WO2021223635A1 - Matériau d'électrode positive au cobaltate de lithium, procédé de préparation s'y rapportant et utilisation associée - Google Patents

Matériau d'électrode positive au cobaltate de lithium, procédé de préparation s'y rapportant et utilisation associée Download PDF

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WO2021223635A1
WO2021223635A1 PCT/CN2021/090461 CN2021090461W WO2021223635A1 WO 2021223635 A1 WO2021223635 A1 WO 2021223635A1 CN 2021090461 W CN2021090461 W CN 2021090461W WO 2021223635 A1 WO2021223635 A1 WO 2021223635A1
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lithium
cobalt oxide
lithium cobalt
cathode material
coating layer
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PCT/CN2021/090461
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English (en)
Chinese (zh)
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岳鹏
李栋梁
刘亚飞
陈彦彬
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北京当升材料科技股份有限公司
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/043—Lithium aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—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
    • 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
    • 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 relates to the technical field of lithium ion battery cathode materials, in particular to a lithium cobalt oxide cathode material and a preparation method and application thereof.
  • lithium cobalt oxide relies on its higher discharge voltage platform and higher volume under high voltage (4.5V). Energy density has become one of the most ideal cathode materials for small high-energy-specific batteries.
  • the theoretical capacity of the lithium cobalt oxide cathode material is 274mAh/g.
  • the charge cut-off voltage of the material is continuously increased to release more lithium to release higher gram-specific energy.
  • the conventional 4.2V lithium cobalt oxide has a capacity of about 140mAh/g, 4.35V lithium cobalt oxide capacity is about 164mAh/g, 4.4V lithium cobalt oxide capacity is about 173mAh/g.
  • the purpose of the present invention is to improve the structural instability and fast cycle life decay of lithium cobalt oxide cathode material in a high delithiation state, and to provide a lithium cobalt oxide cathode material and a preparation method and application thereof.
  • the lithium cobalt oxide cathode material Has excellent structural stability and cycle performance.
  • the first aspect of the present invention provides a lithium cobalt oxide cathode material.
  • the cathode material includes a substrate and a coating layer covering the outer surface of the substrate.
  • the substrate is lithium cobalt oxide doped with metal elements.
  • Matrix wherein the composition of the coating layer is represented by the general formula LiAlO 2 /LiF.
  • the content of the coating layer is 0.1-1% by weight, more preferably 0.3-0.7% by weight.
  • the second aspect of the present invention provides a method for preparing a lithium cobalt oxide cathode material, the method comprising:
  • the cobalt source is selected from Al-doped cobalt tetroxide.
  • the first sintering includes one-stage calcination and two-stage calcination, wherein the conditions of the one-stage calcination include: a temperature of 700-900°C, preferably 750-850°C, and a time of 2-10 hours, preferably 3-6 hours;
  • the conditions of the two-stage calcination include: the temperature is 1000-1200°C, preferably 1000-1100°C, and the time is 2-20h, preferably 5-12h.
  • the third aspect of the present invention provides a lithium cobalt oxide cathode material prepared by the above method.
  • the fourth aspect of the present invention provides an application of the above-mentioned lithium cobalt oxide cathode material in a lithium ion battery.
  • the present invention has the following advantages:
  • the present invention obtains a multi-phase coated modified positive electrode material by doping the matrix of the lithium cobalt oxide positive electrode material with metal elements, and carrying out the composite coating of LiAlO 2 and LiF on the outer surface;
  • the lithium cobalt oxide cathode material provided by the present invention has excellent structural stability and electrochemical performance, especially has a higher gram specific capacity and good cycle performance under high voltage, and prolongs the lithium cobalt oxide cathode material in high temperature.
  • the preparation method provided by the present invention has simple process flow, easy control of reaction conditions, and is suitable for industrial production.
  • FIG. 1 is a TEM image of lithium cobalt oxide cathode material S1 prepared in Example 1;
  • Figure 2 is the XRD pattern of the blank test 1-2 in Example 1.
  • the first aspect of the present invention provides a lithium cobalt oxide cathode material.
  • the cathode material includes a substrate and a coating layer covering the outer surface of the substrate.
  • the substrate is a lithium cobalt oxide substrate doped with metal elements;
  • the composition of the coating layer is represented by the general formula LiAlO 2 /LiF.
  • the metal element-doped lithium cobalt oxide matrix means that the lithium cobalt oxide matrix is doped with other metal elements.
  • the invention uses doped metal elements to modify the matrix of the lithium cobalt oxide cathode material, and aims to suppress the change of the lattice constant a/c during the delithiation process and improve the structural stability of the lithium cobalt oxide in the high delithiation state.
  • the content of the coating layer is 0.1-1% by weight, more preferably 0.3-0.7% by weight.
