Comprehensive recovery method of waste lithium battery positive electrode piece

A waste lithium battery and recycling method technology, which is applied in the field of comprehensive recycling of waste lithium battery positive plates, can solve problems such as difficulty in meeting the national standard requirements of ternary power batteries, affecting product purity and product performance, atmospheric environment, water environment pollution, etc. Achieve the effect of low processing cost, eliminate pollution, and eliminate three wastes

Inactive Publication Date: 2019-08-20
ZHUZHOU SMELTER GRP
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AI Technical Summary

Problems solved by technology

[0004] At present, most of the methods that have been reported to recover valuable metals from waste nickel-cobalt-lithium manganese oxide batteries are hydrometallurgical recovery of valuable metals. During the recovery process, waste gas and waste water with high acid and organic content will inevitably be produced. The air environment and water environment have caused serious pollution
Among them, the positive electrode material regenerated by pyrocalcination contains other impurity elements such as Al content is too high, or Al has not been removed directly, and it can be removed by wet alkaline leaching or fully leached with excessive strong acid in the later hydrometallurgical treatment method. When removing ions in the battery, it is necessary to add a set of aluminum removal process, and it is difficult to completely remove Al, which increases the cost and affects the purity and performance of the product. It is difficult to meet the national standard requirements for the positive electrode material of the ternary power battery

Method used

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  • Comprehensive recovery method of waste lithium battery positive electrode piece

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Experimental program
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Effect test

Embodiment 1

[0035] Step A, pretreatment to remove aluminum: put the nickel-cobalt lithium manganese oxide positive electrode sheet into a vacuum furnace, control the vacuum degree to 0.7, and calcining at a temperature of 440°C, a heating rate of 10°C, and a calcining time of 5 hours. The calcined spent pole piece was put into a vibrating sieve with a particle size of 2 cm and a 5-mesh vibrating sieve for vibrating and sieving. The vibration frequency of the vibrating sieve was 30 rpm to obtain the positive electrode active material and aluminum foil. .

[0036] Step B, carbon removal by leaching: add the positive electrode active material into the sulfuric acid leaching solution for leaching, adopt two-stage leaching, the liquid-solid ratio of low-acid leaching = 4:1, leaching temperature 85 ° C, leaching time = 3 hours, the end point pH is 1.5 ; The liquid-solid ratio of high acid leaching=15:1, the leaching temperature is 95°C, the leaching time is 10 hours, and the leaching is strengt...

Embodiment 2

[0042] Step A, pretreatment to remove aluminum: put the nickel-cobalt lithium manganese oxide positive electrode into a vacuum furnace, control the vacuum degree to 0.8, and calcining under the conditions of 450°C, a heating rate of 12°C, and a calcination time of 4 hours. The calcined waste pole piece was put into a vibrating sieve with a particle size of 1 cm and a 15-mesh vibrating sieve for vibrating and sieving. The vibration frequency of the vibrating sieve was 40 rpm to obtain the positive electrode active material and aluminum foil. .

[0043] Step B, carbon removal by leaching: add the positive electrode active material into the sulfuric acid leaching solution for leaching, adopt two-stage leaching, the liquid-solid ratio of low-acid leaching = 5:1, leaching temperature 82 ° C, leaching time = 4 hours, the end point pH is 2.5 The liquid-solid ratio of high acid leaching=12:1, the leaching temperature is 92°C, the leaching time is 9 hours, and the leaching is strengthe...

Embodiment 3

[0049] Step A, pretreatment to remove aluminum: put the nickel-cobalt lithium manganese oxide positive electrode into a vacuum furnace, the vacuum degree is controlled to 0.9, the calcination temperature is 460°C, the heating rate is 15°C, and the calcination time is 3 hours. The calcined waste pole pieces were put into a vibrating sieve with 0.05 cm zirconia balls and a 30-mesh vibrating sieve with a particle size of 0.05 cm, and vibrated and sieved. The vibrating frequency of the vibrating sieve was 50 rpm to obtain the positive active material and aluminum foil.

[0050] Step B, carbon removal by leaching: add the positive electrode active material into the sulfuric acid leaching solution for leaching, adopt two-stage leaching, the liquid-solid ratio of low-acid leaching = 6:1, leaching temperature 80 ° C, leaching time = 5 hours, and the end point pH is 3.5 The liquid-solid ratio of high acid leaching=10:1, the leaching temperature is 90°C, the leaching time is 8 hours, an...

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Abstract

The invention discloses a comprehensive recovery method of a waste lithium battery positive electrode piece. The method comprises the steps that a positive electrode leftover material and a wasted positive electrode piece are placed into a vacuum furnace to be calcinated, rapping and screening are conducted to obtain a positive active substance, the positive electrode active material is added to asulphuric acid leaching solution, second-stage leaching is conducted, and leached slag carbon and the leaching solution containing nickel, cobalt, manganese and lithium; activated carbon is added tothe leaching solution to perform adsorption deoiling and silica removing, nickel carbonate, cobalt carbonate, manganese carbonate or lithium carbonate is replenished to the filtered residue to obtainprecursors, ball milling, sintering, pulverizing, grinding and mesh screening are conducted on the precursors, and a nickel-cobalt-manganese-acid-lithium positive electrode material is obtained. The method has the advantages that the technology is reasonable, the separation cost is low, and there exists no pollution, toxin or harm.

Description

technical field [0001] The invention relates to the field of recycling and utilization of waste positive pole pieces of nickel-cobalt-manganese lithium batteries, in particular to a comprehensive recovery method for waste and old lithium battery positive pole pieces. Background technique [0002] Lithium-ion batteries are a new generation of secondary batteries developed rapidly in the 1990s, and are widely used in small portable electronic communication products and electric vehicles. Since the service life of lithium-ion batteries is generally 3-5 years, it is predicted that by 2020, my country will produce 2.5 billion pieces, about 520,000 tons of waste new energy power batteries, and waste power batteries will provide at least 50% of the raw material supply. At the same time, new energy power batteries, as discarded electronic products, have been designated as hazardous waste by each country. Every part of the battery has potential hazards. If it is not handled properly,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C22B7/00C22B21/00C22B23/00H01M4/505H01M4/525H01M10/54
CPCC22B7/007C22B21/0023C22B23/043H01M4/505H01M4/525H01M10/54Y02E60/10Y02P10/20Y02W30/84
Inventor 廖贻鹏林文军易鹏飞周玉琳刘敏
Owner ZHUZHOU SMELTER GRP
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