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DE-112023000017-B4 - Manufacturing process for tungsten-doped cobalt tetroxide and its application

DE112023000017B4DE 112023000017 B4DE112023000017 B4DE 112023000017B4DE-112023000017-B4

Abstract

Manufacturing process for tungsten-doped cobalt tetroxide, comprising the following steps: S1: Dissolving a tungsten-containing compound and a molybdenum-containing compound in an alkaline liquid to obtain a mixed solution; S2: simultaneous addition of the mixed solution, a cobalt salt solution and a complexing agent to an alkaline solution to react until a reaction material reaches a target particle size; followed by aging and carrying out a solid-liquid separation (SLS) to obtain a precipitation, wherein the alkaline solution comprises the mixed solution and ammonia water; S3: Roasting the precipitate in an oxygenated atmosphere to obtain a roasted material; and S4: Soaking the roasted material in a sodium sulfide solution, adjusting the pH of the solution to 7.2 to 8.5, and performing SLS to obtain the tungsten-doped cobalt tetroxide.

Inventors

  • Haijun YU
  • Yinghao Xie
  • Aixia LI
  • Xuemei Zhang
  • Changdong LI

Assignees

  • GUANGDONG BRUNP RECYCLING TECHNOLOGY CO., LTD.
  • HUNAN BRUNP EV RECYCLING CO., LTD.
  • Hunan Brunp Recycling Technology Co., Ltd.

Dates

Publication Date
20260513
Application Date
20230220
Priority Date
20220421

Claims (10)

  1. A manufacturing process for tungsten-doped cobalt tetroxide comprising the following steps: S1: Dissolving a tungsten-containing compound and a molybdenum-containing compound in an alkaline liquid to obtain a mixed solution; S2: Simultaneously adding the mixed solution, a cobalt salt solution, and a complexing agent to an alkaline solution to react until a reaction material reaches a target particle size; then aging and performing solid-liquid separation (SLS) to obtain a precipitate, the alkaline solution comprising the mixed solution and ammonia solution; S3: Roasting the precipitate in an oxygen-containing atmosphere to obtain a roasted material; and S4: Soaking the roasted material in a sodium sulfide solution, adjusting the pH of the solution to 7.2 to 8.5, and performing SLS to obtain the tungsten-doped cobalt tetroxide.
  2. Manufacturing process according to Claim 1 , where the alkali liquid in S1 has a concentration of 4.0 mol/l to 10.0 mol/l.
  3. Manufacturing process according to Claim 1 , wherein the molar ratio of tungsten to molybdenum in the mixed solution in S1 is 3:(1-3); and the total concentration of tungsten and molybdenum in the mixed solution is 0.01 mol/l to 1.0 mol/l.
  4. Manufacturing process according to Claim 1 , wherein the tungsten-containing compound in S1 is either sodium tungstate and/or sodium metatungstate (SMT) and/or ammonium tungstate and/or ammonium metatungstate (AMT) and/or potassium tungstate and/or lithium tungstate and/or tungsten trioxide and/or tungstic acid.
  5. Manufacturing process according to Claim 1 , wherein the molybdenum-containing compound in S1 is either sodium molybdate and/or sodium metamolybdate and/or ammonium molybdate and/or ammonium metamolybdate and/or potassium molybdate and/or lithium molybdate and/or molybdenum trioxide and/or molybdic acid.
  6. Manufacturing process according to Claim 1 , where the cobalt salt solution in S2 has a concentration of 1.0 mol/l to 2.0 mol/l.
  7. Manufacturing process according to Claim 1 , wherein the alkaline solution in S2 has a pH value of 10 to 11 and an ammonia concentration of 5.0 g/l to 10.0 g/l.
  8. Manufacturing process according to Claim 1 , wherein the solid-to-liquid ratio of the roasted material to the sodium sulfide solution in S4 is 1 g:(1-5) ml; and wherein the sodium sulfide solution has a concentration of 0.1 mol/l to 1 mol/l.
  9. Manufacturing process according to Claim 1 , whereby the impregnation in S4 is carried out at 70 °C to 80 °C.
  10. Use of the product obtained through the manufacturing process according to one of the Claims 1 until 9 produced with tungsten-doped cobalt tetroxide in the production of lithium cobalt oxide (LCO) or a lithium-ion battery (LIB).

