리튬이온電池 製造工程의 廢陽極活物質로부터 濕式製鍊工程에 의한 코발트의 回收
Recovery of Cobalt from Waste Cathodic Active Material Generated in Manufacturing Lithium Ion Batteries by Hydrometallugical Process
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황산을 사용하여 폐양극활물질, LiCoO2로부터 코발트를 침출한 뒤 용매추출법으로 분리하여 회수하는 습식제련공정을 개발하였다. 최적침출조건은 황산농도 2.0 M, 과산화수소수 첨가량 5 vol.%, 침출온도 75oC, 침출시간 30 min., 초기광액농도 100 g/L 이었으며, 코발트와 리튬의 침출율은 각각 93% 와 94.5% 이었다. 초기 pH 5.0, 유기상과 수용액상의 상비 1.6 : 1, 추출단수 1단의 조건에서 1.5 M Cyanex 272를 추출제로 사용하여 44.72 g/L 코발트와 5.43 g/L 리튬을 함유하는 황산침출액으로부터 85%의 코발트를 추출하였다. 추출잔액에 남아있는 코발트는 Na-Cyanex 272 농도 0.5 M, 초기 pH 5.0, 유기상과 수용액상의 상비 1:1의 조건에서 완전히 추출되었다. 폐LiCoO2의 황산침출-Na-Cyanex 272에 의한 코발트의 용매추출-탄산소다용액에 의한 리튬의 세정-황산용액에 의한 코발트의 탈거 등 일련의 습식제련공정을 이용하여 폐LiCoO2로부터 순도 99.99% 이상의 황산코발트용액을 회수할 수 있었다.
Abstract
A hydrometallurgical process to leach cobalt from the waste cathodic active material, LiCoO2, and subsequently to separate it by solvent extraction was developed. The optimum leaching conditions for high recovery of colbalt and lithium were obtained: 2.0 M sulfuric acid, 5 vol.% hydrogen peroxide, 75oC leaching temperature, 30 minutes leaching time and an initial pulp density of 100 g/L. The respective leaching efficiencies for Co and Li were 93% and 94.5%. About 85% Co was extracted from the sulfuric acid leach liquor containing 44.72 g/L Co and 5.43 g/L Li, using 1.5 M Cyanex 272 as an extractant at the initial pH 5.0 and an organic to aqueous phase ratio of 1.6:1 under the single stage extraction conditions. The Co in the raffinate was completely extracted by 0.5 M Na-Cyanex 272 at the inital pH 5.0, and an organic to aqueous phase ratio of 1 : 1. The cobalt sulfate solution of higher than 99.99% purity could be recovered from waste LiCoO2, using a series of hydrometallurgical processes: sulfuric acid leaching of waste LiCoO2 - solvent extraction of Co by Na-Cyanex 272 - scrubbing of Li by sodium carbonate solution - stripping of Co by sulfuric acid solution.
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