WO2024082929A1 - 一种锂镍复合氧化物正极材料及其制备方法 - Google Patents

一种锂镍复合氧化物正极材料及其制备方法 Download PDF

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WO2024082929A1
WO2024082929A1 PCT/CN2023/121069 CN2023121069W WO2024082929A1 WO 2024082929 A1 WO2024082929 A1 WO 2024082929A1 CN 2023121069 W CN2023121069 W CN 2023121069W WO 2024082929 A1 WO2024082929 A1 WO 2024082929A1
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positive electrode
composite oxide
electrode material
nickel composite
lithium nickel
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PCT/CN2023/121069
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English (en)
French (fr)
Inventor
佘嘉欣
谭欣欣
罗桂
王梦
段辉
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BASF Shanshan Battery Materials Co Ltd
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BASF Shanshan Battery Materials Co Ltd
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Priority to EP23878922.6A priority Critical patent/EP4576260A4/en
Priority to KR1020257010405A priority patent/KR20250056272A/ko
Priority to JP2025516018A priority patent/JP2025532622A/ja
Publication of WO2024082929A1 publication Critical patent/WO2024082929A1/zh
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C01G53/502—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt
    • C01G53/504—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
    • C01G53/506—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5 with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
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    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/362—Composites
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • 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
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    • 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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • C—CHEMISTRY; METALLURGY
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    • C01P2002/50—Solid solutions
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    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to lithium ion battery positive electrode materials, and in particular relates to a lithium nickel composite oxide positive electrode material with abundant pores and uniform pore distribution inside the material and a preparation method thereof.
  • lithium-ion batteries have developed rapidly and have been widely used in mobile electronic devices and automobile manufacturing.
  • the rapid expansion of the new energy vehicle industry has generated a large market demand for lithium-ion batteries, and also put forward requirements for lithium-ion batteries such as high energy density, long service life, low cost, high safety, and green environmental protection.
  • high-nickel ternary lithium-ion positive electrode materials have shown great advantages and have gradually become the focus of researchers' research.
  • the technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background technology and provide a lithium nickel composite oxide positive electrode material with high discharge capacity and excellent rate performance and a preparation method thereof.
  • the technical solution proposed by the present invention is:
  • a lithium nickel composite oxide positive electrode material is observed by cross section using a scanning electron microscope. After the cross section of the lithium nickel composite oxide is divided into four equal parts according to the radius length, the porosity of each cross section is measured to be 3% to 8%. The pores are evenly distributed from the inside to the outside of the particles, and the total cross section porosity is 3% to 8%.
  • the test method for the porosity of lithium nickel composite oxide positive electrode materials is as follows: the positive electrode material particles are cut by an ion beam milling apparatus (CP) to obtain samples with observable particle cross sections, and the cross-sectional images are photographed using a scanning electron microscope (SEM). The image analysis software ImageJ is then used to extract the particle pore area from the photographed photos, and the particle pore area is divided into four regions with a radius of four equal parts using a python script. Finally, the porosity in each region and the total porosity of the particle cross section are calculated using a script program.
  • CP ion beam milling apparatus
  • SEM scanning electron microscope
  • the above-mentioned lithium nickel composite oxide positive electrode material preferably, has a specific surface area of 0.5 ⁇ 1.0m2 /g.
  • the lithium nickel composite oxide positive electrode material is based on Li a Ni 1-xyz Co x Mn y M z O 2 , and the surface of the substrate is coated with a boron coating layer, wherein M represents at least one element selected from Li, Na, K, Mg, Ti, Co, Zn, Zr, Ce, and Al, 0.90 ⁇ a ⁇ 1.10, 0 ⁇ x ⁇ 0.15, 0 ⁇ y ⁇ 0.15, 0 ⁇ z ⁇ 0.02, and x+y+z ⁇ 0.2.
  • M represents at least one element selected from Li, Na, K, Mg, Ti, Co, Zn, Zr, Ce, and Al, 0.90 ⁇ a ⁇ 1.10, 0 ⁇ x ⁇ 0.15, 0 ⁇ y ⁇ 0.15, 0 ⁇ z ⁇ 0.02, and x+y+z ⁇ 0.2.
  • the matrix further contains S element, and the S element accounts for 0.02% to 0.2% of the total mass of the lithium nickel composite oxide positive electrode material.
  • the boron element in the boron coating layer accounts for 0.05% to 0.2% of the total mass of the lithium nickel composite oxide positive electrode material.
  • the present invention also provides a method for preparing the above-mentioned lithium nickel composite oxide positive electrode material, comprising the following steps:
  • the monoalkyl substrate is washed with deionized water, dried, mixed with a coating agent, and then sintered to obtain a lithium nickel composite oxide positive electrode material.
