# US 12,113,187 B2 · Method for recovering valuable metals from spent lithium ion batteries

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- Number: US 12,113,187 B2
- Document ID: US12113187B2
- Status: Granted
- Kind: B2
- Application number: 18/498,037
- Filed: 2023-10-31
- Published: 2024-02-22
- Granted: 2024-10-08
- Earliest claimed: 2021-09-01
- Assignees: Gem Co., Ltd.; Jingmen Gem Co., Ltd.
- Applicants: Gem Co., Ltd.; Jingmen Gem Co., Ltd.
- Inventors: Kaihua Xu; Liangxing Jiang; Jian Yang; Kun Zhang; Chenwei Li; Yongan Chen; Yanqing Lai
- Web page: https://patentgrep.com/patent/US12113187B2

## CPC

- H01M 10/54: Reclaiming serviceable parts of waste accumulators
- B09B 3/70: Chemical treatment, e.g. pH adjustment or oxidation (involving an extraction step B09B3/80)
- C01F 11/22: Fluorides
- C22B 1/005: {Preliminary treatment of scrap (C22B1/02 - C22B1/26 take precedence)}
- C22B 1/02: Roasting processes (C22B1/16 takes precedence)
- C22B 1/06: Sulfating roasting
- C22B 1/248: of metal scrap or alloys
- C22B 3/22: by physical processes, e.g. by filtration, by magnetic means {, or by thermal decomposition} (treatment or purification of solutions by liquid-liquid extraction C22B3/26)
- C22B 7/001: {Dry processes}
- C22B 7/005: {Separation by a physical processing technique only, e.g. by mechanical breaking}
- C22B 7/006: {Wet processes}
- C22B 7/007: {by acid leaching}
- C22B 7/008: {by an alkaline or ammoniacal leaching}
- C22B 15/0004: {without modification of the copper constituent}
- C22B 21/0069: {from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents (C22B21/0046, C22B21/0053 and C22B21/0092 take precedence)}
- C22B 23/0407: {Leaching processes}
- C22B 26/12: Obtaining lithium
- C22B 47/00: Obtaining manganese
- H01M 6/52: Reclaiming serviceable parts of waste cells or batteries {, e.g. recycling}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- B09B 2101/16: Batteries
- Y02E 60/10: Energy storage using batteries
- Y02P 10/20: Recycling
- Y02W 30/84: Recycling of batteries or fuel cells
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- B09B: DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

The present invention provides a method for recovering valuable metals from waste lithium ion batteries. The method comprises: short-circuit discharging, dismantling, crushing, roasting, and screening on waste lithium ion batteries to obtain active electrode powders; using alkaline solution to wash the active electrode powders, then filtering to remove copper and aluminum; drying the activated electrode powder after alkaline washing treatment, mix the dried activated electrode powder with starch and concentrated sulfuric acid and stir evenly to obtain the mixed material; calcining the mixed material with controlling the atmosphere; taking out the product obtained from calcination and using deionized water to extract the leachate and leaching residue with valence metal ions, and then obtaining the leachate after filtering. The present invention can reduce the concentration of impurity ions in the leaching solution, improve the purity and comprehensive recovery rate of valuable metals, and reduce the recovery cost.

## Claims

### Claim 1

A method for recovering metals from waste lithium ion batteries, including the following steps:
step 1, pre-treatment, comprising:
short-circuit discharging, dismantling, crushing, roasting, and screening on waste lithium ion batteries to obtain active electrode powders; wherein the waste lithium ion battery comprises copper and aluminum, and the waste lithium ion battery is one or more of waste lithium nickel oxide lithium ion battery, lithium cobalt oxide lithium ion battery, lithium manganese oxide lithium ion battery, and lithium nickel cobalt manganese oxide lithium ion battery;
step 2, alkaline cleaning and filtering, comprising:
using alkaline solution to clean the active electrode powders, then filtering to remove copper and aluminum from the active electrode powders;
step 3, drying and mixing, comprising:
drying the active electrode powder after step 2, mixing the dried active electrode powder with starch and concentrated sulfuric acid in a predetermined proportion and stirring to obtain a mixed material,
wherein the predetermined proportion comprises:
the dried active electrode powders are mixed with starch, wherein an amount of starch added into the dried active electrode powders is controlled at 5-20 wt. %, and then concentrated sulfuric acid is added at a first solid-liquid ratio of 50-300 g/L and stirred;
step 4, high temperature reduction, comprising:
putting the mixed material into a corundum crucible, then moving the corundum crucible into a tube furnace to calcine, and controlling the atmosphere of the tube furnace during calcination,
wherein controlling the atmosphere of the tube furnace comprises controlling the calcination temperature at 300-800° C., heating rate at 10° C./min, and calcination time at 30-180 min; wherein the atmosphere is a mixture of O2 and N2, and the volume fraction of O2 is greater than 20 and not more than 50; and
step 5, water leaching and filtration, comprising:
taking out a product obtained from calcination in the step 4 and using deionized water to extract leachate and leaching residue with valence metal ions, and then obtaining the leachate after filtering.

### Claim 2 (depends on 1)

The method for recovering metals from waste lithium ion batteries according to claim 1, wherein in the step 1, the waste lithium ion batteries are short-circuit discharged in a sodium sulfite solution until a termination voltage of the waste lithium ion batteries is below 1 V, wherein a solute concentration of the sodium sulfite solution is 5-20%; disassembling the waste lithium ion batteries after short-circuit discharging to obtain battery cells; crushing the battery cells to obtain crushed materials; raising a temperature of the crushed materials to 400-600° C. at a rate of 2-10° C./min in an air atmosphere, preserving heat and calcining to strip adhesive from the crushed materials; lime water with a concentration of not less than 50 mg/L is used to absorb waste gas released during the adhesive stripping process to obtain calcium fluoride; separating stripped product to obtain Al, Cu, and active electrode powders from the stripped product.

### Claim 3 (depends on 1)

The method for recovering metals from waste lithium ion batteries according to claim 1, in the step 2, the alkaline solution is one or more of NaOH, NH4OH and KOH, with a pH value of 10-14, an alkaline cleaning time of 10-60 min, and a temperature of 20-50° C.

### Claim 4 (depends on 3)

The method for recovering metals from waste lithium ion batteries according to claim 3, in the step 2, the pH value of the alkaline solution is 10-12, the alkaline cleaning time is controlled within 10-30 min, and the temperature is controlled between 25-35° C.

### Claim 5 (depends on 1)

The method for recovering metals from waste lithium ion batteries according to claim 1, wherein, in the step 3, the amount of starch added into the dried active electrode powders is controlled at 5-10 wt. %, and the first solid-liquid ratio is controlled between 100-150 g/L.

### Claim 6 (depends on 1)

The method for recovering metals from waste lithium ion batteries according to claim 1, in the step 4, controlling the calcination temperature at 500-800° C., calcination time at 60-120 min.

### Claim 7 (depends on 1)

The method for recovering metals from waste lithium ion batteries according to claim 1, in the deionized water leaching process of the step 5, a second solid-liquid ratio is controlled between 50-100 g/L, the temperature is between 50-90° C., and the leaching time is between 30-180 min.

### Claim 8 (depends on 7)

The method for recovering metals from waste lithium ion batteries according to claim 7, in the deionized water leaching process of the step 5, the second solid-liquid ratio is controlled between 50-80 g/L, the temperature is between 60-80° C., and the leaching time is between 60-90 min.