Description

TECHNICAL AREA The present disclosure relates to the technical field of lithium battery cathode material precursors and relates in particular to a manufacturing process for tungsten-doped cobalt tetroxide and an application thereof. STATE OF THE ART With the iterative upgrading of digital products and the rapid development of various emerging electronic products, such as high-end model aircraft and drones, the demands on lightweight, high-capacity lithium batteries are constantly increasing. Lithium cobalt oxide (LCO) cathode materials have important applications in the digital field, and given the ever-tightening performance requirements that electronic products place on lithium batteries, the iterative upgrading of LCO cathode materials is particularly important. The performance of an LCO cathode material largely depends on the performance of its precursor. Cobalt tetroxide is primarily used as a precursor for LCO in the field of lithium-ion batteries (LIBs), and its performance is a key factor influencing the electrochemical performance of LCO. However, during the charging process of conventional LCO, the lattice changes due to the deintercalation of lithium ions, which limits the material's capacity. A major challenge currently being addressed is improving battery capacity, particularly the charging and discharging performance of lithium batteries at high voltage. Studies have shown that partial elemental doping of a material can not only improve the lattice stability of the substrate material but also significantly enhance the cycle life of a battery material. Therefore, doping a cobalt tetroxide material to improve the structural stability of a cathode material without impairing its electrical performance is a problem that currently deserves attention. The state of the art is described in [reference to be inserted here]. CN 1 08 455 686 A , CN 1 08 217 753 A and CN 1 12 830 523 A referred. SUMMARY The present disclosure is intended to solve at least one of the problems existing in the prior art. Accordingly, the present disclosure provides a manufacturing process for tungsten-doped cobalt tetroxide and an application thereof. The tungsten-doped cobalt tetroxide produced by the manufacturing process exhibits high structural stability, and a cathode material produced therewith exhibits outstanding cycling performance. According to one aspect of the present disclosure, a manufacturing process for tungsten-doped cobalt tetroxide is provided, comprising the following steps: S1: Dissolving a tungsten-containing compound and a molybdenum-containing compound in an alkaline liquid to obtain a mixed solution; S2: simultaneous addition of the mixed solution, a cobalt salt solution and a complexing agent to an alkaline solution to react until a reaction material reaches a target particle size; then aging and carrying out a solid-liquid separation (SLS) to obtain a precipitation, the alkaline solution containing the mixed solution and ammonia water; S3: Roasting the precipitate in an oxygenated atmosphere to obtain a roasted material; and S4: Soaking the roasted material in a sodium sulfide solution, adjusting the pH of the solution to 7.2 to 8.5, and performing SLS to obtain the tungsten-doped cobalt tetroxide. In some embodiments of the present disclosure, the alkali liquid in S1 can have a concentration of 4.0 mol/l to 10.0 mol/l. In some embodiments of the present disclosure, the alkali liquid in S1 may be a sodium hydroxide solution. In some embodiments of the present disclosure, the molar ratio of tungsten to molybdenum in the mixed solution in S1 may be 3:(1-3); and the total concentration of tungsten and molybdenum in the mixed solution may be 0.01 mol/l to 1.0 mol/l. In some embodiments of the present disclosure, the tungsten-containing compound in S1 can be either sodium tungstate and/or sodium metatungstate (SMT) and/or ammonium tungstate and/or ammonium metatungstate (AMT) and/or potassium tungstate and/or lithium tungstate and/or tungsten trioxide and/or tungstic acid. In some embodiments of the present disclosure, the molybdenum-containing compound in S1 can be either sodium molybdate and/or sodium metamolybdate and/or ammonium molybdate and/or ammonium metamolybdate and/or potassium molybdate and/or lithium molybdate and/or molybdenum trioxide and/or molybdic acid. In some embodiments of the present disclosure, the cobalt salt solution in S2 can have a concentration of 1.0 mol/l to 2.0 mol/l. In some embodiments of the present disclosure, the cobalt salt solution in S2 can be either a cobalt sulfate solution and/or a cobalt nitrate solution and/or a cobalt chloride solution. In some embodiments of the present disclosure, the complexing agent in S2 can be ammonia water with a concentration of 6.0 mol/l to 12.0 mol/l. In some embodiments of the present disclosure, the alkaline solution in S2 can have a pH of 10 to 11 and an ammonia concentration of 5.0 g/l to 10.0 g/l. In some embodiments of the prese