WO2023179245A1 - High-nickel ternary positive electrode material and preparation method therefor and application thereof - Google Patents

High-nickel ternary positive electrode material and preparation method therefor and application thereof Download PDF

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WO2023179245A1
WO2023179245A1 PCT/CN2023/075881 CN2023075881W WO2023179245A1 WO 2023179245 A1 WO2023179245 A1 WO 2023179245A1 CN 2023075881 W CN2023075881 W CN 2023075881W WO 2023179245 A1 WO2023179245 A1 WO 2023179245A1
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nickel ternary
speed
additive
cathode material
nickel
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French (fr)
Chinese (zh)
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孙国征
于建
袁徐俊
戚洪亮
孟祥鹤
罗帅
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宁波容百新能源科技股份有限公司
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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
    • C01G53/40—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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 invention relates to the technical field of high-nickel cathode materials, and more specifically, to a high-nickel ternary cathode material and its preparation method and application.
  • lithium cobalt oxide, lithium iron phosphate, lithium manganate and lithium nickel cobalt manganate ternary cathode materials are the most marketed types of materials.
  • the ternary cathode material of lithium nickel cobalt manganate has high specific capacity, cycle stability, thermal stability and low price, and has been well applied in the fields of consumer electronics and power batteries.
  • Nickel cobalt lithium manganate ternary cathode materials are divided into different types according to the proportion of nickel, cobalt and manganese content, such as 111, 523, 622 and 811.
  • the currently recognized solution is to increase the nickel content of the ternary material or increase the voltage platform.
  • the specific capacity of the ternary material When the nickel content ratio in the material is greater than 6, it is generally called a high-nickel ternary cathode material.
  • high-nickel ternary materials have greater advantages than other cathode materials in terms of energy density, they have some shortcomings that restrict the further development and application of the materials. For example, as the Ni content increases, the alkali content of the materials increases. The temperature will increase significantly, which is due to the inherent characteristics of nickel-containing ternary materials. Higher alkalinity will bring inconvenience to processing, such as causing "jelly" in the slurry. After being made into a battery, it will cause gas production problems during long cycles of charge and discharge, resulting in battery bulging, deformation, shortened cycle life, and potential safety hazards. During the synthesis process of high-nickel materials, part of Ni 2+ occupies Li + sites, forming a mixed arrangement of cations.
  • ternary materials are mostly synthesized by co-precipitation method, and the characteristic of co-precipitation is to rely on the agglomeration of nanoscale primary particles to grow into secondary particles.
  • vigorous stirring causes the disordered distribution and agglomeration of primary particles. Therefore, there are varying degrees of stress and distortion in the secondary particles, causing the material to easily form micro-cracks and thus rupture during the cycle, resulting in cycle diving and rapid DCR. Growth and gas production surge.
  • Publication No. CN110862108A discloses a Chinese patent method for improving the electrochemical performance of high-nickel ternary cathode materials through fluorine doping modification.
  • the high-nickel precursor, lithium source and lithium fluoride are fully ground and calcined to obtain fluorine-doped cathode materials.
  • High nickel ternary cathode material, through fluorine ion doping overcomes the problem of high nickel to a certain extent.
  • the defects of the ternary cathode material itself can reduce the mixing of lithium and nickel in the material and improve the stability of the material; however, the above technical solutions do not involve research on fluorine doping to improve particle strength and thereby improve cycle, DCR and gas production performance.
  • the purpose of the present invention is to provide a high-nickel ternary cathode material and its preparation method and application.
  • the present invention can enrich additives at the grain boundaries and obtain grain boundary strengthening (grain boundaries are generally fragile particles). Part, easily corroded), the ternary cathode material has excellent particle pressure resistance and good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material.
  • the invention provides a high-nickel ternary cathode material, which is prepared from a high-nickel ternary precursor, a lithium source and an additive for improving the grain strength; the additive for improving the grain strength is enriched at the grain boundaries.
  • the high-nickel ternary precursor is Nix Co y Mn 1-xy (OH) 2 , where 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.4; the lithium source is selected from lithium carbonate and/or Lithium hydroxide; the molar ratio of the high-nickel ternary precursor to the lithium source is 1: (1.02 ⁇ 1.08).
  • the additive for improving grain strength is selected from one or more oxides or fluorides of the following substances: B, Al, Ta, Ce, W, Nb, Ge, Y, Zr, Ca and Sr.
  • the mass ratio of the high-nickel ternary precursor and the additive for improving grain strength is 100: (0.1-2).
  • the invention also provides a method for preparing the high-nickel ternary cathode material described in the above technical solution, which includes the following steps:
  • step b) The mixed powder obtained in step a) is sintered, washed, dried and back-fired in sequence to obtain a high-nickel ternary cathode material.
  • the high-speed mixing time in step a) is 1h-3h; the low-speed mixing time is 0.2h-2h.
  • the sintering temperature in step b) is 450°C to 900°C, and the time is 8h to 14h; during the sintering process, additives that improve the grain strength are enriched at the grain boundaries and penetrate inward, Penetration depth is from surface to center.
  • the water washing process described in step b) is specifically:
  • the drying temperature in step b) is 80°C to 180°C and the time is 2h to 6h; the backburning temperature is 150°C to 600°C and the time is 8h to 14h.
  • the present invention also provides a lithium-ion battery, the positive electrode of which includes the high-nickel ternary positive electrode material described in the above technical solution.
  • the invention provides a high-nickel ternary cathode material and its preparation method and application;
  • the high-nickel ternary cathode material is prepared from a high-nickel ternary precursor, a lithium source and an additive for improving grain strength;
  • the additives that improve the grain strength are enriched at the grain boundaries;
  • the preparation method includes the following steps: a) After mixing the high-nickel ternary precursor and the lithium source uniformly at high speed in a ball mill, introduce the additives that improve the grain strength through low-speed mixing Additives are added to obtain a mixed powder; the speed of the high-speed mixing is 250rpm ⁇ 600rpm; the speed of the low-speed mixing is 50rpm ⁇ 200rpm; b) the mixed powder obtained in step a) is sequentially sintering, washed, dried and back-burned , to obtain high-nickel ternary cathode materials.
  • the preparation method provided by the present invention adopts specific process steps, conditions and parameters to achieve better overall interaction, which can enrich additives at grain boundaries and obtain grain boundary strengthening (grain boundaries are generally particles).
  • the relatively fragile part is easily corroded
  • the ternary cathode material has excellent particle pressure resistance and good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material.
  • the preparation method provided by the present invention has the advantages of simple process, easy operation and control, economy and environmental protection, and has broad application prospects and potential.
  • Figure 1 is an SEM (magnification 50K) image of a high-nickel cathode material with additives enriched at grain boundaries prepared in Example 1 of the present invention
  • Figure 2 is an SEM (magnification 50K) image of a relatively uniformly distributed sample prepared using the same raw materials as in Example 1;
  • Figure 3 is an SEM (magnification 50K) image prepared using the same raw materials as Example 1 but without adding additives;
  • Figure 4 is a box plot of the particle strength of the high-nickel cathode material prepared in Example 1 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 1 are relatively evenly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 2;
  • Figure 5 is an SEM (magnification: 10K) image of the high-nickel cathode material with additives enriched at the grain boundaries prepared in Example 2 of the present invention
  • Figure 6 is an SEM (magnification 50K) image of the high-nickel cathode material with additives enriched at the grain boundaries prepared in Example 2 of the present invention
  • Figure 7 is an XRD pattern of a high-nickel cathode material with additives enriched at grain boundaries prepared in Example 2 of the present invention.
  • Figure 8 is a box plot of the particle strength of the high-nickel cathode material prepared in Example 3 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 3 are relatively evenly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 4;
  • Figure 9 is a comparative chart of gas production during 7 days/70°C of high-nickel cathode materials prepared in Example 4 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 5 are relatively evenly distributed, and the high-nickel cathode materials prepared without additives in Comparative Example 6. ;
  • Figure 10 shows the overall performance of the high-nickel cathode material prepared in Example 5 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 7 are relatively evenly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 8 under 1C/1C charge and discharge conditions. Comparison chart of electrical cycle capacity retention rate;
  • Figure 11 is a flow chart for preparing the high-nickel cathode material unevenly coated with additives of the present invention.
  • the invention provides a high-nickel ternary cathode material, which is prepared from a high-nickel ternary precursor, a lithium source and an additive for improving the grain strength; the additive for improving the grain strength is enriched at the grain boundary.
  • the present invention enriches the additives at the grain boundaries (specifically, in the SEM image, the particle concentration or mass or area or number of the additives enriched at the grain boundaries is greater than the additives enriched on the crystal planes), Thereby improving the particle strength and improving the circulation, DCR and gas production performance caused by particle breakage during the circulation process of the cathode material.
  • the high-nickel ternary precursor is preferably Nix Co y Mn 1-xy (OH) 2 , where 0.6 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.4.
  • the present invention has no special restrictions on the source of the high-nickel ternary precursor, which can be obtained by technical means well known to those skilled in the art, such as co-precipitation method.
  • the lithium source is preferably lithium carbonate and/or lithium hydroxide, and more preferably is lithium hydroxide.
  • the present invention has no special restrictions on the source of the lithium source, and commercially available products well known to those skilled in the art can be used.
  • the molar ratio of the high-nickel ternary precursor and the lithium source is preferably 1: (1.02-1.08), and more preferably 1:1.05.
  • the additive for improving the grain strength can improve the grain strength and improve the particle pressure resistance, and is preferably selected from one or more oxides or fluorides of the following substances: B, Al, Ta, Ce , W, Nb, Ge, Y, Zr, Ca and Sr, more preferably B oxide, Al oxide, Ta oxide, Ce oxide, W oxide, Nb oxide, Ge One or more of the oxides, Y oxides, Zr oxides, Ca oxides and Sr oxides, more preferably nano boron trioxide, aluminum fluoride, tantalum oxide, cerium oxide or Tungsten trioxide.
  • the present invention has no special restrictions on the source of the additive for improving grain strength, and commercially available products well known to those skilled in the art can be used.
  • the mass ratio of the high-nickel ternary precursor and the additive for improving grain strength is preferably 100: (0.1-2), and more preferably 100: (0.1-0.5).
  • the invention provides a high-nickel ternary cathode material that is doped to improve particle strength.
