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在全球加速推进能源转型的背景下，锂离子电池(LIBs)规模化应用导致退役电池数量激增。石墨具有高导电性、优异比容量和低成本等特性，被广泛用作锂离子电池负极材料。随着全球锂电装机量的快速增长，退役电池将产生大量废旧石墨(S-Gr)，亟须开发高效回收技术以实现资源循环利用。本文聚焦兼具环境污染风险与资源回收价值的S-Gr，系统探讨其循环再生的策略与应用前景。首先基于石墨负极的失效机制，深入解析锂离子在多次嵌入/脱出过程中的结构演化规律及性能衰退机制，阐明影响再生效率的关键制约因素。继而从资源循环利用视角，全面评述当前主流的S-Gr再生技术体系：物理分选(浮选、筛分等)、湿法冶金(包括酸浸、碱处理等)、火法冶金(高温提纯)及湿法–火法联用等。在应用拓展方面，重点探讨再生石墨在新型储能器件(钠/钾/锂离子电池)、高附加值功能材料(氧化石墨烯、掺杂石墨)及环境催化/吸附领域的创新应用路径。最后，本文针对S-Gr回收领域的技术瓶颈与未来发展方向进行了展望，为构建动力电池产业链闭环和推进实现“双碳”战略目标提供了理论支撑与技术参考。
Abstract：The global transition toward renewable energy and electric vehicles has triggered exponential growth in lithium-ion batteries(LIBs), resulting in a surge of retired batteries. As the predominant anode material in LIBs, graphite accounts for a significant mass proportion of batteries. However, improper disposal of spent graphite(S-Gr) through incineration or landfilling poses severe environmental risks, including particulate emissions and toxic residue release. Recycling S-Gr is critical to alleviating resource shortages, reducing production costs of high-purity graphite(which requires energy-intensive graphitization processes at 2500–3000 ℃), and achieving sustainable development goals. This review focuses on the failure mechanisms, recycling strategies, and reuse pathways of S-Gr, providing key insights for advancing closed-loop battery ecosystems. The degradation of graphite anodes during LIB cycling originates from multiscale failure mechanisms. Deterioration of the solid electrolyte interphase(SEI) caused by chemical decomposition, mechanical stress, and thermal instability leads to irreversible lithium loss and capacity fade. Concurrently, lithium dendrite growth on graphite surfaces increases internal short-circuit risks, while repeated Li+ intercalation/deintercalation induces microcracks and structural collapse of graphite layers. These coupled mechanisms initiate a vicious cycle of performance degradation, highlighting the necessity for tailored recycling approaches. Current recycling technologies focus on efficient separation and purification of S-Gr. Physical methods(e.g., flotation and sieving) achieve preliminary separation but suffer from impurity retention(purity <73.56%). Innovative techniques such as Fenton reagent-assisted flotation and pyrolysis-ultrasonic synergy enhance recovery efficiency, but face scalability challenges. Hydrometallurgical processes utilizing HCl, H_2SO4, or organic acids(e.g., citric acid) effectively leach impurities like Li, Al, and Fe but generate corrosive waste. Pyrometallurgical approaches(e.g., inert atmosphere calcination and catalytic graphitization) restore graphite crystallinity but demand high energy consumption(>2600 ℃) and emit hazardous gases. Hybrid strategies combining hydrometallurgical treatment with high-temperature annealing emerge as promising solutions. Regenerated S-Gr demonstrates versatility in energy storage and functional applications. For secondary batteries, carbon-modified S-Gr via rapid thermal shock or phenolic resin coating exhibits superior performance in LIBs. In sodium/potassium-ion batteries, defect-engineered S-Gr shows enhanced kinetics and stability. Beyond energy storage, S-Gr can be transformed into high-value materials. Advanced applications include graphene production through lithium-intercalation exfoliation and catalytic composites for environmental remediation. Summary and prospects Despite progress, critical challenges persist. The heterogeneity of S-Gr sources(natural, synthetic, or composite graphite) complicates standardized recycling. High costs, toxic emissions(e.g., fluorine), and intensive energy-consuming steps hinder process scalability. Future directions should prioritize intelligent sorting systems, AI-driven process optimization, and green alternatives like bioleaching. Integrating ultrasound, microwave, or electrochemical technologies could streamline processes and reduce energy consumption. Expanding S-Gr applications(e.g., flexible electronics, CO2 capture, and defect-engineered catalysts) requires interdisciplinary innovation. Addressing these issues will accelerate commercialization of S-Gr recycling technologies, promote sustainable battery ecosystems, and advance global carbon neutrality goals.
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基本信息:
DOI：10.14062/j.issn.0454-5648.20250081
中图分类号:X705
引用信息:
[1]者荣杰,郑硕航,张凯洋,等.废旧锂离子电池石墨负极材料的回收[J].硅酸盐学报,2025,53(08):2194-2209.DOI:10.14062/j.issn.0454-5648.20250081.
基金信息:
国家自然科学基金(52173246)
2025-05-29
2025-05-29
2025-05-29