  • the low-temperature pre-sintering process is: first, in an air or oxygen atmosphere, the temperature is raised to 150-200°C at a rate of 3-5°C/min, and the temperature is kept at 1-2h for sintering, then the temperature is raised to 300-400°C at a rate of 1-3°C/min, and the temperature is kept at 2-5h for sintering, and finally, the temperature is naturally cooled to room temperature.
  • the high-temperature sintering process is: first, in an air or oxygen atmosphere, the temperature is raised to 450-550°C at a rate of 1-5°C/min, and the temperature is kept at this temperature for 3-7 hours, then the temperature is raised to 600-750°C at a rate of 1-5°C/min, and the temperature is kept at this temperature for 8-15 hours, and finally, the temperature is naturally cooled to room temperature.
  • the sintering process is: heating to 300-400°C at a rate of 1-5°C/min in an air or oxygen atmosphere, keeping the temperature for 3-12 hours, and then naturally cooling to room temperature.
  • the coating agent is one or more of boric acid and boron oxide.
  • the total porosity of the cross section of the lithium nickel composite oxide positive electrode material in the present invention is 3% to 8%, and the porosity of each portion measured after the cross section is divided into four equal parts according to the radius length is also 3% to 8%, which indicates that the particles have abundant pores, uniform size, and uniform distribution, which is conducive to the infiltration of the electrolyte, so that the positive electrode material is in full contact with the electrolyte, shortening the lithium ion transmission path, increasing the discharge capacity of the positive electrode material, reducing the internal resistance of the lithium battery, and exerting better rate performance.
  • metal sulfate is added in the pre-sintering stage, so that the internal porous structure formed in the pre-sintering stage can be retained after the first sintering and is evenly distributed, thereby ensuring the preparation
  • the prepared lithium nickel composite oxide positive electrode material has rich and uniform pore distribution inside, which is beneficial to improving the rate performance of lithium batteries; while the traditional hydroxide precursor dehydrates after pre-sintering to form a loose and porous oxide precursor. This loose and porous structure is difficult to maintain after sintering and is extremely unevenly distributed.
  • the bulk density of the precursor can be increased by pre-sintering, thereby increasing the loading capacity of a single sintering, and the selectable sulfate is diversified, which is conducive to large-scale production.
  • FIG1 is a schematic diagram of four regions obtained by dividing a particle cross section into four equal parts according to the radius during the process of testing the particle porosity of the present invention.
  • FIG. 2 is an electron microscope image of the lithium nickel composite oxide positive electrode material in Example 1 of the present invention at a magnification of x20,000.
  • FIG3 is an electron microscope image of the lithium nickel composite oxide positive electrode material in Comparative Example 1 of the present invention at a magnification of x20000.
  • FIG. 4 is a comparison chart of battery capacities of lithium nickel composite oxide positive electrode materials of various embodiments of the present invention and comparative examples.
  • FIG5 is a comparison chart of battery rates of lithium nickel composite oxide positive electrode material compositions of Example 1 of the present invention and various comparative examples.
  • the particle cross-sectional images and porosity calculations in the following embodiments and comparative examples are obtained by the following method: the positive electrode material particles are cut by an ion beam milling apparatus (CP) to obtain a sample with an observable particle cross section, and the cross-sectional images are photographed using a scanning electron microscope (SEM). Then, the particle pore area is extracted from the photographed photo using the image analysis software: ImageJ, and the particle pore area is divided into four regions with a radius of four equal parts using a python script, as shown in FIG1 , and finally the porosity in each region and the total porosity of the particle cross section are calculated by the script program.
  • CP ion beam milling apparatus
  • SEM scanning electron microscope
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a lithium nickel composite oxide positive electrode material of the present invention is observed by cross section using a scanning electron microscope.
  • the cross section of the lithium nickel composite oxide is divided into four equal parts according to the radius length, and the porosities of the four regions are measured .
  • the porosities from the inside to the outside are 5.02%, 5.63%, 5.57% and 4.82% respectively, the total cross section porosity is 5.22 % , and the specific surface area is 0.64m2 /g.
  • the lithium nickel composite oxide positive electrode material uses Li1.03Ni0.82Co0.10Mn0.07Ti0.01O2.00 as a matrix, and the matrix also contains S element, and the mass of the S element accounts for 0.041% of the total mass of the lithium nickel composite oxide positive electrode material .
  • the surface of the matrix is coated with a boron coating layer, and the boron element in the coating layer accounts for 0.1% of the total mass of the lithium nickel composite oxide positive electrode material.