  • the preparation method includes: first mixing the high-nickel ternary precursor and the lithium source uniformly at high speed, and adding additives through low-speed mixing to make the additives at the grain boundaries. After enrichment, sintering, washing, drying and back-burning are performed to obtain the prepared sample; after the sample is heat treated, the additives are enriched at the grain boundaries to obtain grain boundary strengthening (grain boundaries are generally fragile parts of particles and are easily Corrosion), particle pressure resistance, and ternary cathode materials with good chemical stability and thermal stability have significantly improved the cycle, DCR and gas production performance of the cathode material.
  • the invention also provides a method for preparing a high-nickel ternary cathode material, which includes the following steps:
  • step b) The mixed powder obtained in step a) is sintered, washed, dried and back-fired in sequence to obtain a high-nickel ternary cathode material.
  • the high-nickel ternary precursor and the lithium source are first mixed evenly at high speed in a ball mill, and then passed through a low-temperature Rapid mixing introduces additives that improve the grain strength to obtain mixed powder.
  • the high-nickel ternary precursor is preferably Nix Co y Mn 1-xy (OH) 2 , where 0.6 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.4.
  • the present invention has no special restrictions on the source of the high-nickel ternary precursor, which can be obtained by technical means well known to those skilled in the art, such as co-precipitation method.
  • the lithium source is preferably lithium carbonate and/or lithium hydroxide, and more preferably is lithium hydroxide.
  • the present invention has no special restrictions on the source of the lithium source, and commercially available products well known to those skilled in the art can be used.
  • the molar ratio of the high-nickel ternary precursor and the lithium source is preferably 1: (1.02-1.08), and more preferably 1:1.05.
  • the ball mill tank of the ball mill is preferably a polytetrafluoroethylene ball mill tank or a polyurethane ball mill tank.
  • the speed of the high-speed mixing is 250 to 600 rpm, preferably 300 rpm; the time of the high-speed mixing is preferably 1 to 3 hours, and more preferably 2 hours.
  • the speed of high-speed mixing is greater than that of low-speed mixing.
  • the low-speed mixing speed is 50 rpm to 200 rpm, preferably 150 rpm; the low-speed mixing time is preferably 0.2 h to 2 h, and more preferably 0.5 h.
  • the additive for improving the grain strength can improve the grain strength and improve the particle pressure resistance, and is preferably selected from the group consisting of B oxide, Al oxide, Ta oxide, Ce oxide, and W oxide.
  • B oxide Al oxide
  • Ta oxide Ta oxide
  • Ce oxide Ce oxide
  • W oxide W oxide
  • oxides Nb oxides, Ge oxides, Y oxides, Zr oxides, Ca oxides and Sr oxides, more preferably nano boron trioxide, fluorine aluminum oxide, tantalum oxide, cerium oxide or tungsten trioxide.
  • oxides, Nb oxides, Ge oxides, Y oxides, Zr oxides, Ca oxides and Sr oxides more preferably nano boron trioxide, fluorine aluminum oxide, tantalum oxide, cerium oxide or tungsten trioxide.
  • the present invention has no special restrictions on the source of the additive for improving grain strength, and commercially available products well known to those skilled in the art can be used.
  • the mass ratio of the high-nickel ternary precursor and the additive for improving grain strength is preferably 100: (0.1-2), and more preferably 100: (0.1-0.5).
  • the present invention sequentially performs sintering, water washing, drying and back-burning on the obtained mixed powder to obtain a high-nickel ternary cathode material.
  • the sintering temperature is preferably 450°C to 900°C, and the sintering time is preferably 8h to 14h; in a preferred embodiment of the invention, the sintering process is preferably:
  • the additives that improve the grain strength form a certain concentration at the grain boundaries and penetrate inward, and the penetration depth is from the surface to the center.
  • the water washing process is preferably as follows:
  • the mass ratio of the sintered product and water is preferably 1: (0.5-2), and more preferably 1:1.
  • the drying temperature is preferably 80°C to 180°C, more preferably 140°C, and the time is preferably 2h to 6h, more preferably 5h; the drying method of drying in an oven, which is well known to those skilled in the art, is used That’s it.
  • the temperature of the back-burning is preferably 150°C to 600°C, and the time is preferably 8h-14h; in a preferred embodiment of the invention, the back-burning process is preferably:
  • the preparation method provided by the present invention preferably includes the following steps:
  • Step 1 Put the high-nickel ternary precursor of the lithium-ion battery and the lithium source into a ball mill and mix at high speed for 1 to 3 hours, then add additives to improve the grain strength, and mix at low speed for 0.2 to 2 hours to obtain a mixed powder;
  • Step 2 Heat the mixed powder obtained in Step 1 to a temperature of 450 to 900°C in an oxygen atmosphere, and keep it at this temperature for 8 to 14 hours to obtain a high-nickel ternary cathode material sintered material, whose additives form a certain amount at the grain boundaries. The enrichment and inward penetration;
  • Step 3 Add the ternary cathode material sintered material obtained in step 2 into a beaker with water, wash it with water for 2 to 30 minutes, then place the washed material in a centrifuge device for centrifugation, and finally place the centrifuged material in a drying device. Medium heating and drying; finally, the dried powder is heated to a temperature of 150 to 600°C in an oxygen atmosphere, and kept at this temperature for 8 to 14 hours to obtain a high-nickel ternary cathode material that is doped to increase particle strength.
  • the preparation method provided by the invention adopts specific process steps, conditions and parameters to achieve overall better interaction, which can enrich the additives at the grain boundaries and obtain grain boundary strengthening (grain boundaries are generally relatively fragile parts of particles and are easily Corrosion), particle pressure resistance is excellent, and the ternary cathode material has good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material; at the same time, the preparation method provided by the invention has a process It has the advantages of simplicity, easy operation and control, economy and environmental protection, and has broad application prospects and potential.
  • the present invention also provides a lithium-ion battery, the positive electrode of which includes the high-nickel ternary positive electrode material described in the above technical solution.
  • the lithium-ion battery adopts a technical solution for preparing a positive electrode material into a lithium-ion battery that is well known to those skilled in the art, wherein the positive electrode material is a high-nickel ternary positive electrode material described in the above-mentioned technical solution of the present invention. , thereby realizing the application of this high-nickel ternary cathode material.
  • the invention provides a high-nickel ternary cathode material and a preparation method thereof; the preparation method includes the following steps: a) mix the high-nickel ternary precursor and the lithium source uniformly in a ball mill at high speed, and introduce improved crystals through low-speed mixing. particle strength additives to obtain a mixed powder; the high-speed mixing speed is 250rpm to 600rpm; the low-speed mixing speed is 50rpm to 200rpm; b) the mixed powder obtained in step a) is sequentially sintered, washed, and dried and back-burning to obtain high-nickel ternary cathode materials.
  • the preparation method provided by the present invention adopts specific process steps, conditions and parameters to achieve better overall interaction, which can enrich additives at grain boundaries and obtain grain boundary strengthening (grain boundaries are generally particles).
  • the relatively fragile part is easily corroded
  • the ternary cathode material has excellent particle pressure resistance and good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material.
  • the preparation method provided by the present invention has the advantages of simple process, easy operation and control, economy and environmental protection, and has broad application prospects and potential.
  • a relatively uniformly distributed sample was prepared using the same raw materials as in Example 1.
  • the sample was prepared using the same raw materials as in Example 1 but without adding the additive tungsten trioxide.
  • FIG. 1 is an SEM (magnification 50K) image of a relatively evenly distributed sample prepared using the same raw materials as Example 1
  • Figure 3 is an SEM (magnification 50K) image prepared using the same raw materials as Example 1 but without adding additives.
  • the box plot of the particle strength of the high-nickel cathode material prepared in Example 1 of the present invention is enriched at the grain boundaries, the additives in Comparative Example 1 are relatively uniformly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 2 is shown in Figure 4.
  • the SEM (magnification 10K) picture of the high-nickel cathode material prepared in Example 2 of the present invention is shown in Figure 5.
  • the additive prepared in Example 2 of the present invention is enriched in the grain boundaries.
  • the SEM (magnification 50K) picture of the assembled high-nickel cathode material is shown in Figure 6; the doping element Ta in the picture is enriched at the grain boundaries.
  • the XRD pattern of the high-nickel cathode material with additives enriched at the grain boundaries prepared in Example 2 of the present invention is shown in Figure 7.
  • a relatively uniformly distributed sample was prepared using the same raw materials as in Example 3.
  • the sample was prepared using the same raw materials as in Example 3 but without adding the additive tantalum oxide.
  • Comparative Example 3 is prepared using the same raw materials as Example 3 and has a relatively uniform distribution
  • Comparative Example 4 uses the same raw materials as Example 3 but does not add additives.
  • the box plot of the particle strength of the prepared high-nickel cathode material is shown in Figure 8.
  • a relatively uniformly distributed sample was prepared using the same raw materials as in Example 4.
  • a sample was prepared using the same raw materials as in Example 4 but without adding the additive cerium oxide.
  • a relatively uniformly distributed sample was prepared using the same raw materials as in Example 5.
  • the sample was prepared using the same raw materials as in Example 5 but without adding additive nanoboron trioxide.
  • the high-nickel positive electrode materials obtained in Examples 1 to 5 were assembled into button batteries using technical solutions for preparing positive electrode materials into lithium-ion batteries that are well known to those skilled in the art.
  • the specific method is: adding the prepared additives at the grain boundaries Weigh the enriched high-nickel cathode material, acetylene black and polyvinylidene fluoride (PVDF) at a mass ratio of 94:3:3, mix evenly, add NMP and stir for 2 hours to form a viscous slurry, which is evenly coated on the aluminum foil Then, vacuum bake at 80°C, press into sheets, and cut the positive electrode sheet with a diameter of 14mm; use a pure lithium sheet with a diameter of 16mm as the negative electrode sheet, and use a mixed solution of 1mol/LLiPF 6 + DEC/EC (volume ratio 1:1) is the electrolyte, polyCelgard propylene microporous membrane is used as the separator, and a button cell is assembled in an argon-filled glove box.
  • Comparative Example 5 is prepared using the same raw materials as Example 4 and has a relatively uniform distribution
  • Comparative Example 6 uses the same raw materials as Example 4 but does not add additives.
  • the comparison chart of gas production after 7 days/70°C of the prepared high-nickel cathode material is shown in Figure 9.
  • Example 5 of the present invention After testing, the additives prepared in Example 5 of the present invention are enriched at the grain boundaries, the additives prepared in Comparative Example 7 using the same raw materials as Example 5 are relatively evenly distributed, and the additives prepared in Comparative Example 8 using the same raw materials as Example 5 but without addition
  • Figure 10 The comparison chart of the full electrical cycle capacity retention rate of high-nickel cathode materials prepared with additives under 1C/1C charge and discharge conditions is shown in Figure 10.
