DOI QR코드

DOI QR Code

Leaching of Valuable Metals from NCM Cathode Active Materials in Spent Lithium-Ion Battery by Malic acid

폐리튬이온전지 NCM 양극활물질로부터 말릭산을 이용한 유가금속의 침출

  • Son, Seong Ho (Korea Institute of Industrial Technology) ;
  • Kim, Jin Hwa (Korea Institute of Industrial Technology) ;
  • Kim, Hyun-Jong (Korea Institute of Industrial Technology) ;
  • Kim, Sun Jung (School of Materials Science and Engineering, university of Ulsan) ;
  • Lee, Man Seung (Department of Advanced Material Science and Engineering, Mokpo National University)
  • Received : 2013.04.29
  • Accepted : 2014.05.16
  • Published : 2014.08.30

Abstract

Nickel, cobalt and manganese-based(NCM, $Li(Ni_xCo_yMn_z)O_2$) cathode active materials of spent lithium-ion batteries contained valuable metals such as cobalt(15 ~ 20%), nickel(25 ~ 30%), manganese(10 ~ 15%) and lithium(5 ~ 10%). It was investigated the eco-friendly leaching process for the recovery of valuable metal from spent lithium-ion battery NCM cathode active materials by DL-malic acid($C_4H_5O_6$) as an organic leachant in this research. The experiments were carried out to optimize the process parameters for the recovery of cobalt, nickel and lithium by varying the concentration of lixivant, reductant concentration, solid/liquid ratio and temperature. The leaching solution was analyzed using ICP-OES(Inductively Coupled Plasma Optic Emission Spectrometer). Cathode active materials of 5 wt. % were introduced into the leaching solution which was 2 M DL-malic acid in addition of 5 vol. % $H_2O_2$ at $80^{\circ}C$ and it resulted in the recovery of 99.10% cobalt, 99.80% nickel and 99.75% lithium in 120 min. $H_2O_2$ in DL-malic acid solution acts as an effective reducing agents, which enhance the leaching of metals.

폐리튬이온전지 NCM($Li(Ni_xCo_yMn_z)O_2$)양극활물질 내에는 코발트(15 ~ 20%), 니켈(25 ~ 30%), Mn(10 ~ 15%) 및 리튬(5 ~ 10%) 등의 유가금속이 존재한다. 본 연구에서는 폐리튬이온전지 NCM 양극활물질로부터 친환경 유기산인 말릭산을 이용한 유가금속 침출 공정을 연구하였다. 주요공정인자는 말릭산 농도, 과산화수소 농도, 고액비, 반응온도 등이었으며, 침출액 내 금속농도는 ICP-OES(Inductively Coupled Plasma Optic Emission Spectrometer)를 통해 분석하였다. 환원제($H_2O_2$) 첨가로 인해 유가금속의 침출율이 상승하는 효과를 얻었으며, 최적공정인자는 말릭산 2 M, 과산화수소 5 vol.%, 고액비(solid/liquid ratio) 5 wt.%, 반응온도 $80^{\circ}C$이었으며, 침출율은 코발트 99.10%, 니켈 99.80%, 리튬 99.75%이었다.

