of the material, thereby further improving the precursor material.
  • the unit filling quantity of the material improves the preparation efficiency of the ternary cathode material and reduces the manufacturing cost.
  • the beneficial effect of the preparation method of the ternary positive electrode precursor material provided by the embodiment of the present application is that the process flow is simple, the intermediate process is small, the reaction process is convenient for flexible regulation, and the roasting treatment is carried out at the same time as the atomization, which not only ensures that the product has a smaller The particle size is small, and the reaction speed of the product is fast.
  • the actual reaction time for obtaining the ternary positive electrode precursor material by atomization and roasting is only a few seconds, and the production efficiency is high.
  • the anions in the salt solution are converted into gaseous substances to be removed or recovered in a high-temperature environment, the utilization rate of raw materials is high, the impurity content in the product is low, and the performance is excellent.
  • the ternary cathode precursor material product prepared by this method has better structural stability of the material itself.
  • the beneficial effect of the ternary positive electrode material provided in the embodiment of the present application is that the ternary positive electrode material is obtained by sintering the lithium source and the above-mentioned ternary positive electrode precursor material, and the property of the above-mentioned ternary positive electrode precursor material is relatively high due to its high nickel content.
  • the substance is a metal oxide. Compared with the hydroxide precursor, it can directly generate the positive electrode material when sintered with the lithium source, and improve the preparation efficiency of the ternary positive electrode material. Therefore, the ternary positive electrode material obtained by sintering with the lithium source has characteristics such as high gram capacity, cycle stability, and structural stability.
  • Figure 1 is a scanning electron microscope image 1 of the Ni 0.67 Co 0.05 Mn 0.28 O ternary oxide precursor provided in the embodiment of the present application;
  • Figure 2 is the scanning electron microscope image 2 of the Ni 0.67 Co 0.05 Mn 0.28 O ternary oxide precursor provided in the examples of this application;
  • Fig. 3 is a schematic flow chart of the preparation method of the ternary positive electrode precursor material provided by the embodiment of the present application;
  • Figure 4 is a scanning electron microscope image of the ternary cathode material provided in Example 1 of the present application.
  • FIG. 5 is an XRD test chart of the ternary positive electrode precursor material provided in Example 5 of the present application.
  • the term "and/or” describes the association relationship of associated objects, indicating that there may be three types of relationships, for example, A and/or B may indicate: A exists alone, and A and B exist simultaneously , in the case of B alone. Among them, A and B can be singular or plural.
  • the character "/" generally indicates that the contextual objects are an "or" relationship.
  • At least one means one or more, and “multiple” means two or more. “At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • the weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components.
  • the scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application.
  • the mass in the description of the embodiments of the present application may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
  • first and second are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features.
  • first XX can also be called the second XX
  • second XX can also be called the first XX.
  • a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • ternary positive electrode precursor material includes a ternary oxide precursor with a general chemical formula of Ni (1-yz) Co y Mnz O x , wherein, 1 ⁇ x ⁇ 1.2, 0.03 ⁇ y ⁇ 0.1, 0.2 ⁇ z ⁇ 0.35.
  • the ternary positive electrode precursor material provided by the embodiment of the present application includes a ternary oxide precursor with a general chemical formula of Ni (1-yz) Co y Mnz O x ; on the one hand, the precursor exists in the form of an oxide, and the Compared with the traditional hydroxide precursor, the main metal content of nickel, cobalt and manganese in the oxide precursor is higher, and when sintered into a ternary positive electrode material, the unit filling capacity is increased, thereby increasing the time of sintering into a ternary positive electrode material.
  • the output can reduce the manufacturing cost of the ternary cathode material.
  • the proportion of cobalt is only 0.03 ⁇ y ⁇ 0.1, and the low cobalt content is beneficial to increase the nickel content in the ternary cathode material Furthermore, the actual energy density of the ternary cathode material is increased. If the cobalt content is too high, the actual capacity of the material will be reduced, and if the cobalt content is too low, the structural stability of the material will be reduced.
  • the ratio of manganese is 0.2 ⁇ z ⁇ 0.35, which effectively ensures the stability and safety of the crystal structure of the ternary oxide precursor.
  • the proportion of nickel is 0.55 ⁇ 1-yz ⁇ 0.77, which makes the ternary positive electrode precursor material a high-nickel material, which improves the volume energy density of the ternary positive electrode material, and if the nickel content is too low, the gram capacity of the material is reduced , if the nickel content is too high, it will lead to mixed discharge of lithium and nickel, which will easily lead to lithium precipitation.
  • the ternary positive electrode precursor material in the embodiment of the present application by adjusting the proportion of each main metal element in the ternary oxide precursor, makes the ternary positive electrode precursor material have better structural stability at the same time, thereby improving the corresponding The cycle stability and gram capacity of the ternary cathode material. Moreover, compared to the ternary hydroxide precursor materials that need to be prepared by co-precipitation and other methods with poor structural stability, low density, and poor particle size controllability, the ternary oxide precursors provided in the examples of this application can be crystallized once.
  • the preparation not only shortens the preparation time and improves the preparation efficiency, but also is more conducive to improving the structural stability of the precursor material, increasing the density of the precursor material, improving the controllability of the particle size, and refining the particle size of the material, thereby further improving the precursor material.
  • the unit filling quantity of the material improves the preparation efficiency of the ternary cathode material and reduces the manufacturing cost.
  • the general chemical formula of the ternary oxide precursor is 1 ⁇ x ⁇ 1.14, 0.04 ⁇ y ⁇ 0.08, 0.25 ⁇ z ⁇ 0.30 in Ni (1-yz) Co y Mnz O x .
  • the ternary oxide precursor has better structural stability, thereby improving the stability and capacity of the ternary positive electrode precursor material and the ternary positive electrode material.
  • the crystal structure of the ternary oxide precursor is a single crystal structure among hexagonal layered structure, spinel structure, cubic structure and octahedral structure.
  • the ternary oxide precursor in the embodiment of this application is in a single crystal form.
  • the crystal structure of the material is more stable, and it is beneficial to improve the tap density and loose packing density of the ternary positive electrode precursor material. Density, thereby improving the cycle stability and specific capacity of the corresponding ternary cathode material.
  • the ternary positive electrode precursor material includes but is not limited to layered structures such as hexagonal layered structure, cubic structure, octahedral structure, and various crystal forms such as spinel structure.
  • layered structures such as hexagonal layered structure, cubic structure, octahedral structure, and various crystal forms such as spinel structure.
  • the crystal structure of the ternary oxide precursor can be a hexagonal layered structure; after the formation of the ternary positive electrode material, the hexagonal layered structure is a two-dimensional structure, which is conducive to the deintercalation of lithium ions, thereby enabling Improve the specific capacity of the ternary cathode material.
  • the crystal structure of the ternary oxide precursor can also be a cubic structure, which is conducive to improving the uniformity of the precursor material, reducing agglomeration, good product stability, and better cycle performance and rate performance. high.
  • the crystal structure of the ternary oxide precursor can also be an octahedral structure, and the precursor of the octahedral structure has a higher active specific surface area, which is also conducive to lithium ion deintercalation, and the precursor
  • the particle size uniformity of the bulk particles is high, which is beneficial to improve the film density, flatness and uniformity of the positive electrode sheet, thereby improving the cycle stability of the battery.
  • the crystal structure of the ternary oxide precursor can be a spinel structure, and the spinel type is a three-dimensional cubic structure, and the crystal itself has high structural stability, which is conducive to improving the cycle of the ternary positive electrode material. Stable performance and rate performance.
  • the ternary positive electrode precursor material includes a ternary oxide precursor with a hexagonal layered structure, a ternary oxide precursor with a spinel structure, and a ternary oxide precursor with a cubic structure. 1. At least two of the ternary oxide precursors with octahedral structure, through the synergistic effect of two or more ternary oxide precursors with different crystal structures, it is more conducive to improving the ternary positive electrode precursor material electrochemical performance.
  • the ternary positive electrode precursor material includes both a ternary oxide precursor with a hexagonal layered structure and a ternary oxide precursor with a spinel structure, and the ternary oxide with a hexagonal layered structure
  • the mass ratio of the precursor to the ternary oxide precursor of the spinel structure is (50-100): (1-50), among which, the ternary oxide precursor of the two-dimensional layered structure is beneficial to Li ion
  • the deintercalation improves the capacity of the ternary cathode material; while the spinel structure is a three-dimensional cubic structure, which has high structural stability and is more conducive to improving the cycle performance and rate of the ternary cathode material than the two-dimensional layered structure. performance.
  • the synergistic effect of the hexagonal layered structure and the spinel structure of the ternary oxide precursor with a mass ratio of (50-100): (1-50) makes the obtained ternary positive electrode material It has high capacity, high cycle stability and high rate capability. If the proportion of the ternary oxide precursor of the hexagonal layered structure in the ternary positive electrode precursor material is too high, the stability of the ternary positive electrode material will be reduced; if the content of the ternary oxide precursor of the spinel structure is too high High, it will reduce the capacity of the ternary cathode material.
  • the high capacity of the ternary positive electrode material can be further optimized by adjusting the ratio of the layered structure ternary oxide precursor and the spinel structure ternary oxide precursor in the ternary positive electrode precursor material , high cycle performance and high rate performance.
  • the mass ratio of the ternary oxide precursor of the hexagonal layered structure to the ternary oxide precursor of the spinel structure (60-90): (10- 40), further, the mass ratio is (65-80):(20-35), further, the mass ratio is (65-75):(25-35).
  • the mass ratio of the ternary oxide precursor of the hexagonal layered structure to the ternary oxide precursor of the spinel structure includes but is not limited to 100:1, 90:10, 80:20, 75:25, 70:30, 68:32, 65:35, 60:40, 50:50, etc.
  • the mass ratio of the ternary oxide precursors with layered structure and spinel structure is 90:10, in the case of this mass ratio, the obtained ternary cathode material has high stability and is conducive to the removal of Li. Embedded, the obtained material has good charge and discharge performance.
  • the ternary positive electrode precursor material includes both a ternary oxide precursor with a spinel structure and a ternary oxide precursor with a cubic structure, and the ternary oxide with a spinel structure
  • the mass ratio of the precursor to the ternary oxide precursor with a cubic structure is (10-50): (50-90), wherein the ternary oxide precursor with a cubic structure provides a uniform structure with a certain
  • the spatial structure is conducive to the deintercalation of Li ions, thereby achieving excellent charging and discharging effects and improving efficiency; however, the cubic structure has a large spatial structure and poor stability, so mixing a spinel structure with high stability at the same time can improve the three-dimensional structure.
  • the structural stability of the elemental cathode material enables the obtained material to have high capacity, high cycle performance and high rate capability, ensuring that the obtained ternary cathode material has excellent electrochemical performance.
  • the high capacity, high cycle performance and high rate performance of the ternary positive electrode material can be further optimized by adjusting the ratio of the spinel structure and the cubic structure in the ternary positive electrode precursor material.
  • the mass ratio of the ternary oxide precursor of the spinel structure and the ternary oxide precursor of the cubic structure in the ternary oxide precursor includes but is not limited to 10:90, 15: 85, 20:80, 25:75, 30:70, 35:65, 40:60, 50:50, etc.
  • the obtained ternary positive electrode material has high stability, It is conducive to Li ion intercalation and deintercalation, and the obtained material has good charge and discharge performance.
  • the ternary positive electrode precursor material includes a ternary oxide precursor with an octahedral structure and a ternary oxide precursor with a spinel structure, and the ternary oxide with an octahedral structure
  • the mass ratio of the precursor to the ternary oxide precursor of the spinel structure is (50-80): (15-50);
  • the octahedral structure refers to a polyhedron composed of eight planes called an octahedron , a pyramid composed of 6 vertices and 8 regular triangles, has eight faces, and each face is an equilateral triangle.
  • the octahedral structure has a large space, which is conducive to the action of materials;
  • the spinel structure works together, and the spinel structure is conducive to stabilizing the octahedral structure, and by controlling the mass ratio of the two, it is beneficial to ensure the high stability of the obtained ternary cathode material, which is conducive to the deintercalation of Li,
  • the obtained material has good charge and discharge performance.
  • the mass ratio of the ternary oxide precursor of the octahedral structure and the ternary oxide precursor of the spinel structure in the ternary positive electrode precursor material includes but is not limited to 50:50, 55 :45, 60:40, 65:35, 70:30, 75:25, 80:20, etc.
  • the general chemical formula of the ternary oxide precursor is Ni (1 -yz) Co y Mnz O; at this time, all the oxygen atoms in the ternary oxide precursor are in the -2 valence state.
  • the crystal structure of the ternary oxide precursor is a spinel structure
  • the general chemical formula of the ternary oxide precursor is Ni (1-yz) Co y Mn z O x
  • the material is AB 2 O 4 spinel type, in which nickel and manganese contain some +3 valence ions, so x is greater than 1.
  • the ternary positive electrode precursor material includes: Ni 0.67 Co 0.05 Mn 0.28 O, Ni 0.72 Co 0.03 Mn 0.25 O, Ni 0.7 Co 0.04 Mn 0.26 O , Ni 0.65 Co 0.06 Mn 0.29 O, At least one layered structure ternary oxide precursor in Ni 0.62 Co 0.08 Mn 0.30 O, Ni 0.6 Co 0.10 Mn 0.30 O, and/or Ni 0.67 Co 0.05 Mn 0.28 O 1.02 , Ni 0.72 Co 0.03 Mn 0.25 O 1.01 , Ni 0.60 Co 0.1 Mn 0.3 O 1.19 at least one spinel-type ternary oxide precursor.
  • These specific ternary oxide precursors all have good structural stability and high capacity, which is conducive to improving the cycle stability and gram capacity of the corresponding ternary cathode materials.
  • the crystal structure of the provided Ni 0.67 Co 0.05 Mn 0.28 O ternary oxide precursor is a layered structure such as a hexagonal layered structure, a cubic structure or an octahedral structure, and its electron microscope picture is shown in the figure 1 and Figure 2.
  • the crystal structure of Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary oxide precursor is spinel type.
  • the cobalt content in the obtained ternary oxide precursor is low, only 4.2%, and the properties are relatively stable, which is conducive to improving The gram capacity and stability of the corresponding ternary cathode material are ensured; at the same time, the precursor material is a metal oxide.
  • the main metal content in the oxide is higher, and when sintered into a ternary cathode material, the The unit filling quantity increases the output when sintering into the ternary positive electrode material, and reduces the manufacturing cost of the ternary positive electrode material.
  • Ni 0.72 Co 0.03 Mn 0.25 O is provided, and the crystal structure of the obtained ternary oxide precursor is a layered structure; while the Ni 0.72 Co 0.03 Mn 0.25 O 1.01
  • the crystal structure is spinel type.
  • the provided ternary oxide precursor has low cobalt content and high nickel content, so that the obtained ternary material precursor has higher energy level density, higher material capacity, and more stable properties.
  • the crystalline structure of the obtained Ni 0.72 Co 0.03 Mn 0.25 O ternary oxide precursor is controlled to be a layered structure, and the morphology of its macroscopic material is a spherical structure, wherein the layered structure is a two-dimensional After the positive electrode material is formed, it is conducive to the deintercalation of lithium ions and can increase its capacity; the formed macroscopic spherical structure material has a complete crystal form, which is conducive to the material reaction, making the obtained ternary positive electrode precursor material excellent in properties.
  • Ni 0.60 Co 0.1 Mn 0.3 O 1.19 is provided, and the crystal structure of the obtained ternary oxide precursor is a spinel structure, and the material has high structural stability and high capacity.
  • the crystal structure of the Ni 0.6 Co 0.10 Mn 0.30 O ternary oxide precursor is a layered structure such as hexagonal layered structure, cubic structure or octahedral structure.
  • the macroscopic morphology of the ternary positive electrode precursor material is a porous structure, and the active specific surface area is large, which is conducive to providing more reaction sites, so that the obtained material has higher capacity and cycle performance.
  • the particle size of the ternary oxide precursor is 50-800 nm.
  • the particle size of the ternary oxide precursor crystal particles in the embodiment of the present application can reach not only smaller particles less than 100nm, but also larger particles of 500-800nm, and the crystal particle size distribution range is wide, which broadens the range of ternary oxide precursors.
  • the scope of application of the body The ternary oxide precursor with a single crystal particle size of 50-800nm has a large active specific surface area, which is conducive to the subsequent reaction with lithium salts to form a ternary cathode material, and is also conducive to improving the film-forming uniformity of the ternary cathode material.
  • the crystal particle size of the ternary oxide precursor is 100-700 nm, further 200-600 nm, further 300-500 nm, etc. In some specific embodiments, when the crystal particle size of the ternary oxide precursor is 100-500 nm, the crystal form of the ternary oxide precursor is complete, the particle shape is full, the dispersion is uniform, the structure is stable, and the performance is stable, which can shorten the ternary oxide precursor.
  • the preparation cycle of primary cathode materials is 100-700 nm, further 200-600 nm, further 300-500 nm, etc. In some specific embodiments, when the crystal particle size of the ternary oxide precursor is 100-500 nm, the crystal form of the ternary oxide precursor is complete, the particle shape is full, the dispersion is uniform, the structure is stable, and the performance is stable, which can shorten the ternary oxide precursor.
  • the preparation cycle of primary cathode materials is 100-700 nm, further 200-600 nm, further 300-
  • the macroscopic morphology of the ternary positive electrode precursor material includes at least one of a spherical structure, a porous structure, and a three-dimensional polygonal structure.
  • the subsequent full contact reaction of the positive electrode precursor material with the lithium source is conducive to the incorporation of lithium ions into the crystal structure to form a ternary positive electrode material.
  • the macroscopic morphology of the ternary positive electrode precursor material is a porous structure with a larger active specific surface area, which can improve the ion transport and electrochemical activity of the material, and more lithium storage sites appear, and It can also provide a buffer for the volume change of the electrode to ensure that the obtained material has high power, high energy, and high stability.
  • the macroscopic morphology of the ternary positive electrode precursor material is a three-dimensional polygonal structure, which is conducive to improving cycle performance and rate performance, and making the material performance more excellent.
  • the macroscopic morphology of the ternary positive electrode precursor material includes at least one of a spherical structure, a porous structure, and a three-dimensional polygonal structure, and the particle size D50 of the macroscopic morphology is 1.5 to 3.5 ⁇ m, and further 1.5 to 3.5 ⁇ m. 3 ⁇ m, further 1.5-2 ⁇ m.
  • the loose packing density of the ternary positive electrode precursor material is 0.5-1.0 g/cm 3 , further the loose packing density is 0.6-0.8 g/cm 3 .
  • the tap density of the ternary cathode precursor material is 1.6-2.4 g/cm 3 , further the tap density is 1.8-2 g/cm 3 .
  • the ternary positive electrode material in the embodiment of the present application has a larger loose bulk density and tap density, and when sintered into a ternary positive electrode material, the unit filling capacity is increased, thereby improving the output when sintering into a ternary positive electrode material, and reducing The manufacturing cost of ternary cathode materials.