  • the present invention can effectively dope the cathode material, which is specifically reflected in the enrichment of additives at the grain boundaries of particles (see attached figures 1 to 3 and 5 to 6 for details), thereby improving the grain boundary strength. and corrosion resistance, thereby greatly improving the voltage resistance of the cathode material particles (for specific supporting data, please refer to the examples and effect drawings), so that the cathode material can better maintain the integrity of the particles during the cycle, thereby avoiding cycles
  • the process's circulation, DCR and gas production performance deteriorate sharply due to particle breakage; and the effect diagram shows that the additives are enriched at the grain boundaries, the additives are relatively uniformly distributed, and the pressure resistance performance of the particles corresponding to no additives decreases in sequence.
  • the cycle retention rate for 300 cycles also decreases successively, indicating that the preparation method provided by the present invention can indeed improve the particle withstand voltage through enrichment of additives at the grain boundaries, thereby improving the cycle performance of the cathode material.
  • Enrichment mentioned in the present invention is defined as: on the SEM image, the particle concentration or mass or area or number of the additives enriched at the grain boundaries is greater than that of the additives enriched on the crystal plane; enrichment Some additives at the grain boundaries will also penetrate into the formation of the positive electrode layered structure. The amount of penetration is determined by the characteristics of the additives and the sintering state. The depth of additive penetration is from the surface layer to the center.

Abstract

The present invention provides a high-nickel ternary positive electrode material and a preparation method therefor and an application thereof. The high-nickel ternary positive electrode material is prepared from a high-nickel ternary precursor, a lithium source, and an additive for improving grain strength. The additive for improving the grain strength is enriched at a grain boundary. The preparation method comprises the following steps: a) uniformly mixing a high-nickel ternary precursor and a lithium source in a ball mill at a high speed, and then introducing an additive for improving grain strength by means of low-speed mixing to obtain mixed powder; the speed of the high-speed mixing being 250 rpm-600 rpm, and the speed of the low-speed mixing being 50 rpm-200 rpm; and b) sintering, washing, drying and back-burning the mixed powder obtained in step a) in sequence to obtain the high-nickel ternary positive electrode material. Compared with the prior art, in the present invention, the additive can be enriched at the grain boundary, and the ternary positive electrode material which is strengthened in grain boundary, excellent in particle pressure resistance and good in chemical stability and thermal stability is obtained, so that the cycle performance, the DCR performance and the gas production performance of the positive electrode material are remarkably improved.

Description

一种高镍三元正极材料及其制备方法和应用A high-nickel ternary cathode material and its preparation method and application
本申请要求于2022年3月21日提交中国专利局、申请号为202210277545.1、发明名称为“一种高镍三元正极材料及其制备方法和应用”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 submitted to the China Patent Office on March 21, 2022, with the application number 202210277545.1 and the invention title "A high-nickel ternary cathode material and its preparation method and application", and its entire content incorporated herein by reference.
技术领域Technical field
本发明涉及高镍正极材料技术领域，更具体地说，是涉及一种高镍三元正极材料及其制备方法和应用。The present invention relates to the technical field of high-nickel cathode materials, and more specifically, to a high-nickel ternary cathode material and its preparation method and application.
背景技术Background technique
当前，钴酸锂、磷酸铁锂、锰酸锂和镍钴锰酸锂三元正极材料是市场化程度最高的几类材料。其中镍钴锰酸锂三元正极材料具有较高的比容量、循环稳定性、热稳定性和较低的价格，在消费电子产品和动力电池领域均取得了良好的应用。镍钴锰酸锂三元正极材料根据镍、钴、锰含量的比例又分为111、523、622和811等不同类型，目前公认方案是提升三元材料镍元素的含量或者提高电压平台来提升三元材料的比容量，当材料中镍含量比例大于6时，一般称为高镍三元正极材料。Currently, lithium cobalt oxide, lithium iron phosphate, lithium manganate and lithium nickel cobalt manganate ternary cathode materials are the most marketed types of materials. Among them, the ternary cathode material of lithium nickel cobalt manganate has high specific capacity, cycle stability, thermal stability and low price, and has been well applied in the fields of consumer electronics and power batteries. Nickel cobalt lithium manganate ternary cathode materials are divided into different types according to the proportion of nickel, cobalt and manganese content, such as 111, 523, 622 and 811. The currently recognized solution is to increase the nickel content of the ternary material or increase the voltage platform. The specific capacity of the ternary material. When the nickel content ratio in the material is greater than 6, it is generally called a high-nickel ternary cathode material.
尽管高镍三元材料在能量密度方面相比于其他几种正极材料有较大优势，但其存在的一些缺陷制约着材料的进一步发展与应用，例如：随着Ni含量的提高，材料的碱度会大幅提升，这是含镍三元材料固有的特性所致。较高的碱度，会给加工带来不便，如引起浆料“果冻”。做成电池后，会在充放电长循环过程中引起产气问题，导致电池鼓胀、变形、循环寿命缩短，产生安全隐患。高镍材料在合成过程中部分Ni2+占据Li+位，形成阳离子混排。目前三元材料多采用共沉淀方法合成，而共沉淀的特点就是依靠纳米级一次粒子团聚长大成二次粒子。在共沉淀过程中，剧烈搅拌导致一次粒子无序分布团聚，因此在二次粒子中存在不同程度的应力和畸变，导致材料容易形成微裂纹，从而在循环过程中破裂，导致循环跳水、DCR快速增长和产气骤增。Although high-nickel ternary materials have greater advantages than other cathode materials in terms of energy density, they have some shortcomings that restrict the further development and application of the materials. For example, as the Ni content increases, the alkali content of the materials increases. The temperature will increase significantly, which is due to the inherent characteristics of nickel-containing ternary materials. Higher alkalinity will bring inconvenience to processing, such as causing "jelly" in the slurry. After being made into a battery, it will cause gas production problems during long cycles of charge and discharge, resulting in battery bulging, deformation, shortened cycle life, and potential safety hazards. During the synthesis process of high-nickel materials, part of Ni 2+ occupies Li + sites, forming a mixed arrangement of cations. At present, ternary materials are mostly synthesized by co-precipitation method, and the characteristic of co-precipitation is to rely on the agglomeration of nanoscale primary particles to grow into secondary particles. During the co-precipitation process, vigorous stirring causes the disordered distribution and agglomeration of primary particles. Therefore, there are varying degrees of stress and distortion in the secondary particles, causing the material to easily form micro-cracks and thus rupture during the cycle, resulting in cycle diving and rapid DCR. Growth and gas production surge.
公开号为CN110862108A的公开了一种中国专利通过掺杂氟改性提高高镍三元正极材料电化学性能的方法，其将高镍前驱体、锂源和氟化锂充分研磨、煅烧得到氟掺杂高镍三元正极材料，通过氟离子掺杂，一定程度上克服了高镍 三元正极材料本身存在的缺陷，可以使得材料的锂镍混排降低，改善材料的稳定性；但上述技术方案没有涉及氟掺杂提高颗粒强度从而提高循环、DCR和产气性能等研究。Publication No. CN110862108A discloses a Chinese patent method for improving the electrochemical performance of high-nickel ternary cathode materials through fluorine doping modification. The high-nickel precursor, lithium source and lithium fluoride are fully ground and calcined to obtain fluorine-doped cathode materials. High nickel ternary cathode material, through fluorine ion doping, overcomes the problem of high nickel to a certain extent. The defects of the ternary cathode material itself can reduce the mixing of lithium and nickel in the material and improve the stability of the material; however, the above technical solutions do not involve research on fluorine doping to improve particle strength and thereby improve cycle, DCR and gas production performance.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供一种高镍三元正极材料及其制备方法和应用，本发明能够使添加剂在晶界处富集，得到晶界强化(晶界一般是颗粒比较脆弱的部分，易被腐蚀)、颗粒耐压性能较优兼备化学稳定性、热稳定性良好的三元正极材料，使得正极材料的循环、DCR和产气性能得到明显的改善。In view of this, the purpose of the present invention is to provide a high-nickel ternary cathode material and its preparation method and application. The present invention can enrich additives at the grain boundaries and obtain grain boundary strengthening (grain boundaries are generally fragile particles). Part, easily corroded), the ternary cathode material has excellent particle pressure resistance and good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material.
本发明提供了一种高镍三元正极材料，由高镍三元前驱体、锂源和改善晶粒强度的添加剂制备而成；所述改善晶粒强度的添加剂在晶界处富集。The invention provides a high-nickel ternary cathode material, which is prepared from a high-nickel ternary precursor, a lithium source and an additive for improving the grain strength; the additive for improving the grain strength is enriched at the grain boundaries.
优选的，所述高镍三元前驱体为NixCoyMn1-x-y(OH)2，其中，0.6≤x≤1，0≤y≤0.4；所述锂源选自碳酸锂和/或氢氧化锂；所述高镍三元前驱体和锂源的摩尔比为1：(1.02～1.08)。Preferably, the high-nickel ternary precursor is Nix Co y Mn 1-xy (OH) 2 , where 0.6≤x≤1, 0≤y≤0.4; the lithium source is selected from lithium carbonate and/or Lithium hydroxide; the molar ratio of the high-nickel ternary precursor to the lithium source is 1: (1.02~1.08).
优选的，所述改善晶粒强度的添加剂选自下列物质的氧化物或氟化物的一种或多种：B、Al、Ta、Ce、W、Nb、Ge、Y、Zr、Ca和Sr。Preferably, the additive for improving grain strength is selected from one or more oxides or fluorides of the following substances: B, Al, Ta, Ce, W, Nb, Ge, Y, Zr, Ca and Sr.
优选的，所述高镍三元前驱体和改善晶粒强度的添加剂的质量比为100：(0.1～2)。Preferably, the mass ratio of the high-nickel ternary precursor and the additive for improving grain strength is 100: (0.1-2).
本发明还提供了一种上述技术方案所述的高镍三元正极材料的制备方法，包括以下步骤：The invention also provides a method for preparing the high-nickel ternary cathode material described in the above technical solution, which includes the following steps:
a)将高镍三元前驱体和锂源在球磨机中高速混合均匀后，通过低速混合引入改善晶粒强度的添加剂，得到混合粉料；所述高速混合的速度为250rpm～600rpm；所述低速混合的速度为50rpm～200rpm；a) After mixing the high-nickel ternary precursor and the lithium source uniformly in a ball mill at high speed, an additive to improve the grain strength is introduced through low-speed mixing to obtain a mixed powder; the speed of the high-speed mixing is 250rpm to 600rpm; the low-speed The mixing speed is 50rpm~200rpm;
b)将步骤a)得到的混合粉料依次进行烧结、水洗、干燥和返烧，得到高镍三元正极材料。b) The mixed powder obtained in step a) is sintered, washed, dried and back-fired in sequence to obtain a high-nickel ternary cathode material.
