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CN-117985775-B - Ternary precursor oxide with high specific surface area and high nickel content, and preparation method and application thereof

CN117985775BCN 117985775 BCN117985775 BCN 117985775BCN-117985775-B

Abstract

The invention belongs to the technical field of ternary precursors of lithium ion batteries, and particularly relates to a ternary precursor oxide with high specific surface area and high nickel, a preparation method and application thereof. The high specific surface area high nickel ternary precursor oxide prepared by the method disclosed by the invention has larger specific surface area which can reach 180.19m 2 /g, high tap density, loose and porous particles and high overall consistency, and can effectively improve the electrochemical performance of the positive electrode material when the positive electrode material is prepared. According to the invention, the temperature and time of the calcination process are adjusted, so that the content of moisture and organic impurities is effectively reduced, the sphericity of the final-stage molding is improved, the half-width peak of the ternary precursor oxide is effectively adjusted, and the specific surface area is controlled. According to the preparation method, through oxidative transformation of the loose porous high-nickel ternary precursor hydroxide, the prepared ternary precursor oxide is more stable in structure, and the preparation method has more advantages in the subsequent preparation of ternary positive electrode materials.

Inventors

  • XU KAIHUA
  • LI JUN
  • LIU KUN
  • Luo Qiuzi

Assignees

  • 荆门市格林美新材料有限公司

Dates

Publication Date
20260508
Application Date
20231227

Claims (10)

  1. 1. The preparation method of the high-specific-surface-area high-nickel ternary precursor oxide is characterized in that the high-nickel ternary precursor oxide is (Ni m Co n Mn 100-m-n ) O, wherein m is more than or equal to 90 and less than or equal to 98, n is more than or equal to 0 and less than or equal to 10, and the preparation method comprises the following steps: (1) Adding water, liquid alkali and ammonia water into a reaction kettle, and regulating the pH value to 10-12.0 to obtain reaction base solution; (2) Adding nickel-cobalt-manganese ternary liquid, liquid alkali and ammonia water into a reaction kettle, introducing nitrogen, performing coprecipitation reaction in a nitrogen atmosphere, and controlling the ammonia concentration in a reaction system to be 9-10g/L; (3) When the product particles D50 in the reaction system are maintained at 12-15 mu m, collecting reaction products, and aging, washing and drying to obtain high-nickel ternary precursor hydroxide; (4) And adding the high-nickel ternary precursor hydroxide into an atmosphere furnace for heating and calcining, and simultaneously introducing argon, wherein the heating rate is controlled to be 2-4 ℃ per minute, the calcining temperature is controlled to be 288-292 ℃ and the calcining time is controlled to be 4-6 hours, so that the high-nickel ternary precursor oxide with the high specific surface area is finally obtained.
  2. 2. The method for preparing the ternary precursor oxide with high specific surface area and high nickel according to claim 1, wherein the liquid alkali in the steps (1) and (2) is sodium hydroxide solution with the concentration of 30-35wt%, and the concentration of the ammonia water is 13-17wt%.
  3. 3. The method for preparing the ternary precursor oxide with the high specific surface area and the high nickel content according to claim 1, wherein the step (2) further comprises the step of using a thickener to thicken the reaction system, wherein the reaction kettle and the thickener form a loop, and the reaction system is thickened while coprecipitation reaction is carried out.
  4. 4. The preparation method of the high-specific-surface-area high-nickel ternary precursor oxide is characterized in that the total concentration of metal ions in the nickel-cobalt-manganese ternary liquid in the step (2) is 100-130g/L, wherein the molar ratio of three elements is nickel to cobalt to manganese=m to n (100-m-n), and m is 90 to m <98, and m is 0 to n <10.
  5. 5. The method for preparing the high-specific-surface-area high-nickel ternary precursor oxide according to claim 4, wherein in the step (2), the rate of adding the nickel-cobalt-manganese ternary liquid into the reaction kettle is 200-600L/h, the rate of adding the liquid alkali into the reaction kettle is 70-200L/h, and the rate of adding the ammonia water into the reaction kettle is 10-80L/h.
  6. 6. The method for preparing a ternary precursor oxide with high specific surface area and high nickel according to claim 1, wherein the nitrogen gas in the step (2) is introduced at a rate of 5-7m 3 /h.
  7. 7. The method for preparing a ternary precursor oxide with high specific surface area and high nickel according to claim 1, wherein the argon gas introducing rate in the step (4) is 5-7m 3 /h.
  8. 8. A high specific surface area high nickel ternary precursor prepared using the high specific surface area high nickel ternary precursor oxide of any one of claims 1-7.
  9. 9. A lithium ion battery prepared from the high specific surface area high nickel ternary precursor of claim 8.
  10. 10. Use of the lithium ion battery of claim 9 in a new energy automobile.