  • the bulk density of the ternary positive electrode precursor material is 0.5g/cm 3
  • the tap density of the ternary positive electrode precursor material is 1.6g/cm 3
  • the obtained ternary positive electrode precursor material is relatively Dense and tight.
  • the bulk density of the ternary positive electrode precursor material is 0.7 g/cm 3
  • the tap density of the ternary positive electrode precursor material is 2.0 g/cm 3
  • the structure of the obtained ternary positive electrode precursor material is The interior is dense and of high purity.
  • the bulk density of the ternary positive electrode precursor material is 1 g/cm 3
  • the tap density of the ternary positive electrode precursor material is 2.4 g/cm 3 .
  • the ternary positive electrode precursor material in the examples of the present application can be prepared by the methods in the following examples.
  • some embodiments of the present application provide a method for preparing the above-mentioned ternary positive electrode precursor material, including the following steps:
  • the preparation method of the ternary positive electrode precursor material provided in the embodiment of the present application according to the stoichiometric ratio of the metal elements in the general chemical formula of Ni (1-yz) Co y Mn z O x , nickel salt solution, cobalt salt solution, manganese
  • the concentration of nickel salt, cobalt salt, and manganese salt in the mixed solution is controlled by concentration treatment; the mixed solution is atomized and roasted, and the mixed solution is atomized into fine droplets, and the atomized droplets are directly sprayed.
  • the product has high purity, small particle size and good uniformity as the ternary cathode precursor material.
  • the preparation method has a simple process flow, fewer intermediate processes, and flexible control of the reaction process.
  • the roasting treatment is carried out at the same time as the atomization, which not only ensures that the product has a smaller particle size, but also has a fast reaction speed, and the atomization roasting can obtain a ternary positive electrode.
  • the actual reaction time of the precursor material is only a few seconds, and the production efficiency is high.
  • the anions in the salt solution are converted into gaseous substances to be removed or recovered in a high-temperature environment, the utilization rate of raw materials is high, the impurity content in the product is low, and the performance is excellent.
  • the method of directly preparing the ternary positive electrode oxide precursor material by atomizing and roasting the mixed solution is beneficial to improve the structural stability of the precursor material, increase the density of the precursor material, and refine the particle size of the material, thereby Further increase the unit filling capacity of the precursor material, improve the preparation efficiency of the ternary cathode material, and reduce the manufacturing cost.
  • step S01 after mixing the nickel salt solution, the cobalt salt solution, and the manganese salt solution according to the stoichiometric ratio of the metal elements in the general chemical formula of Ni (1-yz) Co y Mnz O x , Concentration treatment is carried out to obtain a mixed solution, wherein, 1 ⁇ x ⁇ 1.2, 0.03 ⁇ y ⁇ 0.1, 0.2 ⁇ z ⁇ 0.35.
  • Making the metal salt solution in the mixed solution have a suitable atomization concentration is beneficial to control the reaction rate of the metal salt solution and the particle size of the ternary oxide precursor.
  • concentration treatment is performed to control the concentrations of the nickel salt, cobalt salt, and manganese salt in the obtained mixed solution to be 50-300 g/ L, the concentration of the metal salt is conducive to atomization crystallization and granulation.
  • the concentration of metal salts in the mixed solution is lower than 80g/L, the content of metal salts in the droplets after atomization will be too low, which is not conducive to the full reaction of the metal salts in the droplets during the roasting process, crystallization and granulation, and less products obtained , which is not conducive to the enrichment of the precursor; if the concentration of the mixed solution is higher than 300g/L, the concentration of the mixed solution is too high, resulting in too high a metal salt content in the atomized droplets, which is not conducive to the crystallization of the metal salt component during the roasting process Granulation, the particle size is too large, it is easy to cause agglomeration, which is not conducive to the preparation of single crystal materials, and is also not conducive to the regulation of the crystal form of the material, thereby reducing the stability of the ternary positive electrode precursor.
  • the concentrations of nickel salt, cobalt salt and manganese salt are respectively independently 50g/L, 60g/L, 80g/L, 120g/L, 160g/L, 200g/L, 220g /L, 260g/L, 300g/L, etc.
  • the nickel salt solution is selected from at least one of nickel chloride solution, nickel nitrate solution, nickel oxalate solution, and nickel sulfate solution.
  • the cobalt salt solution is selected from at least one of cobalt chloride solution, cobalt nitrate solution, cobalt oxalate solution, and cobalt sulfate solution.
  • the manganese salt solution is selected from at least one of manganese chloride solution, manganese nitrate solution, manganese oxalate solution, and manganese sulfate solution.
  • the salt solution of nickel, cobalt, and manganese main metals in the embodiment of the present application is selected from at least one of chloride salt solution, nitrate solution, oxalate solution, and sulfate solution.
  • chloride salt solution nitrate solution, oxalate solution, and sulfate solution.
  • anions such as chloride ions, nitrate ions, oxalate ions, and sulfate ions can be converted into gaseous substances such as HCl, NO, CO 2 , and SO 2 during the roasting process, which is not only beneficial to recovery, but also reduces the ternary oxides. Impurity elements remain in the precursor material to improve product purity.
  • the corresponding chloride salt solution is prepared by dissolving nickel, cobalt and manganese metal elements with hydrochloric acid. During the preparation process, the impurity content in the solution is strictly controlled to be low. After atomization and sintering, HCl gas can be directly recovered for use in The preparation of the metal salt solution, the experimental recycling, and the improvement of the generation efficiency.
  • the solution containing nickel, cobalt and manganese ions is transferred to a mixing tank for mixing to prepare a mixed solution containing nickel, cobalt and manganese ions, wherein the mixing tank is made of an acid-resistant material with a certain strength.
  • the step of atomization and roasting treatment includes: atomizing the mixed solution into fine droplets under the condition of an atomization air volume of 20-1200m 3 /h, and then the droplets are heated at a temperature of Roasting is carried out under the conditions of 300-1000°C and an oxygen mass percentage of 1.0-13.0%.
  • the liquid droplets are directly converted into ternary oxide precursor crystals to obtain ternary positive electrode precursor materials.
  • the reaction rate is fast and the efficiency is high.
  • the atomizing air volume of 20-1200m 3 /h not only ensures that the mixed solution forms small and uniform droplets, but also provides sufficient time for the reaction between the metal salts in the droplets.
  • the atomizing air volume is 100-1100m 3 /h, further atomizing air volume is 200-1000m 3 /h, further atomizing air volume is 300-800m 3 /h, further atomizing air volume is 400 ⁇ 600m 3 /h etc.
  • the temperature of the calcination treatment is 300-1000° C., which is conducive to the rapid reaction of the metal salt in the atomized liquid droplets to form a ternary oxide precursor single crystal material. If the temperature of the roasting treatment is lower than 300°C, the treatment temperature is too low, which is not conducive to the reaction of the metal salt in the atomized liquid droplets to form the precursor; if the temperature of the roasting treatment is higher than 1000°C, the energy consumption will be large, and it is not conducive to control.
  • the crystal form of the ternary oxide precursor The level of oxygen content will not only affect the reaction rate of the metal salt in the droplet, but also affect the crystal form of the generated ternary oxide precursor. In some specific embodiments, the mass percentage of oxygen may be 1.0-2%, 2-5%, 5-8%, 8-10%, 10-13.0%, etc.
  • the physical properties such as particle size and crystal form of the prepared ternary positive electrode precursor material can be flexibly adjusted, which is conducive to optimization.
  • Physicochemical properties of ternary cathode materials under the condition of atomizing air volume of 20-1200m 3 /h, the mixed solution is atomized into droplets, and the temperature is 300-900°C, and the mass percentage of oxygen is 1.0-13.0%. Bottom firing is conducive to the preparation of ternary oxide precursor materials with hexagonal layered structure, cubic structure, octahedral structure and other crystal forms.
  • the mixed solution is atomized into droplets under the condition of atomizing air volume of 20-1200m 3 /h, and the mixture is atomized into droplets at a temperature of 700-1000°C and an oxygen mass percentage of 1.0-13.0%.
  • the ternary oxide precursor material with spinel structure can be obtained by roasting under the same conditions.
  • the time of the controlled firing treatment is 1-50 seconds.
  • the molding precursor can be guaranteed to be prepared in a short time, the preparation time is short, the efficiency is high, and it is beneficial to wide application.
  • the ternary positive electrode precursor material is prepared, post-processing steps such as grinding or crushing the ternary positive electrode precursor material are also included, and the obtained The particle size of the product makes the particle size distribution of the ternary cathode precursor material more uniform.
  • Some embodiments of the present application provide a ternary positive electrode material, which is obtained by sintering a mixture including a lithium source and a ternary positive electrode precursor material, wherein the ternary positive electrode precursor material is the three Element cathode precursor material.
  • the ternary positive electrode material provided by the present application is obtained by sintering the lithium source and the above-mentioned ternary positive electrode precursor material, because the above-mentioned ternary positive electrode precursor material contains a general structural formula of Ni (1-yz) Co y Mn
  • the ternary oxide precursor of z O x wherein, 1 ⁇ x ⁇ 1.2, 0.03 ⁇ y ⁇ 0.1, 0.2 ⁇ z ⁇ 0.35, high nickel content, relatively stable properties, and the precursor is a metal oxide, and Compared with the hydroxide precursor, the positive electrode material can be directly generated when the lithium source is sintered, which improves the preparation efficiency of the ternary positive electrode material. Therefore, the ternary cathode material obtained by sintering the lithium source has characteristics such as high gram capacity, cycle stability, and structural stability.
  • the lithium source is selected from one or more of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, lithium nitrate, lithium oxalate, lithium acetate, lithium hydroxide, lithium oxide, and these lithium salts can be
  • the ternary cathode material is formed by high-temperature sintering with the ternary precursor material.
  • the molar ratio of the ternary positive electrode precursor material to the lithium source is 1: (1-1.1), which is conducive to the full reaction of the ternary precursor material and the lithium salt to form a nickel-cobalt-manganese ternary positive electrode material . Controlling the molar ratio of the ternary positive electrode precursor material to the lithium source ensures that the obtained ternary positive electrode material has high capacity and cycle performance.
  • the sintering temperature is 450-1000° C.
  • the sintering time is 3-8 h.
  • the sintering conditions can ensure that the ternary precursor material and the lithium salt fully react to form LiNi ( 1-yz) Co y Mn z O 2 , wherein, 0.03 ⁇ y ⁇ 0.1, 0.2 ⁇ z ⁇ 0.35.
  • the ternary cathode materials include but are not limited to: LiNi 0.72 Co 0.03 Mn 0.25 O 2 , LiNi 0.7 Co 0.04 Mn 0.26 O 2 , LiNi 0.67 Co 0.05 Mn 0.28 O 2 , LiNi 0.65 Co 0.06 Mn 0.29 O 2 , LiNi 0.62 Co 0.08 Mn 0.30 O 2 , LiNi 0.6 Co 0.10 Mn 0.30 O 2 , etc.
  • a method for preparing a ternary positive electrode material comprising the following steps: performing mixed sintering treatment on the ternary positive electrode precursor material and lithium source to obtain the ternary positive electrode material; wherein, the mixed sintered The temperature is 300-1000°C. By grinding or crushing, the particle uniformity of the obtained ternary cathode material is controlled.
  • the fourth aspect of the present application provides a secondary battery, the positive electrode sheet of the secondary battery includes the above-mentioned ternary positive electrode material.
  • the positive electrode sheet includes the above-mentioned ternary positive electrode material
  • the ternary positive electrode material has characteristics such as higher gram capacity, cycle stability, and structural stability, thereby improving the performance of the secondary battery. Excellent energy density, cycle stability, and safety performance.
  • the ternary cathode material includes, but is not limited to: LiNi (1-yz) Co y Mnz O 2 , where 0.03 ⁇ y ⁇ 0.1, 0.2 ⁇ z ⁇ 0.35.
  • the ternary cathode materials include but are not limited to: LiNi 0.72 Co 0.03 Mn 0.25 O 2 , LiNi 0.7 Co 0.04 Mn 0.26 O 2 , LiNi 0.67 Co 0.05 Mn 0.28 O 2 , LiNi 0.65 Co 0.06 Mn 0.29 O 2. LiNi 0.62 Co 0.08 Mn 0. 30 O 2 , LiNi 0.6 Co 0.10 Mn 0.30 O 2 , etc. These ternary cathode materials also have the characteristics of good structural stability, high capacity, and good cycle stability.
  • the positive electrode sheet in the secondary battery includes a laminated current collector and an active material layer, and the active material layer includes a ternary material, a conductive agent, a binder, and the like.
  • the preparation process of making the positive electrode material into the positive electrode sheet is: mixing the ternary positive electrode material, the conductive agent and the binder to obtain the electrode slurry, coating the electrode slurry on the current collector, drying,
  • the positive electrode sheet is prepared by rolling, die-cutting and other steps.
  • the positive electrode current collector includes, but is not limited to, any one of copper foil and aluminum foil.
  • the content of the binder in the electrode slurry is 2wt%-4wt%. In a specific embodiment, the content of the binder may be 2wt%, 3wt%, 4wt% and other typical and non-limiting contents.
  • the binder includes polyvinylidene chloride, soluble polytetrafluoroethylene, styrene-butadiene rubber, hydroxypropyl methyl cellulose, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, acrylonitrile copolymer One or more of substances, sodium alginate, chitosan and chitosan derivatives.
  • the content of the conductive agent in the electrode paste is 3wt%-5wt%. In a specific embodiment, the content of the conductive agent may be 3wt%, 4wt%, 5wt% and other typical and non-limiting contents. In a specific embodiment, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fiber, C60 and carbon nanotube.
  • the secondary battery in the embodiment of the present application may be a system such as a lithium ion battery or a lithium metal battery.
  • This application does not specifically limit the negative electrode sheet, electrolyte, separator, etc. in the secondary battery of the embodiment, and can be applied to any battery system.
  • a Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with a hexagonal layered structure the preparation of which comprises the steps of:
  • Ni 0.67 Co 0.05 Mn 0.28 O After mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 163.7g/L, 12.3g/L, 64.0g/L.
  • the mixed solution is atomized into droplets, and roasted at a temperature of 710°C and an oxygen content of 5.0% by mass, and crushed to obtain Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material, its crystal structure is a hexagonal layered structure, and its morphologies of different photographed sizes are shown in the attached electron microscope images 1 and 2.
  • a kind of LiNi 0.67 Co 0.05 Mn 0.28 O ternary cathode material its preparation process comprises steps:
  • a kind of lithium ion battery, its preparation step comprises:
  • ternary positive electrode material conductive agent (acetylene black): binder (PVDF) proportioning is 85wt.%: 10wt.%: 5wt.%, weigh Post-mixing and grinding. Then, N-methylpyrrolidone (NMP) solvent was added to form a uniform positive electrode slurry.
  • the positive electrode slurry is evenly coated on the aluminum foil with a doctor blade, and dried to obtain a positive electrode sheet that can be directly assembled into a battery.
  • 8Battery assembly In a glove box with a high-purity argon atmosphere, assemble the prepared positive electrode sheet into a CR2025 button-type battery, and assemble it into a button-type battery with lithium as the counter electrode for subsequent electrochemical performance tests .
  • the diaphragm is a polyolefin porous film
  • the electrolyte is ethylene carbonate.
  • a spinel-type Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary positive electrode precursor material the preparation of which comprises the steps of:
  • the mixed solution is atomized into droplets, and roasted at a temperature of 740°C and an oxygen mass percentage of 11.0%, and crushed to obtain Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary positive electrode precursor material, its crystal structure is spinel type.
  • a LiNi 0.67 Co 0.05 Mn 0.28 O 2 ternary positive electrode material the difference from Example 1 is that the ternary positive electrode material is made of spinel-type Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary positive electrode precursor Material made.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 2.
  • a Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with an octahedral structure comprising the steps of:
  • Ni 0.67 Co 0.05 Mn 0.28 O After mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 95.5g/L, 7.15g/L, 37.35g/L.
  • the O ternary positive electrode precursor material has an octahedral crystal structure.
  • a LiNi 0.67 Co 0.05 Mn 0.28 O ternary positive electrode material which differs from Example 1 in that: the ternary positive electrode material is made of Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with octahedral structure in Example 3 be made of.
  • a kind of lithium ion battery, and its difference with embodiment 1 is: positive electrode sheet adopts the ternary positive electrode material prepared in embodiment 3 in the lithium ion battery.
  • a kind of Ni 0.67 Co 0.05 Mn 0.28 O ternary cathode precursor material of cubic structure its preparation comprises steps:
  • Ni 0.67 Co 0.05 Mn 0.28 O After mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 95.5g/L, 7.15g/L, 37.35g/L.
  • the O ternary positive electrode precursor material has a cubic crystal structure.
  • a LiNi 0.67 Co 0.05 Mn 0.28 O ternary positive electrode material the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with a cubic structure in Example 4 have to.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 4.
  • Ni 0.67 Co 0.05 Mn 0.28 O After mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 150.0g/L, 11.2g/L, 58.8g/L.
  • the mixed solution is atomized into droplets, and roasted at a temperature of 730°C and an oxygen mass percentage of 6.0%, and broken to obtain a ternary positive electrode precursor material , its crystal structure contains both hexagonal layered structure Ni 0.67 Co 0.05 Mn 0.28 O and spinel Ni 0.67 Co 0.05 Mn 0.28 O 1.02 , where the mass ratio of hexagonal layered structure to spinel type is 7:3 .
  • Its XRD test pattern is shown in accompanying drawing 5, from which it can be seen that the prepared ternary positive electrode precursor material contains peaks of layered structure and peak of spinel structure at the same time.
  • a ternary positive electrode material which is different from Example 1 in that: the ternary positive electrode material is made from the ternary positive electrode precursor material of both the hexagonal layered structure and the spinel type in Example 5.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 5.
  • a layered Ni 0.72 Co 0.03 Mn 0.25 O ternary positive electrode precursor material the preparation of which comprises the steps of:
  • the O ternary positive electrode precursor material has a layered crystal structure.
  • a LiNi 0.72 Co 0.03 Mn 0.25 O ternary positive electrode material the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.72 Co 0.03 Mn 0.25 O ternary positive electrode precursor material with a layered structure in Example 6 have to.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 6.
  • a spinel-type Ni 0.72 Co 0.03 Mn 0.25 O 1.01 ternary positive electrode precursor material the preparation of which comprises the steps of:
  • the mixed solution is atomized into liquid droplets, and roasted at a temperature of 730°C and an oxygen mass percentage of 11.0%, and crushed to obtain Ni 0.72 Co 0.03 Mn 0.25 O 1.01 Ternary positive electrode precursor material, its crystal structure is spinel type.