优选的，步骤a)中所述高速混合的时间为1h～3h；所述低速混合的时间为0.2h～2h。Preferably, the high-speed mixing time in step a) is 1h-3h; the low-speed mixing time is 0.2h-2h.
优选的，步骤b)中所述烧结的温度为450℃～900℃，时间为8h～14h；所述烧结的过程中，改善晶粒强度的添加剂在晶界处形成富集并向内渗透，渗透深度为表层到中心。 Preferably, the sintering temperature in step b) is 450°C to 900°C, and the time is 8h to 14h; during the sintering process, additives that improve the grain strength are enriched at the grain boundaries and penetrate inward, Penetration depth is from surface to center.
优选的，步骤b)中所述水洗的过程具体为：Preferably, the water washing process described in step b) is specifically:
将烧结后的产物加入到有水的烧杯中，水洗2min～30min，随后将水洗料在800rpm～1500rpm下离心5min～100min，得到离心好的物料；所述烧结后的产物和水的质量比为1：(0.5～2)。Add the sintered product into a beaker with water, wash with water for 2 to 30 minutes, and then centrifuge the washed material at 800 to 1500 rpm for 5 to 100 minutes to obtain the centrifuged material; the mass ratio of the sintered product to water is 1: (0.5～2).
优选的，步骤b)中所述干燥的温度为80℃～180℃，时间为2h～6h；所述返烧的温度为150℃～600℃，时间为8h～14h。Preferably, the drying temperature in step b) is 80°C to 180°C and the time is 2h to 6h; the backburning temperature is 150°C to 600°C and the time is 8h to 14h.
本发明还提供了一种锂离子电池，所述锂离子电池的正极包括上述技术方案所述的高镍三元正极材料。The present invention also provides a lithium-ion battery, the positive electrode of which includes the high-nickel ternary positive electrode material described in the above technical solution.
本发明提供了一种高镍三元正极材料及其制备方法和应用；所述高镍三元正极材料，由高镍三元前驱体、锂源和改善晶粒强度的添加剂制备而成；所述改善晶粒强度的添加剂在晶界处富集；该制备方法包括以下步骤：a)将高镍三元前驱体和锂源在球磨机中高速混合均匀后，通过低速混合引入改善晶粒强度的添加剂，得到混合粉料；所述高速混合的速度为250rpm～600rpm；所述低速混合的速度为50rpm～200rpm；b)将步骤a)得到的混合粉料依次进行烧结、水洗、干燥和返烧，得到高镍三元正极材料。与现有技术相比，本发明提供的制备方法采用特定工艺步骤、条件及参数，实现整体较好的相互作用，能够使添加剂在晶界处富集，得到晶界强化(晶界一般是颗粒比较脆弱的部分，易被腐蚀)、颗粒耐压性能较优兼备化学稳定性、热稳定性良好的三元正极材料，使得正极材料的循环、DCR和产气性能得到明显的改善。The invention provides a high-nickel ternary cathode material and its preparation method and application; the high-nickel ternary cathode material is prepared from a high-nickel ternary precursor, a lithium source and an additive for improving grain strength; The additives that improve the grain strength are enriched at the grain boundaries; the preparation method includes the following steps: a) After mixing the high-nickel ternary precursor and the lithium source uniformly at high speed in a ball mill, introduce the additives that improve the grain strength through low-speed mixing Additives are added to obtain a mixed powder; the speed of the high-speed mixing is 250rpm ~ 600rpm; the speed of the low-speed mixing is 50rpm ~ 200rpm; b) the mixed powder obtained in step a) is sequentially sintering, washed, dried and back-burned , to obtain high-nickel ternary cathode materials. Compared with the existing technology, the preparation method provided by the present invention adopts specific process steps, conditions and parameters to achieve better overall interaction, which can enrich additives at grain boundaries and obtain grain boundary strengthening (grain boundaries are generally particles). The relatively fragile part is easily corroded), the ternary cathode material has excellent particle pressure resistance and good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material.
同时，本发明提供的制备方法具有工艺简单、操作易控、经济环保等优点，具有广阔的应用前景和潜力。At the same time, the preparation method provided by the present invention has the advantages of simple process, easy operation and control, economy and environmental protection, and has broad application prospects and potential.
附图说明Description of the drawings
图1为本发明实施例1制得的添加剂在晶界处富集的高镍正极材料的SEM(倍数50K)图；Figure 1 is an SEM (magnification 50K) image of a high-nickel cathode material with additives enriched at grain boundaries prepared in Example 1 of the present invention;
图2为采用与实施例1相同原料制备得到的较均匀分布的样品的SEM(倍数50K)图；Figure 2 is an SEM (magnification 50K) image of a relatively uniformly distributed sample prepared using the same raw materials as in Example 1;
图3为采用与实施例1相同原料但不添加添加剂制备的SEM(倍数50K)图； Figure 3 is an SEM (magnification 50K) image prepared using the same raw materials as Example 1 but without adding additives;
图4为本发明实施例1制得的添加剂在晶界处富集、对比例1添加剂较均匀分布和对比例2不添加添加剂制备的高镍正极材料的颗粒强度箱式图；Figure 4 is a box plot of the particle strength of the high-nickel cathode material prepared in Example 1 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 1 are relatively evenly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 2;
图5为本发明实施例2制得的添加剂在晶界处富集的高镍正极材料的SEM(倍数10K)图；Figure 5 is an SEM (magnification: 10K) image of the high-nickel cathode material with additives enriched at the grain boundaries prepared in Example 2 of the present invention;
图6为本发明实施例2制得的添加剂在晶界处富集的高镍正极材料的SEM(倍数50K)图；Figure 6 is an SEM (magnification 50K) image of the high-nickel cathode material with additives enriched at the grain boundaries prepared in Example 2 of the present invention;
图7为本发明实施例2制得的添加剂在晶界处富集的高镍正极材料的XRD图；Figure 7 is an XRD pattern of a high-nickel cathode material with additives enriched at grain boundaries prepared in Example 2 of the present invention;
图8为本发明实施例3制得的添加剂在晶界处富集、对比例3添加剂较均匀分布和对比例4不添加添加剂制备的高镍正极材料的颗粒强度箱式图；Figure 8 is a box plot of the particle strength of the high-nickel cathode material prepared in Example 3 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 3 are relatively evenly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 4;
图9为本发明实施例4制得的添加剂在晶界处富集、对比例5添加剂较均匀分布和对比例6不添加添加剂制备的高镍正极材料的7天/70℃搁置产气比较图；Figure 9 is a comparative chart of gas production during 7 days/70°C of high-nickel cathode materials prepared in Example 4 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 5 are relatively evenly distributed, and the high-nickel cathode materials prepared without additives in Comparative Example 6. ;
图10为本发明实施例5制得的添加剂在晶界处富集、对比例7添加剂较均匀分布和对比例8不添加添加剂制备的高镍正极材料在1C/1C充放电的条件下的全电循环容量保持率比较图；Figure 10 shows the overall performance of the high-nickel cathode material prepared in Example 5 of the present invention where the additives are enriched at the grain boundaries, the additives in Comparative Example 7 are relatively evenly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 8 under 1C/1C charge and discharge conditions. Comparison chart of electrical cycle capacity retention rate;
图11为本发明添加剂不均匀包覆的高镍正极材料制备流程图。Figure 11 is a flow chart for preparing the high-nickel cathode material unevenly coated with additives of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
本发明提供了一种高镍三元正极材料，由高镍三元前驱体、锂源和改善晶粒强度的添加剂制备而成；所述改善晶粒强度的添加剂在晶界处富集。The invention provides a high-nickel ternary cathode material, which is prepared from a high-nickel ternary precursor, a lithium source and an additive for improving the grain strength; the additive for improving the grain strength is enriched at the grain boundary.
本发明通过将添加剂富集到晶界处(具体表现为：在SEM图上，在晶界处富集的添加剂的颗粒浓度或质量或面积或个数大于在晶面上富集的添加剂)，从而改善颗粒强度，达到改善正极材料循环过程中因颗粒破碎而导致的循环、DCR和产气性能等。 The present invention enriches the additives at the grain boundaries (specifically, in the SEM image, the particle concentration or mass or area or number of the additives enriched at the grain boundaries is greater than the additives enriched on the crystal planes), Thereby improving the particle strength and improving the circulation, DCR and gas production performance caused by particle breakage during the circulation process of the cathode material.
在本发明中，所述高镍三元前驱体优选为NixCoyMn1-x-y(OH)2，其中，0.6≤x≤1，0≤y≤0.4。本发明对所述高镍三元前驱体的来源没有特殊限制，采用本领域技术人员熟知的技术手段如共沉淀方法获得。In the present invention, the high-nickel ternary precursor is preferably Nix Co y Mn 1-xy (OH) 2 , where 0.6≤x≤1 and 0≤y≤0.4. The present invention has no special restrictions on the source of the high-nickel ternary precursor, which can be obtained by technical means well known to those skilled in the art, such as co-precipitation method.
在本发明中，所述锂源优选为碳酸锂和/或氢氧化锂，更优选为氢氧化锂。本发明对所述锂源的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the lithium source is preferably lithium carbonate and/or lithium hydroxide, and more preferably is lithium hydroxide. The present invention has no special restrictions on the source of the lithium source, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述高镍三元前驱体和锂源的摩尔比优选为1：(1.02～1.08)，更优选为1：1.05。In the present invention, the molar ratio of the high-nickel ternary precursor and the lithium source is preferably 1: (1.02-1.08), and more preferably 1:1.05.
