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KR-20260064014-A - MANUFACTURING METHOD FOR POSITIVE ACTIVE MATERIAL

KR20260064014AKR 20260064014 AKR20260064014 AKR 20260064014AKR-20260064014-A

Abstract

The present disclosure relates to a method for manufacturing an anode active material comprising: obtaining a transition metal hydroxide comprising nickel, cobalt, and manganese; heating a first mixture in an oxygen atmosphere and at a first temperature to obtain a preliminary lithium transition metal oxide; and heating a second mixture in an oxygen atmosphere and at a second temperature to obtain a lithium transition metal oxide; wherein the first mixture comprises the transition metal hydroxide and the lithium compound, and the second mixture comprises the preliminary lithium transition metal oxide, and the first temperature is within the range of 700 ℃ to 1000 ℃, and obtaining the preliminary lithium transition metal oxide involves heating the first mixture at a heating rate within the range of 0.1 ℃/min to 1.8 ℃/min at a temperature within the range of 500 ℃ to 600 ℃.

Inventors

  • 이슬기
  • 배진호
  • 신세희
  • 최진혁
  • 김진규

Assignees

  • 주식회사 에코프로비엠

Dates

Publication Date
20260507
Application Date
20241031

Claims (15)

  1. Obtaining transition metal hydroxides containing nickel, cobalt, and manganese; A first mixture is heated in an oxygen atmosphere and at a first temperature to obtain a preliminary lithium transition metal oxide; and A second mixture is heated in an oxygen atmosphere and at a second temperature to obtain a lithium transition metal oxide; comprising, The first mixture above includes the transition metal hydroxide and lithium compound, and The second mixture above includes the preliminary lithium transition metal oxide, and The first temperature is within the range of 700 ℃ to 1000 ℃, and A method for manufacturing an anode active material to obtain the above-mentioned preliminary lithium transition metal oxide by heating the above-mentioned first mixture at a heating rate within the range of 0.1 ℃/min to 1.8 ℃/min at a temperature within the range of 500 ℃ to 600 ℃.
  2. In paragraph 1, The above preliminary lithium transition metal oxide is to obtain Raising the temperature of the first mixture from a reference temperature to the first temperature; and Maintaining the above first mixture at a first temperature; A method for manufacturing a positive electrode active material in which the above reference temperature is within the range of 10 ℃ to 30 ℃.
  3. In paragraph 1, A method for manufacturing an anode active material in which the first mixture is maintained at the first temperature for 180 to 300 minutes to obtain the above-mentioned preliminary lithium transition metal oxide.
  4. In paragraph 1, The first temperature is within the range of 750 ℃ to 800 ℃, and To obtain the above-mentioned preliminary lithium transition metal oxide, the above-mentioned first mixture is heated at a temperature of 500 ℃ to 600 ℃ at a heating rate within the range of 1 ℃/min to 1.6 ℃/min, and A method for manufacturing an anode active material, wherein the first mixture is maintained at the first temperature for 180 to 200 minutes to obtain the above-mentioned pre-lithium transition metal oxide.
  5. In paragraph 1, A method for manufacturing an anode active material in which the nickel content of the above transition metal hydroxide is 60 mol% or more.
  6. In paragraph 1, The above first mixture further comprises a doping element precursor, and A method for manufacturing a positive electrode active material comprising two or more doping elements selected from the group consisting of Ba, Zr, Al, Ce, Hf, Ta, Cr, F, Mg, Cr, V, Ti, Fe, Zn, Si, Y, Nb, Ga, Sn, Mo, W, P, Sr, Ge, Nd, Gd, and Cu.
  7. In paragraph 1, The above doping elements are a method for manufacturing a positive active material including Ba and Zr.
  8. In paragraph 1, A method for manufacturing an anode active material in which the barium precursor content of the first mixture is within the range of 0.1 mol% to 0.5 mol% based on metal elements excluding lithium among the transition metal hydroxides.
  9. In paragraph 1, A method for manufacturing an anode active material in which the zirconium precursor content of the first mixture is within the range of 0.1 mol% to 0.5 mol% based on metal elements excluding lithium among the transition metal hydroxides.
  10. In paragraph 6, The above second mixture further comprises a doping element precursor, and A method for manufacturing a positive electrode active material comprising two or more doping elements selected from the group consisting of Ba, Zr, Al, Ce, Hf, Ta, Cr, F, Mg, Cr, V, Ti, Fe, Zn, Si, Y, Nb, Ga, Sn, Mo, W, P, Sr, Ge, Nd, Gd, and Cu.
  11. In paragraph 1, The above second mixture is a method for manufacturing an anode active material that further includes a cobalt precursor.
  12. In paragraph 1, A method for manufacturing an anode active material in which the cobalt precursor content of the second mixture is within the range of 3 mol% to 4 mol% based on the transition metal excluding lithium in the preliminary lithium transition metal oxide.
  13. In paragraph 1, A method for manufacturing a positive active material in which at least one of the doping element precursors of the second mixture is the same as the doping element precursor of the first mixture.
  14. In paragraph 1, A method for manufacturing a positive electrode active material in which the second temperature is within the range of 650 ℃ to 750 ℃.
  15. In paragraph 3, A method for manufacturing a positive electrode active material in which the ratio of the time for maintaining the first mixture at the first temperature to the time for raising the temperature of the first mixture in obtaining the above-mentioned preliminary lithium transition metal oxide is 0.5 or less.