  • the method for preparing the lithium nickel composite oxide positive electrode material of the present invention comprises the following steps:
  • the pre-calcined precursor prepared in step (1) and LiOH ⁇ H 2 O are mixed in a high-speed mixer at a molar ratio of 1:1.03, wherein the speed of the high-speed mixer is 1500 rpm/min, and the high-speed mixing is performed for 30 min to obtain a mixed material, and the mixed material is placed in a sintering furnace, and heated to 500° C. at a heating rate of 4° C./min in an oxygen atmosphere, and sintered at this temperature for 6 h, and then heated to 720° C. at a heating rate of 1.5° C./min and sintered at this temperature for 12 h, and then naturally cooled to room temperature, crushed, and passed through a 300-mesh sieve to obtain a sintered matrix;
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • a lithium nickel composite oxide positive electrode material of the present invention is observed through a scanning electron microscope.
  • the cross section of the lithium nickel composite oxide is divided into four equal parts according to the radius length, and then the porosities of the four regions are measured . From the inside to the outside, the porosities are 4.28%, 4.56%, 5.03% and 4.55%, respectively.
  • the total cross-sectional porosity is 4.68%, and the specific surface area is 0.75 m2 /g.
  • the lithium nickel composite oxide positive electrode material uses Li1.03Ni0.88Co0.05Mn0.05La0.02O2.00 as a matrix, and the matrix also contains S element, the mass of the S element accounts for 0.036% of the total mass of the lithium nickel composite oxide positive electrode material.
  • the surface of the matrix is coated with a boron coating layer, and the boron element in the coating layer accounts for 0.1% of the total mass of the lithium nickel composite oxide positive electrode material.
  • the method for preparing the lithium nickel composite oxide positive electrode material of the present invention comprises the following steps:
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • a lithium nickel composite oxide positive electrode material of the present invention is observed by cross section using a scanning electron microscope.
  • the cross section of the lithium nickel composite oxide is divided into four equal parts according to the radius length, and the porosities of the four regions are measured .
  • the porosities from the inside to the outside are 6.84%, 6.99%, 7.32% and 6.62% respectively, the total cross section porosity is 6.92 % , and the specific surface area is 0.86m2 /g.
  • the lithium nickel composite oxide positive electrode material uses Li1.07Ni0.92Co0.04Mn0.04O2.00 as a matrix, and the matrix also contains S element, the mass of the S element accounts for 0.054% of the total mass of the lithium nickel composite oxide positive electrode material, and the surface of the matrix is coated with a boron coating layer, and the boron element in the coating layer accounts for 0.1% of the total mass of the lithium nickel composite oxide positive electrode material.
  • the method for preparing the lithium nickel composite oxide positive electrode material of the present invention comprises the following steps:
  • the monoalkyl matrix was washed with deionized water for 15 minutes, with a solid-liquid ratio of 1:1, and the temperature of the deionized water was controlled at 10°C.
  • the sample was placed in a vacuum oven and vacuum dried at 160°C for 8 hours, then naturally cooled to room temperature, and passed through a 300-mesh sieve to obtain a washed sample; the washed sample and boric acid were then put into a high-speed mixer at a mass ratio of 1:0.0019 for mixing, wherein the mixing speed was 1500rpm/min, and the high-speed mixing was performed for 30 minutes to obtain a mixed material, and finally the mixed material was placed in a sintering furnace, and the temperature was increased to 350°C at a heating rate of 2°C/min in an oxygen atmosphere, and the mixture was sintered for 5 hours at this temperature, and then naturally cooled.
  • the mixture was cooled to room temperature and passed through a 300-mesh sieve to obtain a lithium nickel composite oxide positive electrode material.
  • Example 1 The difference between this comparative example and Example 1 is that Ti(SO 4 ) 2 is not added during the pre-calcination process of step (1), and the other conditions and parameters are the same as those of Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that the pre-sintering stage in step (1) does not adopt a staged sintering process, but instead the temperature is raised to 300° C. at a rate of 1° C./min and sintered for 3 hours at this temperature.
  • the other conditions and parameters are the same as those in Example 1.
  • FIG2 is an electron microscope image of the lithium nickel composite oxide positive electrode material in Example 1 of the present invention
  • FIG3 is an electron microscope image of the lithium nickel composite oxide positive electrode material in Comparative Example 1 of the present invention. It can be seen from FIG2 that after sulfate is added in the pre-sintering stage, the number and pore area of pores are significantly increased, and the pore distribution is uniform; while it can be seen from FIG3 that sulfate is not added in the pre-sintering stage, the cross-sectional pore area of the prepared material particles is small and unevenly distributed, there are almost no pores inside and at the center of the particles, and there are more pores outside.
  • Example 1 By comparing the porosity test results of Example 1 and Comparative Example 1, it can be seen that adding sulfate during pre-calcining can significantly increase the porosity of the material particles. Further comparison of the porosity of each area of the particle cross section shows that the pore distribution of Example 1 is more uniform; by comparing the porosity test results of Example 1 and Comparative Example 2, it can be seen that segmented pre-calcining is beneficial to the formation of more abundant pores in the material, thereby helping to improve the electrical properties of the material.
