WO2024036699A1 - 一种正极材料及其制备方法和应用 - Google Patents

一种正极材料及其制备方法和应用 Download PDF

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WO2024036699A1
WO2024036699A1 PCT/CN2022/120626 CN2022120626W WO2024036699A1 WO 2024036699 A1 WO2024036699 A1 WO 2024036699A1 CN 2022120626 W CN2022120626 W CN 2022120626W WO 2024036699 A1 WO2024036699 A1 WO 2024036699A1
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nickel
positive electrode
cathode material
electrode material
cathode
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French (fr)
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余海军
李长东
谢英豪
李爱霞
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 invention belongs to the technical field of lithium ion batteries and relates to a positive electrode material and its preparation method and application.
  • Battery materials are divided into positive electrode materials, negative electrode materials, separators, electrolytes, etc.
  • Cathode material is one of the key materials for manufacturing lithium-ion batteries, accounting for more than 25% of the battery cost. Its performance directly affects various performance indicators of the battery and occupies a core position in lithium-ion batteries.
  • Currently marketed lithium battery cathode materials include lithium cobalt oxide, lithium manganate, lithium nickel oxide, lithium iron phosphate and ternary materials. Among them, ternary materials combine the advantages of the three materials, greatly reducing the cost and improving cycle performance. Good, its comprehensive performance is better than any of the above single cathode materials.
  • High-nickel ternary lithium-ion battery cathode materials have become a hot research topic due to their advantages of high specific capacity, low cost and excellent safety, and are considered to be lithium-ion power battery cathode materials with great application prospects.
  • high nickel content also brings about structural instability and serious problems of high-temperature flatulence, especially when nickel and lithium are mixed.
  • the divalent nickel ions embedded in the lithium layer are oxidized into trivalent nickel ions during the lithium ion extraction process, resulting in local structures. Collapse makes it more difficult for lithium ions to embed into the collapsed sites, resulting in capacity loss. Therefore, research on pre-oxidation of ternary cathode material precursors to reduce nickel-lithium mixing has very important practical significance.
  • CN108511746A uses nitrate to oxidize the high-nickel precursor, so that the trivalent nickel in the precursor material increases.
  • the temperature of the surface of the cathode material is higher than that of the inner layer, and it is easy to decompose to produce divalent nickel. Therefore, the divalent nickel on the surface of the cathode material obtained through this preparation method is still too high, which will affect its initial capacity and cycle performance.
  • N elements that are difficult to remove will be introduced.
  • CN108461731A discloses a high-nickel ternary lithium battery cathode material and a preparation method.
  • This method disperses nano-oxidant powder and paraffin wax at high speed, so that the paraffin wax is evenly wrapped on the surface of the nano-oxidant powder to form a nano-oxidant powder with a shell-core structure; it is then mixed with a nickel source, a cobalt source, and a manganese source, precipitated, and further mixed with a lithium source. , sintering to remove organic matter to prepare high-nickel ternary lithium battery cathode materials.
  • the precursor is also pre-oxidized, and there is also the above-mentioned problem of easy decomposition to obtain divalent nickel.
  • the object of the present invention is to provide a cathode material and its preparation method and application.
  • This invention solves the problem of decomposing trivalent nickel on the surface of the cathode material to produce divalent nickel during oxidation sintering by using potassium hexafluoronickelate to oxidize the high-nickel cathode material to be treated, and incorporating nickel and fluorine into its surface layer. It reduces the mixing of lithium and nickel without introducing electrochemically inert metal materials or impurities that are difficult to remove, thereby improving the capacity and cycle stability of the cathode material.
  • the present invention provides a method for preparing a cathode material.
  • the preparation method includes the following steps:
  • the high-nickel cathode material to be treated is mixed with potassium hexafluoronickelate, and heat-treated in an oxygen atmosphere to obtain the cathode material.
  • the high-nickel cathode material to be treated provided by the present invention is a cathode material obtained by oxidation and sintering. It can be purchased directly or can be obtained by mixing the precursor with the lithium source and then sintering.
  • the high-nickel cathode material in the present invention is Cathode materials with a stoichiometric ratio of nickel >0.6.
  • This invention solves the problem of decomposing trivalent nickel on the surface of the cathode material to produce divalent nickel during oxidation sintering by using potassium hexafluoronickelate to oxidize the high-nickel cathode material to be treated, and incorporating nickel and fluorine into its surface layer. It reduces the mixing of lithium and nickel without introducing electrochemically inert metal materials or impurities that are difficult to remove, thereby improving the capacity and cycle stability of the cathode material.
