Treatment method for waste lithium-ion battery

A technology of lithium ion battery and treatment method, applied in the field of waste lithium ion battery treatment, can solve the problems of online production of active substances, neglect of recycling treatment, secondary environmental pollution, etc., so as to increase battery recycling treatment and shorten production process , the effect of strong applicability

Inactive Publication Date: 2016-07-20

CHINA ELECTRONICS ENG DESIGN INST

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AI-Extracted Technical Summary

Problems solved by technology

[0008] The treatment methods of waste lithium-ion batteries in the prior art are all focused on the recovery of positive electrode materials, non-ferrous metals, etc., or the treatment methods can only be applied to specific waste lithium-ion batteries, ignoring the recovery and treatment of electrolytes and other ...

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Method used

As can be seen from the above description, the processing method of the waste lithium ion battery provided by the present embodiment, by carrying out pretreatment to the waste lithium battery, comprises dismantling, discharging, crushing, organic solvent dissolution, sorting, after sorting After alkali conversion, acid dissolution, and impurity removal, the electrode materials are chemically separated. Extraction and separation is a key step. Part of the cobalt and lithium is separated to obtain nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salts, lithium salts, and cobalt salts; the mixed salts are chemically synthesized to regenerate positive electrode materials. Moreover, the electrolyte and positive electrode materials can be obtained during the whole process, the recovery rate of positive electrode materials is improved, and the recovery purity of copper and aluminum is improved; in addition, the direct production of positive electrode materials shortens the production process and increases battery production-battery recycling treatment- Construction of circular industrial chain for battery production.

As can be se...

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Abstract

The invention relates to the technical field of comprehensive utilization of resources and discloses a treatment method for a waste lithium-ion battery. The method comprises the following steps: carrying out disassembling, discharging, breaking, crushing and sorting; carrying out alkaline transfer, acid dissolution and impurity removal on the sorted electrode material; and then carrying out chemical separation through pretreatment on the waste lithium-ion battery, wherein extraction and separation are a key step; partial cobalt is separated from lithium to obtain a nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salt, a lithium salt and a cobalt salt; mixed sulfate regenerates a cathode material through chemical synthesis; an electrolyte and the cathode material can be obtained in the overall treatment process; the recovery rate of the cathode material is improved; and the recovery purity of copper, aluminum and the like are improved. In addition, the cathode material is directly produced; the production process is shortened; and construction of the circulating industry chain of battery production, battery recovery treatment and battery production is increased.

Application Domain

Waste accumulators reclaimingBattery recycling

Technology Topic

Chemical synthesisAluminium +15

Image

Examples

Experimental program(1)

Example Embodiment

[0033] Specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

[0034] like figure 1 as shown, figure 1 A flow chart of a method for treating a spent lithium-ion battery provided by an embodiment of the present invention.

[0035] The embodiment of the present invention provides a kind of processing method of waste lithium ion battery, and this method comprises the following steps:

[0036] Disassemble the waste lithium-ion battery to obtain the shell, tabs and battery core;

[0037] Pulverize the battery core to obtain a solid mixture, electrolyte, and diaphragm;

[0038] Sorting and filtering the obtained solid mixture, electrolyte and diaphragm to obtain a solid mixture;

[0039] Dissolving and removing the binder in the solid mixture, sorting and filtering to obtain powder;

[0040] Put the obtained powder into the alkali solution for alkali conversion, and the aluminum in the powder is dissolved and recovered;

[0041] After alkali leaching, the precipitate obtained by filtration is dissolved with acid solution + hydrogen peroxide to form a mixed solution;

[0042] adjusting the pH value of the mixed solution with alkali to remove iron and aluminum impurities in the mixed solution;

[0043] Perform countercurrent multi-stage cooperative extraction on the mixed solution to obtain lithium salt raffinate, nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salt;

[0044] Cobalt salts are obtained by acid stripping;

[0045] The precursor of positive electrode material is obtained by chemical precipitation after conditioning and tempering of nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salt, and a new type of positive electrode material is prepared.

[0046] It can be seen from the above description that the treatment method for waste lithium-ion batteries provided in this embodiment includes pretreatment of waste lithium batteries, including disassembly, discharge, crushing, organic solvent dissolution, and sorting, and the sorted electrode materials After alkali conversion, acid dissolution and impurity removal, chemical separation is carried out. Extraction and separation is a key step. Part of the cobalt and lithium is separated to obtain nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salts, lithium salts, and cobalt salts; the mixed salts are chemically synthesized to regenerate positive electrode materials. Moreover, the electrolyte and positive electrode materials can be obtained during the whole process, the recovery rate of positive electrode materials is improved, and the recovery purity of copper and aluminum is improved; in addition, the direct production of positive electrode materials shortens the production process and increases battery production-battery recycling treatment- Construction of circular industrial chain for battery production.

[0047] In order to facilitate the understanding of the present invention, the method for processing waste and recycled electronics provided by the embodiments of the present invention will be described in detail below with specific examples.

[0048] Step 1. Disassemble and discharge the waste lithium-ion battery;

[0049] Specifically, since waste lithium-ion batteries often still have a certain amount of electricity, it is necessary to remove the plastic shell or metal shell and tabs of the battery, and then put it into a sodium chloride solution to fully discharge it.

[0050] Step 2, after pulverizing the battery core, sorting, and filtering to obtain a diaphragm, a solid mixture, and an electrolyte;

[0051] Specifically, use a pulverizer or crusher to crush the battery core to 1 mm to 8 mm, then filter to obtain the oversize and electrolyte, and sort the oversize to obtain a solid mixture and a diaphragm; the electrolyte and the diaphragm are recovered separately.