  • the lithium nickel composite oxide positive electrode materials of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 are respectively mixed with carbon black (Super-P) and binder (PVDF) in a ratio of 92.5:5:2.5, and then an appropriate amount of organic solvent N-methylpyrrolidone (NMP) is added to prepare a slurry.
  • the positive electrode slurry is evenly spread on the aluminum foil using a coating machine.
  • the coated positive electrode sheet is placed in a blast drying oven and dried at 120°C for 20 hours. Finally, a circular positive electrode sheet with a diameter of 14 mm is cut.
  • the negative electrode metal lithium sheet
  • diaphragm positive electrode
  • the sheets were assembled into CR2032 button cells in a glove box for electrical performance testing.
  • the button cell test voltage is 3.0-4.3V
  • the first charge capacity is the charge capacity at 25°C and 0.1C rate
  • the first discharge capacity is the discharge capacity at 25°C and 0.1C rate.
  • the normal temperature cycle test is the cycle retention rate at 25°C and 1C/1C charge and discharge rate
  • the high temperature cycle test is the cycle retention rate at 45°C and 0.5C/0.5C charge and discharge rate.
  • FIG4 is a battery capacity comparison diagram of the positive electrode material compositions of various embodiments and comparative examples
  • FIG5 is a battery rate comparison diagram of the positive electrode material compositions of Example 1 and various comparative examples.
  • the electrochemical performance results of various embodiments and comparative examples are shown in Table 2.
  • Example 1 By comparing the electrical performance test results of Example 1 and Comparative Example 1, it can be seen that adding sulfate during pre-burning can significantly improve the discharge capacity and rate performance of the material, while maintaining good room temperature and high temperature cycle retention rates; by comparing the electrical performance test results of Example 1 and Comparative Example 2, it can be seen that segmented pre-burning can further improve the discharge capacity and rate performance of the material. It can be seen that the lithium nickel composite oxide positive electrode material of the present invention exhibits good discharge capacity and excellent rate performance.