在本发明中，所述改善晶粒强度的添加剂能够改善晶粒强度，提高颗粒耐压性能，优选选自下列物质的氧化物或氟化物的一种或多种：B、Al、Ta、Ce、W、Nb、Ge、Y、Zr、Ca和Sr，更优选为B的氧化物、Al的氧化物、Ta的氧化物、Ce的氧化物、W的氧化物、Nb的氧化物、Ge的氧化物、Y的氧化物、Zr的氧化物、Ca的氧化物和Sr的氧化物中的一种或多种，更更优选为纳米三氧化二硼、氟化铝、氧化钽、氧化铈或三氧化钨。本发明对所述改善晶粒强度的添加剂的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the additive for improving the grain strength can improve the grain strength and improve the particle pressure resistance, and is preferably selected from one or more oxides or fluorides of the following substances: B, Al, Ta, Ce , W, Nb, Ge, Y, Zr, Ca and Sr, more preferably B oxide, Al oxide, Ta oxide, Ce oxide, W oxide, Nb oxide, Ge One or more of the oxides, Y oxides, Zr oxides, Ca oxides and Sr oxides, more preferably nano boron trioxide, aluminum fluoride, tantalum oxide, cerium oxide or Tungsten trioxide. The present invention has no special restrictions on the source of the additive for improving grain strength, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述高镍三元前驱体和改善晶粒强度的添加剂的质量比优选为100：(0.1～2)，更优选为100：(0.1～0.5)。In the present invention, the mass ratio of the high-nickel ternary precursor and the additive for improving grain strength is preferably 100: (0.1-2), and more preferably 100: (0.1-0.5).
本发明提供了一种掺杂提高颗粒强度的高镍三元正极材料，制备方法包括：将高镍三元前驱体、锂源先进行高速混合均匀，通过低速混合加入添加剂使添加剂在晶界处富集，烧结、水洗后经过干燥、返烧得到制备样品；所述的样品经过热处理后，使添加剂在晶界处富集，得到晶界强化(晶界一般是颗粒比较脆弱的部分，易被腐蚀)、颗粒耐压性能较优兼备化学稳定性、热稳定性良好的三元正极材料，使得正极材料的循环、DCR和产气性能得到明显的改善。The invention provides a high-nickel ternary cathode material that is doped to improve particle strength. The preparation method includes: first mixing the high-nickel ternary precursor and the lithium source uniformly at high speed, and adding additives through low-speed mixing to make the additives at the grain boundaries. After enrichment, sintering, washing, drying and back-burning are performed to obtain the prepared sample; after the sample is heat treated, the additives are enriched at the grain boundaries to obtain grain boundary strengthening (grain boundaries are generally fragile parts of particles and are easily Corrosion), particle pressure resistance, and ternary cathode materials with good chemical stability and thermal stability have significantly improved the cycle, DCR and gas production performance of the cathode material.
本发明还提供了一种高镍三元正极材料的制备方法，包括以下步骤：The invention also provides a method for preparing a high-nickel ternary cathode material, which includes the following steps:
a)将高镍三元前驱体和锂源在球磨机中高速混合均匀后，通过低速混合引入改善晶粒强度的添加剂，得到混合粉料；所述高速混合的速度为250rpm～600rpm；所述低速混合的速度为50rpm～200rpm；a) After mixing the high-nickel ternary precursor and the lithium source uniformly in a ball mill at high speed, an additive to improve the grain strength is introduced through low-speed mixing to obtain a mixed powder; the speed of the high-speed mixing is 250rpm to 600rpm; the low-speed The mixing speed is 50rpm~200rpm;
b)将步骤a)得到的混合粉料依次进行烧结、水洗、干燥和返烧，得到高镍三元正极材料。b) The mixed powder obtained in step a) is sintered, washed, dried and back-fired in sequence to obtain a high-nickel ternary cathode material.
本发明首先将高镍三元前驱体和锂源在球磨机中高速混合均匀后，通过低 速混合引入改善晶粒强度的添加剂，得到混合粉料。在本发明中，所述高镍三元前驱体优选为NixCoyMn1-x-y(OH)2，其中，0.6≤x≤1，0≤y≤0.4。本发明对所述高镍三元前驱体的来源没有特殊限制，采用本领域技术人员熟知的技术手段如共沉淀方法获得。In the present invention, the high-nickel ternary precursor and the lithium source are first mixed evenly at high speed in a ball mill, and then passed through a low-temperature Rapid mixing introduces additives that improve the grain strength to obtain mixed powder. In the present invention, the high-nickel ternary precursor is preferably Nix Co y Mn 1-xy (OH) 2 , where 0.6≤x≤1 and 0≤y≤0.4. The present invention has no special restrictions on the source of the high-nickel ternary precursor, which can be obtained by technical means well known to those skilled in the art, such as co-precipitation method.
在本发明中，所述锂源优选为碳酸锂和/或氢氧化锂，更优选为氢氧化锂。本发明对所述锂源的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the lithium source is preferably lithium carbonate and/or lithium hydroxide, and more preferably is lithium hydroxide. The present invention has no special restrictions on the source of the lithium source, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述高镍三元前驱体和锂源的摩尔比优选为1：(1.02～1.08)，更优选为1：1.05。In the present invention, the molar ratio of the high-nickel ternary precursor and the lithium source is preferably 1: (1.02-1.08), and more preferably 1:1.05.
在本发明中，所述球磨机的球磨罐优选为聚四氟乙烯球磨罐或聚氨酯球磨罐。In the present invention, the ball mill tank of the ball mill is preferably a polytetrafluoroethylene ball mill tank or a polyurethane ball mill tank.
在本发明中，所述高速混合的速度为250rpm～600rpm，优选为300rpm；所述高速混合的时间优选为1h～3h，更优选为2h。高速混合的速度大于低速混合的速度。在本发明中，所述低速混合的速度为50rpm～200rpm，优选为150rpm；所述低速混合的时间优选为0.2h～2h，更优选为0.5h。In the present invention, the speed of the high-speed mixing is 250 to 600 rpm, preferably 300 rpm; the time of the high-speed mixing is preferably 1 to 3 hours, and more preferably 2 hours. The speed of high-speed mixing is greater than that of low-speed mixing. In the present invention, the low-speed mixing speed is 50 rpm to 200 rpm, preferably 150 rpm; the low-speed mixing time is preferably 0.2 h to 2 h, and more preferably 0.5 h.
在本发明中，所述改善晶粒强度的添加剂能够改善晶粒强度，提高颗粒耐压性能，优选选自B的氧化物、Al的氧化物、Ta的氧化物、Ce的氧化物、W的氧化物、Nb的氧化物、Ge的氧化物、Y的氧化物、Zr的氧化物、Ca的氧化物和Sr的氧化物中的一种或多种，更优选为纳米三氧化二硼、氟化铝、氧化钽、氧化铈或三氧化钨。本发明对所述改善晶粒强度的添加剂的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the additive for improving the grain strength can improve the grain strength and improve the particle pressure resistance, and is preferably selected from the group consisting of B oxide, Al oxide, Ta oxide, Ce oxide, and W oxide. One or more of oxides, Nb oxides, Ge oxides, Y oxides, Zr oxides, Ca oxides and Sr oxides, more preferably nano boron trioxide, fluorine aluminum oxide, tantalum oxide, cerium oxide or tungsten trioxide. The present invention has no special restrictions on the source of the additive for improving grain strength, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述高镍三元前驱体和改善晶粒强度的添加剂的质量比优选为100：(0.1～2)，更优选为100：(0.1～0.5)。In the present invention, the mass ratio of the high-nickel ternary precursor and the additive for improving grain strength is preferably 100: (0.1-2), and more preferably 100: (0.1-0.5).
得到所述混合粉料后，本发明将得到的混合粉料依次进行烧结、水洗、干燥和返烧，得到高镍三元正极材料。After obtaining the mixed powder, the present invention sequentially performs sintering, water washing, drying and back-burning on the obtained mixed powder to obtain a high-nickel ternary cathode material.
在本发明中，所述烧结的温度优选为450℃～900℃，时间优选为8h～14h；在本发明优选的实施例中，所述烧结的过程优选具体为：In the present invention, the sintering temperature is preferably 450°C to 900°C, and the sintering time is preferably 8h to 14h; in a preferred embodiment of the invention, the sintering process is preferably:
通入氧气气氛(氧浓度≥60％)，在450℃～700℃进行预烧结，然后升温到700℃～900℃进行烧结8h～14h，冷却至室温；Pour in an oxygen atmosphere (oxygen concentration ≥ 60%), perform pre-sintering at 450°C to 700°C, then raise the temperature to 700°C to 900°C for sintering for 8h to 14h, and cool to room temperature;
更优选为： More preferably:
通入氧气气氛(氧浓度≥80％)，在600℃进行预烧结，然后升温到750℃进行烧结12h，冷却至室温。Pour in an oxygen atmosphere (oxygen concentration ≥ 80%), perform pre-sintering at 600°C, then raise the temperature to 750°C for sintering for 12 hours, and then cool to room temperature.
在本发明中，所述烧结的过程中，改善晶粒强度的添加剂在晶界处形成一定的富集并向内渗透，渗透深度为表层到中心。In the present invention, during the sintering process, the additives that improve the grain strength form a certain concentration at the grain boundaries and penetrate inward, and the penetration depth is from the surface to the center.
在本发明中，所述水洗的过程优选具体为：In the present invention, the water washing process is preferably as follows:
将烧结后的产物加入到有水的烧杯中，水洗2min-30min，随后将水洗料在800rpm～1500rpm下离心5min～100min，得到离心好的物料；Add the sintered product into a beaker with water, wash with water for 2min-30min, and then centrifuge the washed material at 800rpm-1500rpm for 5min-100min to obtain the centrifuged material;
更优选为：More preferably:
将烧结后的产物加入到有水的烧杯中，水洗10min，随后将水洗料在1000rpm下离心15min，得到离心好的物料。Add the sintered product into a beaker with water, wash with water for 10 minutes, and then centrifuge the washed material at 1000 rpm for 15 minutes to obtain the centrifuged material.
在本发明中，所述烧结后的产物和水的质量比优选为1：(0.5～2)，更优选为1：1。In the present invention, the mass ratio of the sintered product and water is preferably 1: (0.5-2), and more preferably 1:1.
在本发明中，所述干燥的温度优选为80℃～180℃，更优选为140℃，时间优选为2h～6h，更优选为5h；采用本领域技术人员熟知的烘箱下烘干的干燥方式即可。In the present invention, the drying temperature is preferably 80°C to 180°C, more preferably 140°C, and the time is preferably 2h to 6h, more preferably 5h; the drying method of drying in an oven, which is well known to those skilled in the art, is used That’s it.