  • the potassium hexafluoronickelate oxidizes the divalent nickel on the surface of the cathode material into trivalent nickel, and at the same time, the hexafluoronickelate Potassium is reduced to obtain nickel trifluoride and potassium fluoride.
  • trivalent nickel, fluorine and potassium are doped into the surface of the cathode material.
  • Trivalent nickel can increase the capacity of the cathode material, and fluorine can replace the oxygen position doping, which can further The stability of the cathode material is improved, and the potassium on the surface can be easily removed through a water washing step.
  • the preparation method provided by the present invention can solve the problem of decomposition of trivalent nickel on the surface of the cathode material to produce divalent nickel during oxidation sintering by introducing potassium hexafluoronickelate to oxidize and dope the cathode material, and does not require long-term low temperature Sintering can reduce costs and reduce the mixing of lithium and nickel. At the same time, it does not introduce electrochemically inert metal materials or impurities that are difficult to remove, and improves the capacity and cycle stability of the cathode material.
  • oxidants such as potassium permanganate and other strong oxidants
  • the divalent nickel on the surface of the cathode material can be oxidized to trivalent nickel to a certain extent, manganese dioxide will be formed on the surface of the material. , thus seriously affecting the gram capacity and conductive properties of the cathode material.
  • the amount of potassium hexafluoronickelate added is 0.1 to 10% of the mass of the high-nickel cathode material to be treated, such as 0.1%, 1%, 2%, 3%, 4%, 5% , 5.3%, 5.5%, 5.8%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 9.8% or 10%, etc., preferably 5 to 10%.
  • the addition amount of potassium hexafluoronickelate provided by the present invention can achieve better results in the range of 5 to 10%. Within this range, the oxidation of divalent nickel will be more complete. At the same time, because of the doped It is nickel, and it will not reduce the capacity of the material. If the amount is too much, more than 10%, the surface nickel content will be too high and the manganese and cobalt content is too low, thereby reducing the cycle stability. If the amount is too little, it will be less than 10%. 5%, although the effect of reducing surface divalent nickel can be achieved to a certain extent, there will still be cases where some divalent nickel is not completely oxidized.
  • the temperature of the heat treatment is 200-500°C, such as 200°C, 205°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C , 350°C, 400°C, 450°C or 500°C, etc., preferably 200 to 300°C.
  • the heat treatment temperature is in the range of 200 to 300°C
  • the divalent nickel on the surface of the positive electrode material can be oxidized into trivalent nickel.
  • the temperature is too high, exceeding 300°C, on the one hand, unnecessary energy consumption will be increased. On the other hand, it may promote the decomposition of trivalent nickel.
  • the heat treatment time is 1 to 10 h, such as 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., preferably 1 to 3 h.
  • the preparation method provided by the invention does not require too long time during the heat treatment process.
  • the addition of potassium hexafluoronickelate can effectively reduce the heat treatment time. Heat treatment within 1 to 3 hours can also more effectively avoid surface damage. Valent nickel is decomposed, and if the heat treatment time is too long, more than 3 hours, the potassium hexafluoronickelate may be completely consumed, and the divalent nickel produced by the decomposition of trivalent nickel on the surface cannot be oxidized.
  • the preparation method of the high-nickel cathode material to be treated includes:
  • the high-nickel cathode precursor is mixed with the lithium source and sintered in an oxygen atmosphere to obtain the cathode material to be processed.
  • the general chemical formula of the high-nickel cathode precursor is Ni x Co y M 1-xy (OH) 2 , x>0.6, y ⁇ 0, M includes Mn and/or Al, for example, x can be 0.63, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.93 or 0.95, etc., and the y can be 0.05, 0.1, 0.13, 0.15, 0.2, 0.25, 0.3 or 0.33, etc.
  • x>0.9 such as 0.91, 0.92, 0.93, 0.94 or 0.95, etc.
  • the lithium source includes lithium hydroxide.
  • lithium hydroxide is selected as the lithium source, and the reaction is more thorough. However, if other lithium sources, such as lithium carbonate, are used, incomplete decomposition may occur.
  • the sintering temperature is 750-800°C, such as 750°C, 760°C, 770°C, 780°C, 790°C or 800°C.
  • the sintering time is 8 to 20h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, etc., preferably 8 to 12h.
  • the present invention When preparing the high-nickel cathode material to be processed, the present invention will subsequently perform an oxidation heat treatment process, and when potassium hexafluoronickelate is used as the oxidant, the oxidation sintering time can be shortened and sintering costs can be saved.
  • the heat-treated material is washed with water and dried in sequence.