Description

Ternary precursor oxide with high specific surface area and high nickel content, and preparation method and application thereof Technical Field The invention belongs to the technical field of ternary precursors of lithium ion batteries, and particularly relates to a ternary precursor oxide with high specific surface area and high nickel, a preparation method and application thereof. Background In lithium ion batteries, ternary nickel cobalt manganese positive electrode materials are typically calcined using lithium salts and nickel cobalt manganese ternary precursor hydroxides. The precursor is critical to the production of the ternary material, because the quality of the precursor, such as morphology, particle size distribution, specific surface area, impurity content, tap density and the like, directly determine the physicochemical index of the final sintered product and influence the electrochemical performance of the final sintered product, and the technical content of 60% of the ternary material is recognized in the precursor in the industry. And the ternary precursor hydroxide is pre-oxidized into ternary precursor oxide, so that the original defects can be eliminated, the ternary precursor components can be regulated, and the performance of the final battery can be improved. At present, a liquid phase coprecipitation method is mainly adopted for industrially preparing ternary precursors, namely, a nickel cobalt manganese salt solution, a precipitator, a complexing agent and the like are injected into a reaction kettle in proportion, react under certain control conditions, and are washed and dried to obtain nickel cobalt manganese hydroxide. The oxidation is to put the ternary precursor hydroxide into an atmosphere furnace for calcination. There are three key factors in the calcination process, namely calcination time, calcination temperature and calcination atmosphere. The calcination temperature and the calcination time are the most important factors, and influence the BET, moisture and other physical and chemical properties of the ternary precursor, and at the same time, the hydroxide is not completely converted into oxide when the calcination temperature is too low, and the oxide is excessively burned when the calcination temperature is too high. In the prior art, in order to completely convert the hydroxide raw material into the oxide, the waste of the raw material is avoided, a higher calcining temperature and a longer calcining time are generally adopted, the BET of the ternary precursor prepared by adopting a conventional calcining method in the prior art is only about 65m 2/g, and the BET of the ternary precursor is limited to be improved by a calcining process. Disclosure of Invention Aiming at the problems existing in the prior art, the invention provides a high specific surface area high nickel ternary precursor oxide, and a preparation method and application thereof, and specifically comprises the following contents: a preparation method of a high-specific-surface-area high-nickel ternary precursor oxide, wherein the high-nickel ternary precursor oxide is (Ni mConMn100-m-n) O, m is more than or equal to 90 and less than or equal to 98, n is more than or equal to 0 and less than or equal to 10, and the preparation method comprises the following steps: (1) Adding water, liquid alkali and ammonia water into a reaction kettle, and regulating the pH value to 10-12.0 to obtain reaction base solution; (2) Adding nickel-cobalt-manganese ternary liquid, liquid alkali and ammonia water into a reaction kettle, introducing nitrogen, performing coprecipitation reaction in a nitrogen atmosphere, and controlling the ammonia concentration in a reaction system to be 9-10g/L; (3) When the product particles D50 in the reaction system are maintained at 12-15 mu m, collecting reaction products, and aging, washing and drying to obtain high-nickel ternary precursor hydroxide; (4) And adding the high-nickel ternary precursor hydroxide into an atmosphere furnace for heating and calcining, and simultaneously introducing argon, wherein the heating rate is controlled to be 2-4 ℃ per minute, the calcining temperature is controlled to be 288-292 ℃ and the calcining time is controlled to be 4-6 hours, so that the high-nickel ternary precursor oxide with the high specific surface area is finally obtained. Preferably, the liquid alkali in the steps (1) - (2) is sodium hydroxide solution with the concentration of 30-35wt%, and the concentration of the ammonia water is 13-17wt%. Preferably, the step (2) further comprises the step of using a thickener to thicken the reaction system, wherein the reaction kettle and the thickener form a loop, and the reaction system is thickened while coprecipitation reaction is carried out. Preferably, the total concentration of metal ions in the nickel-cobalt-manganese ternary liquid in the step (2) is 100-130g/L, wherein the molar ratio of the three elements is nickel to cobalt to manganes