  • a LiNi 0.72 Co 0.03 Mn 0.25 O 2 ternary positive electrode material the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.72 Co 0.03 Mn 0.25 O 1.01 ternary positive electrode precursor of the spinel type in Example 7 Material made.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 7.
  • a layered Ni 0.6 Co 0.10 Mn 0.30 O ternary cathode precursor material the preparation of which comprises the steps of:
  • the O ternary positive electrode precursor material has a layered crystal structure.
  • a LiNi 0.6 Co 0.10 Mn 0.30 O ternary positive electrode material the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.6 Co 0.10 Mn 0.30 O ternary positive electrode precursor material with a layered structure in Example 6 have to.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 6.
  • a spinel-type Ni 0.60 Co 0.1 Mn 0.3 O 1.19 ternary positive electrode precursor material the preparation of which comprises the steps of:
  • the mixed solution is atomized into droplets, and roasted at a temperature of 750°C and an oxygen mass percentage of 11.0%, and crushed to obtain Ni 0.60 Co 0.1 Mn 0.3 O 1.19 Ternary positive electrode precursor material, its crystal structure is spinel type.
  • a LiNi 0.60 Co 0.1 Mn 0.3 O 2 ternary positive electrode material the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.60 Co 0.1 Mn 0.3 O 1.191 ternary positive electrode precursor of the spinel type in Example 9 Material made.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 9.
  • a kind of Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 ternary positive electrode precursor material its preparation comprises steps:
  • Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 1According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 , mix nickel chloride solution, cobalt chloride solution and manganese chloride solution; then mix with ammonia water and NaOH solution according to the ratio of ammonia to nickel: 0.5:1, alkali-nickel ratio: 2:1, add ammonia water and sodium hydroxide, control the reaction temperature at 55°C, and the pH value is 12.0. After the reaction, the Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 precursor is separated.
  • a LiNi 0.67 Co 0.05 Mn 0.28 O 2 ternary positive electrode material the difference from Example 1 is that the ternary positive electrode material is made of Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 ternary positive electrode of the spinel type in Comparative Example 1 Precursor materials are produced.
  • a lithium ion battery which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Comparative Example 1.
  • the loose packing density, tap density (TD), and particle size of the ternary cathode precursor materials prepared in Examples 1-9 and Comparative Example 1 of the present application were measured respectively.
  • the lithium-ion batteries prepared in Examples 1-9 and Comparative Example 1 were discharged at 0.1C and charged to 2.5V at 0.1C, and the first lithium insertion capacity and delithiation capacity were recorded, and the first effect was calculated.
  • the capacity retention rate and 1c energy density of each battery after 50 cycles of charging and discharging were measured. The test results are shown in Table 1 below:
  • the ternary positive electrode oxide precursor materials prepared in Examples 1 to 9 of the present application have relatively high loose packing density and tap density; while the ternary positive electrode hydroxide material prepared in Comparative Example 1 It is a secondary particle, and its loose packing density and tap density are lower than those in the examples of the present application, indicating that the ternary oxide precursor prepared in the examples of the present application has better density and high structural stability.
  • the lithium-ion batteries prepared in Examples 1-9 of the present application exhibit higher energy density, first effect and cycle stability.

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Abstract

Disclosed are a ternary positive electrode precursor material, a method for preparing same, and a ternary positive electrode material. The ternary positive electrode precursor material comprises a ternary oxide precursor having a general formula of Ni(1-y-z)CoyMnzOx, wherein 1≤x≤1.2, 0.03≤y≤0.1, and 0.2≤z≤0.35. The material provided by the present application is a ternary positive electrode precursor material. By means of regulating the proportions of major metal elements in the ternary oxide precursor, the present invention effectively elevates the content of nickel and reduces the content of cobalt in the ternary positive electrode precursor material, such that the ternary positive electrode precursor material has good structural stability and high capacity, and the cycling stability and the per-gram capacity of the corresponding ternary positive electrode material are improved.

Description

三元正极前驱体材料及制备方法与三元正极材料Ternary positive electrode precursor material and preparation method and ternary positive electrode material
本申请要求于2022年02月17日在中国专利局提交的、申请号为202210148225.6、发明名称为“三元正极前驱体材料及制备方法与三元正极材料”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202210148225.6 and the title of the invention "ternary positive electrode precursor material and preparation method and ternary positive electrode material" submitted at the China Patent Office on February 17, 2022. The entire contents are incorporated by reference in this application.
技术领域technical field
本申请涉及电池材料技术领域，具体涉及一种三元正极前驱体材料及制备方法与三元正极材料。The present application relates to the technical field of battery materials, in particular to a ternary positive electrode precursor material, a preparation method and a ternary positive electrode material.
背景技术Background technique
新能源汽车是指采用非常规的车用燃料作为动力来源(或使用常规的车用燃料、采用新型车载动力装置)，综合车辆的动力控制和驱动方面的先进技术，形成的技术原理先进、具有新技术、新结构的汽车。随着新能源汽车的迅速发展，动力电池的需求越来越大，同时也面临着更大的挑战，特别是对正极材料的性能提出了更加严苛的条件。动力电池中，三元正极材料前驱体产品，是以镍盐、钴盐、锰盐为原料，其中镍钴锰的比例可以根据实际需要调整。目前，公开的三元正极材料前驱体产品大多是氢氧化物，主流的制备技术是：将镍盐、锰盐、钴盐溶解形成混合溶液，与氨水和碱液混合处理，通过氨水的络合作用，碱液的共沉淀作用，形成晶核后，晶体通过团聚继续生长，得到三元正极氢氧化物前驱体。目前，三元正极氢氧化物前驱体往往制备工艺控制难度大，导致容易影响产品的稳定性；另外，由于三元正极前驱体氢氧化物本身为二次球，使制备的三元正极材料结构稳定性差、密度低，在极片辊压过程中容易出现破碎，导致电池的循环稳定性差，能量密度低。New energy vehicles refer to the use of unconventional vehicle fuels as power sources (or the use of conventional vehicle fuels, the use of new vehicle power devices), integrated vehicle power control and advanced technology in driving, the formation of advanced technical principles, with Automobiles with new technology and new structure. With the rapid development of new energy vehicles, the demand for power batteries is increasing, and they are also facing greater challenges, especially the stricter conditions for the performance of cathode materials. In the power battery, the precursor product of the ternary cathode material is based on nickel salt, cobalt salt, and manganese salt, and the ratio of nickel, cobalt, and manganese can be adjusted according to actual needs. At present, most of the public ternary positive electrode material precursor products are hydroxides. The mainstream preparation technology is: dissolving nickel salt, manganese salt, and cobalt salt to form a mixed solution, mixing with ammonia water and lye, and complexing the ammonia water Function, the co-precipitation of lye, after the formation of crystal nuclei, the crystals continue to grow through agglomeration, and the ternary positive electrode hydroxide precursor is obtained. At present, the preparation process of the ternary positive electrode hydroxide precursor is often difficult to control, which easily affects the stability of the product; in addition, because the ternary positive electrode precursor hydroxide itself is a secondary ball, the structure of the prepared ternary positive electrode material Poor stability and low density are prone to breakage during the rolling process of the pole piece, resulting in poor cycle stability and low energy density of the battery.
技术问题technical problem
本申请实施例的目的之一在于：提供一种三元正极前驱体材料及其制备方法，以及一种三元正极材料，旨在解决三元正极氢氧化物前驱体结构稳定性差，密度低，影响三元正极材料的循环稳定性及能量密度等技术问题。One of the purposes of the embodiments of the present application is to provide a ternary positive electrode precursor material and its preparation method, as well as a ternary positive electrode material, aiming at solving the problem of poor structural stability and low density of the ternary positive electrode hydroxide precursor. Affect the technical issues such as cycle stability and energy density of ternary cathode materials.
技术解决方案technical solution
为解决上述技术问题，本申请实施例采用的技术方案是：In order to solve the above-mentioned technical problems, the technical solution adopted in the embodiment of the present application is:
第一方面，提供了一种三元正极前驱体材料，所述三元正极前驱体材料包括化学通式为Ni (1-y-z)Co yMn zO x的三元氧化物前驱体，其中，1≤x≤1.2，0.03≤y≤0.1，0.2≤z≤0.35。 In a first aspect, a ternary positive electrode precursor material is provided, the ternary positive electrode precursor material includes a ternary oxide precursor with a general chemical formula of Ni (1-yz) Co y Mn z O x , wherein, 1≤x≤1.2, 0.03≤y≤0.1, 0.2≤z≤0.35.
第二方面，提供了一种三元正极前驱体材料的制备方法，包括如下步骤：In a second aspect, a method for preparing a ternary positive electrode precursor material is provided, comprising the following steps:
将镍盐溶液、钴盐溶液、锰盐溶液混合后，进行浓缩处理，得到混合溶液；After mixing the nickel salt solution, the cobalt salt solution and the manganese salt solution, performing concentration treatment to obtain a mixed solution;
对所述混合溶液进行雾化焙烧处理，得到三元正极前驱体材料。The mixed solution is atomized and calcined to obtain a ternary positive electrode precursor material.
第三方面，提供一种三元正极材料，所述三元正极材料由锂源和三元正极前驱体材料烧结得到，其中，所述三元正极前驱体材料包括上述三元正极前驱体材料。In a third aspect, a ternary positive electrode material is provided, the ternary positive electrode material is obtained by sintering a lithium source and a ternary positive electrode precursor material, wherein the ternary positive electrode precursor material includes the above-mentioned ternary positive electrode precursor material.
本申请实施例提供的三元正极前驱体材料的有益效果在于：一方面，前驱体以氧化物形式存在，相较于传统的氢氧化物前驱体，氧化物前驱体中镍钴锰主金属含量更高，在烧 结成三元正极材料时，提高了单位装钵量，从而提高了烧结成三元正极材料时的产量，降低三元正极材料的制造成本。另一方面，Ni (1-y-z)Co yMn zO x三元氧化物前驱体中，钴的配比仅为0.03≤y≤0.1，低钴含量有利于提高三元正极材料中的镍含量进而提高三元正极材料的实际能量密度，若钴含量过高会导致材料的实际容量降低，若钴含量过低会降低材料的结构稳定性。锰的配比为0.2≤z≤0.35，该配比有效确保了三元氧化物前驱体晶体结构的稳定性和安全性，若锰含量过高会降低材料的结构稳定性，并降低材料的比容量，若锰含量过低同样会降低材料的结构稳定性和安全性。另外，镍的配比为0.55≤1-y-z≤0.77，使得三元正极前驱体材料为高镍材料，提高了三元正极材料的体积能量密度，若镍含量过低则降低了材料的克容量，若镍含量过高会导致锂镍混排，容易导致锂析出。因此，本申请三元正极前驱体材料，通过调控三元氧化物前驱体中各主金属元素的配比，使得三元正极前驱体材料同时具有较好的结构稳定性，从而提高了对应的三元正极材料的循环稳定性和克容量。并且，相对于需通过共沉淀法等方法制得的结构稳定性差、密度低、粒径可控性差的三元氢氧化物前驱体材料，本申请提供的三元氧化物前驱体能够通过一次结晶制得，不但缩短了制备时间提高了制备效率，而且更有利于提高前驱体材料的结构稳定性，提高前驱体材料密度，提高粒径可控度，细化材料粒径，从而进一步提高前驱体材料的单位装钵量，提高三元正极材料的制备效率，降低制造成本。 The beneficial effect of the ternary positive electrode precursor material provided by the embodiment of the present application is that: on the one hand, the precursor exists in the form of oxides. Compared with the traditional hydroxide precursors, the content of nickel, cobalt and manganese main metals in the oxide precursors Higher, when sintering into a ternary cathode material, the unit loading amount is increased, thereby increasing the output when sintering into a ternary cathode material, and reducing the manufacturing cost of the ternary cathode material. On the other hand, in the Ni (1-yz) Co y Mn z O x ternary oxide precursor, the proportion of cobalt is only 0.03≤y≤0.1, and the low cobalt content is beneficial to increase the nickel content in the ternary cathode material Furthermore, the actual energy density of the ternary cathode material is increased. If the cobalt content is too high, the actual capacity of the material will be reduced, and if the cobalt content is too low, the structural stability of the material will be reduced. The ratio of manganese is 0.2≤z≤0.35, which effectively ensures the stability and safety of the crystal structure of the ternary oxide precursor. If the manganese content is too high, the structural stability of the material will be reduced, and the ratio of the material will be reduced. If the manganese content is too low, the structural stability and safety of the material will also be reduced. In addition, the proportion of nickel is 0.55≤1-yz≤0.77, which makes the ternary positive electrode precursor material a high-nickel material, which improves the volume energy density of the ternary positive electrode material, and if the nickel content is too low, the gram capacity of the material is reduced , if the nickel content is too high, it will lead to mixed discharge of lithium and nickel, which will easily lead to lithium precipitation. Therefore, the ternary positive electrode precursor material of the present application, by adjusting the proportion of each main metal element in the ternary oxide precursor, makes the ternary positive electrode precursor material have better structural stability at the same time, thereby improving the corresponding three-component Cycling stability and gram capacity of primary cathode materials. Moreover, compared to the ternary hydroxide precursor material which needs to be prepared by coprecipitation method and other methods with poor structural stability, low density and poor particle size controllability, the ternary oxide precursor provided by this application can be crystallized once The preparation not only shortens the preparation time and improves the preparation efficiency, but also is more conducive to improving the structural stability of the precursor material, increasing the density of the precursor material, improving the controllability of the particle size, and refining the particle size of the material, thereby further improving the precursor material. The unit filling quantity of the material improves the preparation efficiency of the ternary cathode material and reduces the manufacturing cost.
本申请实施例提供的三元正极前驱体材料的制备方法的有益效果在于：工艺流程简单，中间流程少，反应过程便于灵活调控，在雾化的同时进行焙烧处理，不但确保了产品具有较小的粒径，而产品反应速度快，雾化焙烧获得三元正极前驱体材料的实际反应时间仅需数秒，生产效率高。另外，由于盐溶液中阴离子在高温环境中转化成气体物质去除或被回收，原料利用率高，产品中杂质含量低，性能优异。同时，通过该方法制备的三元正极前驱体材料产品，相对于传统的共沉淀方法，其材料本身的结构稳定性更优异。The beneficial effect of the preparation method of the ternary positive electrode precursor material provided by the embodiment of the present application is that the process flow is simple, the intermediate process is small, the reaction process is convenient for flexible regulation, and the roasting treatment is carried out at the same time as the atomization, which not only ensures that the product has a smaller The particle size is small, and the reaction speed of the product is fast. The actual reaction time for obtaining the ternary positive electrode precursor material by atomization and roasting is only a few seconds, and the production efficiency is high. In addition, because the anions in the salt solution are converted into gaseous substances to be removed or recovered in a high-temperature environment, the utilization rate of raw materials is high, the impurity content in the product is low, and the performance is excellent. At the same time, compared with the traditional co-precipitation method, the ternary cathode precursor material product prepared by this method has better structural stability of the material itself.
本申请实施例提供的三元正极材料的有益效果在于：该三元正极材料由锂源和上述三元正极前驱体材料烧结得到，由于上述三元正极前驱体材料镍含量较高，性质较稳定，同时该物质为金属氧化物，与氢氧化物前驱体相比，与锂源烧结时能够可以直接生成正极材料，提高三元正极材料的制备效率。从而使与锂源烧结得到的三元正极材料具有较高的克容量、循环稳定性能、结构稳定性等特性。The beneficial effect of the ternary positive electrode material provided in the embodiment of the present application is that the ternary positive electrode material is obtained by sintering the lithium source and the above-mentioned ternary positive electrode precursor material, and the property of the above-mentioned ternary positive electrode precursor material is relatively high due to its high nickel content. At the same time, the substance is a metal oxide. Compared with the hydroxide precursor, it can directly generate the positive electrode material when sintered with the lithium source, and improve the preparation efficiency of the ternary positive electrode material. Therefore, the ternary positive electrode material obtained by sintering with the lithium source has characteristics such as high gram capacity, cycle stability, and structural stability.
附图说明Description of drawings
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或示范性技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the accompanying drawings that need to be used in the embodiments or exemplary technical descriptions. Obviously, the accompanying drawings in the following descriptions are only for this application. For some embodiments, those skilled in the art can also obtain other drawings based on these drawings without creative efforts.
图1是本申请实施例提供的Ni 0.67Co 0.05Mn 0.28O三元氧化物前驱体的扫描电镜图一； Figure 1 is a scanning electron microscope image 1 of the Ni 0.67 Co 0.05 Mn 0.28 O ternary oxide precursor provided in the embodiment of the present application;
图2是本申请实施例提供的Ni 0.67Co 0.05Mn 0.28O三元氧化物前驱体的扫描电镜图二； Figure 2 is the scanning electron microscope image 2 of the Ni 0.67 Co 0.05 Mn 0.28 O ternary oxide precursor provided in the examples of this application;
图3是本申请实施例提供的三元正极前驱体材料的制备方法的流程示意图；Fig. 3 is a schematic flow chart of the preparation method of the ternary positive electrode precursor material provided by the embodiment of the present application;
图4是本申请实施例1提供的三元正极材料的扫描电镜图；Figure 4 is a scanning electron microscope image of the ternary cathode material provided in Example 1 of the present application;
图5是本申请实施例5提供的三元正极前驱体材料的XRD测试图。FIG. 5 is an XRD test chart of the ternary positive electrode precursor material provided in Example 5 of the present application.
本发明的实施方式Embodiments of the present invention
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。In order to make the purpose, technical solution and advantages of the present application clearer, the present application will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present application, not to limit the present application.
需说明的是，本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。It should be noted that, in this application, the term "and/or" describes the association relationship of associated objects, indicating that there may be three types of relationships, for example, A and/or B may indicate: A exists alone, and A and B exist simultaneously , in the case of B alone. Among them, A and B can be singular or plural. The character "/" generally indicates that the contextual objects are an "or" relationship.
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。In this application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items.
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。Terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates otherwise.
本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地，本申请实施例说明书中的质量可以是μg、mg、g、kg等化工领域公知的质量单位。The weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components. The scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be μg, mg, g, kg and other well-known mass units in the chemical industry.
术语“第一”、“第二”仅用于描述目的，用来将目的如物质彼此区分开，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如，在不脱离本申请实施例范围的情况下，第一XX也可以被称为第二XX，类似地，第二XX也可以被称为第一XX。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。The terms "first" and "second" are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX can also be called the second XX, and similarly, the second XX can also be called the first XX. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features.
为了说明本申请所述的技术方案，以下结合具体附图及实施例进行详细说明。In order to illustrate the technical solutions described in this application, the following will be described in detail in conjunction with specific drawings and embodiments.
本申请一些实施例提供一种三元正极前驱体材料，该三元正极前驱体材料包括化学通式为Ni (1-y-z)Co yMn zO x的三元氧化物前驱体，其中，1≤x≤1.2，0.03≤y≤0.1，0.2≤z≤0.35。 Some embodiments of the present application provide a ternary positive electrode precursor material, the ternary positive electrode precursor material includes a ternary oxide precursor with a general chemical formula of Ni (1-yz) Co y Mnz O x , wherein, 1 ≤ x ≤ 1.2, 0.03 ≤ y ≤ 0.1, 0.2 ≤ z ≤ 0.35.
