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2025 Vol.34, Issue 5 Preview Page

Research Paper

Reduction Roasting of Black Mass Recovered from NCM-based Spent Lithium-ion Batteries Using CH4 Gas

NCM계 폐리튬이온 배터리에서 회수한 Black Mass의 CH4 가스에 의한 환원배소

Sang-Yeop Lee1†
,
Jae-Ho Hwang1†
,
Ho-Sang Sohn2*
이 상엽1†
,
황 재호1†
,
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
†These authors contributed equally to this work as first author.
*Corresponding Author
31 October 2025. pp. 93-100
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Abstract

In this study, the effect of temperature on the reduction roasting by CH4(g) of the black mass (B/M) recovered from NCM (LiNixCoyMn1–x–yO2)-based spent lithium-ion batteries was investigated through thermogravimetric analysis, exhaust gas analysis, and X-ray diffraction analysis of the products. When the B/M sample was subjected to thermogravimetric analysis up to 1,100 °C in a 50 vol.% CH4(g)+Ar atmosphere, the sample weight decreased rapidly from about 760 °C and then increased again from about 1,020 °C. At this time, CO(g) reached its maximum value and then decreased rapidly. This rapid decrease in sample weight is thought to be largely due to the contribution of C solution loss caused by the Boudouard reaction. In the isothermal reduction 713 ℃~1,000 ℃), CO2(g) and CO(g) were generated before CH4(g) supply, and the sample weight began to decrease. With the supply of CH4(g), the sample weight further decreased, reaching the minimum value before increasing significantly again, and at 1,000°C, it showed a value much higher than the weight of the original sample weight. Regardless of the reduction roasting temperature, oxides such as Ni and Co were reduced, and the Li recovery rate was approximately 87% or higher, independent of the isothermal roasting temperature. At 802 °C and 908 °C, LiOH was also detected, suggesting that the cathode material was reduced by H2(g) through the thermal decomposition of CH4(g).

Keywords
lithium-ion battery
black mass
methane
reduction roasting
recycling

본 연구에서는 NCM(LiNixCoyMn1–x–yO2)계 폐리튬이온배터리에서 회수한 black mass(B/M)의 CH4(g)에 의한 환원배소에 미치는 온도의 영향을 열중량 분석과 배가스 분석 및 생성물의 X-선 회절분석을 통하여 조사하였다. B/M 시료를 50 vol.%CH4(g)+Ar 분위기에서 1,100 ℃까지 열중량 분석했을 때 시료의 무게가 약 760 ℃부터 급격히 감소한 후 약 1,020 ℃부터 다시 증가하였으며, 이 때 CO(g)는 최곳값을 보인 후 급격하게 감소하였다. 이러한 시료 무게의 급격한 감소는 부도아 반응에 의한 C solution loss의 기여가 큰 것으로 생각된다. 등온 배소(713 ℃~1,000 ℃)에서는 CH4(g) 공급 전에 CO2(g)와 CO(g)는 발생하면서 시료의 무게도 감소하기 시작하여 CH4(g) 공급과 함께 시료 무게가 더욱더 감소하여 최솟값을 보인 후 다시 현저하게 증가하여 1,000 ℃에서는 원시료 무게보다 훨씬 높은 값을 나타내었다. 환원배소 온도와 무관하게 Ni, Co 등의 산화물이 환원되어 Li 회수율은 등온배소 온도와 무관하게 약 87 % 이상을 나타내었다. 802 ℃와 908 ℃에서는 LiOH도 검출되어 CH4(g)의 열분해에 의한 H2(g)에 의해 양극재의 환원이 일어난 것으로 생각된다.

키워드
리튬이온배터리
블랙매스
메테인
환원배소
리사이클링
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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 :5
  • Pages :93-100
  • Received Date : 2025-08-29
  • Revised Date : 2025-09-30
  • Accepted Date : 2025-10-02
  • DOI :https://doi.org/10.7844/kirr.2025.34.5.93
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