Method for preparing ternary positive electrode material through recovering waste ternary lithium battery

A ternary lithium battery and cathode material technology, which is applied in battery recycling, battery electrode, waste collector recycling, etc., can solve the problems of high impurity content in precursor products, affecting the electrochemical performance of ternary cathode materials, and low recovery rate.

Active Publication Date: 2020-05-29
NINGBO RONBAY LITHIUM BATTERY MATERIAL CO LTD
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AI Technical Summary

Problems solved by technology

[0003] The ternary lithium battery contains metal elements such as cobalt and nickel. If it is not recycled, it will not only cause a great waste of resources, but also cause pollution to the ecological environment, thereby limiting the sustainable development of the new energy automobile industry.
[0005] This all-wet recovery method has the following problems: (1) after the manganese, nickel, cobalt, and lithium in the positive electrode material are reduced and leached together, the lithium elem

Method used

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  • Method for preparing ternary positive electrode material through recovering waste ternary lithium battery
  • Method for preparing ternary positive electrode material through recovering waste ternary lithium battery
  • Method for preparing ternary positive electrode material through recovering waste ternary lithium battery

Examples

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Effect test

Embodiment 1

[0062] (1) Put the waste lithium battery in a 1.5mol / L NaCl solution for discharge treatment. After the discharged waste lithium battery is cleaned and dried, it is coarsely crushed and finely crushed, and placed in a rotary kiln at 300°C under nitrogen protection. Pyrolysis, and then by sorting, 100kg of waste ternary cathode powder (Li: 11.76, Ni: 25.63, Co: 8.91, Mn: 13.38wt%) was obtained.

[0063] (2) Mix the waste ternary positive electrode powder obtained from the pretreatment with ammonium sulfate 1.2 times the theoretical amount, send it to a high-temperature furnace, and bake it at a temperature of 500° C. for 2 hours.

[0064] (3) Add pure water to leaching the roasted waste positive electrode powder with a liquid-solid ratio of 5:1, the water immersion time is 3 hours, and the water immersion temperature is 65°C. The slurry after water immersion is press-filtered to obtain a lithium-containing leaching solution, and lithium is recovered by removing impurities, conc...

Embodiment 2

[0072] This embodiment has been further optimized on the basis of embodiment 1, specifically:

[0073] S1 Enrich the concentration of lithium in the water immersion solution obtained in Example 1 to 17g / L by evaporation and concentration, then add liquid caustic soda, that is, a sodium hydroxide solution with a mass concentration of 30%, adjust the pH value to 12, and feed CO 2 Impurity ions are precipitated and separated by filtration.

[0074] S2 Add 1.1 times the theoretical amount of sodium carbonate solution to the purified lithium solution obtained by filtration, the concentration is 270g / L, react at 95°C for 2h, and then prepare battery-grade lithium carbonate by washing and drying.

[0075] In Example 2, the recovery rate of lithium was 96%, and the purity reached 99.53%.

Embodiment 3

[0077] This embodiment provides a method for recovering and preparing precursors from waste ternary lithium batteries, including the following steps:

[0078] (1) Put the waste lithium battery in a 2mol / L NaCl solution for discharge treatment. After the discharged waste lithium battery is cleaned and dried, it is coarsely crushed and finely crushed, and placed in a rotary kiln at 400 ° C under anaerobic conditions. Pyrolysis, and then by sorting, 100kg of waste ternary cathode powder (Li: 11.67, Ni: 28.87, Co: 9.82, Mn: 9.62wt%) was obtained.

[0079] (2) Mix the waste ternary positive electrode powder obtained from the pretreatment with 1.5 times the theoretical amount of sodium bisulfate, send it to a high-temperature furnace, and roast it at a temperature of 600°C for 2 hours.

[0080] (3) Add pure water to leaching the roasted positive electrode powder with a liquid-solid ratio of 4:1, the water immersion time is 3 hours, and the water immersion temperature is 60°C. The slu...

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Abstract

The invention provides a method for preparing a ternary positive electrode material through recovering a waste ternary lithium battery. The method comprises the following steps of 1) mixing pretreatednickel cobalt lithium manganate waste positive electrode powder with sulfate, and roasting to obtain a roasted product; 2) immersing the roasted product in water to obtain water immersion liquid andwater immersion slag; wherein the water immersion liquid contains lithium salt; 3) reacting the water immersion slag with an acid solution and hydrogen peroxide to obtain a nickel-cobalt-manganese leaching solution; 4) removing impurities from the nickel-cobalt-manganese leaching solution, then extracting cobalt, manganese and nickel, and saponifying and reversely extracting obtained organic phaseto obtain a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution; and 5) co-precipitating the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution with a sodium hydroxide solution and ammonia water, mixing obtained precursor with lithium carbonate, sintering, and screening iron to obtain the ternary positive electrode material. According to the method, lithium is extracted firstly, so that the influence of a lithium element on subsequent nickel-cobalt-manganese extraction is reduced, the impurity content in the ternary positiveelectrode material is reduced, and the recovery rate of nickel-cobalt-manganese is greatly improved; and meanwhile the recovery rate of the lithium can be improved.

Description

technical field [0001] The invention belongs to the technical field of recycling waste lithium batteries, and in particular relates to a method for preparing ternary cathode materials by recycling waste ternary lithium batteries. Background technique [0002] In the past 10 years, China's electric vehicle industry has achieved rapid development. At the same time, the earliest electric vehicles to enter the market have now entered the stage of battery decommissioning, and the number of decommissioned batteries will increase sharply in the next few years. According to market research forecasts, by 2020, the amount of scrapped lithium batteries for vehicles in my country will reach 32GWh, and the quality of scrapped batteries will reach about 500,000 tons; by 2030, the amount of scrapped lithium batteries for vehicles will reach 300GWh, and the amount of scrapped lithium batteries will reach about 3 million tons. Lithium batteries are mainly divided into lithium iron phosphate...

Claims

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Application Information

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IPC IPC(8): C22B1/02C22B7/00C22B3/38C22B1/16C22B23/02C22B47/00C22B26/12H01M10/54H01M4/505H01M4/525
CPCC22B1/02C22B7/006C22B7/001C22B1/16C22B23/02C22B23/04C22B47/00C22B26/12H01M10/54H01M4/505H01M4/525C22B3/3846C22B3/3844Y02W30/84Y02P10/20Y02E60/10
Inventor 王本平彭伟文张梦龙何几文蔡运何王大伟史锡娇陈明峰
Owner NINGBO RONBAY LITHIUM BATTERY MATERIAL CO LTD
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