本申请实施例提供的三元正极前驱体材料，包括化学通式为Ni (1-y-z)Co yMn zO x的三元氧化物前驱体；一方面，前驱体以氧化物形式存在，相较于传统的氢氧化物前驱体，氧化物前驱体中镍钴锰主金属含量更高，在烧结成三元正极材料时，提高了单位装钵量，从而提高了烧结成三元正极材料时的产量，降低三元正极材料的制造成本。另一方面，Ni (1-y-z)Co yMn zO x三元氧化物前驱体中，钴的配比仅为0.03≤y≤0.1，低钴含量有利于提高三元正极材料中的镍含量进而提高三元正极材料的实际能量密度，若钴含量过高会导致材料的实际容量降低，若钴含量过低会降低材料的结构稳定性。锰的配比为0.2≤z≤0.35，该配比有效确保了三元氧化物前驱体晶体结构的稳定性和安全性，若锰含量过高会降低材料的结构稳 定性，并降低材料的比容量，若锰含量过低同样会降低材料的结构稳定性和安全性。另外，镍的配比为0.55≤1-y-z≤0.77，使得三元正极前驱体材料为高镍材料，提高了三元正极材料的体积能量密度，若镍含量过低则降低了材料的克容量，若镍含量过高会导致锂镍混排，容易导致锂析出。因此，本申请实施例三元正极前驱体材料，通过调控三元氧化物前驱体中各主金属元素的配比，使得三元正极前驱体材料同时具有较好的结构稳定性，从而提高了对应的三元正极材料的循环稳定性和克容量。并且，相对于需通过共沉淀等方法制得结构稳定性差、密度低、粒径可控性差的三元氢氧化物前驱体材料，本申请实施例提供的三元氧化物前驱体能够通过一次结晶制得，不但缩短了制备时间提高了制备效率，而且更有利于提高前驱体材料的结构稳定性，提高前驱体材料密度，提高粒径可控度，细化材料粒径，从而进一步提高前驱体材料的单位装钵量，提高三元正极材料的制备效率，降低制造成本。 The ternary positive electrode precursor material provided by the embodiment of the present application includes a ternary oxide precursor with a general chemical formula of Ni (1-yz) Co y Mnz O x ; on the one hand, the precursor exists in the form of an oxide, and the Compared with the traditional hydroxide precursor, the main metal content of nickel, cobalt and manganese in the oxide precursor is higher, and when sintered into a ternary positive electrode material, the unit filling capacity is increased, thereby increasing the time of sintering into a ternary positive electrode material. The output can reduce the manufacturing cost of the ternary cathode material. On the other hand, in the Ni (1-yz) Co y Mn z O x ternary oxide precursor, the proportion of cobalt is only 0.03≤y≤0.1, and the low cobalt content is beneficial to increase the nickel content in the ternary cathode material Furthermore, the actual energy density of the ternary cathode material is increased. If the cobalt content is too high, the actual capacity of the material will be reduced, and if the cobalt content is too low, the structural stability of the material will be reduced. The ratio of manganese is 0.2≤z≤0.35, which effectively ensures the stability and safety of the crystal structure of the ternary oxide precursor. If the manganese content is too high, the structural stability of the material will be reduced, and the ratio of the material will be reduced. If the manganese content is too low, the structural stability and safety of the material will also be reduced. In addition, the proportion of nickel is 0.55≤1-yz≤0.77, which makes the ternary positive electrode precursor material a high-nickel material, which improves the volume energy density of the ternary positive electrode material, and if the nickel content is too low, the gram capacity of the material is reduced , if the nickel content is too high, it will lead to mixed discharge of lithium and nickel, which will easily lead to lithium precipitation. Therefore, the ternary positive electrode precursor material in the embodiment of the present application, by adjusting the proportion of each main metal element in the ternary oxide precursor, makes the ternary positive electrode precursor material have better structural stability at the same time, thereby improving the corresponding The cycle stability and gram capacity of the ternary cathode material. Moreover, compared to the ternary hydroxide precursor materials that need to be prepared by co-precipitation and other methods with poor structural stability, low density, and poor particle size controllability, the ternary oxide precursors provided in the examples of this application can be crystallized once. The preparation not only shortens the preparation time and improves the preparation efficiency, but also is more conducive to improving the structural stability of the precursor material, increasing the density of the precursor material, improving the controllability of the particle size, and refining the particle size of the material, thereby further improving the precursor material. The unit filling quantity of the material improves the preparation efficiency of the ternary cathode material and reduces the manufacturing cost.
在一些实施例中，三元氧化物前驱体的化学通式为Ni (1-y-z)Co yMn zO x中的1≤x≤1.14，0.04≤y≤0.08，0.25≤z≤0.30。通过优化三元氧化物前驱体中各元素的配比，使得三元氧化物前驱体有更好的结构稳定性，从而提高三元正极前驱体材料及三元正极材料的稳定性和容量。 In some embodiments, the general chemical formula of the ternary oxide precursor is 1≤x≤1.14, 0.04≤y≤0.08, 0.25≤z≤0.30 in Ni (1-yz) Co y Mnz O x . By optimizing the proportion of each element in the ternary oxide precursor, the ternary oxide precursor has better structural stability, thereby improving the stability and capacity of the ternary positive electrode precursor material and the ternary positive electrode material.
在一些实施例中，三元氧化物前驱体的晶体结构为六方层状结构、尖晶石型结构、立方体型结构、八面体型结构中的一种单晶结构。本申请实施例三元氧化物前驱体为单晶形态，相对于二次氢氧化物前驱体，材料晶体结构更加稳定，且有利于提高三元正极前驱体材料的振实密度、松散堆积密度等密度，从而提高对应的三元正极材料的循环稳定性和比容量。In some embodiments, the crystal structure of the ternary oxide precursor is a single crystal structure among hexagonal layered structure, spinel structure, cubic structure and octahedral structure. The ternary oxide precursor in the embodiment of this application is in a single crystal form. Compared with the secondary hydroxide precursor, the crystal structure of the material is more stable, and it is beneficial to improve the tap density and loose packing density of the ternary positive electrode precursor material. Density, thereby improving the cycle stability and specific capacity of the corresponding ternary cathode material.
在一些实施例中，三元正极前驱体材料中包括但不限于六方层状结构、立方体型结构、八面体型结构等层状结构，以及尖晶石型结构等多种晶型，利用不同晶型的结构优势，可提高锂离子的嵌入脱出效率，从而提高三元正极材料的电化学性能。In some embodiments, the ternary positive electrode precursor material includes but is not limited to layered structures such as hexagonal layered structure, cubic structure, octahedral structure, and various crystal forms such as spinel structure. The advantages of the type structure can improve the intercalation and extraction efficiency of lithium ions, thereby improving the electrochemical performance of the ternary cathode material.
在一些具体实施例中，三元氧化物前驱体的晶型结构可以是六方层状结构；形成三元正极材料之后，六方层状结构为二维结构，有利于锂离子的脱嵌，从而能够提高三元正极材料的比容量。In some specific embodiments, the crystal structure of the ternary oxide precursor can be a hexagonal layered structure; after the formation of the ternary positive electrode material, the hexagonal layered structure is a two-dimensional structure, which is conducive to the deintercalation of lithium ions, thereby enabling Improve the specific capacity of the ternary cathode material.
在一些具体实施例中，三元氧化物前驱体的晶型结构也可以是立方体型结构，有利于提高前驱体材料的均匀性，降低团聚现象，产品稳定性好，使循环性能和倍率性能较高。In some specific embodiments, the crystal structure of the ternary oxide precursor can also be a cubic structure, which is conducive to improving the uniformity of the precursor material, reducing agglomeration, good product stability, and better cycle performance and rate performance. high.
在一些具体实施例中，三元氧化物前驱体的晶型结构也可以是八面体型结构，八面体型结构的前驱体具有较高的活性比表面积，同样有利于锂离子脱嵌，且前驱体颗粒粒径均一度高，有利于提高正极片的膜层致密性、平整度以及均匀性，从而提高电池的循环稳定性。In some specific embodiments, the crystal structure of the ternary oxide precursor can also be an octahedral structure, and the precursor of the octahedral structure has a higher active specific surface area, which is also conducive to lithium ion deintercalation, and the precursor The particle size uniformity of the bulk particles is high, which is beneficial to improve the film density, flatness and uniformity of the positive electrode sheet, thereby improving the cycle stability of the battery.
在一些具体实施例中，三元氧化物前驱体的晶型结构可以是尖晶石型结构，尖晶石型是三维立方结构，晶体本身结构稳定性高，有利于提高三元正极材料的循环稳定性能和倍率性能。In some specific embodiments, the crystal structure of the ternary oxide precursor can be a spinel structure, and the spinel type is a three-dimensional cubic structure, and the crystal itself has high structural stability, which is conducive to improving the cycle of the ternary positive electrode material. Stable performance and rate performance.
在一些实施例中，三元正极前驱体材料中，包括六方层状结构的三元氧化物前驱体、尖晶石型结构的三元氧化物前驱体、立方体型结构的三元氧化物前驱体、八面体型结构的三元氧化物前驱体中的至少两种，通过两种或两种以上不同晶体结构的三元氧化物前驱体的协同配合作用，更有利于提高三元正极前驱体材料的电化学性能。In some embodiments, the ternary positive electrode precursor material includes a ternary oxide precursor with a hexagonal layered structure, a ternary oxide precursor with a spinel structure, and a ternary oxide precursor with a cubic structure. 1. At least two of the ternary oxide precursors with octahedral structure, through the synergistic effect of two or more ternary oxide precursors with different crystal structures, it is more conducive to improving the ternary positive electrode precursor material electrochemical performance.
在一些实施例中，三元正极前驱体材料中同时包括六方层状结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体，且六方层状结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体的质量比为(50～100)：(1～50)，其中，二维层状结构的三元氧化物前驱体，有利于Li离子的脱嵌，提高了三元正极材料的容量；而尖晶石结构是三维立方结构，其本身结构稳定性高，相对与二维层状结构更有利于提高三元正极材料的循环性能和倍率性能。因而，本申请实施例通过质量比为(50～100)：(1～50)的六方层状结构和尖晶石型结构的三元氧化物前驱体协同配合作用，使得到的三元正极材料具有高容量、高循环稳定性能和高倍率性。若三元正极前驱体材料中六方层状结构的三元氧化物前驱体占比过高，则会降低三元正极材料的稳定性；若尖晶石型结构的三元氧化物前驱体含量过高，则会降低三元正极材料的容量。In some embodiments, the ternary positive electrode precursor material includes both a ternary oxide precursor with a hexagonal layered structure and a ternary oxide precursor with a spinel structure, and the ternary oxide with a hexagonal layered structure The mass ratio of the precursor to the ternary oxide precursor of the spinel structure is (50-100): (1-50), among which, the ternary oxide precursor of the two-dimensional layered structure is beneficial to Li ion The deintercalation improves the capacity of the ternary cathode material; while the spinel structure is a three-dimensional cubic structure, which has high structural stability and is more conducive to improving the cycle performance and rate of the ternary cathode material than the two-dimensional layered structure. performance. Therefore, in the embodiment of the present application, the synergistic effect of the hexagonal layered structure and the spinel structure of the ternary oxide precursor with a mass ratio of (50-100): (1-50) makes the obtained ternary positive electrode material It has high capacity, high cycle stability and high rate capability. If the proportion of the ternary oxide precursor of the hexagonal layered structure in the ternary positive electrode precursor material is too high, the stability of the ternary positive electrode material will be reduced; if the content of the ternary oxide precursor of the spinel structure is too high High, it will reduce the capacity of the ternary cathode material.
本申请实施例通过调整三元正极前驱体材料中层状结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体的配比，可进一步优化三元正极材料的高容量、高循环性能和高倍率性的性能。在一些实施例中，三元正极前驱体材料中，六方层状结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体的质量比(60～90)：(10～40)，进一步地，质量比为(65～80)：(20～35)，进一步地，质量比为(65～75)：(25～35)。在一些具体实施例中，三元正极前驱体材料中，六方层状结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体的质量比包括但不限于100：1、90：10、80：20、75：25、70：30、68：32、65：35、60：40、50：50等。当层状结构和尖晶石型结构的三元氧化物前驱体的质量比为90：10时，在该质量比的情况下，得到的三元正极材料稳定性高，且有利于Li进行脱嵌，得到的材料充放电性能好。In the embodiment of the present application, the high capacity of the ternary positive electrode material can be further optimized by adjusting the ratio of the layered structure ternary oxide precursor and the spinel structure ternary oxide precursor in the ternary positive electrode precursor material , high cycle performance and high rate performance. In some embodiments, in the ternary positive electrode precursor material, the mass ratio of the ternary oxide precursor of the hexagonal layered structure to the ternary oxide precursor of the spinel structure (60-90): (10- 40), further, the mass ratio is (65-80):(20-35), further, the mass ratio is (65-75):(25-35). In some specific embodiments, in the ternary positive electrode precursor material, the mass ratio of the ternary oxide precursor of the hexagonal layered structure to the ternary oxide precursor of the spinel structure includes but is not limited to 100:1, 90:10, 80:20, 75:25, 70:30, 68:32, 65:35, 60:40, 50:50, etc. When the mass ratio of the ternary oxide precursors with layered structure and spinel structure is 90:10, in the case of this mass ratio, the obtained ternary cathode material has high stability and is conducive to the removal of Li. Embedded, the obtained material has good charge and discharge performance.
在一些实施例中，三元正极前驱体材料中同时包括尖晶石型结构的三元氧化物前驱体和立方体型结构的三元氧化物前驱体，且尖晶石型结构的三元氧化物前驱体和立方体型结构的三元氧化物前驱体的质量比为(10～50)：(50～90)，其中，立方体结构的三元氧化物前驱体提供大小均匀的结构，且具有一定的空间结构，有利于Li离子脱嵌，进而实现优异的充放电效果，提高效率；但是立方体型结构空间结构较大，稳定性较差，因此同时混合稳定性高的尖晶石结构，可提高三元正极材料的结构稳定性，使得到的材料具有高容量、高循环性能和高倍率性，确保得到的三元正极材料电化学性能优异。In some embodiments, the ternary positive electrode precursor material includes both a ternary oxide precursor with a spinel structure and a ternary oxide precursor with a cubic structure, and the ternary oxide with a spinel structure The mass ratio of the precursor to the ternary oxide precursor with a cubic structure is (10-50): (50-90), wherein the ternary oxide precursor with a cubic structure provides a uniform structure with a certain The spatial structure is conducive to the deintercalation of Li ions, thereby achieving excellent charging and discharging effects and improving efficiency; however, the cubic structure has a large spatial structure and poor stability, so mixing a spinel structure with high stability at the same time can improve the three-dimensional structure. The structural stability of the elemental cathode material enables the obtained material to have high capacity, high cycle performance and high rate capability, ensuring that the obtained ternary cathode material has excellent electrochemical performance.
本申请实施例通过调整三元正极前驱体材料中尖晶石型结构和立方体型结构的配比，可进一步优化三元正极材料的高容量、高循环性能和高倍率性的性能。在一些具体实施例中，三元氧化物前驱体中尖晶石型结构的三元氧化物前驱体和立方体型结构的三元氧化物前驱体的质量比包括但不限于10：90、15：85、20：80、25：75、30：70、35：65、40： 60、50：50等。当三元正极前驱体材料中尖晶石型结构的三元氧化物前驱体和立方体型结构的三元氧化物前驱体的质量比为35：65时，得到的三元正极材料稳定性高，有利于Li离子进行脱嵌，得到的材料充放电性能好。In the embodiment of the present application, the high capacity, high cycle performance and high rate performance of the ternary positive electrode material can be further optimized by adjusting the ratio of the spinel structure and the cubic structure in the ternary positive electrode precursor material. In some specific embodiments, the mass ratio of the ternary oxide precursor of the spinel structure and the ternary oxide precursor of the cubic structure in the ternary oxide precursor includes but is not limited to 10:90, 15: 85, 20:80, 25:75, 30:70, 35:65, 40:60, 50:50, etc. When the mass ratio of the ternary oxide precursor of the spinel structure and the ternary oxide precursor of the cubic structure in the ternary positive electrode precursor material is 35:65, the obtained ternary positive electrode material has high stability, It is conducive to Li ion intercalation and deintercalation, and the obtained material has good charge and discharge performance.
在一些实施例中，三元正极前驱体材料中同时包括八面体型结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体，且八面体型结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体的质量比为(50～80)：(15～50)；八面体型结构是指由八个平面所组成的多面体皆称为八面体，由6个顶点与8个正三角形构成的棱锥体，有八个面，每个面都是一个等边三角形，八面体型结构空间大，有利于材料作用；但稳定性较低，因此结合尖晶石型结构共同作用，尖晶石型结构有利于稳定八面体型结构，并且通过控制二者的质量比，有利于确保得到的三元正极材料稳定性高，有利于Li进行脱嵌，得到的材料充放电性能好。在一些具体实施例中，三元正极前驱体材料中八面体型结构的三元氧化物前驱体和尖晶石型结构的三元氧化物前驱体的质量比包括但不限于50：50、55：45、60：40、65：35、70：30、75：25、80：20等。In some embodiments, the ternary positive electrode precursor material includes a ternary oxide precursor with an octahedral structure and a ternary oxide precursor with a spinel structure, and the ternary oxide with an octahedral structure The mass ratio of the precursor to the ternary oxide precursor of the spinel structure is (50-80): (15-50); the octahedral structure refers to a polyhedron composed of eight planes called an octahedron , a pyramid composed of 6 vertices and 8 regular triangles, has eight faces, and each face is an equilateral triangle. The octahedral structure has a large space, which is conducive to the action of materials; The spinel structure works together, and the spinel structure is conducive to stabilizing the octahedral structure, and by controlling the mass ratio of the two, it is beneficial to ensure the high stability of the obtained ternary cathode material, which is conducive to the deintercalation of Li, The obtained material has good charge and discharge performance. In some specific embodiments, the mass ratio of the ternary oxide precursor of the octahedral structure and the ternary oxide precursor of the spinel structure in the ternary positive electrode precursor material includes but is not limited to 50:50, 55 :45, 60:40, 65:35, 70:30, 75:25, 80:20, etc.