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Abstract

一种锂镍复合氧化物正极材料，通过使用扫描电子显微镜进行截面观察，将锂镍复合氧化物的截面按照半径长度平均四等分后，测定的每一份截面的孔隙率为3％～8％，截面总孔隙率为3％～8％。其制备方法：将镍钴锰的氢氧化物与含M的硫酸盐混合后进行低温分段预烧结，得预烧前驱体；将锂源与预烧前驱体混合后进行高温烧结，得一烧基体；将一烧基体用去离子水洗涤、干燥后，再与包覆剂混合进行烧结，得锂镍复合氧化物正极材料。本发明的锂镍复合氧化物正极材料颗粒内部孔隙丰富、大小均一、分布均匀，有利于电解液的浸润，使正极材料与电解液充分接触，缩短锂离子传输路径，提高正极材料的放电容量，降低锂电池的内阻，发挥更优的倍率性能。

Description

一种锂镍复合氧化物正极材料及其制备方法 技术领域
本发明属于锂离子电池正极材料，尤其涉及一种孔隙丰富且孔隙在材料内部呈均匀分布的锂镍复合氧化物正极材料及其制备方法。
背景技术
近年来，锂离子电池飞速发展，已广泛应用于移动电子设备及汽车制造领域。特别是新能源汽车产业的快速扩张，对锂离子电池产生大量的市场需求，同时也对锂离子电池提出了高能量密度、长使用寿命、低成本、高安全、绿色环保等要求。在现有的多种电池材料中，高镍三元锂离子正极材料显示出了极大的优势，逐渐成为研究人员的重点研究方向。
随着消费者对锂离子电池长续航里程及快充的需求，这要求电池具有更高的能量密度及更优的倍率性能。从正极材料的角度出发，提高能量密度最为有效的办法是提高材料中的镍含量，但镍含量的提升可能导致电池稳定性快速下降，产生严重的安全问题；而倍率性能的提升常通过前驱体多孔设计或表面包覆实现，但是多孔前驱体可能在烧结后孔隙减少或在烧结后导致孔隙分布不均匀，这种不均匀的孔隙分布可能在充放电过程中导致材料内部产生各向异性的应力，最终导致颗粒破碎，电性能快速恶化；而表面包覆快离子导体作为一种提升倍率性能的一般方法，却常常以牺牲容量作为代价。高能量密度和良好倍率性能的正极材料是当前行业研究重点，但现有改性方法难以同时提升正极材料的容量和倍率性能。
发明内容
本发明所要解决的技术问题是，克服以上背景技术中提到的不足和缺陷，提供一种高放电容量、优倍率性能的锂镍复合氧化物正极材料及其制备方法。
为解决上述技术问题，本发明提出的技术方案为：
一种锂镍复合氧化物正极材料，通过使用扫描电子显微镜进行截面观察，将所述锂镍复合氧化物的截面按照半径长度平均四等分后，测定的每一份截面的孔隙率为3％～8％，孔隙在颗粒内部由内至外呈均匀分布，其截面总孔隙率为3％～8％。
锂镍复合氧化物正极材料的孔隙率的测试方法为：通过离子束研磨仪(CP)对正极材料颗粒进行切割，得到可观察颗粒截面的样品，使用扫描电子显微镜(SEM)对截面图像进行拍摄，然后使用图像分析软件：ImageJ从所拍摄的照片中提取颗粒孔隙区域，使用python脚本将颗粒孔隙区域以半径四等分成四个区域，最后通过脚本程序计算出每个区域内的孔隙率及颗粒截面总孔隙率。
上述的锂镍复合氧化物正极材料，优选的，锂镍复合氧化物正极材料的比表面积为 0.5～1.0m2/g。
上述的锂镍复合氧化物正极材料，优选的，所述锂镍复合氧化物正极材料以LiaNi1-x-y-zCoxMnyMzO2为基体，基体表面包覆有硼包覆层，其中，M表示选自Li、Na、K、Mg、Ti、Co、Zn、Zr、Ce、Al中的至少一种元素，0.90≤a≤1.10，0＜x≤0.15，0＜y≤0.15，0＜z≤0.02，x+y+z≤0.2。
上述的锂镍复合氧化物正极材料，优选的，所述基体中还含有S元素，S元素占锂镍复合氧化物正极材料总质量的0.02％～0.2％。
上述的锂镍复合氧化物正极材料，优选的，硼包覆层中的硼元素占锂镍复合氧化物正极材料总质量的0.05％～0.2％。
作为一个总的发明构思，本发明还提供一种上述的锂镍复合氧化物正极材料的制备方法，包括以下步骤：
(1)将镍钴锰的氢氧化物与含M的硫酸盐混合后进行低温分段预烧结，得到预烧前驱体；
(2)按照化学计量比，将锂源与预烧前驱体混合后进行高温烧结，得到一烧基体；
(3)将一烧基体用去离子水洗涤、干燥后，再与包覆剂混合后进行烧结，得到锂镍复合氧化物正极材料。
上述的制备方法，优选的，步骤(1)中，低温预烧结过程为：在空气或氧气气氛下先以3-5℃/min的速度升温至150-200℃，保温烧结1-2h，再以1-3℃/min的速度升温至300-400℃，保温烧结2-5h，最后自然冷却至室温。