  • the preparation method includes the following steps:
  • step (2) Mix the cathode material to be modified described in step (1) with potassium hexafluoronickelate in an amount of 5 to 10% of the mass of the cathode material to be modified in an oxygen atmosphere Heat treatment is performed at a temperature of 200 to 300°C for 1 to 3 hours, washed with water, and dried to obtain the cathode material;
  • the general chemical formula of the cathode precursor is Nix Co y M 1-xy (OH) 2 , x>0.9, y ⁇ 0, and M includes Mn and/or Al.
  • the present invention provides a cathode material prepared by the method for preparing a cathode material as described in the first aspect; the surface layer of the cathode material is doped with fluorine and nickel.
  • fluorine and nickel will penetrate into the surface layer of the cathode material during the heat treatment process.
  • the present invention also provides a lithium ion battery, which includes the cathode material as described in the second aspect.
  • the present invention has the following beneficial effects:
  • the preparation method provided by the invention can solve the problem of decomposing trivalent nickel on the surface of the cathode material to produce divalent nickel during oxidation sintering by introducing potassium hexafluoronickelate to oxidize and dope the cathode material, and does not require long-term low-temperature sintering. It can reduce costs and reduce the mixing of lithium and nickel. At the same time, it does not introduce electrochemically inert metal materials or impurities that are difficult to remove, and fluorine and nickel are incorporated into the surface layer of the high-nickel cathode material, which improves the capacity and cycle of the cathode material. stability, achieving a comprehensive improvement in the electrochemical performance of the cathode material.
  • the battery provided by the invention has a discharge capacity of more than 206.9mAh/g at 0.1C, and after 100 cycles, its capacity retention rate can reach more than 85.3%.
  • Figure 1 is an SEM image of the high-nickel cathode material provided in Example 1.
  • This embodiment provides a high-nickel cathode material, the surface layer of the high-nickel cathode material is doped with fluorine and nickel.
  • the preparation method of the high-nickel cathode material is as follows:
  • Figure 1 shows an SEM image of the high-nickel cathode material provided in Example 1. It can be seen from Figure 1 that the high-nickel cathode material in Example 1 has a polycrystalline structure, and there is a coating layer on its surface, with obvious The reaction traces are intact and the particles are intact.
  • This embodiment provides a high-nickel cathode material, the surface layer of the high-nickel cathode material is doped with fluorine and nickel.
  • the preparation method of the high-nickel cathode material is as follows:
  • This embodiment provides a high-nickel cathode material, the surface layer of the high-nickel cathode material is doped with fluorine and nickel.
  • the preparation method of the high-nickel cathode material is as follows:
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the mass ratio of the high-nickel positive electrode material to be processed in step (2) of this embodiment to potassium hexafluoronickelate is 100:3.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the mass ratio of the high-nickel positive electrode material to be processed in step (2) of this embodiment to potassium hexafluoronickelate is 100:10.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the mass ratio of the high-nickel positive electrode material to be processed in step (2) of this embodiment to potassium hexafluoronickelate is 100:15.
  • the difference between this embodiment and Embodiment 1 is that the heat treatment time in step (2) of this embodiment is 5 hours.
  • the difference between this embodiment and Embodiment 1 is that the temperature of the heat treatment in step (2) of this embodiment is 500°C.
  • Example 1 The difference between this comparative example and Example 1 is that potassium hexafluornickelate is not added in step (2) of this comparative example.
  • Example 1 uses potassium permanganate for oxidation, and the preparation process is as follows:
  • Example 3 The difference between this comparative example and Example 3 is that potassium hexafluoronickelate is not added in step (2) of this comparative example.
  • the high-nickel cathode materials provided in Examples 1-8 and Comparative Examples 1-3 were formed into button batteries for electrochemical performance testing of lithium ion batteries.
  • the specific steps were: using N-methylpyrrolidone as the solvent, according to the mass ratio of 9.2 Mix the positive active material, acetylene black, and PVDF in a ratio of :0.5:0.3 evenly, apply it on the aluminum foil, air dry it at 80°C for 8 hours, and then vacuum dry it at 120°C for 12 hours. Assemble the battery in an argon-protected glove box.
  • the cathode is a lithium metal sheet
  • the separator is a polypropylene film
  • the electrolyte is 1M LiPF 6 -EC/DMC (1:1, v/v)
  • a 2032 button battery case is used. Assemble the coin cells in an argon-protected glove box, and then conduct electrochemical performance tests at 3.0-4.5V at 25°C. The results are shown in Table 1 below.