在一些实施例中，当三元氧化物前驱体的晶体结构为六方层状结构、立方体型结构或八面体型结构等层状结构时，三元氧化物前驱体的化学通式为Ni (1-y-z)Co yMn zO；此时三元氧化物前驱体中氧原子全部为-2价态。而当三元氧化物前驱体的晶体结构为尖晶石型结构时，三元氧化物前驱体的化学通式为Ni (1-y-z)Co yMn zO x，此时，材料为AB 2O 4尖晶石型，其中镍、锰含有部分+3价态的离子，因而x大于1。 In some embodiments, when the crystal structure of the ternary oxide precursor is a layered structure such as a hexagonal layered structure, a cubic structure or an octahedral structure, the general chemical formula of the ternary oxide precursor is Ni (1 -yz) Co y Mnz O; at this time, all the oxygen atoms in the ternary oxide precursor are in the -2 valence state. When the crystal structure of the ternary oxide precursor is a spinel structure, the general chemical formula of the ternary oxide precursor is Ni (1-yz) Co y Mn z O x , and the material is AB 2 O 4 spinel type, in which nickel and manganese contain some +3 valence ions, so x is greater than 1.
在一些实施例中，三元正极前驱体材料中，包括：Ni 0.67Co 0.05Mn 0.28O、Ni 0.72Co 0.03Mn 0. 25O、Ni 0.7Co 0.04Mn 0.26O、Ni 0.65Co 0.06Mn 0.29O、Ni 0.62Co 0.08Mn 0.30O、Ni 0.6Co 0.10Mn 0.30O中的至少一种层状结构三元氧化物前驱体，和/或Ni 0.67Co 0.05Mn 0.28O 1.02、Ni 0.72Co 0.03Mn 0.25O 1.01、Ni 0.60Co 0.1Mn 0.3O 1.19中的至少一种尖晶石型三元氧化物前驱体。这些具体的三元氧化物前驱体，均具有较好的结构稳定性，且容量高，有利于提高对应的三元正极材料的循环稳定性和克容量。 In some embodiments, the ternary positive electrode precursor material includes: Ni 0.67 Co 0.05 Mn 0.28 O, Ni 0.72 Co 0.03 Mn 0.25 O, Ni 0.7 Co 0.04 Mn 0.26 O , Ni 0.65 Co 0.06 Mn 0.29 O, At least one layered structure ternary oxide precursor in Ni 0.62 Co 0.08 Mn 0.30 O, Ni 0.6 Co 0.10 Mn 0.30 O, and/or Ni 0.67 Co 0.05 Mn 0.28 O 1.02 , Ni 0.72 Co 0.03 Mn 0.25 O 1.01 , Ni 0.60 Co 0.1 Mn 0.3 O 1.19 at least one spinel-type ternary oxide precursor. These specific ternary oxide precursors all have good structural stability and high capacity, which is conducive to improving the cycle stability and gram capacity of the corresponding ternary cathode materials.
在一些具体实施例中，提供的Ni 0.67Co 0.05Mn 0.28O三元氧化物前驱体的晶体结构为六方层状结构、立方体型结构或八面体型结构等层状结构，其的电镜图如图1和图2所示。而Ni 0.67Co 0.05Mn 0.28O 1.02三元氧化物前驱体的晶体结构为尖晶石型。本申请实施例通过控制三元氧化物前驱体中的镍、钴、锰的摩尔比，使得到的三元氧化物前驱体中钴含量较低，仅为4.2％，性质较稳定，有利于提高了对应三元正极材料的克容量和稳定性；同时该前驱体物质为金属氧化物，与氢氧化物相比，氧化物中主金属含量较高，在烧结成三元正极材料时，提高了单位装钵量，从而提高了烧结成三元正极材料时的产量，降低三元正极材料的制造成本。 In some specific embodiments, the crystal structure of the provided Ni 0.67 Co 0.05 Mn 0.28 O ternary oxide precursor is a layered structure such as a hexagonal layered structure, a cubic structure or an octahedral structure, and its electron microscope picture is shown in the figure 1 and Figure 2. The crystal structure of Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary oxide precursor is spinel type. In the embodiment of the present application, by controlling the molar ratio of nickel, cobalt, and manganese in the ternary oxide precursor, the cobalt content in the obtained ternary oxide precursor is low, only 4.2%, and the properties are relatively stable, which is conducive to improving The gram capacity and stability of the corresponding ternary cathode material are ensured; at the same time, the precursor material is a metal oxide. Compared with the hydroxide, the main metal content in the oxide is higher, and when sintered into a ternary cathode material, the The unit filling quantity increases the output when sintering into the ternary positive electrode material, and reduces the manufacturing cost of the ternary positive electrode material.
在一些具体实施例中，提供的Ni 0.72Co 0.03Mn 0.25O，得到的三元氧化物前驱体的晶型结构为层状结构；而Ni 0.72Co 0.03Mn 0.25O 1.01三元氧化物前驱体的晶体结构为尖晶石型。提供的三元氧化物前驱体中钴含量低，镍含量高，使得到的三元材料前驱体的能级密度较高，材 料容量高，性质较稳定。在一些具体实施例中，控制得到的Ni 0.72Co 0.03Mn 0.25O三元氧化物前驱体的晶型结构为层状结构，其宏观材料的形貌为球状结构，其中，层状结构为二维结构，形成正极材料之后，有利于锂离子的脱嵌，能够提高其容量；形成的宏观球状结构的材料晶型完整，有利于材料反应，使得到的三元正极前驱体材料性质优异。 In some specific embodiments, Ni 0.72 Co 0.03 Mn 0.25 O is provided, and the crystal structure of the obtained ternary oxide precursor is a layered structure; while the Ni 0.72 Co 0.03 Mn 0.25 O 1.01 The crystal structure is spinel type. The provided ternary oxide precursor has low cobalt content and high nickel content, so that the obtained ternary material precursor has higher energy level density, higher material capacity, and more stable properties. In some specific embodiments, the crystalline structure of the obtained Ni 0.72 Co 0.03 Mn 0.25 O ternary oxide precursor is controlled to be a layered structure, and the morphology of its macroscopic material is a spherical structure, wherein the layered structure is a two-dimensional After the positive electrode material is formed, it is conducive to the deintercalation of lithium ions and can increase its capacity; the formed macroscopic spherical structure material has a complete crystal form, which is conducive to the material reaction, making the obtained ternary positive electrode precursor material excellent in properties.
在一些具体实施例中，提供的Ni 0.60Co 0.1Mn 0.3O 1.19，得到的三元氧化物前驱体的晶型结构为尖晶石型结构，材料结构稳定性高，且容量高。而Ni 0.6Co 0.10Mn 0.30O三元氧化物前驱体的晶体结构为六方层状结构、立方体型结构或八面体型结构等层状结构。进一步地，三元正极前驱体材料的宏观形貌为多孔结构，活性比表面积大，有利于提供更多反应位点，使得到的材料具有较高的容量和循环性能。 In some specific embodiments, Ni 0.60 Co 0.1 Mn 0.3 O 1.19 is provided, and the crystal structure of the obtained ternary oxide precursor is a spinel structure, and the material has high structural stability and high capacity. The crystal structure of the Ni 0.6 Co 0.10 Mn 0.30 O ternary oxide precursor is a layered structure such as hexagonal layered structure, cubic structure or octahedral structure. Furthermore, the macroscopic morphology of the ternary positive electrode precursor material is a porous structure, and the active specific surface area is large, which is conducive to providing more reaction sites, so that the obtained material has higher capacity and cycle performance.
在一些实施例中，三元氧化物前驱体的粒度为50～800nm。本申请实施例三元氧化物前驱体晶体颗粒的粒度，既可以达到小于100nm的较小颗粒，又可以达到500～800nm较大的颗粒，晶体颗粒粒度分布区间宽，拓宽了三元氧化物前驱体的应用范围。50～800nm单晶颗粒粒度的三元氧化物前驱体，有较大的活性比表面积，有利于后续与锂盐反应形成三元正极材料，同时有利于提高三元正极材料的成膜均匀性、稳定性、表面平整度等，从而进一步提高了正极片的稳定性。在一些实施例中，三元氧化物前驱体的晶体颗粒粒度为100～700nm，进一步地为200～600nm，进一步地为300～500nm等。在一些具体实施例中，三元氧化物前驱体的晶体颗粒粒度为100～500nm时，三元氧化物前驱体的晶型完整、颗粒形态饱满、分散均一、结构稳定、性能稳定，可缩短三元正极材料的制备周期。In some embodiments, the particle size of the ternary oxide precursor is 50-800 nm. The particle size of the ternary oxide precursor crystal particles in the embodiment of the present application can reach not only smaller particles less than 100nm, but also larger particles of 500-800nm, and the crystal particle size distribution range is wide, which broadens the range of ternary oxide precursors. The scope of application of the body. The ternary oxide precursor with a single crystal particle size of 50-800nm has a large active specific surface area, which is conducive to the subsequent reaction with lithium salts to form a ternary cathode material, and is also conducive to improving the film-forming uniformity of the ternary cathode material. Stability, surface flatness, etc., thereby further improving the stability of the positive electrode sheet. In some embodiments, the crystal particle size of the ternary oxide precursor is 100-700 nm, further 200-600 nm, further 300-500 nm, etc. In some specific embodiments, when the crystal particle size of the ternary oxide precursor is 100-500 nm, the crystal form of the ternary oxide precursor is complete, the particle shape is full, the dispersion is uniform, the structure is stable, and the performance is stable, which can shorten the ternary oxide precursor. The preparation cycle of primary cathode materials.
在一些实施例中，三元正极前驱体材料的宏观形貌包括球形结构、多孔结构、立体多边形结构中的至少一种，这些宏观形貌与锂源的接触活性比表面积大，有利于三元正极前驱体材料后续与锂源充分接触反应，有利于锂离子结合到晶体结构中形成三元正极材料。In some embodiments, the macroscopic morphology of the ternary positive electrode precursor material includes at least one of a spherical structure, a porous structure, and a three-dimensional polygonal structure. The subsequent full contact reaction of the positive electrode precursor material with the lithium source is conducive to the incorporation of lithium ions into the crystal structure to form a ternary positive electrode material.
在一些具体实施例中，三元正极前驱体材料的宏观形貌为多孔结构，有更大的活性比表面积，能够提高材料的离子传输性以及电化学活性，出现更多储锂位点，并且也能为电极体积变化提供缓冲确保得到的材料具有高功率、高能量、高稳定。在一些具体实施例中，三元正极前驱体材料的宏观形貌为立体多边形结构，有利于提高循环性能和倍率性能，使材料性能更优异。In some specific embodiments, the macroscopic morphology of the ternary positive electrode precursor material is a porous structure with a larger active specific surface area, which can improve the ion transport and electrochemical activity of the material, and more lithium storage sites appear, and It can also provide a buffer for the volume change of the electrode to ensure that the obtained material has high power, high energy, and high stability. In some specific embodiments, the macroscopic morphology of the ternary positive electrode precursor material is a three-dimensional polygonal structure, which is conducive to improving cycle performance and rate performance, and making the material performance more excellent.
在一些实施例中，三元正极前驱体材料的宏观形貌包括球形结构、多孔结构、立体多边形结构中的至少一种，宏观形貌的粒径D50为1.5～3.5μm，进一步地为1.5～3μm，进一步地为1.5～2μm。In some embodiments, the macroscopic morphology of the ternary positive electrode precursor material includes at least one of a spherical structure, a porous structure, and a three-dimensional polygonal structure, and the particle size D50 of the macroscopic morphology is 1.5 to 3.5 μm, and further 1.5 to 3.5 μm. 3 μm, further 1.5-2 μm.
在一些实施例中，三元正极前驱体材料的松散堆积密度为0.5～1.0g/cm 3，进一步地松散堆积密度为0.6～0.8g/cm 3。在一些实施例中，三元正极前驱体材料的振实密度为1.6～2.4g/cm 3，进一步地振实密度为1.8～2g/cm 3。本申请实施例三元正极材料有较大的松散堆积密度和振实密度，在烧结成三元正极材料时，提高了单位装钵量，从而提高了烧结成三元正极材料时的产量，降低三元正极材料的制造成本。 In some embodiments, the loose packing density of the ternary positive electrode precursor material is 0.5-1.0 g/cm 3 , further the loose packing density is 0.6-0.8 g/cm 3 . In some embodiments, the tap density of the ternary cathode precursor material is 1.6-2.4 g/cm 3 , further the tap density is 1.8-2 g/cm 3 . The ternary positive electrode material in the embodiment of the present application has a larger loose bulk density and tap density, and when sintered into a ternary positive electrode material, the unit filling capacity is increased, thereby improving the output when sintering into a ternary positive electrode material, and reducing The manufacturing cost of ternary cathode materials.
在一些具体实施例中，三元正极前驱体材料的松散密度为0.5g/cm 3，三元正极前驱体 材料的振实密度为1.6g/cm 3，得到的三元正极前驱体材料内部较密实紧致。在另一些实施例中，三元正极前驱体材料的松散密度为0.7g/cm 3，三元正极前驱体材料的振实密度为2.0g/cm 3，得到的三元正极前驱体材料的结构内部致密且纯度较高。在另一些实施例中，三元正极前驱体材料的松散密度为1g/cm 3，三元正极前驱体材料的振实密度为2.4g/cm 3。 In some specific embodiments, the bulk density of the ternary positive electrode precursor material is 0.5g/cm 3 , the tap density of the ternary positive electrode precursor material is 1.6g/cm 3 , and the obtained ternary positive electrode precursor material is relatively Dense and tight. In other embodiments, the bulk density of the ternary positive electrode precursor material is 0.7 g/cm 3 , the tap density of the ternary positive electrode precursor material is 2.0 g/cm 3 , and the structure of the obtained ternary positive electrode precursor material is The interior is dense and of high purity. In other embodiments, the bulk density of the ternary positive electrode precursor material is 1 g/cm 3 , and the tap density of the ternary positive electrode precursor material is 2.4 g/cm 3 .
本申请实施例三元正极前驱体材料可通过下述实施例方法制得。The ternary positive electrode precursor material in the examples of the present application can be prepared by the methods in the following examples.
如附图3所示，本申请一些实施例提供提供一种上述三元正极前驱体材料的制备方法，包括如下步骤：As shown in Figure 3, some embodiments of the present application provide a method for preparing the above-mentioned ternary positive electrode precursor material, including the following steps:
S01.将镍盐溶液、钴盐溶液、锰盐溶液混合后，进行浓缩处理，得到混合溶液；S01. After mixing the nickel salt solution, the cobalt salt solution and the manganese salt solution, carry out concentration treatment to obtain a mixed solution;
S02.对混合溶液进行雾化焙烧处理，得到三元正极前驱体材料。S02. Perform atomization and roasting treatment on the mixed solution to obtain a ternary positive electrode precursor material.
本申请实施例提供的三元正极前驱体材料的制备方法，按照Ni (1-y-z)Co yMn zO x化学通式中金属元素的化学计量比，将镍盐溶液、钴盐溶液、锰盐溶液混合后，通过浓缩处理调控混合溶液中镍盐、钴盐、锰盐的浓度；对混合溶液进行雾化焙烧处理，混合溶液雾化成细小的液滴的同时，直接对雾化液滴进行焙烧，使液滴中镍、钴、锰等金属阳离子在高温环境中迅速反应生成三元氧化物前驱体单晶，而盐溶液中阴离子在高温环境中转化成气体物质去除或被回收，从而得到产品纯度高，粒径小且均一度好的三元正极前驱体材料。该制备方法工艺流程简单，中间流程少，反应过程便于灵活调控，在雾化的同时进行焙烧处理，不但确保了产品具有较小的粒径，而且产品反应速度快，雾化焙烧获得三元正极前驱体材料的实际反应时间仅需数秒，生产效率高。另外，由于盐溶液中阴离子在高温环境中转化成气体物质去除或被回收，原料利用率高，产品中杂质含量低，性能优异。本申请实施例通过对混合溶液进行雾化焙烧处理直接制备三元正极氧化物前驱体材料的方法，有利于提高前驱体材料的结构稳定性，提高前驱体材料密度，细化材料粒径，从而进一步提高前驱体材料的单位装钵量，提高三元正极材料的制备效率，降低制造成本。相对于传统通过共沉淀法等制备三元氢氧化物前驱体的方法，不但提高了材料的制备效率，简化了工艺，减少了废水等工业废弃物的排放，生产过程更加环保，降低了生产成本；而且更有利于调控前驱体材料晶体结构、粒径、松散度、密度等性能。克服现有二次结晶包覆三元氢氧化物前驱体材料存在的结构稳定性差、密度低、粒径可控性差等问题。 The preparation method of the ternary positive electrode precursor material provided in the embodiment of the present application, according to the stoichiometric ratio of the metal elements in the general chemical formula of Ni (1-yz) Co y Mn z O x , nickel salt solution, cobalt salt solution, manganese After the salt solution is mixed, the concentration of nickel salt, cobalt salt, and manganese salt in the mixed solution is controlled by concentration treatment; the mixed solution is atomized and roasted, and the mixed solution is atomized into fine droplets, and the atomized droplets are directly sprayed. Roasting, so that metal cations such as nickel, cobalt, and manganese in the droplets react rapidly in a high-temperature environment to form a ternary oxide precursor single crystal, while the anions in the salt solution are converted into gaseous substances in a high-temperature environment to be removed or recovered, thereby obtaining The product has high purity, small particle size and good uniformity as the ternary cathode precursor material. The preparation method has a simple process flow, fewer intermediate processes, and flexible control of the reaction process. The roasting treatment is carried out at the same time as the atomization, which not only ensures that the product has a smaller particle size, but also has a fast reaction speed, and the atomization roasting can obtain a ternary positive electrode. The actual reaction time of the precursor material is only a few seconds, and the production efficiency is high. In addition, because the anions in the salt solution are converted into gaseous substances to be removed or recovered in a high-temperature environment, the utilization rate of raw materials is high, the impurity content in the product is low, and the performance is excellent. In the embodiment of the present application, the method of directly preparing the ternary positive electrode oxide precursor material by atomizing and roasting the mixed solution is beneficial to improve the structural stability of the precursor material, increase the density of the precursor material, and refine the particle size of the material, thereby Further increase the unit filling capacity of the precursor material, improve the preparation efficiency of the ternary cathode material, and reduce the manufacturing cost. Compared with the traditional method of preparing ternary hydroxide precursors by co-precipitation method, it not only improves the preparation efficiency of materials, simplifies the process, reduces the discharge of industrial waste such as wastewater, the production process is more environmentally friendly, and reduces production costs ; And it is more beneficial to control the crystal structure, particle size, looseness, density and other properties of the precursor material. It overcomes the problems of poor structural stability, low density, and poor particle size controllability existing in existing secondary crystallization-coated ternary hydroxide precursor materials.