[0052] Step 3, dissolving and removing the binder in the solid mixture, sorting, and filtering to obtain a powder;

[0053] Specifically, the solid mixture in step 2 is dissolved in a mixed solvent (such as an organic solvent, ethanol or a mixed solution of esters and water), then filtered to obtain a solution and a solid mixture, and the solid mixture is sorted to obtain copper, aluminum and powder body.

[0054] Step 4, put the obtained powder into the lye to carry out alkali conversion, and the aluminum is recovered;

[0055] Specifically, put the powder into the lye (NaOH, KOH or ammonia water, and the concentration of the above-mentioned lye is 0.1-4.0mol/l) in the reaction kettle for reaction. It needs to be sealed during the reaction. After the reaction is complete, the positive electrode material Metaaluminate (AlO 2 ) is replaced by hydroxide (OH) to form a hydroxide compound, and the recovery rate of aluminum can reach more than 97%. The lye can be used at any concentration between 0.1 mol/l, 1.5 mol/l, 2.0 mol/l, 2.5 mol/l, 3.0 mol/l, 3.5 mol/l, 4.0 mol/l, etc. between 0.1 and 4.0 mol /l of lye.

[0056] Step 5, after alkaline leaching, filter to obtain the precipitate and dissolve it with acid solution + hydrogen peroxide to form a mixed solution;

[0057] Specifically, after the upper reaction, the solution is filtered to obtain a precipitate, and the separated substance is added to an acid solution (sulfuric acid, hydrochloric acid, nitric acid) with a concentration of 0.2 to 4 mol/l + a hydrogen peroxide leaching system with a concentration of 0.2 to 10 wt%. In the process, after sufficient reaction, the substances in the positive electrode materials such as cobalt ions and lithium ions all enter the solution in the form of ions to form a mixed solution. The acid solution can be used at any concentration between 0.2 mol/l, 1.5 mol/l, 2.0 mol/l, 2.5 mol/l, 3.0 mol/l, 3.5 mol/l, 4.0 mol/l, etc. /l of acid. The hydrogen peroxide can be any hydrogen peroxide with a concentration of 0.2wt%, 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, etc. between 0.2-10wt%.

[0058] Step 6, adjusting the pH value of the mixed solution with alkali to remove iron and aluminum impurities in the mixed solution;

[0059] Specifically, after leaching with sulfuric acid hydrogen peroxide, adjust the pH of the leaching solution to 5 with NaOH (1-8 mol/l) solution, so that the Al in the solution 3+ , Fe 3+ Wait for impurity ions to precipitate and filter. The removal rate of impurity ions can reach 99%. Wherein, the concentration of NaOH can be: 1 mol/l, 4 mol/l, 6 mol/l, 8 mol/l, etc. any concentration between 1-8 mol/l.

[0060] Step 7, performing countercurrent multi-stage cooperative extraction on the mixed solution to obtain lithium salt raffinate, nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salt;

[0061] Specifically, use extraction agents P507 and P204, P507 and Cyanex272, P204 and TBP, Cyanex272 and N235 (the concentration of each extraction agent is 0.5-2.8mol/l) (4:1-1:4), P204, P507 Co-extract with N235 (the concentration of each extractant is 0.5-2.8mol/l) (4:1:1-1:4:4). For example, the mass fraction of extract P507 and extract P204 is: 1:4, 2:3, 1:1, 2:1, 2:1, 4:1, etc. in any ratio between 4:1 and 1:4. The concentration of extractant P507 and extractant P204 can be 0.5 mol/l, 1 mol/l, 2 mol/l, 2.8 mol/l, etc. any concentration between 0.5-2.8 mol/l.

[0062] Lithium salt raffinate, nickel cobalt lithium (10:1:1~1:10:10), nickel cobalt (1:10~10:1) or nickel cobalt manganese (10:1:1~1:10: 10) mixed salt;

[0063] Step 8. The nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salts are subjected to chemical precipitation after tempering to obtain a positive electrode material precursor to prepare a new type of positive electrode material.

[0064] Specifically, according to the different positive electrode materials to be prepared, a mixed salt solution is drawn from the tank, nickel-cobalt-lithium (10:1:1~1:10:10), nickel-cobalt (1:10-10:1) or nickel Cobalt-manganese (10:1:1-1:10:10) reacts by adding excess sodium carbonate and oxalic acid after tempering to obtain the precursor of the positive electrode material and prepare a new type of positive electrode material.

[0065] It can be seen from the above description that the treatment method for waste lithium-ion batteries provided in this example includes pretreatment of waste lithium batteries, including disassembly, discharge, pulverization, organic solvent dissolution, sorting, and electrode materials after sorting. After alkali conversion, acid dissolution and impurity removal, chemical separation is carried out. Extraction and separation is a key step. Part of the cobalt and lithium is separated to obtain nickel-cobalt-lithium, nickel-cobalt or nickel-cobalt-manganese mixed salts, lithium salts, and cobalt salts; the mixed salts are chemically synthesized to regenerate positive electrode materials. In addition, the electrolyte and positive electrode materials can be obtained during the entire treatment process, the recovery rate of positive electrode materials is improved, and the recovery purity of copper and aluminum is improved; in addition, the raffinate can directly produce positive electrode materials, which shortens the production process and increases battery production. Recycling - the construction of a circular industrial chain for battery production.

[0066] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.

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