DOI QR코드

DOI QR Code

NCM계 리튬이온 배터리 양극재의 그라파이트 첨가 탄산화 배소와 수침출에 의한 Li 회수

Lithium Recovery from NCM Lithium-ion Battery by Carbonation Roasting with Graphite Followed by Water Leaching

  • 이소연 (경북대학교 신소재공학부) ;
  • 이대현 (경북대학교 신소재공학부) ;
  • 이소영 (경북대학교 신소재공학부) ;
  • 손호상 (경북대학교 신소재공학부)
  • Lee, So-Yeon (School of Materials Science and Engineering, Kyungpook National University) ;
  • Lee, Dae-Hyeon (School of Materials Science and Engineering, Kyungpook National University) ;
  • Lee, So-Yeong (School of Materials Science and Engineering, Kyungpook National University) ;
  • Sohn, Ho-Sang (School of Materials Science and Engineering, Kyungpook National University)
  • 투고 : 2022.07.20
  • 심사 : 2022.08.01
  • 발행 : 2022.08.31

초록

리튬이온배터리의 수요가 증가함에 따라 향후 발생할 폐리튬이온배터리 중의 유가금속 회수가 필요하다. 대량의 폐리튬이온배터리 리사이클링에는 건식제련이 적합하지만 Li이 슬래그나 분진으로 손실되는 문제점이 있다. 본 연구에서는 폐리튬이온배터리의 NCM계 양극재로부터 Li을 회수하기 위해 그라파이트 첨가에 따른 탄산화 배소와 수침출 거동에 대해 조사하였다. 그라파이트를 10 wt% 첨가 시, Ar 및 CO2 분위기에서 승온 중 약 850 K에서 급격한 무게 감소와 함께 CO 및 CO2 가스가 배출되었다. 급격한 무게 감소 후 NCM은 금속 산화물 및 순금속으로 분해되고 환원되었다. 따라서 블랙파우더(NCM+그라파이트)의 탄산화 배소에서는 NCM의 분해에 의해 O2가 발생하면서 Li2O, NiO 등의 산화물이 생성되고, 이어서 Li2O가 CO2와 반응하여 Li2CO3를 생성하며, NiO의 일부는 그라파이트에 의해 환원되어 금속 Ni을 생성한다. 그리고 탄산화 배소 후 수침출에 의해 약 99.95 % 순도의 Li2CO3를 최대 94.5 %까지 회수하였다.

Owing to the demand for lithium-ion batteries, the recovery of valuable metals from waste lithium-ion batteries is required in future. A pyrometallurgical treatment is appropriate for recycling a large number of waste lithium-ion batteries, but Li loss to slag and dust present a significant challenge. This research investigated carbonation roasting and water leaching behaviors in Li-ion batteries by graphite addition to recover Li from the NCM-based cathode materials of waste Li-ion batteries. When 10 wt% of graphite was added, CO and CO2 gases were emitted with a rapid weight reduction at apporoximately 850 K, when heated in Ar and CO2 atmosphere. After the rapid weight reduction, NCM was decomposed and reduced to metal oxides and pure metals. In the carbonation roasting of black powder (NCM+graphite), O2 is generated via the decomposition of NCM, and an oxides, such as Li2O and NiO were were also generated. Subsequently, Li2O reacts with CO2 to generate Li2CO3, and a part of NiO was reduced by graphite to produce metal Ni. In addition, up to 94.5 % Li2CO3 with ~99.95 % purity was recovered via water leaching after carbonation roasting.

키워드

참고문헌

  1. Sohn, Ho-Sang, 2022 : Extractive Metallurgy of Lithium, Resources Recycling, 31(3), pp.3-15.
  2. Nayaka, G. P., Pai, K. V., Santhosh, G., et al., 2016 : Recovery of cobalt as cobalt oxalate from spent lithium ion batteries by using glycine as leaching agent, Journal of Environmental Chemical Engineering, 4(2), pp.2378-2383. https://doi.org/10.1016/j.jece.2016.04.016
  3. Huang, Z., Liu, F., Makuza, B., et al., 2022 : Metal Reclamation from Spent Lithium-Ion Battery Cathode Materials: Directional Conversion of Metals Based on Hydrogen Reduction, ACS Sustainable Chemistry & Engineering, 10(2), pp.756-765. https://doi.org/10.1021/acssuschemeng.1c05721
  4. Gao, W., Zhang, X., Zheng, X., et al., 2017 : Lithium carbonate recovery from cathode scrap of spent lithium-ion battery: a closed-loop process. Environmental Science & Technology, 51(3), pp.1662-1669. https://doi.org/10.1021/acs.est.6b03320
  5. Higuchi, A., Ankei, N., Nishihama, S., et al., 2016 : Selective recovery of lithium from cathode materials of spent lithium ion battery, The Journal of Minerals, Metals & Materials Society, 68, pp.2624-2631. https://doi.org/10.1007/s11837-016-2027-6
  6. Georgi-Maschler, T., Friedrich, B., Weyhe, R., et al., 2012 : Development of a recycling process for Li-ion batteries, Journal of Power Sources, 207, pp.173-182. https://doi.org/10.1016/j.jpowsour.2012.01.152
  7. Xiao, J., Niu, B., Xu, Z., 2021 : Highly efficient selective recovery of lithium from spent lithium-ion batteries by thermal reduction with cheap ammonia reagent, Journal of Hazardous Materials, 418, p.126319.
  8. Pyo, Je-Jung and Wang, Jei-Pil, 2019 : Recovery of Lithium Carbonate and Nickel from Cathode Active Material LNO (Li2NiO2) of Precursor Process Byproducts, J. of Korean Inst. of Resources Recycling, 28(4), pp.30-36.
  9. Sohn, Hosang, 2019 : Engineering of Resources Recycling, p.355, KNU Press, Daegu, Korea.
  10. Sohn, Hosang, 2020 : Recycling of Common Metals, p.315, KNU Press, Daegu, Korea.