上述的制备方法，优选的，步骤(2)中，高温烧结过程为：在空气或氧气气氛下先以1-5℃/min的速度升温至450-550℃，保温烧结3-7h，再以1-5℃/min的速度升温至600-750℃，保温8-15h，最后自然冷却降至室温。
上述的制备方法，优选的，步骤(3)中，烧结过程为：在空气或氧气气氛下以1-5℃/min的速度升温至300-400℃，保温3-12h，然后自然冷却至室温。
上述的制备方法，优选的，步骤(3)中，所述包覆剂为硼酸、氧化硼的一种或几种。
与现有技术相比，本发明的优点在于：
(1)本发明中的锂镍复合氧化物正极材料的截面总孔隙率为3％～8％，且将截面按照半径长度平均四等分后测定的每一份的孔隙率也为3％～8％，这表明颗粒内部具有孔隙丰富，大小均一，分布均匀的特点，有利于电解液的浸润，使正极材料与电解液充分接触，缩短锂离子传输路径，提高正极材料的放电容量，降低锂电池的内阻，发挥更优的倍率性能。
(2)本发明在锂镍复合氧化物正极材料的制备过程中，在预烧阶段加入金属硫酸盐，可以使预烧阶段形成的内部多孔结构在一次烧结后得以保留，并呈均匀分布，从而可以保证制 备的锂镍复合氧化物正极材料内部有丰富且均匀的孔隙分布，这有利于改善锂电池的倍率性能；而传统的氢氧化物前驱体在预烧后发生脱水，形成疏松多孔的氧化物前驱体，这种疏松多孔结构在烧结后难以保持且分布极为不均。
(3)本发明在锂镍复合氧化物正极材料的制备过程中，通过预烧结可以增大前驱体的松装密度，从而增加一次烧结的装钵量，且可选择的硫酸盐多样化，有利于大规模生产。
附图说明
图1为本发明测试颗粒孔隙率过程中颗粒截面按照半径四等分得到的四个区域示意图。
图2为本发明实施例1中锂镍复合氧化物正极材料的x20000倍电镜图。
图3为本发明对比例1中锂镍复合氧化物正极材料的x20000倍电镜图。
图4为本发明各实施例及对比例的锂镍复合氧化物正极材料组成的电池容量对比图。
图5为本发明实施例1及各对比例的锂镍复合氧化物正极材料组成的电池倍率对比图。
具体实施方式
为了便于理解本发明，下文将结合说明书附图和较佳的实施例对本文发明做更全面、细致地描述，但本发明的保护范围并不限于以下具体实施例。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
下述实施例和对比例中颗粒截面图像及孔隙率计算通过以下方法得到：通过离子束研磨仪(CP)对正极材料颗粒进行切割，得到可观察颗粒截面的样品，使用扫描电子显微镜(SEM)对截面图像进行拍摄。然后使用图像分析软件：ImageJ从所拍摄的照片中提取颗粒孔隙区域，使用python脚本将颗粒孔隙区域以半径四等分成四个区域，示意图如图1所示，最后通过脚本程序计算出每个区域内的孔隙率及颗粒截面总孔隙率。
实施例1：
一种本发明的锂镍复合氧化物正极材料，通过使用扫描电子显微镜进行截面观察，将锂镍复合氧化物的截面按照半径长度平均四等分后测定四个区域孔隙率，由内至外分别为5.02％、5.63％、5.57％和4.82％，截面总孔隙率为5.22％，比表面积为0.64m2/g；该锂镍复合氧化物正极材料以Li1.03Ni0.82Co0.10Mn0.07Ti0.01O2.00为基体，且基体中还含有S元素，S元素的质量占锂镍复合氧化物正极材料总质量为0.041％；基体的表面包覆有硼包覆层，包覆层中的硼元素占锂镍复合氧化物正极材料总质量的0.1％。
本发明的锂镍复合氧化物正极材料的制备方法，包括以下步骤：
(1)将高镍正极材料前驱体Ni0.83Co0.10Mn0.07(OH)2、Ti(SO4)2按照1:0.01的摩尔比投入高速混合机中进行混合，其中，高速混合机的转速为1500rpm/min，高速混合30min，得到混合物料，然后将混合物料置于烧结炉中，在氧气气氛下，以3℃/min的速度升温至150℃，保温烧结2h，随后以1℃/min的速度升温至300℃，保温烧结3h，自然冷却至室温，得到预烧前驱体；
(2)将步骤(1)制备的预烧前驱体与LiOH·H2O按1:1.03的摩尔比投入高速混合机中进行混合，其中，高速混合机的转速为1500rpm/min，高速混合30min，得到混合物料，将混合物料置于烧结炉中，在氧气气氛下，以4℃/min的升温速率升温至500℃，保温烧结6h，随后以1.5℃/min的升温速率升温至720℃并保温烧结12h，随后自然冷却至室温，粉碎，过300目筛，得到一烧基体；
(3)将一烧基体用去离子水洗涤15min，洗涤的固液比为1:1，去离子水的温度控制在10℃，水洗后将样品置于真空烘箱中，在160℃下真空干燥8h，随后自然冷却至室温，过筛300目，得到水洗后的样品；将水洗后的样品与硼酸按1:0.0019的质量比投入高速混合机进行混合，其中，高速混合机的转速为1500rpm/min，高速混合30min，得到混合物料，将混合物料置于烧结炉中，在氧气气氛下，以2℃/min的升温速率升温至350℃并保温烧结8h，随后自然冷却至室温，过300目筛，得到锂镍复合氧化物正极材料。