  • Example 1 It can be seen from the data results of Example 1 and Examples 4-6 that the mass proportion of potassium hexafluoronickelate is less than 5%, which is not conducive to increasing the gram capacity and improving the cycle stability, while being greater than 10% will cause surface nickel The content is too high, resulting in reduced cycle stability.
  • Example 7 From the data results of Example 1 and Example 7, it can be seen that after adding potassium hexafluoronickelate, the heat treatment time is too long, which on the one hand consumes more energy, on the other hand causes the trivalent nickel on the surface to decompose and reduces the gram capacity. .
  • Example 1 and Example 8 It can be seen from the data results of Example 1 and Example 8 that after adding potassium hexafluoronickelate, the temperature of the heat treatment is too high, which will cause the trivalent nickel on the surface to decompose, reduce the gram capacity, and at the same time enhance the mixing of lithium and nickel, reducing the cycle stability.
  • Example 3 From the data results of Example 1 and Comparative Example 1, Example 3 and Comparative Example 3, it can be seen that without adding potassium hexafluoronickelate for oxidation, the divalent nickel content on the surface of the cathode material cannot be reduced, resulting in serious nickel-lithium The mixed discharge phenomenon causes a significant reduction in cycle stability and gram capacity.
  • the preparation method provided by the present invention can solve the problem of decomposition of trivalent nickel on the surface of the cathode material to produce divalent nickel during oxidation sintering by introducing potassium hexafluoronickelate to oxidize and dope the cathode material, without the need for Long-term low-temperature sintering can reduce costs and reduce the mixing of lithium and nickel.
  • it does not introduce electrochemically inert metal materials or impurities that are difficult to remove, and fluorine and nickel are incorporated into the surface layer of high-nickel cathode materials to improve the performance of the cathode.