在一些实施例中，上述步骤S01中，按照Ni (1-y-z)Co yMn zO x化学通式中金属元素的化学计量比，将镍盐溶液、钴盐溶液、锰盐溶液混合后，进行浓缩处理，得到混合溶液，其中，1≤x≤1.2，0.03≤y≤0.1，0.2≤z≤0.35。使混合溶液中金属盐溶液有合适的雾化浓度，有利于调控金属盐溶液的反应速率，以及三元氧化物前驱体的颗粒大小。 In some embodiments, in the above step S01, after mixing the nickel salt solution, the cobalt salt solution, and the manganese salt solution according to the stoichiometric ratio of the metal elements in the general chemical formula of Ni (1-yz) Co y Mnz O x , Concentration treatment is carried out to obtain a mixed solution, wherein, 1≤x≤1.2, 0.03≤y≤0.1, 0.2≤z≤0.35. Making the metal salt solution in the mixed solution have a suitable atomization concentration is beneficial to control the reaction rate of the metal salt solution and the particle size of the ternary oxide precursor.
在一些实施例中，将镍盐溶液、钴盐溶液、锰盐溶液混合后，进行浓缩处理，控制得到的混合溶液中，镍盐、钴盐和锰盐的浓度分别独立地为50～300g/L，金属盐的该浓度有利于进行雾化结晶造粒。若混合溶液中金属盐的浓度低于80g/L，会导致雾化后液滴中金属盐含量过低，不利于液滴中金属盐在焙烧过程充分反应，结晶造粒，得到的产物较少，不利于前驱体的富集；若混合溶液的浓度高于300g/L，则混合溶液浓度过高，导致得到雾化液 滴中金属盐含量过高，在焙烧过程中不利于金属盐成分结晶造粒，颗粒粒径过大，易造成团聚，不利于制得单晶材料，也不利于调控材料晶型，从而降低三元正极前驱体的稳定性。在一些具体实施例中，混合溶液中，镍盐、钴盐和锰盐的浓度分别独立地为50g/L、60g/L、80g/L、120g/L、160g/L、200g/L、220g/L、260g/L、300g/L等。In some embodiments, after mixing the nickel salt solution, the cobalt salt solution, and the manganese salt solution, concentration treatment is performed to control the concentrations of the nickel salt, cobalt salt, and manganese salt in the obtained mixed solution to be 50-300 g/ L, the concentration of the metal salt is conducive to atomization crystallization and granulation. If the concentration of metal salts in the mixed solution is lower than 80g/L, the content of metal salts in the droplets after atomization will be too low, which is not conducive to the full reaction of the metal salts in the droplets during the roasting process, crystallization and granulation, and less products obtained , which is not conducive to the enrichment of the precursor; if the concentration of the mixed solution is higher than 300g/L, the concentration of the mixed solution is too high, resulting in too high a metal salt content in the atomized droplets, which is not conducive to the crystallization of the metal salt component during the roasting process Granulation, the particle size is too large, it is easy to cause agglomeration, which is not conducive to the preparation of single crystal materials, and is also not conducive to the regulation of the crystal form of the material, thereby reducing the stability of the ternary positive electrode precursor. In some specific embodiments, in the mixed solution, the concentrations of nickel salt, cobalt salt and manganese salt are respectively independently 50g/L, 60g/L, 80g/L, 120g/L, 160g/L, 200g/L, 220g /L, 260g/L, 300g/L, etc.
在一些实施例中，镍盐溶液选自：氯化镍溶液、硝酸镍溶液、草酸镍溶液、硫酸镍溶液中的至少一种。在一些实施例中，钴盐溶液选自：氯化钴溶液、硝酸钴溶液、草酸钴溶液、硫酸钴溶液中的至少一种。在一些实施例中，锰盐溶液选自：氯化锰溶液、硝酸锰溶液、草酸锰溶液、硫酸锰溶液中的至少一种。本申请实施例镍、钴、锰主金属的盐溶液选自氯化物盐溶液、硝酸盐溶液、草酸盐溶液、硫酸盐溶液中的至少一种，这些盐溶液不但具有较好的溶解性能，而且氯离子、硝酸根离子、草酸根离子、硫酸根离子等阴离子，在焙烧过程中可转化成HCl、NO、CO 2、SO 2等气态物质，既有利于回收，也降低了三元氧化物前驱体材料中残留杂质元素，提高产品纯度。 In some embodiments, the nickel salt solution is selected from at least one of nickel chloride solution, nickel nitrate solution, nickel oxalate solution, and nickel sulfate solution. In some embodiments, the cobalt salt solution is selected from at least one of cobalt chloride solution, cobalt nitrate solution, cobalt oxalate solution, and cobalt sulfate solution. In some embodiments, the manganese salt solution is selected from at least one of manganese chloride solution, manganese nitrate solution, manganese oxalate solution, and manganese sulfate solution. The salt solution of nickel, cobalt, and manganese main metals in the embodiment of the present application is selected from at least one of chloride salt solution, nitrate solution, oxalate solution, and sulfate solution. These salt solutions not only have good solubility, Moreover, anions such as chloride ions, nitrate ions, oxalate ions, and sulfate ions can be converted into gaseous substances such as HCl, NO, CO 2 , and SO 2 during the roasting process, which is not only beneficial to recovery, but also reduces the ternary oxides. Impurity elements remain in the precursor material to improve product purity.
在一些具体实施例中，采用镍钴锰金属单质经由盐酸溶解制备得相应的氯化盐溶液，在制备过程中严格控制溶液内的杂质含量较低，雾化烧结后HCl气体可直接回收用于金属盐溶液的制备，实验循环利用，提高生成效率。In some specific embodiments, the corresponding chloride salt solution is prepared by dissolving nickel, cobalt and manganese metal elements with hydrochloric acid. During the preparation process, the impurity content in the solution is strictly controlled to be low. After atomization and sintering, HCl gas can be directly recovered for use in The preparation of the metal salt solution, the experimental recycling, and the improvement of the generation efficiency.
在一些实施例中，将含镍钴锰离子的溶液转移至混合罐混合，制备含镍钴锰离子的混合溶液，其中，混合罐材质为具有一定强度的耐酸材料。In some embodiments, the solution containing nickel, cobalt and manganese ions is transferred to a mixing tank for mixing to prepare a mixed solution containing nickel, cobalt and manganese ions, wherein the mixing tank is made of an acid-resistant material with a certain strength.
在一些实施例中，上述步骤S02中，雾化焙烧处理的步骤包括：在雾化风量为20～1200m 3/h的条件下，将混合溶液雾化成细小的液滴，然后液滴在温度为300～1000℃、氧气质量百分含量为1.0～13.0％的条件下进行焙烧，液滴直接转化成三元氧化物前驱体晶体，得到三元正极前驱体材料，反应速率快，效率高。其中，20～1200m 3/h的雾化风量，既确保了混合溶液形成粒径小且均匀的液滴，又为液滴中金属盐之间的反应提供的充足时间，若雾化风量过低，则形成的液滴粒径过大，不利于获得小粒径的液滴，液滴容易沉降，不利于液滴中金属盐在焙烧过程中充分反应；若雾化风量过高，液滴在焙烧环境中停留时间过短，同样不利于液滴中金属盐充分接触反应。在一些实施例中，雾化风量为100～1100m 3/h，进一步地雾化风量为200～1000m 3/h，进一步地雾化风量为300～800m 3/h，进一步地雾化风量为400～600m 3/h等。另外，焙烧处理的温度为300～1000℃，该温度条件有利于雾化液滴中金属盐迅速反应生成三元氧化物前驱体单晶材料。若焙烧处理的温度低于300℃，则处理温度过低，不利于雾化液滴中金属盐反应得到成型前驱体；若焙烧处理的温度高于1000℃，则能耗大，且不利于控制三元氧化物前驱体的晶型。氧气含量的高低，既会影响液滴中金属盐的反应速率，也会影响生成的三元氧化物前驱体的晶型。在一些具体实施例中，氧气质量百分含量可以是1.0～2％、2～5％、5～8％、8～10％、10～13.0％等。 In some embodiments, in the above step S02, the step of atomization and roasting treatment includes: atomizing the mixed solution into fine droplets under the condition of an atomization air volume of 20-1200m 3 /h, and then the droplets are heated at a temperature of Roasting is carried out under the conditions of 300-1000°C and an oxygen mass percentage of 1.0-13.0%. The liquid droplets are directly converted into ternary oxide precursor crystals to obtain ternary positive electrode precursor materials. The reaction rate is fast and the efficiency is high. Among them, the atomizing air volume of 20-1200m 3 /h not only ensures that the mixed solution forms small and uniform droplets, but also provides sufficient time for the reaction between the metal salts in the droplets. If the atomizing air volume is too low , the particle size of the formed droplets is too large, which is not conducive to obtaining small-sized droplets, and the droplets are easy to settle, which is not conducive to the full reaction of the metal salt in the droplets during the roasting process; if the atomization air volume is too high, the droplets are in The residence time in the roasting environment is too short, which is also unfavorable for the full contact reaction of the metal salt in the droplet. In some embodiments, the atomizing air volume is 100-1100m 3 /h, further atomizing air volume is 200-1000m 3 /h, further atomizing air volume is 300-800m 3 /h, further atomizing air volume is 400 ~600m 3 /h etc. In addition, the temperature of the calcination treatment is 300-1000° C., which is conducive to the rapid reaction of the metal salt in the atomized liquid droplets to form a ternary oxide precursor single crystal material. If the temperature of the roasting treatment is lower than 300°C, the treatment temperature is too low, which is not conducive to the reaction of the metal salt in the atomized liquid droplets to form the precursor; if the temperature of the roasting treatment is higher than 1000°C, the energy consumption will be large, and it is not conducive to control. The crystal form of the ternary oxide precursor. The level of oxygen content will not only affect the reaction rate of the metal salt in the droplet, but also affect the crystal form of the generated ternary oxide precursor. In some specific embodiments, the mass percentage of oxygen may be 1.0-2%, 2-5%, 5-8%, 8-10%, 10-13.0%, etc.
本申请实施例通过对雾化焙烧处理过程中的雾化风量、焙烧温度、氧气含量的调节，可灵活调控制备的三元正极前驱体材料的颗粒大小、晶型等物理特性，从而有利于优化三元正极材料的物理化学性能。在一些实施例中，在雾化风量为20～1200m 3/h的条件下，将 混合溶液雾化成液滴，并在温度为300～900℃、氧气质量百分含量为1.0～13.0％的条件下焙烧，有利于制得六方层状结构、立方体型结构、八面体型结构等晶型的三元氧化物前驱体材料。在另一些实施例中，在雾化风量为20～1200m 3/h的条件下，将混合溶液雾化成液滴，并在温度为700～1000℃、氧气质量百分含量为1.0～13.0％的条件下焙烧，可制得尖晶石型结构的三元氧化物前驱体材料。 In the embodiment of the present application, by adjusting the atomization air volume, calcination temperature, and oxygen content during the atomization calcination process, the physical properties such as particle size and crystal form of the prepared ternary positive electrode precursor material can be flexibly adjusted, which is conducive to optimization. Physicochemical properties of ternary cathode materials. In some embodiments, under the condition of atomizing air volume of 20-1200m 3 /h, the mixed solution is atomized into droplets, and the temperature is 300-900°C, and the mass percentage of oxygen is 1.0-13.0%. Bottom firing is conducive to the preparation of ternary oxide precursor materials with hexagonal layered structure, cubic structure, octahedral structure and other crystal forms. In some other embodiments, the mixed solution is atomized into droplets under the condition of atomizing air volume of 20-1200m 3 /h, and the mixture is atomized into droplets at a temperature of 700-1000°C and an oxygen mass percentage of 1.0-13.0%. The ternary oxide precursor material with spinel structure can be obtained by roasting under the same conditions.
在一些实施例中，控制焙烧处理的时间为1～50秒。该制备方法中，在短时间内就可以保证制备得到成型前驱体，制备时间短，效率较高，有利于广泛应用。In some embodiments, the time of the controlled firing treatment is 1-50 seconds. In the preparation method, the molding precursor can be guaranteed to be prepared in a short time, the preparation time is short, the efficiency is high, and it is beneficial to wide application.
在一些实施例中，制得三元正极前驱体材料后，还包括对三元正极前驱体材料进行研磨或破碎处理等后处理步骤，通过控制磨盘间距或破碎气体压力流量等条件，可控制所得产品粒径，使得三元正极前驱体材料粒径分布更均一。In some embodiments, after the ternary positive electrode precursor material is prepared, post-processing steps such as grinding or crushing the ternary positive electrode precursor material are also included, and the obtained The particle size of the product makes the particle size distribution of the ternary cathode precursor material more uniform.
本申请一些实施例提供一种三元正极材料，该三元正极材料由包括锂源和三元正极前驱体材料的混合物经烧结处理得到，其中，三元正极前驱体材料为上述实施例中三元正极前驱体材料。Some embodiments of the present application provide a ternary positive electrode material, which is obtained by sintering a mixture including a lithium source and a ternary positive electrode precursor material, wherein the ternary positive electrode precursor material is the three Element cathode precursor material.
本申请提供的三元正极材料，该三元正极材料由锂源和上述三元正极前驱体材料烧结得到，由于上述三元正极前驱体材料包含结构通式为Ni (1-y-z)Co yMn zO x的三元氧化物前驱体，其中，1≤x≤1.2，0.03≤y≤0.1，0.2≤z≤0.35，镍含量较高，性质较稳定，同时该前驱体为金属氧化物，与氢氧化物前驱体相比，锂源烧结时可以直接生成正极材料，提高三元正极材料的制备效率。从而使锂源烧结得到的三元正极材料具有较高的克容量、循环稳定性能、结构稳定性等特性。 The ternary positive electrode material provided by the present application is obtained by sintering the lithium source and the above-mentioned ternary positive electrode precursor material, because the above-mentioned ternary positive electrode precursor material contains a general structural formula of Ni (1-yz) Co y Mn The ternary oxide precursor of z O x , wherein, 1≤x≤1.2, 0.03≤y≤0.1, 0.2≤z≤0.35, high nickel content, relatively stable properties, and the precursor is a metal oxide, and Compared with the hydroxide precursor, the positive electrode material can be directly generated when the lithium source is sintered, which improves the preparation efficiency of the ternary positive electrode material. Therefore, the ternary cathode material obtained by sintering the lithium source has characteristics such as high gram capacity, cycle stability, and structural stability.
在一些实施例中，锂源选自碳酸锂、一水合氢氧化锂、醋酸锂、硝酸锂、草酸锂、乙酸锂、氢氧化锂、氧化锂中的一种或多种，这些锂盐均可与三元前驱体材料通过高温烧结形成三元正极材料。In some embodiments, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, lithium nitrate, lithium oxalate, lithium acetate, lithium hydroxide, lithium oxide, and these lithium salts can be The ternary cathode material is formed by high-temperature sintering with the ternary precursor material.
在一些实施例中，三元正极前驱体材料和锂源的摩尔比为1：(1～1.1)，该配比有利于三元前驱体材料与锂盐充分反应生成镍钴锰三元正极材料。控制三元正极前驱体材料和锂源的摩尔比，确保得到的三元正极材料具有较高的容量和循环性能。In some embodiments, the molar ratio of the ternary positive electrode precursor material to the lithium source is 1: (1-1.1), which is conducive to the full reaction of the ternary precursor material and the lithium salt to form a nickel-cobalt-manganese ternary positive electrode material . Controlling the molar ratio of the ternary positive electrode precursor material to the lithium source ensures that the obtained ternary positive electrode material has high capacity and cycle performance.
在一些实施例中，三元前驱体材料与锂盐混合后，烧结温度为450-1000℃、烧结时间为3-8h，该烧结条件可确保三元前驱体材料与锂盐充分反应生成LiNi (1-y-z)Co yMn zO 2，其中，0.03≤y≤0.1，0.2≤z≤0.35。在一些在具体实施例中，三元正极材料包括但不限于：LiNi 0.72Co 0.03Mn 0.25O 2、LiNi 0.7Co 0.04Mn 0.26O 2、LiNi 0.67Co 0.05Mn 0.28O 2、LiNi 0.65Co 0.06Mn 0.29O 2、LiNi 0.62Co 0.08Mn 0.30O 2、LiNi 0.6Co 0.10Mn 0.30O 2等。 In some embodiments, after the ternary precursor material is mixed with the lithium salt, the sintering temperature is 450-1000° C., and the sintering time is 3-8 h. The sintering conditions can ensure that the ternary precursor material and the lithium salt fully react to form LiNi ( 1-yz) Co y Mn z O 2 , wherein, 0.03≤y≤0.1, 0.2≤z≤0.35. In some specific embodiments, the ternary cathode materials include but are not limited to: LiNi 0.72 Co 0.03 Mn 0.25 O 2 , LiNi 0.7 Co 0.04 Mn 0.26 O 2 , LiNi 0.67 Co 0.05 Mn 0.28 O 2 , LiNi 0.65 Co 0.06 Mn 0.29 O 2 , LiNi 0.62 Co 0.08 Mn 0.30 O 2 , LiNi 0.6 Co 0.10 Mn 0.30 O 2 , etc.
在一些具体实施例中，提供了一种三元正极材料的制备方法，包括如下步骤：将三元正极前驱体材料与锂源进行混合烧结处理，得到三元正极材料；其中，混合烧结处理的温度为300～1000℃。通过研磨或破碎处理，控制得到的三元正极材料颗粒均匀性。In some specific embodiments, a method for preparing a ternary positive electrode material is provided, comprising the following steps: performing mixed sintering treatment on the ternary positive electrode precursor material and lithium source to obtain the ternary positive electrode material; wherein, the mixed sintered The temperature is 300-1000°C. By grinding or crushing, the particle uniformity of the obtained ternary cathode material is controlled.
本申请第四方面提供一种二次电池，该二次电池的正极片中包括上述三元正极材料。The fourth aspect of the present application provides a secondary battery, the positive electrode sheet of the secondary battery includes the above-mentioned ternary positive electrode material.
本申请第四方面提供的二次电池，由于正极片中包括上述三元正极材料，该三元正极 材料具有较高的克容量、循环稳定性能、结构稳定性等特性，因而提高了二次电池的能量密度，循环稳定性，以及安全性能。In the secondary battery provided by the fourth aspect of the present application, since the positive electrode sheet includes the above-mentioned ternary positive electrode material, the ternary positive electrode material has characteristics such as higher gram capacity, cycle stability, and structural stability, thereby improving the performance of the secondary battery. Excellent energy density, cycle stability, and safety performance.
在一些实施例中，三元正极材料包括但不限于：LiNi (1-y-z)Co yMn zO 2，其中，0.03≤y≤0.1，0.2≤z≤0.35。在一些具体实施例中，三元正极材料包括但不限于：LiNi 0.72Co 0.03Mn 0.25O 2、LiNi 0.7Co 0.04Mn 0.26O 2、LiNi 0.67Co 0.05Mn 0.28O 2、LiNi 0.65Co 0.06Mn 0.29O 2、LiNi 0.62Co 0.08Mn 0. 30O 2、LiNi 0.6Co 0.10Mn 0.30O 2等。这些三元正极材料同时具有结构稳定性好，可容量高，循环稳定性好等特性。 In some embodiments, the ternary cathode material includes, but is not limited to: LiNi (1-yz) Co y Mnz O 2 , where 0.03≤y≤0.1, 0.2≤z≤0.35. In some specific embodiments, the ternary cathode materials include but are not limited to: LiNi 0.72 Co 0.03 Mn 0.25 O 2 , LiNi 0.7 Co 0.04 Mn 0.26 O 2 , LiNi 0.67 Co 0.05 Mn 0.28 O 2 , LiNi 0.65 Co 0.06 Mn 0.29 O 2. LiNi 0.62 Co 0.08 Mn 0. 30 O 2 , LiNi 0.6 Co 0.10 Mn 0.30 O 2 , etc. These ternary cathode materials also have the characteristics of good structural stability, high capacity, and good cycle stability.
