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Method for recovering and preparing nickel-cobalt-manganese-aluminum quaternary positive electrode material from waste nickel-cobalt-manganese ternary lithium-ion battery

A lithium-ion battery and cathode material technology, which is applied in the field of waste lithium-ion battery recycling, can solve problems such as ineffective use of metal elements, and achieve the effects of improving electrochemical performance, shortening the process flow, and high repeatability

Active Publication Date: 2017-05-31
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This patent uses the precipitation method to prepare the corresponding ternary cathode material precursor, but does not propose effective solutions to the remaining lithium-containing liquid, and the addition of lithium salt is still required in the subsequent preparation of the cathode material; at the same time, this method For the removal of impurities by precipitation filtration, the metal elements in it have not been effectively utilized

Method used

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  • Method for recovering and preparing nickel-cobalt-manganese-aluminum quaternary positive electrode material from waste nickel-cobalt-manganese ternary lithium-ion battery
  • Method for recovering and preparing nickel-cobalt-manganese-aluminum quaternary positive electrode material from waste nickel-cobalt-manganese ternary lithium-ion battery

Examples

Experimental program
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Effect test

Embodiment 1

[0064] Disassemble the waste ternary lithium-ion battery after safe discharge, and obtain the core after magnetic separation and iron removal. The core is broken and soaked in NMP for 3 hours, the active material and the pole piece are screened, and the powder (active material) Placed in sulfuric acid leaching. After the reaction is complete, filter out the black insoluble matter, add thiourea to the filtrate until no precipitation occurs, and filter the insoluble matter.

[0065] Measure the Al, Ni, Co, Mn ratio of the filtrate after impurity removal, and add corresponding vitriol wherein according to the ratio, adjust Ni, Co, Mn proportioning to 8: 1: 1, control Al content to be 2% (with The total molar weight of Al, Ni, Co, Mn is based on). Then add 2mol / L NaOH solution to adjust pH=10. After the reaction is complete, add salt of wormwood to it, control the addition so that Li: (Ni+Co+Mn+Al)=1.05, make Li 2 CO 3 Uniformly precipitated on the surface of NCMA hydroxide to...

Embodiment 2

[0070] Disassemble the waste ternary lithium-ion battery after safe discharge, and obtain the core after magnetic separation and iron removal. The core is broken and soaked in NMP for 3 hours, the active material and the pole piece are screened, and the powder (active material) Placed in sulfuric acid leaching. After the reaction is complete, filter out the black insoluble matter, add sodium thiosulfate to the filtrate until no precipitation occurs, and filter the insoluble matter.

[0071] Measure the Al, Ni, Co, Mn ratio of the filtrate after impurity removal, and add corresponding vitriol wherein according to the ratio, adjust Ni, Co, Mn proportioning to 8: 1: 1, control Al content to be 5% (with The total molar weight of Al, Ni, Co, Mn is based on). Then add 6mol / L NaOH solution to adjust pH=11. After the reaction is complete, potassium carbonate is added thereto, and the amount of control added makes Li:(Ni+Co+Mn+Al)=1.1, making Li 2 CO 3 Uniformly precipitated on the...

Embodiment 3

[0074] Disassemble the waste ternary lithium-ion battery after safe discharge, obtain the core after magnetic separation and iron removal, break the core and soak it in THF for 2 hours, sieve the active material and pole piece, and mix the powder (active material) Placed in sulfuric acid leaching. After the reaction is complete, filter out the black insoluble matter, add thiourea to the filtrate until no precipitation occurs, and filter the insoluble matter.

[0075] Measure the Al, Ni, Co, Mn ratio of the filtrate after the impurity removal, and add corresponding vitriol wherein according to the ratio, adjust Ni, Co, Mn proportioning to 6: 2: 2, control Al content to be 5% (with The total molar weight of Al, Ni, Co, Mn is based on). Then add 4mol / L NaOH solution to adjust pH=11. After the reaction is complete, add salt of wormwood wherein, control the addition and make Li:(Ni+Co+Mn+Al)=1.07, make Li 2 CO 3 Uniformly precipitated on the surface of NCMA hydroxide to prepare...

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Abstract

The invention discloses a method for recovering and preparing a nickel-cobalt-manganese-aluminum quaternary positive electrode material from a waste nickel-cobalt-manganese ternary lithium-ion battery. The method comprises the following steps of (1) obtaining a leach solution containing Cu<2+>, Al<3+>, Li<+>, Ni<2+>, Co<2+> and Mn<2+> from the waste ternary lithium-ion battery through manual disassembly, magnetic separation, crushing, organic solvent soaking, screening and sulfuric acid leaching, and carrying out purification (Cu<2+>) treatment on the leach solution to obtain a purified liquid; (2) adjusting the molar ratio of Al to Ni to Co to Mn in the purified liquid, adding alkali metal hydroxide, adjusting the pH of a system until the pH is greater than or equal to 10 and carrying out primary precipitation to obtain a turbid liquid in which NCM hydroxide is precipitated; (3) adding carbonate to the turbid liquid in the step (2) for secondary precipitation, and carrying out solid-liquid separation to obtain a quaternary material precursor; and (4) burning the quaternary material precursor in air to obtain an Al-doped NCM quaternary positive electrode material. The method is simple in technology, wide in raw material source and high in repeatability; the prepared quaternary positive electrode material is excellent in cycle performance; and large-scale production can be carried out.

Description

technical field [0001] The invention relates to the field of waste lithium-ion battery recycling, in particular to a method for preparing aluminum-doped nickel-cobalt-manganese quaternary positive electrode materials in one step by using waste nickel-cobalt-manganese ternary lithium-ion batteries as raw materials. Background technique [0002] The increasing shortage of energy and the serious changes in the earth's ecological environment are gradually becoming two major obstacles to the development of human civilization. It is imperative to develop new energy sources and research and develop new, non-polluting energy-saving materials and energy storage and conversion materials. With the increase of energy demand and the continuous development of the electronic market and electric vehicle market, lithium-ion batteries are favored by people due to their superior performance such as safety, environmental protection, high specific energy and good electrochemical performance. [...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/54
CPCY02W30/84H01M10/54
Inventor 张治安赖延清王麒羽洪波方静张凯李劼
Owner CENT SOUTH UNIV
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