WO2024036699A1 - Matériau d'électrode positive, son procédé de préparation et son utilisation - Google Patents

Matériau d'électrode positive, son procédé de préparation et son utilisation 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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PCT/CN2022/120626
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Chinese (zh)
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余海军
李长东
谢英豪
李爱霞
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024036699A1 publication Critical patent/WO2024036699A1/fr

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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—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
    • 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
    • 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

La présente invention concerne un matériau d'électrode positive, son procédé de préparation et son utilisation. Le procédé de préparation comprend les étapes suivantes consistant à : mélanger un matériau d'électrode positive à haute teneur en nickel à traiter avec de l'hexafluoronickelate de potassium, et effectuer un traitement thermique dans une atmosphère d'oxygène pour obtenir un matériau d'électrode positive. Selon la présente invention, le matériau d'électrode positive à haute teneur en nickel est soumis à un traitement d'oxydation au moyen de l'utilisation d'hexafluoronickélate de potassium, et du nickel et du fluor sont dopés dans la couche de surface du matériau d'électrode positive à haute teneur en nickel, ce qui permet de résoudre le problème de production de nickel divalent à partir de la décomposition de nickel trivalent sur la surface du matériau d'électrode positive pendant le frittage par oxydation, et de réduire le mélange de lithium-nickel. En même temps, un matériau métallique électrochimiquement inerte ou des impuretés qui sont difficiles à éliminer ne sont pas introduits, ce qui permet d'augmenter la capacité et la stabilité de cyclage du matériau d'électrode positive.
PCT/CN2022/120626 2022-08-15 2022-09-22 Matériau d'électrode positive, son procédé de préparation et son utilisation WO2024036699A1 (fr)

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US5599642A (en) * 1993-05-31 1997-02-04 Hitachi Maxell, Ltd. Lithium secondary battery containing organic electrolyte, active material for cathode thereof, and method for manufacturing the active material
JP2008234988A (ja) * 2007-03-20 2008-10-02 Sony Corp 負極およびその製造方法、ならびに電池およびその製造方法
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CN105047905A (zh) * 2015-07-13 2015-11-11 中南大学 一种富镍正极材料的表面改性方法
WO2020147670A1 (fr) * 2019-01-17 2020-07-23 浙江工业大学 Procédé de préparation de matériau de cathode ternaire de batterie au lithium-ion
CN114864947A (zh) * 2022-06-21 2022-08-05 远东电池江苏有限公司 一种包覆型高镍三元正极材料的补锂方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5599642A (en) * 1993-05-31 1997-02-04 Hitachi Maxell, Ltd. Lithium secondary battery containing organic electrolyte, active material for cathode thereof, and method for manufacturing the active material
JP2008234988A (ja) * 2007-03-20 2008-10-02 Sony Corp 負極およびその製造方法、ならびに電池およびその製造方法
CN101878185A (zh) * 2007-11-30 2010-11-03 气体产品与化学公司 十二硼酸盐自由基负离子组合物以及制备和使用该组合物的方法
CN105047905A (zh) * 2015-07-13 2015-11-11 中南大学 一种富镍正极材料的表面改性方法
WO2020147670A1 (fr) * 2019-01-17 2020-07-23 浙江工业大学 Procédé de préparation de matériau de cathode ternaire de batterie au lithium-ion
CN114864947A (zh) * 2022-06-21 2022-08-05 远东电池江苏有限公司 一种包覆型高镍三元正极材料的补锂方法

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