在本发明中，所述返烧的温度优选为150℃～600℃，时间优选为8h～14h；在本发明优选的实施例中，所述返烧的过程优选具体为：In the present invention, the temperature of the back-burning is preferably 150°C to 600°C, and the time is preferably 8h-14h; in a preferred embodiment of the invention, the back-burning process is preferably:
通入氧气气氛(氧浓度≥80％)，在150℃～600℃下烧结8h～14h；Pour into oxygen atmosphere (oxygen concentration ≥ 80%), and sinter at 150°C to 600°C for 8h to 14h;
更优选为：More preferably:
通入氧气气氛(氧浓度≥80％)，在350℃下烧结12h。Pour in an oxygen atmosphere (oxygen concentration ≥ 80%) and sinter at 350°C for 12 hours.
通过上述内容可知，本发明提供的制备方法优选包括以下步骤：As can be seen from the above, the preparation method provided by the present invention preferably includes the following steps:
步骤一、将锂离子电池高镍三元前驱体和锂源放入球磨机中高速混合1～3h，再将改善晶粒强度的添加剂加入，并低速混合0.2～2h，得到混合粉料；Step 1: Put the high-nickel ternary precursor of the lithium-ion battery and the lithium source into a ball mill and mix at high speed for 1 to 3 hours, then add additives to improve the grain strength, and mix at low speed for 0.2 to 2 hours to obtain a mixed powder;
步骤二、将步骤一所得混合粉料在氧气气氛下加热至450～900℃温度，并在此温度下保温8～14h，得到高镍三元正极材料烧结料，其添加剂在晶界处形成一定的富集并向内渗透；Step 2: Heat the mixed powder obtained in Step 1 to a temperature of 450 to 900°C in an oxygen atmosphere, and keep it at this temperature for 8 to 14 hours to obtain a high-nickel ternary cathode material sintered material, whose additives form a certain amount at the grain boundaries. The enrichment and inward penetration;
步骤三、将步骤二所得到的三元正极材料烧结料加入到有水的烧杯中，水洗2～30min，随后将水洗料置于离心设备中离心，最后将离心好的物料放在烘干设备中加热烘干；最后将烘干后的粉料在氧气气氛下加热至150～600℃温度，并在此温度下保温8～14h，得到掺杂提高颗粒强度的高镍三元正极材料。 Step 3: Add the ternary cathode material sintered material obtained in step 2 into a beaker with water, wash it with water for 2 to 30 minutes, then place the washed material in a centrifuge device for centrifugation, and finally place the centrifuged material in a drying device. Medium heating and drying; finally, the dried powder is heated to a temperature of 150 to 600°C in an oxygen atmosphere, and kept at this temperature for 8 to 14 hours to obtain a high-nickel ternary cathode material that is doped to increase particle strength.
本发明提供的制备方法采用特定工艺步骤、条件及参数，实现整体较好的相互作用，能够使添加剂在晶界处富集，得到晶界强化(晶界一般是颗粒比较脆弱的部分，易被腐蚀)、颗粒耐压性能较优兼备化学稳定性、热稳定性良好的三元正极材料，使得正极材料的循环、DCR和产气性能得到明显的改善；同时，本发明提供的制备方法具有工艺简单、操作易控、经济环保等优点，具有广阔的应用前景和潜力。The preparation method provided by the invention adopts specific process steps, conditions and parameters to achieve overall better interaction, which can enrich the additives at the grain boundaries and obtain grain boundary strengthening (grain boundaries are generally relatively fragile parts of particles and are easily Corrosion), particle pressure resistance is excellent, and the ternary cathode material has good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material; at the same time, the preparation method provided by the invention has a process It has the advantages of simplicity, easy operation and control, economy and environmental protection, and has broad application prospects and potential.
本发明还提供了一种锂离子电池，所述锂离子电池的正极包括上述技术方案所述的高镍三元正极材料。在本发明中，所述锂离子电池采用本领域技术人员熟知的将正极材料制备成锂离子电池的技术方案，其中，所述正极材料为本发明上述技术方案所述的高镍三元正极材料，从而实现该高镍三元正极材料的应用。The present invention also provides a lithium-ion battery, the positive electrode of which includes the high-nickel ternary positive electrode material described in the above technical solution. In the present invention, the lithium-ion battery adopts a technical solution for preparing a positive electrode material into a lithium-ion battery that is well known to those skilled in the art, wherein the positive electrode material is a high-nickel ternary positive electrode material described in the above-mentioned technical solution of the present invention. , thereby realizing the application of this high-nickel ternary cathode material.
本发明提供了一种高镍三元正极材料及其制备方法；该制备方法包括以下步骤：a)将高镍三元前驱体和锂源在球磨机中高速混合均匀后，通过低速混合引入改善晶粒强度的添加剂，得到混合粉料；所述高速混合的速度为250rpm～600rpm；所述低速混合的速度为50rpm～200rpm；b)将步骤a)得到的混合粉料依次进行烧结、水洗、干燥和返烧，得到高镍三元正极材料。与现有技术相比，本发明提供的制备方法采用特定工艺步骤、条件及参数，实现整体较好的相互作用，能够使添加剂在晶界处富集，得到晶界强化(晶界一般是颗粒比较脆弱的部分，易被腐蚀)、颗粒耐压性能较优兼备化学稳定性、热稳定性良好的三元正极材料，使得正极材料的循环、DCR和产气性能得到明显的改善。The invention provides a high-nickel ternary cathode material and a preparation method thereof; the preparation method includes the following steps: a) mix the high-nickel ternary precursor and the lithium source uniformly in a ball mill at high speed, and introduce improved crystals through low-speed mixing. particle strength additives to obtain a mixed powder; the high-speed mixing speed is 250rpm to 600rpm; the low-speed mixing speed is 50rpm to 200rpm; b) the mixed powder obtained in step a) is sequentially sintered, washed, and dried and back-burning to obtain high-nickel ternary cathode materials. Compared with the existing technology, the preparation method provided by the present invention adopts specific process steps, conditions and parameters to achieve better overall interaction, which can enrich additives at grain boundaries and obtain grain boundary strengthening (grain boundaries are generally particles). The relatively fragile part is easily corroded), the ternary cathode material has excellent particle pressure resistance and good chemical stability and thermal stability, which significantly improves the cycle, DCR and gas production performance of the cathode material.
同时，本发明提供的制备方法具有工艺简单、操作易控、经济环保等优点，具有广阔的应用前景和潜力。At the same time, the preparation method provided by the present invention has the advantages of simple process, easy operation and control, economy and environmental protection, and has broad application prospects and potential.
为了进一步说明本发明，下面通过以下实施例进行详细说明。本发明以下实施例中所用的原料均为市售。In order to further illustrate the present invention, the following examples will be described in detail. The raw materials used in the following examples of the present invention are all commercially available.
实施例1Example 1
在2L球磨罐中加入1kg通过共沉淀方法获得的前驱体Ni0.85Co0.06Mn0.09(OH)2，按锂化系数摩尔比1：1.05加入氢氧化锂单水合物475g，以300rpm搅拌混合120min，待物料混合均匀，再加入三氧化钨1.23g，以150rpm低速搅拌30min；放入匣钵，通入氧气气氛(氧浓度≥80％)，在600℃进行预 烧结，然后升温到750℃进行烧结12h，冷却至室温，然后用1：1的水，水洗10分钟，然后在1000rpm的离心机下面进行离心15min，然后在140℃烘箱下烘干5小时，将烘干料放入匣钵，通入氧气气氛(氧浓度≥80％)，在350℃下烧结12h；得到颗粒强度优良的晶粒的二次颗粒，超长循环正极材料Li(Ni0.85Co0.06Mn0.09)0.99W0.01O2。Add 1kg of the precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 obtained by co-precipitation method into a 2L ball mill tank, add 475g of lithium hydroxide monohydrate according to the molar ratio of lithiation coefficient 1:1.05, stir and mix at 300rpm for 120min. After the materials are evenly mixed, add 1.23g of tungsten trioxide and stir for 30 minutes at a low speed of 150 rpm; put it into a sagger, introduce oxygen atmosphere (oxygen concentration ≥ 80%), and preheat at 600°C. Sintering, then raise the temperature to 750°C for 12h, cool to room temperature, then wash with 1:1 water for 10 minutes, then centrifuge at 1000rpm for 15min, and then dry in an oven at 140°C for 5 hours. The dried material is placed in a sagger, introduced into an oxygen atmosphere (oxygen concentration ≥ 80%), and sintered at 350°C for 12 hours; secondary particles of crystal grains with excellent particle strength are obtained, and the ultra-long cycle cathode material Li(Ni 0.85 Co 0.06 Mn 0.09 ) 0.99 W 0.01 O 2 .
对比例1Comparative example 1
采用与实施例1相同原料制备得到的较均匀分布的样品。A relatively uniformly distributed sample was prepared using the same raw materials as in Example 1.
对比例2Comparative example 2
采用与实施例1相同原料但不添加添加剂三氧化钨制备得到样品。The sample was prepared using the same raw materials as in Example 1 but without adding the additive tungsten trioxide.
经测试，本发明实施例1制得的添加剂在晶界处富集的高镍正极材料的SEM(倍数50K)图参见图1所示，图中掺杂元素W在晶界处富集，图2为采用与实施例1相同原料制备得到的较均匀分布的样品的SEM(倍数50K)图，图3为采用与实施例1相同原料但不添加添加剂制备的SEM(倍数50K)图。本发明实施例1制得的添加剂在晶界处富集、对比例1添加剂较均匀分布和对比例2不添加添加剂制备的高镍正极材料的颗粒强度箱式图参见图4所示。After testing, the SEM (magnification 50K) picture of the high-nickel cathode material prepared in Example 1 of the present invention with additives enriched at the grain boundaries is shown in Figure 1. In the figure, the doping element W is enriched at the grain boundaries. Figure 2 is an SEM (magnification 50K) image of a relatively evenly distributed sample prepared using the same raw materials as Example 1, and Figure 3 is an SEM (magnification 50K) image prepared using the same raw materials as Example 1 but without adding additives. The box plot of the particle strength of the high-nickel cathode material prepared in Example 1 of the present invention is enriched at the grain boundaries, the additives in Comparative Example 1 are relatively uniformly distributed, and the high-nickel cathode material prepared without additives in Comparative Example 2 is shown in Figure 4.
