Method for recycling lithium cobalt oxide from waste positive electrode of lithium cobalt oxide battery

A technology of lithium cobalt oxide and positive electrode sheet, which is applied in the fields of comprehensive utilization of resources and non-ferrous hydrometallurgy, can solve the problems of a large number of toxic and harmful gases, troublesome post-processing, incomplete separation, etc., to avoid toxic and harmful gases, easy to operate, easy to The effect of industrialization promotion

Active Publication Date: 2013-07-10
河南省冶金研究所有限责任公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The fire method mainly uses the method of calcination to volatilize the binder, carbon powder, etc. in the waste, and then add lithium cobalt to sinter to prepare lithium cobaltate, but this method will generate a large amount of toxic and harmful gases, and post-processing is more troublesome; The recovery method is a relatively mature method. It dissolves the electrode material through strong acid, and then uses precipitation separation, ion exchange and solvent extraction to separate and recover the metal elements contained in the leachate. However, the process of this method The process is long, the operation is cumbersome, and the energy consumption is high; there are also studies using dilute acid to corrode the aluminum foil and the positive electrode material, stirring to separate, but this method takes a long time to separate and the separation is not complete

Method used

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Examples

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Effect test

Embodiment 1

[0021] In this embodiment, the method for reclaiming lithium cobaltate from the waste positive electrode sheet of lithium cobaltate battery comprises the following steps:

[0022] (1) Put 100g of the waste positive electrode sheet of lithium cobaltate battery into 1L of 1mol / L hydrochloric acid leaching solution dissolved with 60g of citric acid, and react at 60°C for 6h;

[0023] (2) Filter the leaching solution in step (1) to separate the aluminum foil and solid particles;

[0024] (3) Stir and wash the solid particles with 100 mL of absolute ethanol at 40°C for 1 hour, and dry at 105°C for 2 hours;

[0025] (4) Add lithium carbonate to the solid particles to adjust the Co / Li mass ratio in the solid particles to 1.15:1, mix well, calcinate at 750°C for 4 hours, and cool to obtain lithium cobaltate.

[0026] According to the method for reclaiming lithium cobalt oxide in the waste positive plate of lithium cobalt oxide battery in this embodiment, the recovery rate of cobalt i...

Embodiment 2

[0028] In this embodiment, the method for reclaiming lithium cobaltate from the waste positive electrode sheet of lithium cobaltate battery comprises the following steps:

[0029] (1) Put 100g of spent lithium cobaltate battery positive electrode sheet into 1L of 1.5mol / L hydrochloric acid leaching solution dissolved with 70g of citric acid, and react at 70°C for 5h;

[0030] (2) Filter the leaching solution in step (1) to separate the aluminum foil and solid particles;

[0031] (3) Stir and wash the solid particles with 100 mL of absolute ethanol at 50°C for 1 hour, and dry at 105°C for 2 hours;

[0032] (4) Add lithium carbonate to the solid particles to adjust the Co / Li mass ratio in the solid particles to 1.10:1, mix well, calcinate at 780°C for 6 hours, and cool to obtain lithium cobaltate.

[0033] According to the method of reclaiming lithium cobalt oxide in the waste positive electrode sheet of lithium cobalt oxide battery in this embodiment, the recovery rate of coba...

Embodiment 3

[0035] In this embodiment, the method for reclaiming lithium cobaltate from the waste positive electrode sheet of lithium cobaltate battery comprises the following steps:

[0036] (1) Put 100g of spent lithium cobalt oxide battery positive electrode sheet into 1L of 2mol / L hydrochloric acid leaching solution dissolved with 80g of citric acid, and react at 80°C for 4h;

[0037] (2) Filter the leaching solution in step (1) to separate the aluminum foil and solid particles;

[0038] (3) Stir and wash the solid particles with 100 mL of absolute ethanol at 60°C for 1 hour, and dry at 105°C for 2 hours;

[0039] (4) Add lithium carbonate to the solid particles to adjust the Co / Li mass ratio in the solid particles to 1.05 / 1, mix well, calcinate at 800° C. for 5 hours, and cool to obtain lithium cobaltate.

[0040] According to the method for reclaiming lithium cobalt oxide in the waste positive electrode sheet of lithium cobalt oxide battery in this embodiment, the recovery rate of ...

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PUM

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Abstract

The invention discloses a method for recycling lithium cobalt oxide from a waste positive electrode of a lithium cobalt oxide battery. The method comprises the following steps of: (1) feeding the waste positive electrode of the lithium cobalt oxide battery into a 1-2mol/L hydrochloric acid lixivium in which citric acid is dissolved, and reacting for 4-6 hours at 60-80 DEG C; (2) filtering the lixivium in the step (1) so as to separate aluminum foil and solid grains; and (3) washing and drying the solid grains; and (4) adding a lithium source into the solid grains to adjust the mass ratio of Co/Li in the solid grains, uniformly mixing, calcining and cooling so as to obtain lithium cobalt oxide. The method adopts the mixed acid of citric acid and hydrochloric acid as the lixivium so as to effectively separate a positive electrode material and the aluminum foil, the process is simple, and no toxic or harmful gases are generated. The first discharge capacity of recovered lithium cobalt oxide can still be 140mAh/g, and the discharge capacity after 40 times of charge and discharge circulation is not less than 90%.

Description

technical field [0001] The invention relates to a method for recovering lithium cobaltate from waste positive plates of lithium cobaltate batteries, and belongs to the technical fields of comprehensive resource utilization and nonferrous hydrometallurgy. Background technique [0002] Lithium cobalt oxide is a common cathode active material for lithium-ion batteries. Because of its good electrochemical performance, processability, high tap density and stable product performance, lithium cobalt oxide batteries occupy a large market share. As a big country in the production and use of lithium cobalt oxide batteries in my country, the recycling of used batteries and production waste has always been a major event involving the long-term occurrence of the country. According to the classification method of my country's solid waste formulated by the State Environmental Protection Administration, lithium-ion batteries and their production wastes belong to the category of hazardous wa...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/54C22B7/00
CPCY02P10/20Y02W30/84
Inventor 高岩李金辉罗春祥许小菊李鹏举胡卫杰
Owner 河南省冶金研究所有限责任公司
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