在一些实施例中，二次电池中正极片包括叠层贴合设置的集流体和活性材料层，活性材料层中包括三元材料、导电剂与粘结剂等。In some embodiments, the positive electrode sheet in the secondary battery includes a laminated current collector and an active material layer, and the active material layer includes a ternary material, a conductive agent, a binder, and the like.
在一些实施例中，将正极材料制成正极片的制备过程为：将三元正极材料、导电剂与粘结剂混合得到电极浆料，将电极浆料涂布在集流体上，经干燥、辊压、模切等步骤制备得到正极片。In some embodiments, the preparation process of making the positive electrode material into the positive electrode sheet is: mixing the ternary positive electrode material, the conductive agent and the binder to obtain the electrode slurry, coating the electrode slurry on the current collector, drying, The positive electrode sheet is prepared by rolling, die-cutting and other steps.
在一些实施例中，正极集流体包括但不限于铜箔、铝箔中的任意一种。In some embodiments, the positive electrode current collector includes, but is not limited to, any one of copper foil and aluminum foil.
在一些实施例中，粘结剂在电极浆料中的含量为2wt％-4wt％。具体实施例中，粘结剂的含量可以是2wt％、3wt％、4wt％等典型而非限制的含量。具体实施例中，粘结剂包括聚偏氯乙烯、可溶性聚四氟乙烯、丁苯橡胶、羟丙基甲基纤维素、甲基纤维素、羧甲基纤维素、聚乙烯醇、丙烯腈共聚物、海藻酸钠、壳聚糖和壳聚糖衍生物中的一种或多种。在一些实施例中，导电剂在电极浆料中的含量为3wt％-5wt％。具体实施例中，导电剂的含量可以是3wt％、4wt％、5wt％等典型而非限制的含量。具体实施例中，导电剂包括石墨、碳黑、乙炔黑、石墨烯、碳纤维、C60和碳纳米管中的一种或多种。In some embodiments, the content of the binder in the electrode slurry is 2wt%-4wt%. In a specific embodiment, the content of the binder may be 2wt%, 3wt%, 4wt% and other typical and non-limiting contents. In a specific embodiment, the binder includes polyvinylidene chloride, soluble polytetrafluoroethylene, styrene-butadiene rubber, hydroxypropyl methyl cellulose, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, acrylonitrile copolymer One or more of substances, sodium alginate, chitosan and chitosan derivatives. In some embodiments, the content of the conductive agent in the electrode paste is 3wt%-5wt%. In a specific embodiment, the content of the conductive agent may be 3wt%, 4wt%, 5wt% and other typical and non-limiting contents. In a specific embodiment, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fiber, C60 and carbon nanotube.
本申请实施例二次电池可以是锂离子电池或锂金属电池等体系。The secondary battery in the embodiment of the present application may be a system such as a lithium ion battery or a lithium metal battery.
本申请对实施例二次电池中负极片、电解液、隔膜等不作具体限定，可适用于任意电池体系。This application does not specifically limit the negative electrode sheet, electrolyte, separator, etc. in the secondary battery of the embodiment, and can be applied to any battery system.
为使本申请上述实施细节和操作能清楚地被本领域技术人员理解，以及本申请实施例三元正极前驱体材料及其制备方法、三元正极材料、二次电池的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。In order to make the above-mentioned implementation details and operations of the present application clearly understood by those skilled in the art, as well as the embodiment of the present application, the embodiment of the ternary positive electrode precursor material and its preparation method, the ternary positive electrode material, and the remarkable performance of the progress of the secondary battery, The above technical solutions are illustrated below through multiple embodiments.
实施例1Example 1
一种六方层状结构的Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料，其制备包括步骤： A Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with a hexagonal layered structure, the preparation of which comprises the steps of:
①按照Ni 0.67Co 0.05Mn 0.28O化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为163.7g/L、12.3g/L、64.0g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.67 Co 0.05 Mn 0.28 O, after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 163.7g/L, 12.3g/L, 64.0g/L.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为710℃、氧气质量百分含量为5.0％的条件下焙烧，破碎得到Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料，其晶体结构为六方层状结构，其不同拍摄尺寸的形貌如附图1和2电镜图所示。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 710°C and an oxygen content of 5.0% by mass, and crushed to obtain Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material, its crystal structure is a hexagonal layered structure, and its morphologies of different photographed sizes are shown in the attached electron microscope images 1 and 2.
一种LiNi 0.67Co 0.05Mn 0.28O 2三元正极材料，其制备过程包括步骤： A kind of LiNi 0.67 Co 0.05 Mn 0.28 O ternary cathode material, its preparation process comprises steps:
③将Ni 0.67Co 0.05Mn 0.28O和LiOH按摩尔比为1.05:1称取对应量；混合后在温度为600℃的条件下烧结处理时间为8小时，破碎得到LiNi 0.67Co 0.05Mn 0.28O 2三元正极材料，其形貌图如附图4所示。 ③Weigh the corresponding amount of Ni 0.67 Co 0.05 Mn 0.28 O and LiOH with a molar ratio of 1.05:1; after mixing, sinter at 600°C for 8 hours and crush to obtain LiNi 0.67 Co 0.05 Mn 0.28 O 2 The topography of the ternary cathode material is shown in Figure 4.
一种锂离子电池，其制备步骤包括：A kind of lithium ion battery, its preparation step comprises:
④正极片制备：按LiNi 0.67Co 0.05Mn 0.28O 2三元正极材料：导电剂(乙炔黑)：粘结剂(PVDF)的配比为85wt.％：10wt.％：5wt.％，称取后混合研磨。然后，添加N-甲基吡咯烷酮(NMP)溶剂配置成均匀的正极浆料。将正极浆料采用刮刀均匀涂布在铝箔上，干燥即得到可直接组装到电池中的正极电极片。 ④Preparation of positive electrode sheet: according to LiNi 0.67 Co 0.05 Mn 0.28 O ternary positive electrode material: conductive agent (acetylene black): binder (PVDF) proportioning is 85wt.%: 10wt.%: 5wt.%, weigh Post-mixing and grinding. Then, N-methylpyrrolidone (NMP) solvent was added to form a uniform positive electrode slurry. The positive electrode slurry is evenly coated on the aluminum foil with a doctor blade, and dried to obtain a positive electrode sheet that can be directly assembled into a battery.
⑧电池组装：在高纯氩气氛的手套箱中，将准备好的正极片组装到型号为CR2025的纽扣式电池中，组装成以锂为对电极的扣式电池，用于后续电化学性能测试。其中，隔膜为聚烯烃多孔膜，电解液为碳酸乙烯酯。⑧Battery assembly: In a glove box with a high-purity argon atmosphere, assemble the prepared positive electrode sheet into a CR2025 button-type battery, and assemble it into a button-type battery with lithium as the counter electrode for subsequent electrochemical performance tests . Wherein, the diaphragm is a polyolefin porous film, and the electrolyte is ethylene carbonate.
实施例2Example 2
一种尖晶石型的Ni 0.67Co 0.05Mn 0.28O 1.02三元正极前驱体材料，其制备包括步骤： A spinel-type Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary positive electrode precursor material, the preparation of which comprises the steps of:
①按照Ni 0.67Co 0.05Mn 0.28O 1.02化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为68.2g/L、5.1g/L、26.7g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.67 Co 0.05 Mn 0.28 O 1.02 , after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt The concentrations of salt and manganese salt were 68.2g/L, 5.1g/L, and 26.7g/L, respectively.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为740℃、氧气质量百分含量为11.0％的条件下焙烧，破碎得到Ni 0.67Co 0.05Mn 0.28O 1.02三元正极前驱体材料，其晶体结构为尖晶石型。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 740°C and an oxygen mass percentage of 11.0%, and crushed to obtain Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary positive electrode precursor material, its crystal structure is spinel type.
一种LiNi 0.67Co 0.05Mn 0.28O 2三元正极材料，其与实施例1的区别在于：三元正极材料由实施例2尖晶石型的Ni 0.67Co 0.05Mn 0.28O 1.02三元正极前驱体材料制得。 A LiNi 0.67 Co 0.05 Mn 0.28 O 2 ternary positive electrode material, the difference from Example 1 is that the ternary positive electrode material is made of spinel-type Ni 0.67 Co 0.05 Mn 0.28 O 1.02 ternary positive electrode precursor Material made.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用实施例2制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 2.
实施例3Example 3
一种八面体型结构的Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料，其制备包括步骤： A Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with an octahedral structure, the preparation of which comprises the steps of:
①按照Ni 0.67Co 0.05Mn 0.28O化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为95.5g/L、7.15g/L、37.35g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.67 Co 0.05 Mn 0.28 O, after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 95.5g/L, 7.15g/L, 37.35g/L.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为700℃、氧气质量百分含量为7.0％的条件下焙烧，破碎得到Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料，其晶体结构为八面体型结构。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 700°C and an oxygen mass percentage of 7.0%, and crushed to obtain Ni 0.67 Co 0.05 Mn 0.28 The O ternary positive electrode precursor material has an octahedral crystal structure.
一种LiNi 0.67Co 0.05Mn 0.28O 2三元正极材料，其与实施例1的区别在于：三元正极材料由实施例3八面体型结构的Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料制得。 A LiNi 0.67 Co 0.05 Mn 0.28 O ternary positive electrode material, which differs from Example 1 in that: the ternary positive electrode material is made of Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with octahedral structure in Example 3 be made of.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片材采用实施例3制 备的三元正极材料。A kind of lithium ion battery, and its difference with embodiment 1 is: positive electrode sheet adopts the ternary positive electrode material prepared in embodiment 3 in the lithium ion battery.
实施例4Example 4
一种立方体型结构的Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料，其制备包括步骤： A kind of Ni 0.67 Co 0.05 Mn 0.28 O ternary cathode precursor material of cubic structure, its preparation comprises steps:
①按照Ni 0.67Co 0.05Mn 0.28O化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为95.5g/L、7.15g/L、37.35g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.67 Co 0.05 Mn 0.28 O, after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 95.5g/L, 7.15g/L, 37.35g/L.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为680℃、氧气质量百分含量为5.0％的条件下焙烧，破碎得到Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料，其晶体结构为立方体型。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 680°C and an oxygen content of 5.0% by mass, and crushed to obtain Ni 0.67 Co 0.05 Mn 0.28 The O ternary positive electrode precursor material has a cubic crystal structure.
一种LiNi 0.67Co 0.05Mn 0.28O 2三元正极材料，其与实施例1的区别在于：三元正极材料由实施例4立方体型结构的Ni 0.67Co 0.05Mn 0.28O三元正极前驱体材料制得。 A LiNi 0.67 Co 0.05 Mn 0.28 O ternary positive electrode material, the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.67 Co 0.05 Mn 0.28 O ternary positive electrode precursor material with a cubic structure in Example 4 have to.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用实施例4制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 4.
实施例5Example 5
一种六方层状结构Ni 0.67Co 0.05Mn 0.28O和尖晶石型Ni 0.67Co 0.05Mn 0.28O 1.02的混合三元正极前驱体材料，其制备包括步骤： A mixed ternary cathode precursor material of hexagonal layered structure Ni 0.67 Co 0.05 Mn 0.28 O and spinel Ni 0.67 Co 0.05 Mn 0.28 O 1.02 , the preparation of which comprises the steps of:
①按照Ni 0.67Co 0.05Mn 0.28O化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为150.0g/L、11.2g/L、58.8g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.67 Co 0.05 Mn 0.28 O, after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt and manganese salt concentrations were 150.0g/L, 11.2g/L, 58.8g/L.
②在雾化风量为75m 3/h的条件下，将混合溶液雾化成液滴，并在温度为730℃、氧气质量百分含量为6.0％的条件下焙烧，破碎得到三元正极前驱体材料，其晶体结构同时包含六方层状结构Ni 0.67Co 0.05Mn 0.28O和尖晶石型Ni 0.67Co 0.05Mn 0.28O 1.02，其中，六方层状结构与尖晶石型的质量配比为7：3。其XRD测试图如附图5所示，从附图5可以看出制备的三元正极前驱体材料中同时含有层状结构峰和尖晶石结构的峰。 ②Under the condition of atomizing air volume of 75m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 730°C and an oxygen mass percentage of 6.0%, and broken to obtain a ternary positive electrode precursor material , its crystal structure contains both hexagonal layered structure Ni 0.67 Co 0.05 Mn 0.28 O and spinel Ni 0.67 Co 0.05 Mn 0.28 O 1.02 , where the mass ratio of hexagonal layered structure to spinel type is 7:3 . Its XRD test pattern is shown in accompanying drawing 5, from which it can be seen that the prepared ternary positive electrode precursor material contains peaks of layered structure and peak of spinel structure at the same time.
一种三元正极材料，其与实施例1的区别在于：三元正极材料由实施例5同时包含为六方层状结构和尖晶石型的三元正极前驱体材料制得。A ternary positive electrode material, which is different from Example 1 in that: the ternary positive electrode material is made from the ternary positive electrode precursor material of both the hexagonal layered structure and the spinel type in Example 5.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用实施例5制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 5.
实施例6Example 6
一种层状结构的Ni 0.72Co 0.03Mn 0.25O三元正极前驱体材料，其制备包括步骤： A layered Ni 0.72 Co 0.03 Mn 0.25 O ternary positive electrode precursor material, the preparation of which comprises the steps of:
①按照Ni 0.72Co 0.03Mn 0.25O化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为68.2g/L、5.1g/L、26.7g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.72 Co 0.03 Mn 0.25 O, after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt The concentrations of manganese and manganese salts were 68.2g/L, 5.1g/L, and 26.7g/L, respectively.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为700℃、氧气质量百分含量为5.0％的条件下焙烧，破碎得到Ni 0.72Co 0.03Mn 0.25O三元正极前驱体材料，其 晶体结构为层状结构。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 700°C and an oxygen mass percentage of 5.0%, and crushed to obtain Ni 0.72 Co 0.03 Mn 0.25 The O ternary positive electrode precursor material has a layered crystal structure.
一种LiNi 0.72Co 0.03Mn 0.25O 2三元正极材料，其与实施例1的区别在于：三元正极材料由实施例6层状结构的Ni 0.72Co 0.03Mn 0.25O三元正极前驱体材料制得。 A LiNi 0.72 Co 0.03 Mn 0.25 O ternary positive electrode material, the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.72 Co 0.03 Mn 0.25 O ternary positive electrode precursor material with a layered structure in Example 6 have to.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用实施例6制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 6.
实施例7Example 7
一种尖晶石型的Ni 0.72Co 0.03Mn 0.25O 1.01三元正极前驱体材料，其制备包括步骤： A spinel-type Ni 0.72 Co 0.03 Mn 0.25 O 1.01 ternary positive electrode precursor material, the preparation of which comprises the steps of:
①按照Ni 0.72Co 0.03Mn 0.25O 1.01化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为68.2g/L、5.1g/L、26.7g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.72 Co 0.03 Mn 0.25 O 1.01 , after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt The concentrations of salt and manganese salt were 68.2g/L, 5.1g/L, and 26.7g/L, respectively.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为730℃、氧气质量百分含量为11.0％的条件下焙烧，破碎得到Ni 0.72Co 0.03Mn 0.25O 1.01三元正极前驱体材料，其晶体结构为尖晶石型。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into liquid droplets, and roasted at a temperature of 730°C and an oxygen mass percentage of 11.0%, and crushed to obtain Ni 0.72 Co 0.03 Mn 0.25 O 1.01 Ternary positive electrode precursor material, its crystal structure is spinel type.
一种LiNi 0.72Co 0.03Mn 0.25O 2三元正极材料，其与实施例1的区别在于：三元正极材料由实施例7尖晶石型的Ni 0.72Co 0.03Mn 0.25O 1.01三元正极前驱体材料制得。 A LiNi 0.72 Co 0.03 Mn 0.25 O 2 ternary positive electrode material, the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.72 Co 0.03 Mn 0.25 O 1.01 ternary positive electrode precursor of the spinel type in Example 7 Material made.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用实施例7制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 7.
实施例8Example 8
一种层状结构的Ni 0.6Co 0.10Mn 0.30O三元正极前驱体材料，其制备包括步骤： A layered Ni 0.6 Co 0.10 Mn 0.30 O ternary cathode precursor material, the preparation of which comprises the steps of:
①按照Ni 0.6Co 0.10Mn 0.30O化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为68.2g/L、5.1g/L、26.7g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.6 Co 0.10 Mn 0.30 O, after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt salt The concentrations of manganese and manganese salts were 68.2g/L, 5.1g/L, and 26.7g/L, respectively.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为720℃、氧气质量百分含量为5.0％的条件下焙烧，破碎得到Ni 0.6Co 0.10Mn 0.30O三元正极前驱体材料，其晶体结构为层状结构。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 720°C and an oxygen content of 5.0% by mass, and crushed to obtain Ni 0.6 Co 0.10 Mn 0.30 The O ternary positive electrode precursor material has a layered crystal structure.
一种LiNi 0.6Co 0.10Mn 0.30O 2三元正极材料，其与实施例1的区别在于：三元正极材料由实施例6层状结构的Ni 0.6Co 0.10Mn 0.30O三元正极前驱体材料制得。 A LiNi 0.6 Co 0.10 Mn 0.30 O ternary positive electrode material, the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.6 Co 0.10 Mn 0.30 O ternary positive electrode precursor material with a layered structure in Example 6 have to.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用实施例6制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 6.
实施例9Example 9
一种尖晶石型的Ni 0.60Co 0.1Mn 0.3O 1.19三元正极前驱体材料，其制备包括步骤： A spinel-type Ni 0.60 Co 0.1 Mn 0.3 O 1.19 ternary positive electrode precursor material, the preparation of which comprises the steps of:
①按照Ni 0.60Co 0.1Mn 0.3O 1.19化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后，进行浓缩处理，得到混合溶液；其中镍盐、钴盐和锰盐的浓度分别为68.2g/L、5.1g/L、26.7g/L。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.60 Co 0.1 Mn 0.3 O 1.19 , after mixing nickel chloride solution, cobalt chloride solution and manganese chloride solution, concentrated treatment is carried out to obtain a mixed solution; wherein nickel salt, cobalt The concentrations of salt and manganese salt were 68.2g/L, 5.1g/L, and 26.7g/L, respectively.