实施例2Example 2
在2L球磨罐中加入1kg通过共沉淀方法获得的前驱体Ni0.85Co0.06Mn0.09(OH)2，按锂化系数摩尔比1：1.05加入氢氧化锂单水合物475g，以300rpm搅拌混合120min，待物料混合均匀，再加入纳米氟化铝3.03g，以150rpm低速搅拌30min；放入匣钵，通入氧气气氛(氧浓度≥80％)，在600℃进行预烧结，然后升温到750℃进行烧结12h，冷却至室温，然后用1：1的水，水洗10分钟，然后在1000rpm的离心机下面进行离心15min，然后在140℃烘箱下烘干5小时，将烘干料放入匣钵，通入氧气气氛(氧浓度≥80％)，在350℃下烧结12h；得到颗粒强度优良的晶粒的二次颗粒，超长循环正极材料Li(Ni0.85Co0.06Mn0.09)0.99Al0.01O2。Add 1kg of the precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 obtained by co-precipitation method into a 2L ball mill tank, add 475g of lithium hydroxide monohydrate according to the molar ratio of lithiation coefficient 1:1.05, stir and mix at 300rpm for 120min. After the materials are evenly mixed, add 3.03g of nano-aluminum fluoride and stir at a low speed of 150 rpm for 30 minutes; put it in a sagger, introduce an oxygen atmosphere (oxygen concentration ≥ 80%), pre-sinter at 600°C, and then heat it up to 750°C. Sintering for 12 hours, cooled to room temperature, then washed with 1:1 water for 10 minutes, then centrifuged under a 1000 rpm centrifuge for 15 minutes, and then dried in a 140°C oven for 5 hours. Put the dried material into a sagger. Pour in an oxygen atmosphere (oxygen concentration ≥80%) and sinter at 350°C for 12 hours; obtain secondary particles of crystal grains with excellent particle strength, ultra-long cycle cathode material Li (Ni 0.85 Co 0.06 Mn 0.09 ) 0.99 Al 0.01 O 2 .
经测试，本发明实施例2制得的添加剂在晶界处富集的高镍正极材料的SEM(倍数10K)图参见图5所示，本发明实施例2制得的添加剂在晶界处富集的高镍正极材料的SEM(倍数50K)图参见图6所示；图中的掺杂元素Ta在晶界处富集。本发明实施例2制得的添加剂在晶界处富集的高镍正极材料的XRD图参见图7所示。 After testing, the SEM (magnification 10K) picture of the high-nickel cathode material prepared in Example 2 of the present invention is shown in Figure 5. The additive prepared in Example 2 of the present invention is enriched in the grain boundaries. The SEM (magnification 50K) picture of the assembled high-nickel cathode material is shown in Figure 6; the doping element Ta in the picture is enriched at the grain boundaries. The XRD pattern of the high-nickel cathode material with additives enriched at the grain boundaries prepared in Example 2 of the present invention is shown in Figure 7.
实施例3Example 3
在2L球磨罐中加入1kg通过共沉淀方法获得的前驱体Ni0.85Co0.06Mn0.09(OH)2，按锂化系数摩尔比1：1.05加入氢氧化锂单水合物475g，以300rpm搅拌混合120min，待物料混合均匀，再加入氧化钽1.19g，以150rpm低速搅拌30min；放入匣钵，通入氧气气氛(氧浓度≥80％)，在600℃进行预烧结，然后升温到750℃进行烧结12h，冷却至室温，然后用1：1的水，水洗10分钟，然后在1000rpm的离心机下面进行离心15min，然后在140℃烘箱下烘干5小时，将烘干料放入匣钵，通入氧气气氛(氧浓度≥80％)，在350℃下烧结12h；得到颗粒强度优良的晶粒的二次颗粒，超长循环正极材料Li(Ni0.85Co0.06Mn0.09)0.99Ta0.01O2。Add 1kg of the precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 obtained by co-precipitation method into a 2L ball mill tank, add 475g of lithium hydroxide monohydrate according to the molar ratio of lithiation coefficient 1:1.05, stir and mix at 300rpm for 120min. After the materials are evenly mixed, add 1.19g of tantalum oxide and stir at a low speed of 150 rpm for 30 minutes; put it in a sagger, introduce an oxygen atmosphere (oxygen concentration ≥ 80%), pre-sinter at 600°C, and then raise the temperature to 750°C for sintering for 12 hours. , cool to room temperature, then wash with 1:1 water for 10 minutes, then centrifuge for 15 minutes under a 1000rpm centrifuge, and then dry in a 140°C oven for 5 hours. Put the drying material into a sagger and pass it through Oxygen atmosphere (oxygen concentration ≥ 80%), sintering at 350°C for 12 hours; obtaining secondary particles of crystal grains with excellent particle strength, ultra-long cycle cathode material Li (Ni 0.85 Co 0.06 Mn 0.09 ) 0.99 Ta 0.01 O 2 .
对比例3Comparative example 3
采用与实施例3相同原料制备得到的较均匀分布的样品。A relatively uniformly distributed sample was prepared using the same raw materials as in Example 3.
对比例4Comparative example 4
采用与实施例3相同原料但不添加添加剂氧化钽制备得到样品。The sample was prepared using the same raw materials as in Example 3 but without adding the additive tantalum oxide.
经检测，本发明实施例3制得的添加剂在晶界处富集、对比例3采用与实施例3相同原料制备得到的较均匀分布和对比例4采用与实施例3相同原料但不添加添加剂制备的高镍正极材料的颗粒强度箱式图参见图8所示。After testing, the additives prepared in Example 3 of the present invention are enriched at the grain boundaries, Comparative Example 3 is prepared using the same raw materials as Example 3 and has a relatively uniform distribution, and Comparative Example 4 uses the same raw materials as Example 3 but does not add additives. The box plot of the particle strength of the prepared high-nickel cathode material is shown in Figure 8.
实施例4Example 4
在2L球磨罐中加入1kg通过共沉淀方法获得的前驱体Ni0.85Co0.06Mn0.09(OH)2，按锂化系数摩尔比1：1.05加入氢氧化锂单水合物475g，以300rpm搅拌混合120min，待物料混合均匀，再加入氧化铈1.20g，以150rpm低速搅拌30min；放入匣钵，通入氧气气氛(氧浓度≥80％)，在600℃进行预烧结，然后升温到750℃进行烧结12h，冷却至室温，然后用1：1的水，水洗10分钟，然后在1000rpm的离心机下面进行离心15min，然后在140℃烘箱下烘干5小时，将烘干料放入匣钵，通入氧气气氛(氧浓度≥80％)，在350℃下烧结12h；得到颗粒强度优良的晶粒的二次颗粒，超长循环正极材料Li(Ni0.85Co0.06Mn0.09)0.99Ce0.01O2。Add 1kg of the precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 obtained by co-precipitation method into a 2L ball mill tank, add 475g of lithium hydroxide monohydrate according to the molar ratio of lithiation coefficient 1:1.05, stir and mix at 300rpm for 120min. After the materials are evenly mixed, add 1.20g of cerium oxide and stir at a low speed of 150 rpm for 30 minutes; put it in a sagger, introduce an oxygen atmosphere (oxygen concentration ≥ 80%), pre-sinter at 600°C, and then raise the temperature to 750°C for sintering for 12 hours. , cool to room temperature, then wash with 1:1 water for 10 minutes, then centrifuge at 1000 rpm for 15 minutes, and then dry in a 140°C oven for 5 hours. Put the drying material into a sagger and pass it through Oxygen atmosphere (oxygen concentration ≥ 80%), sintering at 350°C for 12 hours; obtaining secondary particles of crystal grains with excellent particle strength, ultra-long cycle cathode material Li (Ni 0.85 Co 0.06 Mn 0.09 ) 0.99 Ce 0.01 O 2 .
对比例5Comparative example 5
采用与实施例4相同原料制备得到的较均匀分布的样品。A relatively uniformly distributed sample was prepared using the same raw materials as in Example 4.
对比例6 Comparative example 6
采用与实施例4相同原料但不添加添加剂氧化铈制备得到样品。A sample was prepared using the same raw materials as in Example 4 but without adding the additive cerium oxide.
实施例5Example 5
在2L球磨罐中加入1kg通过共沉淀方法获得的前驱体Ni0.85Co0.06Mn0.09(OH)2，按锂化系数摩尔比1：1.05加入氢氧化锂单水合物475g，以300rpm搅拌混合120min，待物料混合均匀，再加入纳米三氧化二硼3.14g，以150rpm低速搅拌30min；放入匣钵，通入氧气气氛(氧浓度≥80％)，在600℃进行预烧结，然后升温到750℃进行烧结12h，冷却至室温，然后用1：1的水，水洗10分钟，然后在1000rpm的离心机下面进行离心15min，然后在140℃烘箱下烘干5小时，将烘干料放入匣钵，通入氧气气氛(氧浓度≥80％)，在350℃下烧结12h；得到颗粒强度优良的晶粒的二次颗粒，超长循环正极材料Li(Ni0.85Co0.06Mn0.09)0.99B0.01O2。Add 1kg of the precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 obtained by co-precipitation method into a 2L ball mill tank, add 475g of lithium hydroxide monohydrate according to the molar ratio of lithiation coefficient 1:1.05, stir and mix at 300rpm for 120min. After the materials are evenly mixed, add 3.14g of nano boron trioxide and stir for 30 minutes at a low speed of 150 rpm; put it in a sagger, introduce an oxygen atmosphere (oxygen concentration ≥ 80%), pre-sinter at 600°C, and then heat it up to 750°C Carry out sintering for 12 hours, cool to room temperature, then wash with 1:1 water for 10 minutes, then centrifuge at 1000 rpm for 15 minutes, then dry in a 140°C oven for 5 hours, and put the dried material into a sagger. , pass into oxygen atmosphere (oxygen concentration ≥ 80%), and sinter at 350°C for 12 hours; obtain secondary particles of crystal grains with excellent particle strength, ultra-long cycle cathode material Li (Ni 0.85 Co 0.06 Mn 0.09 ) 0.99 B 0.01 O 2 .
对比例7Comparative example 7
采用与实施例5相同原料制备得到的较均匀分布的样品。A relatively uniformly distributed sample was prepared using the same raw materials as in Example 5.
对比例8Comparative example 8
采用与实施例5相同原料但不添加添加剂纳米三氧化二硼制备得到样品。The sample was prepared using the same raw materials as in Example 5 but without adding additive nanoboron trioxide.
