Key Takeaways & Executive Findings
- •• A novel two-step chlorination roasting process achieves simultaneous recovery of Li and Co from spent LiCoO2 with leaching efficiencies of 99.43% and 99.05%, respectively. • The activation energy for the chlorination reaction is 88.41 kJ/mol, with a kinetic model transition from first-order (F1) to second-order (F2) at a conversion rate of 0.5. • Optimal conditions are low temperature (400°C), short time (20 min), and NH4Cl/LiCoO2 mass ratio of 3:1, offering energy-efficient and environmentally friendly recycling. • The technology provides a crystal-structure-based mechanism, enabling high recovery efficiency and high added value, supporting the circular economy for LIBs.
Abstract
With the continuous increase in the disposal volume of spent lithium-ion batteries (LIBs), properly recycling spent LIBs has become essential for the advancement of the circular economy. This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials. The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free, model-fitting, and Z(α) function (α is conversion rate). Results indicated that the reaction was dominated by the first-order (F1) model when the conversion rate was less than or equal to 0.5 and shifted to the second-order (F2) model when the conversion rate exceeded 0.5. Optimal conditions were determined by thoroughly investigating the effects of roasting temperature, roasting time, and the mass ratio of NH4Cl to LiCoO2. Under the optimal conditions, namely 400°C, 20 min, and NH4Cl/LiCoO2 mass ratio of 3:1, the leaching efficiency of Li and Co reached 99.43% and 99.05%, respectively. Analysis of the roasted products revealed that valuable metals in LiCoO2 transformed into CoCl2 and LiCl. Furthermore, the reaction mechanism was elucidated, providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective. This technology can guide the development of LIB recycling processes with low energy consumption, low secondary pollution, high recovery efficiency, and high added value.
1. Introduction
Lithium-ion batteries (LIBs), with their high energy density, long cycle life, small size, and high safety, are widely used in electric vehicles and consumer battery products [1], contributing to the mitigation of greenhouse gas emissions [2–5]. As the popularity of electric vehicles and consumer electronics continues to increase, the demand for LIBs and raw materials, such as Li and Co, has considerably increased. Thus, the number of spent LIBs generated after their life cycles end has substantially increased [6–7]. In China alone, the production of LIBs reached 108 GWh in 2018 and increased to 324 GWh in 2021, and by 2030, the global LIB recycling market is predicted to reach $23.72 billion [8]. Furthermore, the content of valuable metals, such as Li and Co, in spent LIBs is much higher than that of natural minerals [9–12]. This situation highlights the importance of recycling spent LIBs as sustainable raw materials for producing new LIBs. This approach alleviates the demand for virgin resources. Additionally, the disposal of spent LIBs poses environmental and health risks because they contain high amounts of heavy metals and fluoride-bearing electrolytes [13–15]. Therefore, the recovery of spent LIBs is crucial for the circular economy, resource conservation, and environmental sustainability. Global efforts have been dedicated to the development of various technologies that maximize the recovery rates of valuable metals from spent LIBs [16–17].
In chlorination roasting, the metal compound in a material is converted into the corresponding metal chloride through calcination with a chlorination agent in a specific atmosphere. The method is widely used in the extraction of metals from tailings [18–19], electronic waste [20–21], and industrial solid waste [22–23]. Liu et al. [20] developed a vacuum chlorinating process by using CaCl2 and SiO2 as reagents to simultaneously fix sulfur and recover high-purity PbCl2 from spent lead paste; the PbCl2 recovery rate reached 99.7wt% at 350°C under vacuum. Liu et al. [22] extracted Fe and Mn selectively by destroying the typical encompassed structure with NH4Cl; the manganese and iron chlorination ratios reached 95% and 72%, respectively, under the following optimal conditions: NH4Cl/slag mass ratio of 2:1, NaCl/NH4Cl mass ratio of 0.308:1, 800°C, and 4 h; their method had the advantages of having a low roasting temperature requirement, simple operation, high selectivity, and strong adaptability. The potential application of chlorination roasting in the recovery of LIB cathode materials has been explored. Currently, chlorination roasting involves the use of additives, such as Cl2 [24–25], CaCl2 [26–27], and NH4Cl [28–31]. Li et al. [32] revealed the pyrolysis kinetics and reaction mechanism of spent LiCoO2, showing that reactions ...
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Junjie Shi, Changle Hou, Jingjing Dong, Dong Chen, Jianzhong Li (2025). Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO2 cathode material. Int. Journal of Minerals, Metallurgy and Materials (矿物冶金与材料学报). https://doi.org/10.1007/s12613-024-2898-4
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Frequently Asked Questions
What is the optimal condition for recovering Li and Co from spent LiCoO2 using chlorination roasting?
The optimal conditions are a roasting temperature of 400°C, a roasting time of 20 minutes, and a NH4Cl/LiCoO2 mass ratio of 3:1, achieving leaching efficiencies of 99.43% for Li and 99.05% for Co.
What is the activation energy for the chlorination reaction of LiCoO2?
The activation energy is 88.41 kJ/mol, as determined by thermogravimetric analysis and kinetic modeling.
How does the reaction kinetic model change during the chlorination roasting process?
The reaction is dominated by the first-order (F1) model when the conversion rate is ≤0.5, and shifts to the second-order (F2) model when the conversion rate exceeds 0.5.
What are the advantages of the proposed low-temperature chlorination roasting technology?
The technology offers low energy consumption, low secondary pollution, high recovery efficiency, and high added value, making it a sustainable solution for LIB recycling.
What is the significance of this study for the circular economy?
By efficiently recovering valuable metals from spent LIBs, the technology supports resource conservation and reduces environmental hazards, contributing to the circular economy.
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