Keywords

References

  1. Rabah MA, Farqhaly FE, Abd-El Motaleb MA, 2008: Recovery of nickel, cobalt and some salts from spent Ni-MH batteries, Waste Management 28 (7), pp. 1159-1167. https://doi.org/10.1016/j.wasman.2007.06.007
  2. M. Contestabile, S. Panero, B. Scrosati, 2001: A laboratory-scale lithium-ion battery recycling process, J. Power Sources 92, pp. 65-69. https://doi.org/10.1016/S0378-7753(00)00523-1
  3. Jinhui Li et al.,2009: Study of extraction and purification of Ni, Co and Mn from spent battery material, Hydrometallurgy 99, pp. 7-12. https://doi.org/10.1016/j.hydromet.2009.05.018
  4. Sung-Keun Kim et al., 2008: Characteristics of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ Cathode Powder Prepared by Different Method in Lithium Rechargeable Batteries, Int. J. Electrochem. Sci, 3, pp. 1504-1511.
  5. Jin-Hwa Kim et al., 2012: Effect of aluminum fluoride coating on the electrochemical and thermal properties of $0.5Li_2MnO_3{\cdot}0.5LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$ composite material, J. of alloys and compounds, 517, pp. 20-25 https://doi.org/10.1016/j.jallcom.2011.11.117
  6. I. Belharouak, D. Vissers and K. Amine, 2006: Thermal Stability of the $Li(Ni_{0.8}Co_{0.15}Al_{0.05})O_2$ Cathode in the Presence of Cell Components, J. Eectrochem. Soc, 153, pp. A2030-A2035. https://doi.org/10.1149/1.2336994
  7. C. K. Lee and N. H. Lim, 2001: Reductive Leaching of $LiCoO_2$ in a sulfuric acid solution, J. Korean Inst. of Resources Recycling, 10(6), pp. 9-14
  8. Junmin Nan, Dongmei Han, Xiaoxi Zuo, 2005: Recovery of metal values from spent lithium-ion batteries with chemical deposition and solvent extraction, J. of Power Sources, 152, pp. 278-284. https://doi.org/10.1016/j.jpowsour.2005.03.134
  9. Liang Sun and Keqiang Qiu, 2012: Organic oxalate as leachant and precipitant for the recovery of valuble metals from spent lithium-ion batteries, Waste Management 32, pp. 1575-1582 https://doi.org/10.1016/j.wasman.2012.03.027
  10. Li Li et al., 2010: Recovery of cobalt and lithium from spent lithium batteries using organic citric acid s leachant, J. of Hazardous Materials, 176, pp. 288-293. https://doi.org/10.1016/j.jhazmat.2009.11.026
  11. Li Li et al., 2010: Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries, Waste Management, 30, pp. 2615-2612. https://doi.org/10.1016/j.wasman.2010.08.008
  12. Jae-Woo Ahn and Hyo-jin Ahn, 2011: Chemical Leaching of Cobalt and Lithium form the Cathode Active Materials of Spent Lithium-ion Batteries by Organic Acid, J. of Korean Inst. of Resources Recycling, 20, No 4, pp. 65-70. https://doi.org/10.7844/kirr.2011.20.4.065
  13. Mulliqan CN, Kamali M, Gibbs BF., 2004: Bioleaching of heavy metals from a low-grade mining ore using Aspergillus niger, J. of Hazardous Materials, 110, pp. 77-84. https://doi.org/10.1016/j.jhazmat.2004.02.040
  14. Ahn Jae-Woo et al., 2005: Bioleaching of valuable metals from electronic scrap using fungi(Aspergillus niger) as a microorganism, J. of Korean Inst. of Resources Recycling, vol. 14, No. 5, pp. 24-31
  15. Fozia Anjum et al., 2010: Leaching of metal ions from black shale by organic acids produced by Aspergillus niger, Applied Clay Science, vol. 47, pp. 356-361 https://doi.org/10.1016/j.clay.2009.11.052
  16. Aung KM, Ting YP, 2005: Bioleaching of spent fluid catalytic cracking catalyst using Aspergillus niger, J. of Biotechnology, 116, pp. 159-170 https://doi.org/10.1016/j.jbiotec.2004.10.008
  17. Rong-Chi Wang, Yu-Chuan Lin, She-Huang Wu, 2009: A novel recovery process of metal values from the cathode active materials of the lithium-ion secondary batteries, Hydrometallurge, vol. 99, pp. 194-201. https://doi.org/10.1016/j.hydromet.2009.08.005
  18. CHEN Liang et al., Separation and recovery of Ni, Co and Mn from spent lithium ion batteries, The Chinese J. of Nonferrous Metals., 21(5), pp, 1192-1198.
  19. Churl Kyoung Lee, Kang-In Rhee, 2003: Reductive leaching of cathode active materials from lithium ion battery wastes, Hydrometallurgy 68, pp, 5-10. https://doi.org/10.1016/S0304-386X(02)00167-6