  • the coating layer comprising the two compounds, and LiF LiAlO 2, and LiAlO 2 molar ratio of LiF to 1:2.98-3.01, preferably 1:3.
  • the lithium cobalt oxide cathode material provided by the present invention has a specific coating layer.
  • the inventors of the present invention have realized in research that LiAlO 2 can be used as a lithium ion conductor, providing good chemical stability, can increase the transmission rate of lithium ions through the particle surface, improve the rate characteristics, and effectively isolate the corrosion of the particle surface by the electrolyte; LiF can provide good electrochemical and chemical stability, can effectively protect the surface of particles and withstand high voltage.
  • the inventor of the present invention adopts a LiAlO 2 /LiF composite coating layer to provide the positive electrode material in a specific composite ratio to have excellent structural stability and electrochemical performance, and the actual service life under high voltage is prolonged.
  • the second aspect of the present invention provides a method for preparing a lithium cobalt oxide cathode material, the method comprising:
  • the cobalt source is selected from Al-doped cobalt tetroxide.
  • the content of Al doping in the cobalt source is not particularly limited, as long as it satisfies the chemical formula of the lithium cobalt oxide matrix.
  • the lithium source refers to a compound containing elemental lithium.
  • the lithium source is a lithium-containing compound, and is more preferably selected from lithium nitrate, lithium hydroxide, lithium carbonate and At least one of lithium oxide is more preferably lithium carbonate, but the present invention is not limited to this.
  • the metal compound is a compound containing at least one element selected from Mg, Ni, Sr, La, Mn, Ti, Zr, W, Nb, and Mo. More preferably, the metal compound At least one selected from Mg 2 CO 3 , TiO 2 , ZrO 2 , Mn 2 O 3 , La 2 O 3 , NiO, SrCO 3 , Nb 2 O 5 and WO 2 , but the present invention is not limited thereto.
  • the method of the first mixing is not particularly limited, as long as the Al-doped cobalt source, lithium source, and metal compound are uniformly mixed.
  • the first mixing is performed in a mixer, but the present invention is not limited to this.
  • the molar ratio of the cobalt source as cobalt ion to the lithium source as lithium ion is 1:1-1.1, more preferably 1:1.01-1.07.
  • the first sintering conditions are not particularly limited, as long as the mixture of the cobalt source doped with Al, the lithium source and the metal compound obtains a lithium cobalt oxide matrix uniformly doped with metal elements.
  • the first sintering includes one-stage calcination and two-stage calcination, wherein the conditions of the one-stage calcination include: a temperature of 700-900°C, preferably 750-850°C, and a time of 2-10 hours, preferably 3-6 hours;
  • the conditions of the two-stage calcination include: the temperature is 1000-1200°C, preferably 1000-1100°C, and the time is 2-20h, preferably 5-12h.
  • the method further includes: crushing and sieving the first sintered product to obtain a metal element-doped lithium cobalt oxide matrix.
  • the molar ratio of Li 2 CO 3 and AlF 3 is 2:0.985-1, preferably 2:1, that is, the ratio of Li 2 CO 3 and AlF 3 in the coating agent mixture
  • the amount of the substance at least satisfies the molar ratio in the chemical formula 2Li 2 CO 3 +AlF 3 LiAlO 2 +3LiF+CO 2.
  • the mass ratio of the lithium cobaltate matrix and the coating agent mixture is 1:0.0016-0.0161, preferably 1:0.0048-0.0113. Using the preferred mass ratio is beneficial to balance the gram specific capacity and cycle performance of the final product.
  • the second mixing method is not particularly limited, as long as Li 2 CO 3 and AlF 3 are uniformly mixed at a certain molar ratio.
  • the second mixing is performed in a mixer , But the present invention is not limited to this.
  • the third mixing method is not particularly limited, as long as the lithium cobaltate matrix A and the coating agent mixture are uniformly mixed.
  • the third mixing is performed in a mixer, but the present invention is not limited to this.
  • the second sintering conditions are not particularly limited, as long as the lithium cobalt oxide matrix and the coating agent mixture are formed into a lithium cobalt oxide cathode material with a coating layer, namely: Li 2 CO 3
  • the LiAlO 2 /LiF product obtained by the second sintering with AlF 3 is uniformly coated on the outer surface of the lithium cobalt oxide cathode material.
  • the second sintering conditions include: a temperature of 700-950°C, preferably 750-900°C, and a time of 2-15 hours, preferably 5-10 hours. The use of the preferred second sintering conditions is more conducive to the full reaction of the coating agent and the formation of a tightly-coated composite coating layer on the surface of the substrate.
  • the method further includes: crushing and sieving the second sintered product to obtain a lithium cobalt oxide cathode material with a coating layer.
  • the lithium cobalt oxide substrate and the coating layer refer to the above-mentioned definitions, and will not be repeated here.