实施例2：
一种本发明的锂镍复合氧化物正极材料，通过使用扫描电子显微镜进行截面观察，将锂镍复合氧化物的截面按照半径长度平均四等分后测定四个区域孔隙率，由内至外分别为4.28％，4.56％，5.03％，4.55％，截面总孔隙率为4.68％，比表面积为0.75m2/g；该锂镍复合氧化物正极材料以Li1.03Ni0.88Co0.05Mn0.05La0.02O2.00为基体，且基体中还含有S元素，S元素的质量占锂镍复合氧化物正极材料总质量为0.036％，基体的表面包覆有硼包覆层，包覆层中硼元素占锂镍复合氧化物正极材料总质量的0.1％。
本发明的锂镍复合氧化物正极材料的制备方法，包括以下步骤：
(1)将高镍正极材料前驱体Ni0.90Co0.05Mn0.05(OH)2和La2(SO4)3按照1:0.01的摩尔比投入高速混合机中进行混合，其中，高速混合机的转速为1500rpm/min，高速混合30min，得到混合物料，然后将混合物料置于烧结炉中，在氧气气氛下，以3℃/min的速度升温至150℃，保温烧结2h，随后以1℃/min的速度升温至300℃，保温烧结3h，自然冷却至室温，得到预烧前驱体；
(2)将上述预烧前驱体、LiOH·H2O按1:1.03的摩尔比投入高速混合机中进行混合，其中，高速混合机的转速为1500rpm/min，高速混合30min，得到混合物料，将混合物料置于 烧结炉中，在氧气气氛下，以3℃/min的升温速率升温至520℃，保温烧结6h，随后以2℃/min的升温速率升温至700℃并保温烧结11h，随后自然冷却至室温，粉碎，过300目筛，得到一烧基体；
(3)将一烧基体用去离子水洗涤15min，固液比为1:1，去离子水的温度控制在10℃，水洗后将样品置于真空烘箱中160℃下真空干燥8h，随后自然冷却至室温，过300目筛，得到水洗后的样品；将水洗后的样品与硼酸按1:0.0019的质量比投入高速混合机进行混合，高速混合机的转速为1500rpm/min，高速混合30min，得到混合物料，然后将混合物料置于烧结炉中，在氧气气氛下，以2℃/min的升温速率升温至350℃并保温烧结5h，随后自然冷却至室温，过300目筛，得到锂镍复合氧化物正极材料。
实施例3：
一种本发明的锂镍复合氧化物正极材料，通过使用扫描电子显微镜进行截面观察，将锂镍复合氧化物的截面按照半径长度平均四等分后测定四个区域孔隙率，由内至外分别为6.84％，6.99％，7.32％，6.62％，截面总孔隙率为6.92％，比表面积为0.86m2/g；该锂镍复合氧化物正极材料以Li1.07Ni0.92Co0.04Mn0.04O2.00为基体，且基体中还含有S元素，S元素的质量占锂镍复合氧化物正极材料总质量为0.054％，基体的表面包覆有硼包覆层，包覆层中硼元素占锂镍复合氧化物正极材料总质量的0.1％。
本发明的锂镍复合氧化物正极材料的制备方法，包括以下步骤：
(1)将高镍正极材料前驱体Ni0.92Co0.04Mn0.04(OH)2和Li2SO4按1:0.02的摩尔比投入高速混合机中进行混合，其中，高速混合机的转速为1500rpm/min，高速混合30min，得到混合物料；然后将混合物料置于烧结炉中，在氧气气氛下，以3℃/min的速度升温至150℃，保温烧结2h，随后以1℃/min的速度升温至300℃，保温烧结3h，自然冷却至室温，得到预烧前驱体；
(2)将预烧前驱体与LiOH·H2O按1:1.03的摩尔比投入高速混合机中进行混合，混合机的转速为1500rpm/min，高速混合30min，得到混合物料，然后将混合物料置于烧结炉中，在氧气气氛下，以3℃/min的升温速率升温至520℃，保温烧结6h，随后以2℃/min的升温速率升温至680℃并保温烧结10h，随后自然冷却至室温，粉碎，过300目筛，得到一烧基体；
(3)将一烧基体用去离子水洗涤15min，固液比为1:1，去离子水的温度控制在10℃，水洗后将样品置于真空烘箱中，在160℃下真空干燥8h，随后自然冷却至室温，过300目筛，得到水洗后的样品；再将水洗后的样品与硼酸按1:0.0019的质量比投入高速混合机进行混合，其中，混合的转速为1500rpm/min，高速混合30min，得到混合物料，最后将混合物料置于烧结炉中，在氧气气氛下，以2℃/min的升温速率升温至350℃并保温烧结5h，随后自然冷却 至室温，过300目筛，得到锂镍复合氧化物正极材料。
对比例1：
本对比例和实施例1相比，区别在于步骤(1)的预烧过程中没有加入Ti(SO4)2，其余条件与参数均与实施例1相同。
对比例2：
本对比例和实施例1相比，区别在于：步骤(1)的预烧阶段没有采用分段烧结工艺，而是以1℃/min的速度升温至300℃，保温烧结3h烧结，其余条件与参数均与实施例1相同。