  • the capacity and cycle stability of the material achieve a comprehensive improvement in the electrochemical performance of the cathode material.
  • the battery provided by the invention has a discharge capacity of more than 206.9mAh/g at 0.1C, and after 100 cycles, its capacity retention rate can reach more than 85.3%.

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Abstract

本发明提供了一种正极材料及其制备方法和应用。所述制备方法包括以下步骤：将待处理的高镍正极材料与六氟合镍酸钾混合，氧气气氛下进行热处理，得到所述正极材料。本发明通过采用六氟合镍酸钾对待处理的高镍正极材料进行氧化处理，在其表层掺入了镍和氟，解决了氧化烧结中正极材料表面三价镍分解产生二价镍的问题，减少了锂镍混排，同时不会引入电化学惰性的金属材料或者难以去除的杂质，从而提高了正极材料的容量和循环稳定性。

Description

一种正极材料及其制备方法和应用 技术领域
本发明属于锂离子电池技术领域，涉及一种正极材料及其制备方法和应用。
背景技术
电池材料分为正极材料、负极材料、隔膜、电解液等。正极材料是制造锂离子电池的关键材料之一，占据电池成本的25％以上，其性能直接影响电池的各项性能指标，在锂离子电池中占据核心地位。目前已经市场化的锂电池正极材料包括钴酸锂、锰酸锂、镍酸锂、磷酸铁锂和三元材料等产品，其中三元材料综合了三种材料的优点，成本大大降低，循环性能良好，其综合性能优于以上任一单一正极材料。
高镍三元锂离子电池正极材料凭借比容量高、成本较低和安全性优良等优势，成为研究的热点，被认为是极具应用前景的锂离子动力电池正极材料。但高镍含量同时带来了结构不稳定和高温胀气严重的问题，尤其是镍锂混排，嵌入锂层的二价镍离子在锂离子脱出过程中被氧化为三价镍离子，导致局部结构坍塌，锂离子更难以嵌入坍塌的位点，从而导致容量损失。因此针对三元正极材料前驱体的预氧化降低镍锂混排的研究具有十分重要的实际意义。
高镍正极材料(Ni＞0.6)，如NCM和NCA的生成过程中，需要进行氧气烧结，使得其前驱体中的二价镍氧化成三价。随着镍含量的提高，通过常规氧化烧结方式很难将二价镍氧化成三价镍，现有技术中一般通过延长氧化烧结时间或提高氧化烧结温度的方式解决这一问题，然而效果不佳，因为三价镍在高温下容易分解产生二价镍，长时间低温烧结又会导致成本的明显上升。
现有技术中，有人通过对前驱体进行预氧化的方式以提高二价镍的氧化效果，比如CN108511746A通过硝酸盐对高镍前驱体进行氧化，使得前驱体材料中的三价镍增多，然而因为在氧化烧结时，正极材料表面的温度较内层高，容易分解产生二价镍，因此通过此制备方法得到的正极材料表面的二价镍仍然过高，如此会影响其初始容量和循环性能，同时会引入难以去除的N元素。
再如CN108461731A公开了一种高镍三元锂电池正极材料及制备方法。该方法将纳米氧化剂粉末与石蜡高速分散，使石蜡均匀包裹在纳米氧化剂粉末表面，形成壳核结构的纳米氧化剂粉末；然后与镍源、钴源、锰源混合，沉淀处理，进一步与锂源混合，烧结除去有机质，制得高镍三元锂电池正极材料，该专利申请中同样对前驱体进行了预氧化过程，也存在上述提到的容易分解得到二价镍的问题。
因此，如何降低高镍正极材料氧化烧结过程中出现的三价镍分解的问题，提升其容量和循环性能，是亟待解决的技术问题。
发明内容
本发明的目的在于提供一种正极材料及其制备方法和应用。本发明通过采用六氟合镍酸钾对待处理的高镍正极材料进行氧化处理，在其表层掺入了镍和氟，解决了氧化烧结中正极材料表面三价镍分解产生二价镍的问题，减少了锂镍混排，同时不会引入电化学惰性的金属材料或者难以去除的杂质，从而提高了正极材料的容量和循环稳定性。
为达到此发明目的，本发明采用以下技术方案：
第一方面，本发明提供一种正极材料的制备方法，所述制备方法包括以下步骤：
将待处理的高镍正极材料与六氟合镍酸钾混合，氧气气氛下进行热处理， 得到所述正极材料。
本发明提供的待处理的高镍正极材料，为经过氧化烧结得到的正极材料，既可以直接购买得到，也可以将前驱体与锂源混合后烧结得到，且本发明中的高镍正极材料为镍的化学计量比＞0.6的正极材料。
本发明通过采用六氟合镍酸钾对待处理的高镍正极材料进行氧化处理，在其表层掺入了镍和氟，解决了氧化烧结中正极材料表面三价镍分解产生二价镍的问题，减少了锂镍混排，同时不会引入电化学惰性的金属材料或者难以去除的杂质，从而提高了正极材料的容量和循环稳定性。
