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Method for recycling metallic lithium from waste lithium ion batteries

A lithium-ion battery and metal lithium technology, applied in the field of selective recovery of valuable metal lithium, can solve the problems of poor selectivity of waste acid and waste alkali, complex element content testing, increased cost and difficulty, etc., to overcome difficult separation and good application Prospect, effect of reducing dissolution loss

Active Publication Date: 2018-09-07
INST OF PROCESS ENG CHINESE ACAD OF SCI
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AI Technical Summary

Problems solved by technology

Although this method realizes the recovery and reuse of nickel, cobalt, lithium and other metals in waste lithium-ion batteries, it needs to classify the recovered waste lithium-ion batteries according to the content of the metals, which increases the cost and difficulty of recycling, and requires complex elements. Content test
[0005] Combining the experience of the research group in the synthesis and application of ionic liquids, the present invention designs and synthesizes a functional ionic liquid, which effectively solves the problem of a large amount of waste acid and alkali generated in the traditional extraction process and the conventional extraction agent in the leach solution system of waste electrode materials. The problem of poor selectivity

Method used

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  • Method for recycling metallic lithium from waste lithium ion batteries

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] The positive electrode material in the waste lithium-ion battery that reclaims obtains and contains 2wt%H 2 o 2 The 2M sulfuric acid solution was mixed according to the solid-to-liquid ratio of 50g / L, stirred at 80°C for 3h, and filtered to obtain the leaching solution.

[0019] Table 1 The composition of leachate

[0020] Ion species

[0021] As a comparative example, take an appropriate amount of the above leachate to adjust the pH to 1, 2, 3 and 4 respectively, mix it with pure tributyl phosphate according to the ratio (O / A) = 1:1, stir at room temperature for 30 minutes, and then centrifuge at 6000rpm for 10 minutes. The separated organic phase was analyzed, and the extraction rates of metal lithium were calculated to be 2.43%, 2.38%, 2.51% and 2.49%, respectively.

Embodiment 2

[0023] The extraction system is composed of 1-carboxymethyl-3-methylimidazole bistrifluoromethanesulfonimide salt and tributyl phosphate at a volume ratio of 1:9.

[0024] Take an appropriate amount of the above leachate to adjust the pH to 3, mix it with the above extraction system according to the ratio (O / A)=1:1, stir at room temperature for 30 minutes, and then centrifuge at 6000rpm for 10 minutes. Analyzing the separated organic phase and raffinate, it is calculated that the extraction rate of metal lithium can reach more than 85%.

[0025] As a comparative example, the pH of the leaching solution was adjusted to 1, 2 and 4 respectively, and after extraction using the same method as above, the extraction rates of lithium metal were calculated to be 79.54%, 83.29% and 80.1%, respectively.

Embodiment 3

[0027] The extraction system is composed of 1-carboxyethyl-3-methylimidazole bistrifluoromethanesulfonimide salt and tributyl phosphate at a volume ratio of 1:9.

[0028] Adjust the pH value of the above leachate to 3, mix it with the above extraction system according to the ratio (O / A)=1:1, stir at room temperature for 30min, and then centrifuge at 6000rpm for 10min. Analyzing the separated organic phase and raffinate, it is calculated that the extraction rate of metal lithium can reach more than 85%.

[0029] As a comparative example, adjust the volume ratio of 1-carboxyethyl-3-methylimidazole bis-trifluoromethanesulfonimide salt to tributyl phosphate to be 1:4, 3:7 and 2:3 to form the extraction system, After extraction by the same method as above, the extraction rates of lithium metal were calculated to be 80.75%, 81.2% and 70.17%, respectively.

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Abstract

The invention provides a method for recycling metallic lithium from waste lithium ion batteries. According to the method, an extraction system is formed by ionic liquid and tributyl phosphate, and selective extraction is conducted on aqueous phase leachate containing nickel ions, cobalt ions, manganese ions and lithium ions, so that the recovery rate of the metallic lithium is effectively increased. The volume ratio of the ionic liquid to the tributyl phosphate is not greater than 1: 1; and the pH value of the aqueous phase leachate containing the lithium ions is not greater than 7. The methodis easy to operate and efficient; after reverse extraction, the extraction system can be utilized cyclically; compared with a traditional wet method recycling process, the defects that plenty of acid-base solutions are consumed, and a great amount of waste water is generated are effectively avoided; and the good application prospect is achieved.

Description

technical field [0001] The invention belongs to the field of recycling waste lithium ion batteries, and relates to a method for selectively recovering valuable metal lithium from waste lithium ion batteries. Background technique [0002] Lithium-ion batteries have the advantages of high energy density, wide operating temperature range, small self-discharge, and long service life. They are widely used in 3C electronic products, new energy vehicles and other fields. Especially in the field of new energy vehicles, my country has now become the largest country in the promotion of new energy vehicles. In 2016, the sales volume of new energy vehicles in my country reached 507,000. According to the new energy vehicle development plan, by 2020, the production and sales of new energy vehicles will reach 2 million, and the stock will reach 5 million. The service life of power batteries is generally 3 to 5 years. With the rapid development of new energy vehicles, the amount of scrappe...

Claims

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Application Information

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IPC IPC(8): C22B7/00C22B26/12
CPCC22B7/007C22B26/12
Inventor 郑硕航董陶沙一凡张锁江
Owner INST OF PROCESS ENG CHINESE ACAD OF SCI
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