图2为本发明实施例1中锂镍复合氧化物正极材料的电镜图，图3为本发明对比例1中锂镍复合氧化物正极材料的电镜图，从图2中可以看出，在预烧阶段加入硫酸盐后，孔隙数量和孔隙面积明显增加，且孔隙分布均匀；而从图3中可以看出，预烧阶段没有加入硫酸盐，制备得到的材料颗粒截面孔隙面积较小，且呈不均匀分布，颗粒内部及中心处几乎无孔隙，外部孔隙较多。
各实施例和对比例的锂镍复合氧化物正极材料的S元素含量，比表面积和孔隙分布对比见表1所示。
表1实施例和对比例的锂镍复合氧化物正极材料的S含量、比表面积和孔隙分布
通过对比实施例1和对比例1的孔隙率测试结果，可以看出在预烧时加入硫酸盐可以显著提高材料颗粒的孔隙率，进一步对比颗粒截面各个区域的孔隙率可以发现实施例1的孔隙分布更加均匀；通过对比实施例1和对比例2的孔隙率测试结果，可以看出分段预烧有利于材料中形成更丰富的孔隙，从而有利于提升材料的电性能。
将实施例1、实施例2、对比例1和对比例2的锂镍复合氧化物正极材分别与炭黑(Super-P)、粘结剂(PVDF)按照92.5:5:2.5的比例充分混合均匀，然后加入适量有机溶剂N-甲基吡咯烷酮(NMP)，制备成浆料，使用涂布机，将正极浆料均匀地徒步在铝箔上。涂布好的正极极片放入鼓风干燥箱中，在120℃下，干燥20小时，最后裁剪得到直径14mm的圆形正极极片。将负极(金属锂片)，电解液(溶质：1mol/L LiPF6溶剂体积比:EC/DEC＝1:2)，隔膜，正极极 片在在手套箱中组装成CR2032型扣式电池用于电性能测试。扣电池测试电压：3.0-4.3V，首次充电容量为25℃、0.1C倍率下的充电容量，首次放电容量为25℃、0.1C倍率下的放电容量。常温循环测试的是在25℃、1C/1C充放电倍率下循环保持率；高温循环测试的是45℃、0.5C/0.5C充放电倍率下循环保持率。
图4为各实施例及对比例的正极材料组成的电池容量对比图；图5为实施例1及各对比例的正极材料组成的电池倍率对比图，各实施例和对比例的电化学性能结果见表2所示。
表2实施例和对比例的锂镍复合氧化物正极材料的电化学性能
对比实施例1和对比例1的电性能测试结果，可以看出在预烧时加入硫酸盐可以显著提升材料的放电容量和倍率性能，同时可以保持良好的常温和高温循环保持率；通过对比实施例1和对比例2的电性能测试结果，可以看出分段预烧可以进一步提升材料的放电容量和倍率性能。由此可以看出，本发明的锂镍复合氧化物正极材料展现出良好的放电容量和优异的倍率性能。

Claims (10)

  1. 一种锂镍复合氧化物正极材料，其特征在于，通过使用扫描电子显微镜进行截面观察，将所述锂镍复合氧化物的截面按照半径长度平均四等分后，测定的每一份截面的孔隙率为3％～8％，截面总孔隙率为3％～8％。
  2. 如权利要求1所述的锂镍复合氧化物正极材料，其特征在于，所述锂镍复合氧化物正极材料的比表面积为0.5～1.0m2/g。
  3. 如权利要求1所述的锂镍复合氧化物正极材料，其特征在于，所述锂镍复合氧化物正极材料以LiaNi1-x-y-zCoxMnyMzO2为基体，基体表面包覆有硼包覆层，其中，M表示选自Li、Na、K、Mg、Ti、Co、Zn、Zr、Ce、Al中的至少一种元素，0.90≤a≤1.10，0＜x≤0.15，0＜y≤0.15，0＜z≤0.02，x+y+z≤0.2。
  4. 如权利要求3所述的锂镍复合氧化物正极材料，其特征在于，所述基体中还含有S元素，S元素占锂镍复合氧化物正极材料总质量的0.02％～0.2％。
  5. 如权利要求3所述的锂镍复合氧化物正极材料，其特征在于，硼包覆层中的硼元素占锂镍复合氧化物正极材料总质量的0.05％～0.2％。
  6. 一种如权利要求1-5中任一项所述的锂镍复合氧化物正极材料的制备方法，其特征在于，包括以下步骤：
    (1)将镍钴锰的氢氧化物与含M的硫酸盐混合后进行低温分段预烧结，得到预烧前驱体；
    (2)按照化学计量比，将锂源与预烧前驱体混合后进行高温烧结，得到一烧基体；
    (3)将一烧基体用去离子水洗涤、干燥后，再与包覆剂混合后进行烧结，得到锂镍复合氧化物正极材料。
  7. 如权利要求6所述的制备方法，其特征在于，步骤(1)中，低温分段预烧结过程为：在空气或氧气气氛下先以3-5℃/min的速度升温至150-200℃，保温烧结1-2h，再以1-3℃/min的速度升温至300-400℃，保温烧结2-5h，最后自然冷却至室温。
  8. 如权利要求6所述的制备方法，其特征在于，步骤(2)中，高温烧结过程为：在空气或氧气气氛下先以1-5℃/min的速度升温至450-550℃，保温烧结3-7h，再以1-5℃/min的速度升温至600-750℃，保温8-15h，最后自然冷却降至室温。
  9. 如权利要求6所述的制备方法，其特征在于，步骤(3)中，烧结过程为：在空气或氧气气氛下以1-5℃/min的速度升温至300-400℃，保温3-12h，然后自然冷却至室温。
  10. 如权利要求6所述的制备方法，其特征在于，步骤(3)中，所述包覆剂为硼酸、氧化硼的一种或几种。
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