US 12,331,381 B1
Method of using a chlorination method to recycle metal elements in lithium batteries
Faping Zhong, Shenzhen (CN); Chihuan He, Shenzhen (CN); Subin Jiang, Shenzhen (CN); Hongbing Liu, Shenzhen (CN); Jiqun Zhu, Shenzhen (CN); and Shuifa Tan, Shenzhen (CN)
Assigned to Shenzhen Huineng Energy Storage Materials Engineering Research Center Co., LTD, Shenzhen (CN); and National Engineering Research Center of Advanced Energy Storage Materials (Shenzhen) Co., Ltd, Shenzhen (CN)
Filed by Shenzhen Huineng Energy Storage Materials Engineering Research Center Co., LTD, Shenzhen (CN); and National Engineering Research Center of Advanced Energy Storage Materials (Shenzhen) Co., Ltd, Shenzhen (CN)
Filed on Apr. 18, 2024, as Appl. No. 18/639,474.
Claims priority of application No. 202311736266.8 (CN), filed on Dec. 18, 2023.
Int. Cl. C22B 26/12 (2006.01); C22B 7/00 (2006.01); C22B 21/00 (2006.01); H01M 10/54 (2006.01)
CPC C22B 7/002 (2013.01) [C22B 21/0069 (2013.01); C22B 26/12 (2013.01); H01M 10/54 (2013.01)] 9 Claims
OG exemplary drawing
 
1. A method of using a chlorination method to recycle metal elements in lithium batteries, including the following steps:
Step 1, removing organic components in the lithium battery through oxygen-free pyrolysis at a temperature of 400-600° C. for one hour, so as to obtain a mixture of powders containing positive-electrode material and carbon,
wherein removing organic components in the lithium battery further comprises pumping gas products of the oxygen-free pyrolysis into a gas outlet, passing the gas products through a gas-solid filtration device to a combustion furnace, burning under oxygen-enriched atmosphere, where the excess oxygen coefficient is 100%, sending the flue gas after combustion to pass through a flue gas heat exchanger, deacidfying the flue gas by saturated limewater, sending the flue gas to pass through an activated-carbon absorption tower, taking out the solid products after pyrolysis, using two stages of vibration screenings to obtain the metal sheets of current collectors, and adding carbon powders to the mixture of powders to achieve a carbon content of 10 wt % in the mixture of powders,
wherein removing organic components further comprises discharging the lithium battery, dissembling the lithium battery, crushing the lithium battery so a longest side of the crushed lithium battery is ≤4 cm, performing magnetic separation, and winnowing,
Step 2, heating and chlorinating the powders by chlorine at a heating temperature of 500-1200° C., wherein the initial gas pressure before heating is 1 atm,
wherein heating and chlorinating the powders by chlorine further comprises vacuuming and heating chlorine until the chlorine gas pressure in the furnace is 110 kPa and the excess of chlorine gas is adjusted to be at least 10%,
Step 3, outputting gas products of the chlorination through a gas-solid filtration device at a high temperature of 320° C. or above, and then performing two stages of desublimation, wherein the temperature during the first-stage desublimation is set to be below 306° C. and above 178° C., so that FeCl3 is desublimated into solid deposition, which is used for recycling Fe element; the temperature of the second-stage desublimation is set to be below 178° C., so that AlCl3 is desublimated into solid deposition, which is used for recycling Al element;
Step 4, taking out solid products of the chlorination for recycling the Li element,
wherein taking out solid products of the chlorination for recycling the Li element further comprises leaching the solid products by water, obtaining a first filtrate by filtering and removing the filter residue, adding 10 wt % NaOH aqueous solution into the first filtrate to precipitate nickel, cobalt, and manganese elements, filtering to obtain a second filtrate, and obtaining a precipitation of lithium carbonate by using sodium carbonate as the precipitating agent, wherein the sodium carbonate is heated to 95° C. and the second filtrate is added and held for more than 30 minutes.