本发明中，通过将氧化烧结后的高镍正极材料与六氟合镍酸钾均匀混合，六氟合镍酸钾将正极材料表面的二价镍氧化成三价镍，同时六氟合镍酸钾还原得到三氟化镍和氟化钾，在烧结过程中三价镍、氟和钾掺杂进入正极材料表面，三价镍可以提高正极材料的容量、氟可以取代氧位置掺杂，可以进一步提高正极材料的稳定性，而表面的钾可以通过水洗步骤很容易清除。
因此，本发明提供的制备方法，通过引入六氟合镍酸钾对正极材料进行氧化和掺杂，可以解决氧化烧结中正极材料表面三价镍分解产生二价镍的问题，不需要长时间低温烧结从而可以降低成本，还减少锂镍混排，同时不会引入电化学惰性的金属材料或者难以去除的杂质，提高了正极材料的容量和循环稳定性。
本发明中，如果选用其他种类的氧化剂，如高锰酸钾等强氧化剂，虽然一定程度上可以实现将正极材料的表面的二价镍氧化为三价镍，但是会在材料表面形成二氧化锰，从而严重影响了正极材料的克容量和导电性能。
优选地，所述六氟合镍酸钾的加入量为所述待处理的高镍正极材料的质量的0.1～10％，例如0.1％、1％、2％、3％、4％、5％、5.3％、5.5％、5.8％、6％、 6.5％、7％、7.5％、8％、8.5％、9％、9.5％、9.8％或10％等，优选为5～10％。
本发明提供的六氟合镍酸钾的加入量，其在5～10％的范围内，可发挥更好的效果，在该范围内，二价镍的氧化会更完全，同时因为掺杂的是镍，也不会降低材料的容量，而加入量如果过多，超过10％，会导致表面镍含量过高而锰钴的含量过低，从而降低循环稳定性，而加入量过少，小于5％，虽然一定程度上也可以实现降低表面二价镍的效果，但是仍然会存在部分二价镍未被氧化完全的的情况。
优选地，所述热处理的温度为200～500℃，例如200℃、205℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃、300℃、350℃、400℃、450℃或500℃等，优选为200～300℃。
本发明中，热处理的温度在200～300℃范围内，即可实现将正极材料表面的二价镍氧化为三价镍，而温度过高，超过300℃，一方面增加不必要的能耗，另一方面可能会促进三价镍分解。
优选地，所述热处理的时间为1～10h，例如1h、1.5h、2h、2.5h、3h、4h、5h、6h、7h、8h、9h或10h等，优选为1～3h。
本发明提供的制备方法，热处理过程中，无需过长的时间，六氟合镍酸钾的加入可以有效地降低热处理的时间，在1～3h内热处理，还能更为有效地避免表面的三价镍被分解，而热处理时间过长，超过3h，可能导致六氟合镍酸钾被消耗完全，不能够将表面三价镍分解产生的二价镍进行氧化。
优选地，所述待处理的高镍正极材料的制备方法包括：
将高镍正极前驱体与锂源混合，氧气气氛下烧结，得到待处理正极材料。
优选地，所述高镍正极前驱体的化学通式为Ni xCo yM 1-x-y(OH) 2，x＞0.6，y≥0，M包括Mn和/或Al，例如所述x可以为0.63、0.65、0.7、0.75、0.8、0.85、0.9、 0.93或0.95等，所述y可以为0.05、0.1、0.13、0.15、0.2、0.25、0.3或0.33等。
优选地，所述高镍正极前驱体的化学通式Ni xCo yM 1-x-y(OH) 2中，x＞0.9，例如0.91、0.92、0.93、0.94或0.95等。
优选地，所述锂源包括氢氧化锂。
本发明中，选用氢氧化锂作为锂源，反应更彻底，而如果选用其他锂源，如碳酸锂，可能会出现分解不完全的情况。
优选地，所述烧结的温度为750～800℃，例如750℃、760℃、770℃、780℃、790℃或800℃等。
优选地，所述烧结的时间为8～20h，例如8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等，优选为8～12h。
本发明制备待处理高镍正极材料时，后续会进行氧化热处理的过程，且以六氟合镍酸钾为氧化剂时，可以缩短氧化烧结时间，节约了烧结成本。
优选地，对所述热处理后物质依次进行水洗和干燥。
作为优选的技术方案，所述制备方法包括以下步骤：
(1)将正极前驱体与氢氧化锂混合，氧气气氛下以750～800℃的烧结温度烧结8～12h，得到待改性正极材料；
(2)将步骤(1)所述待改性正极材料与六氟合镍酸钾混合，六氟合镍酸钾的加入量为待改性的正极材料的质量的5～10％，氧气气氛下以200～300℃的温度进行热处理1～3h，水洗，干燥，得到所述正极材料；
其中，所述正极前驱体的化学通式为Ni xCo yM 1-x-y(OH) 2，x＞0.9，y≥0，M包括Mn和/或Al。
第二方面，本发明提供一种正极材料，所述正极材料由如第一方面所述的正极材料的制备方法制备得到；所述正极材料的表层掺杂氟和镍。
本发明提供的正极材料，氟和镍会在热处理过程中，渗入正极材料的表层。
第三方面，本发明还提供一种锂离子电池，所述锂离子电池包括如第二方面所述的正极材料。
相对于现有技术，本发明具有以下有益效果：
