Recovery of Cobalt from Waste Cathodic Active Material Generated in Manufacturing Lithium Ion Batteries by Hydrometallugical Process

리튬이온전지 제조공정의 폐양극활물질로부터 습식제련공정에 의한 코발트의 회수

  • Swain Basudev (Chungnam Nationnal University, Graduate School, Department of Chemistry, Minerals & Maaterials Processing Division, Korea Institute of Geoscience & Mineral Resources) ;
  • Jeong Jinki (Minerals & Maaterials Processing Division, Korea Institute of Geoscience & Mineral Resources) ;
  • Kim Min Seuk (Minerals & Maaterials Processing Division, Korea Institute of Geoscience & Mineral Resources) ;
  • Lee Jae-chun (Minerals & Maaterials Processing Division, Korea Institute of Geoscience & Mineral Resources) ;
  • Sohn Jeong-Soo (Minerals & Maaterials Processing Division, Korea Institute of Geoscience & Mineral Resources)
  • ;
  • 정진기 (한국지질자원연구원 자원활용소재연구부) ;
  • 김민석 (한국지질자원연구원 자원활용소재연구부) ;
  • 이재천 (한국지질자원연구원 자원활용소재연구부) ;
  • 손정수 (한국지질자원연구원 자원활용소재연구부)
  • Published : 2005.12.01

Abstract

A hydrometallurgical process to leach cobalt from the waste cathodic active material, $LiCoO_{2}$, 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, $75^{\circ}C$ 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 Cyanex272 as an extractant at the initial pH 5.0 and in organic to aqueous phase ratio of 1.6:1 under the single stage extraction conditions. The Co in the raraffinate was completely extracted by 0.5 M Na-Cyanex272 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 $LiCoO_{2}$, using a series of hydrometallurgical processes: sulfuric acid leaching of waste $LiCoO_{2}$- solvent extraction of Co by Na-Cyanex 271 - scrubbing of Li by sodium carbonate solution - stripping of Co by sulfuric acid solution.

황산을 사용하여 폐양극활물질, $LiCoO_{2}$로부터 코발트를 침출한 뒤 용매추출법으로 분리하여 회수하는 습식제련공정을 개발하였다. 최적침출조건은 황산농도 2.0 M, 과산화수소수 첨가량 5 $vol.\%$, 침출온도 $75^{\circ}C$, 침출시간 30 min., 초기정액농도 100 g/L 이었으며, 코발트와 리튬의 침출율은 각각 $93\%$$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 272농도 0.5M, 초기 pH 5.0, 유기상과 수용액상의 상비 1:1의 조건에서 완전히 추출되었다. 폐 $LiCoO_{2}$의 황산침출-Na-Cyanex 272에 의한 코발트의 용매추출-탄산소다용액에 의한 리튬의 세정-황산용액에 의한 코발트의 탈거 등 일련의 습식제련공정을 이용하여 폐$LiCoO_{2}$로부터 순도 $99.99\%$이상의 황산코발트용액을 회수할 수 있었다.

Keywords

References

  1. Sohn, J.-S. et al., 2004: Recovery of cobalt in sulfuric acid leaching solution using oxalic acid, Proceedings of International Symposium on Green technology for Resources and Materials Recycling, pp. 80-84, Industrial Waste Recycling R&D Center and The Korean Institute of Resources Recycling, COEX, Seoul, 24-27 November 2004, Printed in Korea
  2. Contestabile, M., Panero, S. and Scrosati, B., 2001: A laboratory-scale lithium-ion battery recycling process, Journal of Power Sources, 92, pp. 65-69 https://doi.org/10.1016/S0378-7753(00)00523-1
  3. 이철경, 양동효, 2001: 폐리튬이온전지로부터 유기금속 회수, 공업화학, 12(8), pp. 890-895
  4. Lee, C.K. and Rhee, K.-I., 2003: Reductive leaching of cathodic active materials from lithium ion battery wastes, Hydrometallurgy, 68, pp. 5-10 https://doi.org/10.1016/S0304-386X(02)00167-6
  5. Zhang, Pingwei, et al., 1998: Hydrometallurgical process for recovery of metal values from spent lithium-ion secondary batteries, Hydrometallurgy, 47, pp. 259-271 https://doi.org/10.1016/S0304-386X(97)00050-9
  6. Pranolo, Y., and Cheng, C.Y., 2005: The recovery of cobalt and lithium from spent battery leach solutions by solvent extraction, A. J. Parker/CSIRO Minerals Report DMR-2624, pp. 6, The A. J. Parker CRC for hydrometallurgy, February 2005, Murdoch, Australia
  7. Cyanex 272, 1989: Technical Brochure, American Cyanamid Company
  8. Han, K.N. and Lawson, F., 1980: Leaching behaviour of cobaltous and cobalto-cobaltic oxides in ammonia and in acidic solutions, Hydrometallurgy, 6, pp. 75-87 https://doi.org/10.1016/0304-386X(80)90009-2
  9. Pourbaix, M., 1974: Atlas of electrochemical equilibria in aqueous solutions, 2nd ed., National Association of Corrosion Engineers, Huston, TX, USA
  10. Sarangi, K., Reddy, B.R. and Das, R.P., 1999: Extraction studies of cobalt (II) and nickel (II) from chloride solutions using Na-Cyanex 272. Separation of Co(II)/Ni(II) by the sodium salts of D2EHPA, PC88A and Cyanex 272 and their mixtures, Hydrometallurgy, 52(1-2), pp. 253-265 https://doi.org/10.1016/S0304-386X(99)00025-0
  11. Basudev Swain, 정진기, 이재천, 이계호, 2005: Recovery of valuable metals from waste cathode active materials of lithium ion battery industry, 2005 춘계학술발표회 논문집, pp. 259-264, 한국지구시스템공학회, 대전, 2005년 4월 15-16일, 한국
  12. Devi, N.B., Nathsarrna, K.C. and Chakravortty, V., 1998: Speparation and recovery of cobalt(II) and nicke(II) from sulphate solutions using sodium salts of D2EHPA, PC 884 and Cyanex 272, Hydrometallurgy, 49, pp.47-61 https://doi.org/10.1016/S0304-386X(97)00073-X
  13. 박경호 등, 2004: 니켈과 코발트를 함유한 황산용액으로부터 Cyanex 272에 의한 코발트의 용매추출, 대한금속.재료학회지, 42(11), pp. 947-951