②在雾化风量为50m 3/h的条件下，将混合溶液雾化成液滴，并在温度为750℃、氧气 质量百分含量为11.0％的条件下焙烧，破碎得到Ni 0.60Co 0.1Mn 0.3O 1.19三元正极前驱体材料，其晶体结构为尖晶石型。 ②Under the condition of atomizing air volume of 50m 3 /h, the mixed solution is atomized into droplets, and roasted at a temperature of 750°C and an oxygen mass percentage of 11.0%, and crushed to obtain Ni 0.60 Co 0.1 Mn 0.3 O 1.19 Ternary positive electrode precursor material, its crystal structure is spinel type.
一种LiNi 0.60Co 0.1Mn 0.3O 2三元正极材料，其与实施例1的区别在于：三元正极材料由实施例9尖晶石型的Ni 0.60Co 0.1Mn 0.3O 1.191三元正极前驱体材料制得。 A LiNi 0.60 Co 0.1 Mn 0.3 O 2 ternary positive electrode material, the difference from Example 1 is that the ternary positive electrode material is made of the Ni 0.60 Co 0.1 Mn 0.3 O 1.191 ternary positive electrode precursor of the spinel type in Example 9 Material made.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用实施例9制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Example 9.
对比例1Comparative example 1
一种Ni 0.67Co 0.05Mn 0.28(OH) 2三元正极前驱体材料，其制备包括步骤： A kind of Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 ternary positive electrode precursor material, its preparation comprises steps:
①按照Ni 0.67Co 0.05Mn 0.28(OH) 2化学式中金属元素的化学计量比，将氯化镍溶液、氯化钴溶液、氯化锰溶液混合后；然后与氨水、NaOH溶液按照氨镍比：0.5:1、碱镍比：2:1，添加氨水和氢氧化钠，控制反应温度55℃，PH值为12.0，反应后，分离得到Ni 0.67Co 0.05Mn 0.28(OH) 2前驱体。 ①According to the stoichiometric ratio of metal elements in the chemical formula of Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 , mix nickel chloride solution, cobalt chloride solution and manganese chloride solution; then mix with ammonia water and NaOH solution according to the ratio of ammonia to nickel: 0.5:1, alkali-nickel ratio: 2:1, add ammonia water and sodium hydroxide, control the reaction temperature at 55°C, and the pH value is 12.0. After the reaction, the Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 precursor is separated.
一种LiNi 0.67Co 0.05Mn 0.28O 2三元正极材料，其与实施例1的区别在于：三元正极材料由对比例1尖晶石型的Ni 0.67Co 0.05Mn 0.28(OH) 2三元正极前驱体材料制得。 A LiNi 0.67 Co 0.05 Mn 0.28 O 2 ternary positive electrode material, the difference from Example 1 is that the ternary positive electrode material is made of Ni 0.67 Co 0.05 Mn 0.28 (OH) 2 ternary positive electrode of the spinel type in Comparative Example 1 Precursor materials are produced.
一种锂离子电池，其与实施例1的区别在于：锂离子电池中正极片采用对比例1制备的三元正极材料。A lithium ion battery, which is different from Example 1 in that: the positive electrode sheet in the lithium ion battery uses the ternary positive electrode material prepared in Comparative Example 1.
进一步的，为了验证本申请实施例的进步性，对本申请实施例1～9和对比例1制备的三元正极前驱体材料的松散堆积密度、振实密度(TD)、粒度分别进行了测量。另外，对实施例1～9和对比例1制备的锂离子电池分别以0.1C放电，以0.1C充电到2.5V，记录首次嵌锂容量和脱锂容量，并计算首效。另外，测量各电池循环充放电50周后的容量保持率，以及1c能量密度。测试结果如下表1所示：Further, in order to verify the progress of the examples of the present application, the loose packing density, tap density (TD), and particle size of the ternary cathode precursor materials prepared in Examples 1-9 and Comparative Example 1 of the present application were measured respectively. In addition, the lithium-ion batteries prepared in Examples 1-9 and Comparative Example 1 were discharged at 0.1C and charged to 2.5V at 0.1C, and the first lithium insertion capacity and delithiation capacity were recorded, and the first effect was calculated. In addition, the capacity retention rate and 1c energy density of each battery after 50 cycles of charging and discharging were measured. The test results are shown in Table 1 below:
表1Table 1
Figure PCTCN2022104342-appb-000001
Figure PCTCN2022104342-appb-000001
Figure PCTCN2022104342-appb-000002
Figure PCTCN2022104342-appb-000002
由上述测试结果可知，本申请实施例1～9制备的三元正极氧化物前驱体材料，具有相对较高的松散堆积密度和振实密度；而对比例1制备的三元正极氢氧化物材料为二次颗粒，其松散堆积密度、振实密度低于本申请实施例，说明本申请实施例制备的三元氧化物前驱体有更好的密度，结构稳定性高。另外，相对于对比例1氢氧化物前驱体材料制备的锂离子电池，本申请实施例1～9制备的锂离子电池表现出更高的能量密度、首效以及循环稳定性。From the above test results, it can be seen that the ternary positive electrode oxide precursor materials prepared in Examples 1 to 9 of the present application have relatively high loose packing density and tap density; while the ternary positive electrode hydroxide material prepared in Comparative Example 1 It is a secondary particle, and its loose packing density and tap density are lower than those in the examples of the present application, indicating that the ternary oxide precursor prepared in the examples of the present application has better density and high structural stability. In addition, compared with the lithium-ion battery prepared from the hydroxide precursor material in Comparative Example 1, the lithium-ion batteries prepared in Examples 1-9 of the present application exhibit higher energy density, first effect and cycle stability.
以上仅为本申请的可选实施例而已，并不用于限制本申请。对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。The above are only optional embodiments of the application, and are not intended to limit the application. For those skilled in the art, various modifications and changes may occur in this application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included within the scope of the claims of the present application.

Claims (20)

  1. 一种三元正极前驱体材料，其中，所述三元正极前驱体材料包括化学通式为Ni (1-y-z)Co yMn zO x的三元氧化物前驱体，其中，1≤x≤1.2，0.03≤y≤0.1，0.2≤z≤0.35。 A ternary positive electrode precursor material, wherein the ternary positive electrode precursor material includes a ternary oxide precursor with a general chemical formula of Ni (1-yz) Co y Mn z O x , wherein 1≤x≤ 1.2, 0.03≤y≤0.1, 0.2≤z≤0.35.
  2. 根据权利要求1所述的三元正极前驱体材料，其中，所述三元氧化物前驱体的晶体结构为六方层状结构、尖晶石型结构、立方体型结构、八面体型结构中的一种单晶结构。The ternary positive electrode precursor material according to claim 1, wherein the crystal structure of the ternary oxide precursor is one of a hexagonal layered structure, a spinel structure, a cubic structure, and an octahedral structure. a single crystal structure.
  3. 根据权利要求2所述的三元正极前驱体材料，其中，所述三元正极前驱体材料中，包括所述六方层状结构的三元氧化物前驱体、所述尖晶石型结构的三元氧化物前驱体、所述立方体型结构的三元氧化物前驱体、所述八面体型结构的三元氧化物前驱体中的至少两种。The ternary positive electrode precursor material according to claim 2, wherein the ternary positive electrode precursor material includes the ternary oxide precursor of the hexagonal layered structure, the ternary oxide precursor of the spinel structure At least two of the primary oxide precursor, the cubic structure ternary oxide precursor, and the octahedral structure ternary oxide precursor.
  4. 根据权利要求3所述的三元正极前驱体材料，其中，所述三元正极前驱体材料中包括所述六方层状结构的三元氧化物前驱体和所述尖晶石型结构的三元氧化物前驱体，且所述六方层状结构的三元氧化物前驱体和所述尖晶石型结构的三元氧化物前驱体的质量比为(50～100)：(1～50)。The ternary positive electrode precursor material according to claim 3, wherein the ternary positive electrode precursor material includes the ternary oxide precursor of the hexagonal layered structure and the ternary oxide precursor of the spinel structure. An oxide precursor, and the mass ratio of the hexagonal layered structure ternary oxide precursor to the spinel structure ternary oxide precursor is (50-100):(1-50).
  5. 根据权利要求3所述的三元正极前驱体材料，其中，所述三元正极前驱体材料中包括所述尖晶石型结构的三元氧化物前驱体和所述立方体型结构的三元氧化物前驱体，且所述尖晶石型结构的三元氧化物前驱体和所述立方体型结构的三元氧化物前驱体的质量比为(10～50)：(50～90)。The ternary positive electrode precursor material according to claim 3, wherein, the ternary oxide precursor of the spinel structure and the ternary oxide of the cubic structure are included in the ternary positive electrode precursor material and the mass ratio of the ternary oxide precursor with spinel structure to the ternary oxide precursor with cubic structure is (10-50):(50-90).
  6. 根据权利要求3所述的三元正极前驱体材料，其中，所述三元正极前驱体材料中包括所述八面体型结构的三元氧化物前驱体和所述尖晶石型结构的三元氧化物前驱体，且所述八面体型结构的三元氧化物前驱体和所述尖晶石型结构的三元氧化物前驱体的质量比为(50～80)：(15～50)。The ternary positive electrode precursor material according to claim 3, wherein the ternary positive electrode precursor material includes the ternary oxide precursor of the octahedral structure and the ternary oxide precursor of the spinel structure. An oxide precursor, and the mass ratio of the ternary oxide precursor with octahedral structure to the ternary oxide precursor with spinel structure is (50-80):(15-50).
  7. 根据权利要求3所述的三元正极前驱体材料，其中，所述三元氧化物前驱体的化学通式为Ni (1-y-z)Co yMn zO，晶体结构为六方层状结构、立方体型结构或者八面体型结构。 The ternary positive electrode precursor material according to claim 3, wherein the general chemical formula of the ternary oxide precursor is Ni (1-yz) Co y Mn z O, and the crystal structure is hexagonal layered structure, cubic type structure or octahedral structure.
  8. 根据权利要求3所述的三元正极前驱体材料，其中，所述三元氧化物前驱体的化学通式为Ni (1-y-z)Co yMn zO x，其中，x大于1；晶体结构为尖晶石型结构。 The ternary positive electrode precursor material according to claim 3, wherein the general chemical formula of the ternary oxide precursor is Ni (1-yz) Co y Mn z O x , wherein x is greater than 1; crystal structure For the spinel structure.
  9. 根据权利要求1所述的三元正极前驱体材料，其中，所述三元正极前驱体材料中，包括：Ni 0.67Co 0.05Mn 0.28O、Ni 0.67Co 0.05Mn 0.28O 1.02、Ni 0.72Co 0.03Mn 0.25O、Ni 0.72Co 0.03Mn 0.25O 1.01、Ni 0.7Co 0.04Mn 0.26O、Ni 0.65Co 0.06Mn 0.29O、Ni 0.62Co 0.08Mn 0.30O、Ni 0.60Co 0.1Mn 0.3O 1.19中的至少一种三元氧化物前驱体。 The ternary positive electrode precursor material according to claim 1, wherein the ternary positive electrode precursor material includes: Ni 0.67 Co 0.05 Mn 0.28 O, Ni 0.67 Co 0.05 Mn 0.28 O 1.02 , Ni 0.72 Co 0.03 Mn At least one of 0.25 O, Ni 0.72 Co 0.03 Mn 0.25 O 1.01 , Ni 0.7 Co 0.04 Mn 0.26 O, Ni 0.65 Co 0.06 Mn 0.29 O, Ni 0.62 Co 0.08 Mn 0.30 O, Ni 0.60 Co 0.1 Mn 0.3 O 1.19 A kind of three Oxide precursors.
  10. 根据权利要求1所述的三元正极前驱体材料，其中，所述三元氧化物前驱体的粒度50～800nm。The ternary positive electrode precursor material according to claim 1, wherein the particle size of the ternary oxide precursor is 50-800 nm.
  11. 根据权利要求1所述的三元正极前驱体材料，其中，所述三元正极前驱体材料的松散堆积密度为0.5～1.0g/cm 3。 The ternary positive electrode precursor material according to claim 1, wherein the loose packing density of the ternary positive electrode precursor material is 0.5˜1.0 g/cm 3 .
  12. 根据权利要求1所述的三元正极前驱体材料，其中，所述三元正极前驱体材料的 振实密度为1.6～2.4g/cm 3。 The ternary positive electrode precursor material according to claim 1, wherein the tap density of the ternary positive electrode precursor material is 1.6˜2.4 g/cm 3 .
  13. 根据权利要求1所述的三元正极前驱体材料，其中，所述三元正极前驱体材料的粒径D50为1.5～3.5μm。The ternary positive electrode precursor material according to claim 1, wherein the particle size D50 of the ternary positive electrode precursor material is 1.5-3.5 μm.
  14. 根据权利要求1所述的三元正极前驱体材料，其中，所述三元正极前驱体材料的宏观形貌包括：球形结构、多孔结构、立体多边形结构中的至少一种。The ternary positive electrode precursor material according to claim 1, wherein the macroscopic morphology of the ternary positive electrode precursor material includes at least one of a spherical structure, a porous structure, and a three-dimensional polygonal structure.
  15. 一种如权利要求1所述的三元正极前驱体材料的制备方法，其中，包括如下步骤：A preparation method of a ternary positive electrode precursor material as claimed in claim 1, wherein, comprising the steps of:
    将镍盐溶液、钴盐溶液、锰盐溶液混合后，进行浓缩处理，得到混合溶液；After mixing the nickel salt solution, the cobalt salt solution and the manganese salt solution, performing concentration treatment to obtain a mixed solution;
    对所述混合溶液进行雾化焙烧处理，得到三元正极前驱体材料。The mixed solution is atomized and calcined to obtain a ternary positive electrode precursor material.
  16. 如权利要求15所述的三元正极前驱体材料的制备方法，其中，所述混合溶液中，镍盐、钴盐和锰盐的浓度分别独立地为50～300g/L。The method for preparing a ternary positive electrode precursor material according to claim 15, wherein, in the mixed solution, the concentrations of nickel salt, cobalt salt and manganese salt are independently 50-300 g/L.
  17. 如权利要求15所述的三元正极前驱体材料的制备方法，其中，所述雾化焙烧处理的步骤包括：在雾化风量为20～1200m 3/h的条件下，将所述混合溶液雾化成液滴，并在温度为300～1000℃、氧气质量百分含量为1.0～13.0％的条件下焙烧，得到所述三元正极前驱体材料。 The preparation method of the ternary positive electrode precursor material according to claim 15, wherein the step of atomizing and roasting treatment comprises: atomizing the mixed solution under the condition that the atomizing air volume is 20-1200m 3 /h forming into liquid droplets, and calcining under the conditions of a temperature of 300-1000° C. and an oxygen mass percentage of 1.0-13.0%, to obtain the ternary cathode precursor material.
  18. 如权利要求15所述的三元正极前驱体材料的制备方法，其中，所述焙烧处理的时长为1～50秒。The method for preparing a ternary positive electrode precursor material according to claim 15, wherein the duration of the calcination treatment is 1-50 seconds.
  19. 如权利要求15所述的三元正极前驱体材料的制备方法，其中，所述镍盐溶液选自：氯化镍溶液、硝酸镍溶液、草酸镍溶液、硫酸镍溶液中的至少一种；The preparation method of ternary positive electrode precursor material as claimed in claim 15, wherein, the nickel salt solution is selected from: at least one of nickel chloride solution, nickel nitrate solution, nickel oxalate solution, and nickel sulfate solution;
    和/或，所述钴盐溶液选自：氯化钴溶液、硝酸钴溶液、草酸钴溶液、硫酸钴溶液中的至少一种；And/or, the cobalt salt solution is selected from at least one of: cobalt chloride solution, cobalt nitrate solution, cobalt oxalate solution, and cobalt sulfate solution;
    和/或，所述锰盐溶液选自：氯化锰溶液、硝酸锰溶液、草酸锰溶液、硫酸锰溶液中的至少一种。And/or, the manganese salt solution is selected from at least one of manganese chloride solution, manganese nitrate solution, manganese oxalate solution and manganese sulfate solution.
  20. 一种三元正极材料，其中，所述三元正极材料由包括锂源和三元正极前驱体材料的混合物经烧结处理得到，其中，所述三元正极前驱体材料包括权利要求1所述的三元正极前驱体材料。A ternary positive electrode material, wherein the ternary positive electrode material is obtained by sintering a mixture comprising a lithium source and a ternary positive electrode precursor material, wherein the ternary positive electrode precursor material comprises the Ternary cathode precursor material.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101369651A (en) * 2008-09-27 2009-02-18 浙江华友钴业股份有限公司 Novel method for preparing lithium ion battery anode ternary material LiCoxNiyMn2O2
JP2010064907A (en) * 2008-09-09 2010-03-25 Sumitomo Metal Mining Co Ltd Lithium transition metal compound oxide, method for producing the same and lithium ion secondary battery using the same
CN107585794A (en) * 2017-09-13 2018-01-16 中南大学 Tertiary cathode material, its presoma and the preparation method of the material and presoma
CN107792891A (en) * 2017-10-16 2018-03-13 深圳力合厚浦科技有限公司 A kind of method and application that cobalt-nickel-manganese oxide compound is produced with nickel cobalt manganese elemental metals
CN111129485A (en) * 2019-12-20 2020-05-08 中南大学 Single-crystal high-nickel ternary cathode material and preparation method thereof
CN114590847A (en) * 2022-02-17 2022-06-07 湖南力合厚浦科技有限公司 Ternary positive electrode precursor material, preparation method thereof and ternary positive electrode material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015182665A1 (en) * 2014-05-29 2015-12-03 住友化学株式会社 Positive electrode active material for lithium secondary batteries, positive electrode for lithium secondary batteries, and lithium secondary battery
CN110265631B (en) * 2018-06-27 2021-12-07 宁德时代新能源科技股份有限公司 Ternary cathode material, preparation method thereof and lithium ion battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010064907A (en) * 2008-09-09 2010-03-25 Sumitomo Metal Mining Co Ltd Lithium transition metal compound oxide, method for producing the same and lithium ion secondary battery using the same
CN101369651A (en) * 2008-09-27 2009-02-18 浙江华友钴业股份有限公司 Novel method for preparing lithium ion battery anode ternary material LiCoxNiyMn2O2
CN107585794A (en) * 2017-09-13 2018-01-16 中南大学 Tertiary cathode material, its presoma and the preparation method of the material and presoma
CN107792891A (en) * 2017-10-16 2018-03-13 深圳力合厚浦科技有限公司 A kind of method and application that cobalt-nickel-manganese oxide compound is produced with nickel cobalt manganese elemental metals
CN111129485A (en) * 2019-12-20 2020-05-08 中南大学 Single-crystal high-nickel ternary cathode material and preparation method thereof
CN114590847A (en) * 2022-02-17 2022-06-07 湖南力合厚浦科技有限公司 Ternary positive electrode precursor material, preparation method thereof and ternary positive electrode material

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