本发明提供的制备方法，通过引入六氟合镍酸钾对正极材料进行氧化和掺杂，可以解决氧化烧结中正极材料表面三价镍分解产生二价镍的问题，不需要长时间低温烧结从而可以降低成本，还减少锂镍混排，同时不会引入电化学惰性的金属材料或者难以去除的杂质，并在高镍正极材料的表层掺入了氟和镍，提高了正极材料的容量和循环稳定性，实现了正极材料电化学性能的综合提升。本发明提供的电池，0.1C下的放电容量为206.9mAh/g以上，且经过100次循环后，其容量保持率可达85.3％以上。
附图说明
图1为实施例1提供的高镍正极材料的SEM图。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
本实施例提供一种高镍正极材料，所述高镍正极材料的表层掺杂有氟和镍。
所述高镍正极材料的制备方法如下：
(1)将Ni 0.9Co 0.05Mn 0.05(OH) 2与LiOH(Li和Ni的摩尔比为1:0.9)混合，在高效球磨机中混合5h，得到混合均匀的混合料；然后将混合料置于气氛炉中，通入3L/min的氧气，以5℃/min升温速度到达800℃，恒温烧结8小时，煅烧完毕后冷却至室温，过300目筛以除去过大的颗粒，即得到待处理的高镍正极 材料LiNi 0.9Co 0.05Mn 0.05O 2；
(2)将上述待处理的高镍正极材料与六氟合镍酸钾(质量比为100:5)在高效混料机中混合20min，得到混合均匀的混合料，然后将混合料置于气氛炉中，通入3L/min的氧气，在300℃的温度下热处理1h，然后进行水洗，干燥后即得到所述高镍正极材料。
图1示出了实施例1提供的高镍正极材料的SEM图，从图1可以看出，实施例1中的高镍正极材料为多晶结构，其表面存在一层包覆层，有明显的反应痕迹，颗粒完整。
实施例2
本实施例提供一种高镍正极材料，所述高镍正极材料的表层掺杂有氟和镍。
所述高镍正极材料的制备方法如下：
(1)将Ni 0.9Co 0.05Mn 0.05(OH) 2与LiOH(Li和Ni的摩尔比为1:0.9)混合，在高效球磨机中混合5h，得到混合均匀的混合料；然后将混合料置于气氛炉中，通入3L/min的氧气，以5℃/min升温速度到达780℃，恒温烧结10小时，煅烧完毕后冷却至室温，过300目筛以除去过大的颗粒，即得到待处理的高镍正极材料LiNi 0.9Co 0.05Mn 0.05O 2；
(2)将上述待处理的高镍正极材料与六氟合镍酸钾(质量比为100:8)在高效混料机中混合20min，得到混合均匀的混合料，然后将混合料置于气氛炉中，通入3L/min的氧气，在250℃的温度下热处理2h，然后进行水洗，干燥后即得到所述高镍正极材料。
实施例3
本实施例提供一种高镍正极材料，所述高镍正极材料的表层掺杂有氟和镍。
所述高镍正极材料的制备方法如下：
(1)将Ni 0.8Co 0.1Mn 0.1(OH) 2与LiOH(Li和Ni的摩尔比为1:0.8)混合，在高效球磨机中混合5h，得到混合均匀的混合料；然后将混合料置于气氛炉中，通入3L/min的氧气，以5℃/min升温速度到达780℃，恒温烧结10小时，煅烧完毕后冷却至室温，过300目筛以除去过大的颗粒，即得到待处理的高镍正极材料LiNi 0.8Co 0.1Mn 0.1O 2；
(2)将上述待处理的高镍正极材料与六氟合镍酸钾(质量比为100:10)在高效混料机中混合20min，得到混合均匀的混合料，然后将混合料置于气氛炉中，通入3L/min的氧气，在200℃的温度下热处理3h，然后进行水洗，干燥后即得到所述高镍正极材料。
实施例4
本实施例与实施例1的区别为，本实施例步骤(2)中待处理的高镍正极材料与六氟合镍酸钾的质量比为100:3。
其余制备方法与参数与实施例1保持一致。
实施例5
本实施例与实施例1的区别为，本实施例步骤(2)中待处理的高镍正极材料与六氟合镍酸钾的质量比为100:10。
其余制备方法与参数与实施例1保持一致。
实施例6
本实施例与实施例1的区别为，本实施例步骤(2)中待处理的高镍正极材料与六氟合镍酸钾的质量比为100:15。
其余制备方法与参数与实施例1保持一致。
实施例7
本实施例与实施例1的区别为，本实施例步骤(2)中热处理的时间为5h。
其余制备方法与参数与实施例1保持一致。
实施例8
本实施例与实施例1的区别为，本实施例步骤(2)中热处理的温度为500℃。
其余制备方法与参数与实施例1保持一致。
对比例1
本对比例与实施例1的区别为，本对比例步骤(2)中不加入六氟合镍酸钾。
其余制备方法与参数与实施例1保持一致。
对比例2
本对比例与实施例1的区别为，本对比例采用高锰酸钾进行氧化，制备过程如下：
使用高锰酸钾(质量比5:100)氧化Ni 0.9Co 0.05Mn 0.05(OH) 2，然后与LiOH(Li和Ni的摩尔比为1:0.9)混合，在高效球磨机中混合5h，得到混合均匀的混合料；将混合料置于气氛炉中，通入3L/min的氧气，以5℃/min升温速度到达800℃，恒温烧结8小时，煅烧完毕后冷却至室温，过300目筛以除去过大的颗粒，即得到高镍正极材料LiNi 0.9Co 0.05Mn 0.05O 2。
对比例3
本对比例与实施例3的区别为，本对比例步骤(2)中不加入六氟合镍酸钾。
其余制备方法与参数与实施例3保持一致。
