Teng Liumei, Liu Weizao, Duan Xu, Li Zhuo, Chen Cai, Wang Zhenghao, Yang Jian, Liu Qingcai
School of Materials Science and Engineering, Chongqing University of Arts and Sciences, 402160, China; College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China.
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China.
Waste Manag. 2025 Feb 1;193:430-442. doi: 10.1016/j.wasman.2024.12.025. Epub 2024 Dec 25.
To alleviate the energy crisis and control environmental pollution raised by spent lithium-ion batteries (LIBs), the development of efficient and economic methods for their recycling is crucial for sustainable development of new energy industry. Herein, a combined pyro - hydrometallurgical process was adopted for recovery of valuable metal elements for spent LiNiCoMnO (NCM523). Different from conventional pyrometallurgical methods with high temperature and energy consumption, the NHHSO roasting strategy works at 400 °C and achieves remarkable leaching efficiencies of Li, Co, Mn, and Ni achieved 97.5 %, 91.4 %, 91.3 %, and 95.50 %, respectively. Under the ideal conditions, abundant water-soluble metal-ammine-sulfates and metal-sulfates were revolved from NCM523. The process factors, including sulfation-roasting temperature, reagent mass ratio, roasting time, are intensively studied. Furthermore, a plausible reaction mechanism was deeply investigated with assistance of macro-micro scale, thermodynamic and kinetic analysis. Wherein, the Li of the NCM523 first react sufficiently with NHHSO owing to higher thermodynamic/kinetic motivation at the primary stage during the sulfation-roasting procedure. Subsequently, the transition metal (Ni, Co, and Mn) from the lithium-depleted NCM523 would revolve to corresponding metal-ammine-sulfates or metal sulfates, and their sulfation-roasting kinetics conformed to the unreacted nuclear model. This study proposed an alternative green route of low energy consumption and acid-free procedure for recovering spent NCM batteries, which is conducive to industrial-scale recycling of waste LIBs in the future.
为缓解废旧锂离子电池（LIBs）引发的能源危机并控制环境污染，开发高效且经济的回收方法对新能源产业的可持续发展至关重要。在此，采用了一种联合火法 - 湿法冶金工艺来回收废旧LiNiCoMnO（NCM523）中的有价金属元素。与传统高温且能耗高的火法冶金方法不同，NHHSO焙烧策略在400℃下进行，Li、Co、Mn和Ni的浸出效率分别达到了97.5%、91.4%、91.3%和95.50%，效果显著。在理想条件下，从NCM523中析出了大量水溶性金属 - 氨 - 硫酸盐和金属硫酸盐。对包括硫酸化焙烧温度、试剂质量比、焙烧时间等工艺因素进行了深入研究。此外，借助宏观 - 微观尺度、热力学和动力学分析对合理的反应机理进行了深入探究。其中，在硫酸化焙烧过程的初始阶段，由于较高的热力学/动力学驱动力，NCM523中的Li首先与NHHSO充分反应。随后，贫锂的NCM523中的过渡金属（Ni、Co和Mn）会转化为相应的金属 - 氨 - 硫酸盐或金属硫酸盐，其硫酸化焙烧动力学符合未反应核模型。本研究提出了一种低能耗且无酸的废旧NCM电池回收绿色替代路线，有利于未来废旧LIBs的工业规模回收利用。