Description

Manufacturing Method for Positive Active Material The present disclosure relates to a method for manufacturing an anode active material. Lithium-ion batteries can repeatedly charge and discharge through the intercalation and deintercalation of lithium ions. Lithium-ion batteries supply power to external devices through these repeated charging and discharging cycles. Lithium composite oxides can be used for the intercalation/deintercalation of lithium ions. Lithium composite oxides form a structure in which lithium ions and transition metals are combined, storing lithium ions internally and releasing them externally. The transition metals in lithium composite oxides may include nickel, cobalt, and manganese. The characteristics of lithium composite oxides can have a significant impact on the lifespan characteristics and performance of lithium secondary batteries. Figures 1 to 3 show the CP-SEM cross-sectional imaging results of Example 1. Figures 4 to 6 show the CP-SEM cross-sectional imaging results of Comparative Example 1. Figures 7 to 9 show the CP-SEM cross-sectional imaging results of Comparative Example 2. Figures 10 to 12 show the CP-SEM cross-sectional imaging results of Comparative Example 3. Figure 13 shows the XRD analysis results of Example 1 and Comparative Examples 1 to 3. The present disclosure is described in detail below. One embodiment of the present disclosure relates to a method for manufacturing a positive electrode active material. A method for manufacturing a positive electrode active material according to the present disclosure comprises: obtaining a transition metal hydroxide comprising nickel, cobalt, and manganese; heating a first mixture in an oxygen atmosphere at a first temperature to obtain a preliminary lithium transition metal oxide; and heating a second mixture in an oxygen atmosphere at a second temperature to obtain a lithium transition metal oxide. The first mixture comprises the transition metal hydroxide and the lithium compound. The second mixture comprises the preliminary lithium transition metal oxide. The first temperature is within the range of 700 °C to 1000 °C. To obtain the preliminary lithium transition metal oxide, the first mixture is heated at a heating rate within the range of 0.1 °C/min to 1.8 °C/min at a temperature of 500 °C to 600 °C. First, the present disclosure may perform obtaining a transition metal hydroxide comprising nickel, cobalt, and manganese. The transition metal hydroxide may be used as a precursor for the lithium transition metal oxide described below. A preliminary lithium transition metal oxide may be obtained by heating the transition metal hydroxide and a lithium compound together. The lithium compound is used as a lithium raw material. The lithium transition metal oxide may be obtained by heating the preliminary lithium transition metal oxide together with a boron precursor. The above transition metal hydroxide can be obtained by using a precursor comprising at least one of the above transition metals. Specifically, the above transition metal hydroxide can be prepared by applying a coprecipitation method using a precursor comprising at least one of the above transition metals. Methods for preparing transition metal hydroxides by coprecipitation are known, and these may be applied without limitation in the present disclosure. In another example, obtaining the above transition metal hydroxide may mean obtaining a commercially available transition metal hydroxide. The present disclosure may perform obtaining a preliminary lithium transition metal oxide by heating a first mixture in an oxygen atmosphere and at a first temperature. The first mixture comprises the transition metal hydroxide and the lithium compound. The lithium compound may be a lithium raw material that reacts with the transition metal hydroxide to form a lithium transition metal oxide. The lithium compound may include one or more selected from the group consisting of lithium hydroxide, lithium carbonate, lithium nitrate, or lithium acetate. It may be preferable that the lithium compound be mixed such that the ratio of the number of lithium atoms (Li) to the total number of metal atoms other than lithium (Metal) in the first mixture (Li/Metal) satisfies a range of 0.95 to 1.10. Lithium anhydrous hydroxide (LiOH· H₂O ) may be provided as a lithium raw material for reacting with the transition metal hydroxide. The lithium anhydrous hydroxide (LiOH· H₂O ) may be converted into lithium hydroxide (LiOH) through a dehydration reaction. The dehydration reaction may be carried out at a relatively low temperature (e.g., 100°C or lower). The lithium hydroxide (LiOH) may react with the transition metal hydroxide. The lithium hydroxide may react with the transition metal hydroxide at a relatively high temperature (e.g., about 500°C to 600°C). Not all of the lithium hydroxide (LiOH) may react with the transition metal hydroxide, but only a portion of the lithium hydroxide (LiOH) may