Method for recycling manganese and copper resources from waste lithium ion batteries

Abstract

The invention relates to a method for recycling manganese and copper resources from waste lithium ion batteries. The method comprises the following steps: (1) recycling Co, Ni, Li, Al and other elements from the waste lithium ion batteries and separating to obtain a solution mainly containing Cu<2+> and Mn<2+>, and adding appropriate amount of dilute sulphuric acid into the solution to adjust the pH value and the electric conductivity of the dilute sulphuric acid, wherein the concentration of the dilute sulphuric acid of the solution after adjustment is 0.1-5mol / L. (2) performing electrolysis, with a copper sheet or a titanium sheet as a cathode, graphite flake or titanium-based manganese dioxide as an anode, and the solution adjusted in the step (1) as electrolyte solution under the condition that the anodic current density is adjusted to be 0.5-50mA / cm<2>; and (3) separating MnO2 out from the anode and separating Cu out from the cathode after electrolysis, recycling the MnO2 separated out from the anode as products, spraying the dilute sulphuric acid on Cu separated out from the cathode in the air for corroding, recycling a Cu<2+> containing solution into an electrolytic cell after corrosion, and recycling metal copper after electrolysis, thus recycling all Cu resources. The method can greatly reduce the voltage of the electrolytic cell during electrolysis and greatly reduce the energy consumption.

Description

technical field [0001] The invention relates to the field of recovery and treatment of waste lithium ion batteries, in particular to a method for recovering manganese and copper resources from waste lithium ion batteries. Background technique [0002] Since the commercialization of lithium-ion batteries at the end of the 20th century, they have been widely used in portable electronic devices such as mobile phones, notebook computers, cameras, and electric vehicles due to their advantages such as high energy density, light weight, long life and no memory. . Waste lithium-ion batteries usually contain valuable materials such as manganese and copper, which have high recycling value; if not handled properly, manganese, copper and other metals will also harm humans through biomagnification. With the increasing application of lithium-ion batteries, recycling valuable materials such as Mn and Cu in lithium-ion batteries has important social and economic significance for reducing e...

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Problems solved by technology

For example, the application publication numbers are CN201310089509, CN201210230857, CN201210017163, CN201210001160, CN201110298498, CN201010209830 and other patents. There are three main types of methods for recovering manganese resources from waste lithium-ion batteries: Add materials such as manganese sources and lithium sources, and finally recover manganese resources in the form of one-element or multi-element cathode materials for lithium-ion batteries by electrolytic deposition, calcination, etc. The performance of the prepared materials is poor and unstable, and it is difficult to make high-quality positive electrode materials; (2) the waste lithium-ion batteries are combined with other manganese-based waste batteries, and ferromanganese is used by crushing, screening, reduction smelting, etc. Manganese resources are recovered in the form of manganese or other alloys. This type of method not only consumes a lot of energy, but is prone to produce waste gas, waste residue and other pollutants, and the product purity is not high; (3) After being dissolved by acid and reducing agent, graphite flakes are used as The working electrode and graphite sheet are electrolyzed by the counter electrode, and the manganese resource is finally recovered in the form of manganese dioxide. This method belongs to the common electrolysis method, and the tank pressure is high and the energy consumption is large.

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