Carbonation Behavior of Black Mass Recovered from NCM-Based Spent Lithium-ion Batteries by CO2(g)

Ji-Yeong So; Ho-Sang Sohn

doi:10.7844/kirr.2026.35.4.66

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2026 Vol.35, Issue 4 Preview Page Next Page

Carbonation Behavior of Black Mass Recovered from NCM-Based Spent Lithium-ion Batteries by CO₂(g) NCM계 폐리튬이온 배터리 Black Mass의 CO₂(g)에 의한 탄산화 배소 거동

31 August 2026. pp. 66-76

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Abstract

The rapid increase in lithium-ion battery (LIB) demand has accelerated the development of efficient recycling processes to recover valuable metals from spent LIBs. In this study, NCM-based black mass powder comprising cathode active materials, a graphite anode material (C), and impurities (including Al) was used as the starting material. As a fundamental study for the selective separation and recovery of Li, isothermal roasting experiments were conducted in a CO₂ atmosphere (500 °C–1,000 °C, pCO2=0.1–0.5 atm). The reduction behavior of the cathode materials was investigated via thermogravimetric and off-gas analyses. Li₂CO₃ formation was observed under all tested conditions. A peak Li recovery of 99.4 % was achieved at approximately 730 °C under pCO2=0.5 atm. However, above ~800 °C, the recovery progressively declined owing to the formation of insoluble LiAlO₂ from reactions between Li₂CO₃ and Al impurities. At temperatures exceeding 860 °C, the Boudouard reaction became prominent and resulted in rapid CO evolution. Concurrently, Ni and Co oxides were reduced by CO and residual carbon, resulting in a significant sample mass decrease. Whereas higher CO₂ partial pressure accelerated the Boudouard reaction kinetics, it had a negligible effect on the final reduction degree. The results indicate the necessity for optimized roasting conditions and Al impurity removal during pretreatment to maximize Li recovery.

Keywords

spent Li-ion battery

carbonation

black mass

thermogravimetric analysis

Boudouard reaction

리튬이온배터리(lithium-ion batteries, LIBs)의 수요 증가에 따라 폐LIBs 중 유가금속을 회수하기 위한 효율적인 리사이클링 공정 개발이 필요하다. 본 연구에 사용한 시료는 NCM계 블랙매스(Black mass, B/M) 분말로, 양극재 및 음극재(C), 그리고 소량의 불순물(Al) 등으로 구성된다. 본 연구는 B/M 중의 Li을 선택적으로 분리 및 회수하기 위한 기초 연구로서, CO₂ 분위기 (500~1,000 ℃, pCO2=0.1~0.5 atm)에서 열중량 분석 및 배가스 농도 분석을 통해 양극재의 환원 거동을 조사하였다. 실험 결과, 전 온도 및 분압 조건에서 Li₂CO₃가 형성되었다. 약 730 ℃, pCO2=0.5 atm 조건에서 최대 99.4 %의 높은 회수율을 보였으나, 약 800 ℃ 이상에서는 불순물인 Al과 일부 Li₂CO₃의 반응으로 불용성 LiAlO₂가 형성되어 회수율이 점차 감소하였다. 약 860 ℃ 이상에서는 부도아 반응(Boudouard reaction)에 의해 CO 가스가 급격히 발생하였고, 동시에 Ni, Co 산화물이 CO 및 잔류 C에 의해 환원되어 시료의 무게가 급격히 감소하는 거동을 확인하였다. 또한, CO₂ 분압의 증가는 부도아 반응의 속도를 가속화하였으나, 최종 환원 정도에는 큰 영향을 미치지 못하였다. 결과적으로, 본 연구는 Li 회수 효율 극대화를 위해 정밀한 배소 온도 제어 및 Al 불순물을 제거하는 전처리 공정의 필요성을 시사한다.

키워드

폐리튬이온배터리

탄산화

블랙매스

열중량분석

부도아 반응

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Information

Publisher :The Korean Institute of Resources Recycling
Publisher(Ko) :한국자원리싸이클링학회
Journal Title :Resources Recycling
Journal Title(Ko) :자원리싸이클링
Volume : 35
No :4
Pages :66-76
Received Date : 2026-06-04
Revised Date : 2026-07-27
Accepted Date : 2026-08-06
DOI :https://doi.org/10.7844/kirr.2026.35.4.66

Resources Recycling ISSN:2765-3439(Print) 2765-3447(Online) 자원리싸이클링

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