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2025 Vol.34, Issue 3 Preview Page

Research Paper

Hydrogen Reduction of Black Mass Recovered from NCM-based Spent Lithium-ion Batteries

NCM계 폐리튬이온 배터리에서 회수한 Black Mass의 수소환원 거동

Jae-Ho Hwang1†
,
Sang-Yeop Lee1†
,
So-Yeong Lee2
,
Ho-Sang Sohn2*
황 재호1†
,
이 상엽1†
,
이 소영2
,
손 호상2*
1School of Materials Science and Engineering, Kyungpook National University, Daegu 41566, Korea
2Department of Materials Science and Metallurgical Engineering, Kyungpook National University, Daegu 41566, Korea
1경북대학교 첨단소재공학부 금속재료공학전공
2경북대학교 금속재료공학과
*Corresponding Author
†These authors contributed equally to this work as first author.
30 June 2025. pp. 34-42
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Abstract

NCM(LiNixCoyMnzO2)-based Li-ion batteries (LIBs) for electric vehicles contain critical metals, such as Li, Ni, Co, and Mn. The black mass recovered from spent LIBs contains a large amount of carbon. Therefore, it is necessary to recover valuable metals from spent LIBs to prevent resource depletion. In this study, we investigated the reduction behavior of cathode materials when a black mass was heated in a H2 atmosphere. When the black mass was heated up to 1,100 °C in a H2 atmosphere, emission of a large amount of CO led to rapid weight loss from approximately 780 °C by the Boudouard reaction. During the isothermal reaction in a H2 atmosphere, the weight loss rate and final weight loss of the sample increased with the reaction temperature. Significant amounts of CO were emitted in the region of rapid weight loss. Above 400 °C, NiO was reduced to Ni; above 890 °C, MnO was reduced, and a MnNi3 phase was observed. Li2CO3 was produced at temperatures above 300 °C although the reaction occurred in a hydrogen atmosphere. When the reduced black mass was treated with water, Li and Al were detected in the leaching residue. The product recovered from the water leaching solution contained LiAl2(OH)7·(H2O)2 together with Li2CO3. When the reduction temperature was above 400°C, the Li recovery ratio was approximately 90 % regardless of the temperature. To improve the Li recovery ratio, it is necessary to control the production of complex hydroxides of Li and Al.

Keywords
lithium-ion battery
black mass
hydrogen reduction
recycling
water leaching

전기자동차용 NCM계 리튬이온 배터리(LIB)에는 Li, Ni, Co, Mn 등의 핵심 금속이 함유되어 있다. 그리고 폐LIB의 전처리 공정에서 회수된 black mass에는 다량의 C이 혼합되어 있다. 따라서 자원 고갈에 대비하여 이러한 폐LIB에서 유가금속의 회수가 필요하다. 본 연구에서는 NCM계 폐LIB에서 회수한 black mass를 수소 분위기에서 가열했을 때 양극재 성분의 환원 거동을 조사하였다. Black mass를 수소 분위기 중 1,100 ℃까지 가열했을 때 부도아 반응에 의해 약 780 ℃부터 급격한 무게 감소와 함께 CO 가스가 현저하게 발생하였다. 수소 분위기 중 등온 가열에서는 반응 온도의 상승과 함께 시료의 무게 감소 속도가 상승하고 무게 감소량이 증가하였으며, 급격한 무게가 감소가 일어날 때 CO 가스가 현저하게 발생하였다. 400 ℃ 이상에서는 NiO가 전부 Ni로 환원되었으며, 890 ℃ 이상에서는 MnO도 환원되어 MnNi3상이 관찰되었다. 수소 분위기 중의 반응이지만 300 ℃부터 Li2CO3가 생성되었다. 수침출 잔사 중에는 소량의 Li과 Al이 잔류하였으며, 침출 여액에서 회수한 생성물에는 Li2CO3와 함께 소량의 복합 수산화물인 LiAl2(OH)7·(H2O)2가 검출되었다. 400 ℃ 이상에서의 Li 회수율은 반응 온도와 무관하게 약 90 % 수준을 나타내었으며, Li 회수율 향상을 위해서는 복합 수산화물의 생성 제어가 필요하다.

키워드
리튬이온배터리
블랙매스
수소환원
리사이클링
수침출
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Information
  • Publisher :The Korean Institute of Resources Recycling
  • Publisher(Ko) :한국자원리싸이클링학회
  • Journal Title :Resources Recycling
  • Journal Title(Ko) :자원리싸이클링
  • Volume : 34
  • No :3
  • Pages :34-42
  • Received Date : 2025-05-07
  • Revised Date : 2025-05-27
  • Accepted Date : 2025-06-05
  • DOI :https://doi.org/10.7844/kirr.2025.34.3.34
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