效果实施例Effect Example
采用本领域技术人员熟知的将正极材料制备成锂离子电池的技术方案，将实施例1～5中得到的高镍正极材料组装成扣式电池，具体方法为：将制得的添加剂在晶界处富集的高镍正极材料、乙炔黑与聚偏氟乙烯(PVDF)按94：3：3质量比称取，混合均匀，加入NMP搅拌2h，成粘稠状浆料，均匀涂布在铝箔上，后80℃真空烘烤，压片，裁切直径为14mm的正极片；以直径16mm的纯锂片作为负极片，以1mol/LLiPF6+DEC/EC(体积比1：1)混合溶液为电解液，以聚Celgard丙烯微孔膜为隔膜，在充满氩气的手套箱中进行组装成扣式电池。The high-nickel positive electrode materials obtained in Examples 1 to 5 were assembled into button batteries using technical solutions for preparing positive electrode materials into lithium-ion batteries that are well known to those skilled in the art. The specific method is: adding the prepared additives at the grain boundaries Weigh the enriched high-nickel cathode material, acetylene black and polyvinylidene fluoride (PVDF) at a mass ratio of 94:3:3, mix evenly, add NMP and stir for 2 hours to form a viscous slurry, which is evenly coated on the aluminum foil Then, vacuum bake at 80°C, press into sheets, and cut the positive electrode sheet with a diameter of 14mm; use a pure lithium sheet with a diameter of 16mm as the negative electrode sheet, and use a mixed solution of 1mol/LLiPF 6 + DEC/EC (volume ratio 1:1) is the electrolyte, polyCelgard propylene microporous membrane is used as the separator, and a button cell is assembled in an argon-filled glove box.
经检测，本发明实施例4制得的添加剂在晶界处富集、对比例5采用与实施例4相同原料制备得到的较均匀分布和对比例6采用与实施例4相同原料但不添加添加剂制备的高镍正极材料的7天/70℃搁置产气比较图参见图9所示。After testing, the additives prepared in Example 4 of the present invention are enriched at the grain boundaries, Comparative Example 5 is prepared using the same raw materials as Example 4 and has a relatively uniform distribution, and Comparative Example 6 uses the same raw materials as Example 4 but does not add additives. The comparison chart of gas production after 7 days/70°C of the prepared high-nickel cathode material is shown in Figure 9.
经检测，本发明实施例5制得的添加剂在晶界处富集、对比例7采用与实施例5相同原料制备得到的添加剂较均匀分布和对比例8采用与实施例5相同原料但不添加添加剂制备的高镍正极材料在1C/1C充放电的条件下的全电循环容量保持率比较图参见图10所示。 After testing, the additives prepared in Example 5 of the present invention are enriched at the grain boundaries, the additives prepared in Comparative Example 7 using the same raw materials as Example 5 are relatively evenly distributed, and the additives prepared in Comparative Example 8 using the same raw materials as Example 5 but without addition The comparison chart of the full electrical cycle capacity retention rate of high-nickel cathode materials prepared with additives under 1C/1C charge and discharge conditions is shown in Figure 10.
本发明添加剂不均匀包覆的高镍正极材料制备流程图参见图11所示。The flow chart for preparing the high-nickel cathode material unevenly coated with additives of the present invention is shown in Figure 11.
综上，本发明与现有技术相比，对正极材料进行有效的掺杂，具体表现在添加剂在颗粒晶界处富集(详见附图1～3、5～6)，改善晶界强度和抗腐蚀性，从而极大地提高正极材料颗粒耐压性能(具体佐证数据可参照实施例及效果附图)，从而使正极材料在循环过程中，较好的保持颗粒的完整性，从而避免循环过程的因颗粒破碎而导致的循环、DCR和产气性能的急剧恶化；并且，效果附图表明，添加剂在晶界处富集、添加剂比较均匀分布和无添加剂对应的颗粒耐压性能是依次递减的，其300圈的循环保持率也是依次递减的，说明本发明提供的制备方法通过添加剂在晶界处富集确实可以改善颗粒耐压从而改善正极的材料的循环性能。In summary, compared with the prior art, the present invention can effectively dope the cathode material, which is specifically reflected in the enrichment of additives at the grain boundaries of particles (see attached figures 1 to 3 and 5 to 6 for details), thereby improving the grain boundary strength. and corrosion resistance, thereby greatly improving the voltage resistance of the cathode material particles (for specific supporting data, please refer to the examples and effect drawings), so that the cathode material can better maintain the integrity of the particles during the cycle, thereby avoiding cycles The process's circulation, DCR and gas production performance deteriorate sharply due to particle breakage; and the effect diagram shows that the additives are enriched at the grain boundaries, the additives are relatively uniformly distributed, and the pressure resistance performance of the particles corresponding to no additives decreases in sequence. , the cycle retention rate for 300 cycles also decreases successively, indicating that the preparation method provided by the present invention can indeed improve the particle withstand voltage through enrichment of additives at the grain boundaries, thereby improving the cycle performance of the cathode material.
注：本发明中提到的“富集”定义为：在SEM图上，在晶界处富集的添加剂的颗粒浓度或质量或面积或个数大于在晶面上富集的添加剂；富集在晶界处的部分添加剂也会在正极层状结构形成中进行渗透，渗透量由添加剂特性和烧结状态决定，添加剂渗透的深度从表层到中心。Note: "Enrichment" mentioned in the present invention is defined as: on the SEM image, the particle concentration or mass or area or number of the additives enriched at the grain boundaries is greater than that of the additives enriched on the crystal plane; enrichment Some additives at the grain boundaries will also penetrate into the formation of the positive electrode layered structure. The amount of penetration is determined by the characteristics of the additives and the sintering state. The depth of additive penetration is from the surface layer to the center.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。 The above are only preferred embodiments of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the principles of the present invention. These improvements and modifications can also be made. should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种高镍三元正极材料，其特征在于，由高镍三元前驱体、锂源和改善晶粒强度的添加剂制备而成；所述改善晶粒强度的添加剂在晶界处富集。A high-nickel ternary cathode material is characterized in that it is prepared from a high-nickel ternary precursor, a lithium source and an additive that improves grain strength; the additive that improves grain strength is enriched at grain boundaries.
  2. 根据权利要求1所述的高镍三元正极材料，其特征在于，所述高镍三元前驱体为NixCoyMn1-x-y(OH)2，其中，0.6≤x≤1，0≤y≤0.4；所述锂源选自碳酸锂和/或氢氧化锂；所述高镍三元前驱体和锂源的摩尔比为1：(1.02～1.08)。The high-nickel ternary cathode material according to claim 1, wherein the high-nickel ternary precursor is Nix Co y Mn 1-xy (OH) 2 , where 0.6≤x≤1, 0≤ y≤0.4; the lithium source is selected from lithium carbonate and/or lithium hydroxide; the molar ratio of the high-nickel ternary precursor and the lithium source is 1: (1.02~1.08).
  3. 根据权利要求1所述的高镍三元正极材料，其特征在于，所述改善晶粒强度的添加剂选自下列物质的氧化物或氟化物的一种或多种：B、Al、Ta、Ce、W、Nb、Ge、Y、Zr、Ca和Sr。The high-nickel ternary cathode material according to claim 1, wherein the additive for improving grain strength is selected from one or more oxides or fluorides of the following substances: B, Al, Ta, Ce , W, Nb, Ge, Y, Zr, Ca and Sr.
  4. 根据权利要求1所述的高镍三元正极材料，其特征在于，所述高镍三元前驱体和改善晶粒强度的添加剂的质量比为100：(0.1～2)。The high-nickel ternary cathode material according to claim 1, wherein the mass ratio of the high-nickel ternary precursor and the additive for improving grain strength is 100: (0.1-2).
  5. 一种权利要求1～4任一项所述的高镍三元正极材料的制备方法，包括以下步骤：A method for preparing the high-nickel ternary cathode material according to any one of claims 1 to 4, comprising the following steps:
    a)将高镍三元前驱体和锂源在球磨机中高速混合均匀后，通过低速混合引入改善晶粒强度的添加剂，得到混合粉料；所述高速混合的速度为250rpm～600rpm；所述低速混合的速度为50rpm～200rpm；a) After mixing the high-nickel ternary precursor and the lithium source uniformly in a ball mill at high speed, an additive to improve the grain strength is introduced through low-speed mixing to obtain a mixed powder; the speed of the high-speed mixing is 250rpm to 600rpm; the low-speed The mixing speed is 50rpm~200rpm;
    b)将步骤a)得到的混合粉料依次进行烧结、水洗、干燥和返烧，得到高镍三元正极材料。b) The mixed powder obtained in step a) is sintered, washed, dried and back-fired in sequence to obtain a high-nickel ternary cathode material.
  6. 根据权利要求5所述的制备方法，其特征在于，步骤a)中所述高速混合的时间为1h～3h；所述低速混合的时间为0.2h～2h。The preparation method according to claim 5, characterized in that the high-speed mixing time in step a) is 1h-3h; the low-speed mixing time is 0.2h-2h.
  7. 根据权利要求5所述的制备方法，其特征在于，步骤b)中所述烧结的温度为450℃～900℃，时间为8h～14h；所述烧结的过程中，改善晶粒强度的添加剂在晶界处形成富集并向内渗透，渗透深度为表层到中心。The preparation method according to claim 5, characterized in that the sintering temperature in step b) is 450°C to 900°C and the time is 8h to 14h; during the sintering process, the additive to improve the grain strength is added Enrichment is formed at the grain boundaries and penetrates inward, with the penetration depth from the surface to the center.
  8. 根据权利要求5所述的制备方法，其特征在于，步骤b)中所述水洗的过程具体为：The preparation method according to claim 5, characterized in that the water washing process in step b) is specifically:
    将烧结后的产物加入到有水的烧杯中，水洗2min～30min，随后将水洗料在800rpm～1500rpm下离心5min～100min，得到离心好的物料；所述烧结后的产物和水的质量比为1：(0.5～2)。Add the sintered product into a beaker with water, wash with water for 2 to 30 minutes, and then centrifuge the washed material at 800 to 1500 rpm for 5 to 100 minutes to obtain the centrifuged material; the mass ratio of the sintered product to water is 1: (0.5～2).
  9. 根据权利要求5所述的制备方法，其特征在于，步骤b)中所述干燥的 温度为80℃～180℃，时间为2h～6h；所述返烧的温度为150℃～600℃，时间为8h～14h。The preparation method according to claim 5, characterized in that the dried in step b) The temperature is 80°C to 180°C, and the time is 2h to 6h; the backburning temperature is 150°C to 600°C, and the time is 8h to 14h.
  10. 一种锂离子电池，其特征在于，所述锂离子电池的正极包括权利要求1～4任一项所述的高镍三元正极材料。 A lithium-ion battery, characterized in that the positive electrode of the lithium-ion battery includes the high-nickel ternary positive electrode material according to any one of claims 1 to 4.
PCT/CN2023/075881 2022-03-21 2023-02-14 High-nickel ternary positive electrode material and preparation method therefor and application thereof WO2023179245A1 (en)

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