将实施例1-8与对比例1-3提供的高镍正极材料配成扣式电池进行锂离子电池电化学性能测试，其具体步骤为：以N-甲基吡咯烷酮为溶剂，按照质量比9.2:0.5:0.3的比例将正极活性物质与乙炔黑、PVDF混合均匀，涂覆于铝箔上，经80℃鼓风干燥8h后，于120℃真空干燥12h。在氩气保护的手套箱中装配电池，负极为金属锂片，隔膜为聚丙烯膜，电解液为1M LiPF 6-EC/DMC(1:1，v/v)， 采用2032型扣式电池壳在氩气保护的手套箱中组装成扣式电池，然后在25℃下3.0-4.5V进行电化学性能测试。结果如下表1所示。
表1
Figure PCTCN2022120626-appb-000001
从实施例1与实施例4-6的数据结果可知，六氟合镍酸钾的质量占比小于5％，不利于提高克容量和改善循环稳定性，而大于10％，又会导致表面镍含量过高，从而导致循环稳定性降低。
从实施例1与实施例7的数据结果可知，加入六氟合镍酸钾后，热处理的时间过长，一方面需要消耗更多的能源，一方面导致表面的三价镍分解，降低克容量。
从实施例1与实施例8的数据结果可知，加入六氟合镍酸钾后，热处理的温度过高，会导致表面的三价镍分解，降低克容量，同时增强锂镍混排，降低循环稳定性。
从实施例1与对比例1，实施例3与对比例3的数据结果可知，不加入六氟合镍酸钾进行氧化，就无法降低正极材料表面的二价镍含量，从而导致严重的镍锂混排现象，造成循环稳定性和克容量明显降低。
从实施例1与对比例2的数据结果可知，选用其他类型的氧化剂，虽然可以一定程度上实现提高正极材料的循环稳定性，但是很难实现容量和循环的双重提升，即某一方面的电化学性能的提升是以牺牲其他的性能为代价的。
综上所述，本发明提供的制备方法，通过引入六氟合镍酸钾对正极材料进行氧化和掺杂，可以解决氧化烧结中正极材料表面三价镍分解产生二价镍的问题，不需要长时间低温烧结从而可以降低成本，还减少锂镍混排，同时不会引入电化学惰性的金属材料或者难以去除的杂质，并在高镍正极材料的表层掺入了氟和镍，提高了正极材料的容量和循环稳定性，实现了正极材料电化学性能的综合提升。本发明提供的电池，0.1C下的放电容量为206.9mAh/g以上，且经过100次循环后，其容量保持率可达85.3％以上。
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种正极材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    将待处理的高镍正极材料与六氟合镍酸钾混合，氧气气氛下进行热处理，得到所述正极材料。
  2. 根据权利要求1所述的正极材料的制备方法，其特征在于，所述六氟合镍酸钾的加入量为所述待处理的高镍正极材料的质量的0.1～10％，优选为5～10％。
  3. 根据权利要求1或2所述的正极材料的制备方法，其特征在于，所述热处理的温度为200～500℃，优选为200～300℃；
    优选地，所述热处理的时间为1～10h，优选为1～3h。
  4. 根据权利要求1-3任一项所述的正极材料的制备方法，其特征在于，所述待处理的高镍正极材料的制备方法包括：
    将高镍正极前驱体与锂源混合，氧气气氛下烧结，得到待处理正极材料；
    优选地，所述高镍正极前驱体的化学通式为Ni xCo yM 1-x-y(OH) 2，x＞0.6，y≥0，M包括Mn和/或Al。
  5. 根据权利要求4所述的正极材料的制备方法，其特征在于，所述高镍正极前驱体的化学通式Ni xCo yM 1-x-y(OH) 2中，x＞0.9。
  6. 根据权利要求4或5所述的正极材料的制备方法，其特征在于，所述锂源包括氢氧化锂。
  7. 根据权利要求4-6任一项所述的正极材料的制备方法，其特征在于，所述烧结的温度为750～800℃；
    优选地，所述烧结的时间为8～20h，优选为8～12h；
    优选地，对所述热处理后物质依次进行水洗和干燥。
  8. 根据权利要求1-7任一项所述的正极材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    (1)将正极前驱体与氢氧化锂混合，氧气气氛下以750～800℃的烧结温度烧结8～12h，得到待改性正极材料；
    (2)将步骤(1)所述待改性正极材料与六氟合镍酸钾混合，六氟合镍酸钾的加入量为待改性的正极材料的质量的5～10％，氧气气氛下以200～300℃的温度进行热处理1～3h，水洗，干燥，得到所述正极材料；
    其中，所述正极前驱体的化学通式为Ni xCo yM 1-x-y(OH) 2，x＞0.9，y≥0，M包括Mn和/或Al。
  9. 一种正极材料，其特征在于，所述正极材料由如权利要求1-8任一项所述的正极材料的制备方法制备得到；所述正极材料的表层掺杂氟和镍。
  10. 一种锂离子电池，其特征在于，所述锂离子电池包括如权利要求9所述的正极材料。
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