  • the third aspect of the present invention provides a lithium cobalt oxide cathode material prepared by the above method.
  • the method provided by the invention modifies the lithium cobalt oxide cathode material to obtain the lithium cobalt oxide anode material with stable structural performance and electrochemical performance.
  • the fourth aspect of the present invention provides an application of the above-mentioned lithium cobalt oxide cathode material in a lithium ion battery.
  • the lithium cobalt oxide cathode material provided by the present invention has excellent electrochemical performance, especially under high voltage, the lithium cobalt oxide cathode material has a higher gram specific capacity and good cycle performance, and prolongs the use of the lithium cobalt oxide cathode material life.
  • the parameters of the lithium cobalt oxide cathode materials prepared in Examples 1-12 and Comparative Examples 1-4 are listed in Table 1. Among them, all the raw materials in the Examples and Comparative Examples participate in the reaction, that is, the cobalt source and lithium in step (1)
  • the molar ratio of the source and the metal compound is equivalent to the molar ratio of each ion in the lithium cobaltate matrix.
  • (1) Perform the first mixing and first sintering of Al-doped Co 3 O 4 , Li 2 CO 3 , MgO and La 2 O 3 , where the conditions of the first sintering include: first heating up to 800 °C and sintering for 5 hours, Continue to heat up to 1040°C for sintering for 8 hours, crush and siev the first sintered product to obtain a metal element-doped lithium cobalt oxide matrix;
  • the TEM image of the lithium cobalt oxide cathode material S1 is shown in FIG. 1, and it can be seen from FIG. 1 that the lithium cobalt oxide cathode material S1 has a composite coating layer structure.
  • sample-2 After mixing Li 2 CO 3 and AlF 3 at a molar ratio of 2:1, they are placed in a kiln for sintering at 800°C for 8 hours. The sintered material is crushed and sieved to obtain sample-2. The XRD pattern of sample-2 is as shown in 2. Show.
  • the coating agent mixture in which Li 2 CO 3 and AlF 3 are uniformly mixed is mixed with the lithium cobalt oxide matrix and sintered, and a LiAlO 2 /LiF coating layer is formed on the surface of the lithium cobalt oxide matrix.
  • the difference is that the mass ratio of the lithium cobaltate matrix and the coating agent mixture is replaced with 1:0.0016 to obtain a lithium cobaltate cathode material S2 with a coating layer.
  • the difference is that the mass ratio of the lithium cobaltate matrix and the coating agent mixture is replaced with 1:0.0048 to obtain a lithium cobaltate cathode material S3 with a coating layer.
  • the difference is that the mass ratio of the lithium cobaltate matrix and the coating agent mixture is replaced with 1:0.0113 to obtain a lithium cobaltate cathode material S4 with a coating layer.
  • the difference is that the mass ratio of the lithium cobaltate matrix and the coating agent mixture is replaced with 1:0.0161 to obtain the lithium cobaltate cathode material S5 with a coating layer.
  • (1) Perform the first mixing and first sintering of Al-doped Co 3 O 4 , Li 2 CO 3 , MgO and La 2 O 3 , where the conditions of the first sintering include: first heating up to 850°C and sintering for 3 hours, Continue to heat up to 1035°C for sintering for 10 hours, and crush and siev the first sintered product to obtain a metal element-doped lithium cobalt oxide matrix;
  • (1) Perform the first mixing and first sintering of Al-doped Co 3 O 4 , Li 2 CO 3 , MgO and La 2 O 3 , where the conditions of the first sintering include: first heating up to 850°C and sintering for 3 hours, Continue to heat up to 1045°C and sinter for 6 hours, crush and siev the first sintered product to obtain a metal element-doped lithium cobalt oxide matrix;
  • (1) Perform the first mixing and first sintering of Al-doped Co 3 O 4 , Li 2 CO 3 , NiO and Mn 2 O 3 , where the conditions for the first sintering include: first heating up to 750°C and sintering for 5 hours, Continue to heat up to 1030°C and sinter for 12 hours, and crush and siev the first sintered product to obtain a metal element-doped lithium cobalt oxide matrix;
  • (1) Perform the first mixing and first sintering of Al-doped Co 3 O 4 , Li 2 CO 3 , MgO and ZrO 2 , where the conditions of the first sintering include: first heating up to 800 °C and sintering for 5 hours, and then continue heating up Sintering at 1040°C for 8 hours, crushing and sieving the first sintered product to obtain a metal element-doped lithium cobalt oxide matrix;
  • the difference is that the first sintering conditions include: first heating up to 800° C. and sintering for 5 hours, then continuing to increase the temperature to 1040° C. and sintering for 15 hours to obtain lithium cobalt oxide cathode material S12.
  • the difference is that the lithium cobalt oxide matrix is not doped with metal elements, namely: (1) Co 3 O 4 and Li 2 CO 3 are first mixed and first sintered to obtain a lithium cobalt oxide matrix , And perform steps (2) and (3) to obtain lithium cobalt oxide cathode material D1.
  • the difference is that steps (2) and (3) are not included, that is, the metal element-doped lithium cobalt oxide matrix obtained in step (1) is used as the lithium cobalt oxide cathode material D2.
  • the difference is that the coating agent mixture is replaced with LiAlO 2 to obtain lithium cobalt oxide cathode material D3.
  • the difference is that the coating agent mixture is replaced with LiF to obtain lithium cobalt oxide cathode material D4.
  • the method provided by the present invention can be used to prepare a lithium cobalt oxide cathode material with a coating layer, wherein the chemical formula of the coating layer is LiAlO 2 /LiF.
  • the lithium cobalt oxide cathode materials (S1-S12 and D1-D4) prepared in Examples 1-12 and Comparative Examples 1-4 were subjected to electrochemical performance tests.
  • the negative electrode uses a Li metal sheet with a diameter of 17mm and a thickness of 1mm; the separator uses a polyethylene porous membrane with a thickness of 25 ⁇ m; the electrolyte uses ethylene carbonate (EC) and diethyl carbonate with 1mol/L LiPF 6 as the electrolyte. DEC) the same amount of mixed liquid.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the positive pole piece, the diaphragm, the negative pole piece and the electrolyte are assembled into a 2025 button cell in an Ar gas glove box with a water content and an oxygen content of less than 5 ppm.
  • the button cell is activated by constant current and constant voltage charging and discharging cycles in the range of 3.0V to 4.6V.
  • the charging and discharging system is as follows: after 2 weeks of charging and discharging at 0.1C, charge to 4.3V at a constant current and constant voltage at a rate of 0.1C, and the cut-off current of constant voltage charging is 0.01C.
  • This battery is regarded as an activated battery.
  • Example 5 183.3 93.0 165.6 88.1
  • Example 6 189.8 95.3 173.6 85.6
  • Example 7 175.6 90.1 156.1 91.1
  • Example 8 184.5 93.9 168.1 86.8
  • Example 9 183.8 93.8 167.0 87.3
  • Example 10 184.0 93.9 167.3 87.6
  • Example 11 184.4 93.9 168.3 86.6
  • Comparative example 1 194.5 97.2 179.2 41.6
  • Comparative example 2 183.7 92.6 164.1 72.3
  • Comparative example 3 183.4 93.9 167.0 83.5
  • Comparative example 4 182.9 92.3 163.2 84.2
  • the lithium cobalt oxide cathode provided by the present invention has excellent electrochemical performance, especially under high pressure conditions, the lithium cobalt oxide cathode material has good cycle performance, thereby prolonging the actual application life.

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Abstract

La présente invention se rapporte au domaine technique des matériaux d'électrode positive de batteries au lithium-ion, et en particulier, à un matériau d'électrode positive au cobaltate de lithium, à un procédé de préparation s'y rapportant et à une utilisation associée. Le matériau d'électrode positive au cobaltate de lithium comprend un substrat et une couche de revêtement appliquée sur la surface extérieure du substrat. Le substrat est un substrat cobaltate de lithium dopé avec un élément métallique. La composition de la couche de revêtement est représentée par une formule générale deLiAlO2/LiF. Le matériau d'électrode positive au cobaltate de lithium selon la présente invention présente une excellente stabilité structurale et une excellente performance électrochimique, et en particulier, présente une capacité spécifique de gramme élevé et une bonne performance de cycle sous une tension élevée, ce qui permet de prolonger la durée de vie réelle du matériau d'électrode positive au cobaltate de lithium sous tension élevée.
PCT/CN2021/090461 2020-05-08 2021-04-28 Matériau d'électrode positive au cobaltate de lithium, procédé de préparation s'y rapportant et utilisation associée WO2021223635A1 (fr)

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CN114068939A (zh) * 2022-01-17 2022-02-18 英德市科恒新能源科技有限公司 钴酸锂正极材料及其制备方法、锂离子电池
CN114267834A (zh) * 2021-12-14 2022-04-01 合肥融捷能源材料有限公司 改性钴酸锂及其制备方法和应用
CN114373902A (zh) * 2021-11-25 2022-04-19 西安交通大学 制备表面包覆氟化物的三元ncm的方法、ncm及电极
CN114975965A (zh) * 2022-06-28 2022-08-30 北京当升材料科技股份有限公司 核壳型正极材料及其制备方法与应用
CN114975960A (zh) * 2022-06-24 2022-08-30 合肥融捷能源材料有限公司 掺杂TiO2纳米管包覆钴酸锂及其制备方法、锂离子电池

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