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伴随着新能源产业发展，锂离子电池（LIBs）产量激增，其三至八年使用寿命使其即将迎来退役高峰。当前退役LIBs回收多聚焦正极Li、Co、Ni等贵金属，负极石墨（占电池质量12%～21%）常被忽视，既造成石墨资源浪费，又容易引发环境污染。本文从锂离子电池负极石墨失效机理出发，重点阐述了锂离子电池石墨负极的修复再生方法以及产业化前景，旨在为退役锂离子电池负极石墨修复再生提供参考。
Abstract：With the explosive growth of the new energy industry, lithium-ion batteries(LIBs), as core energy storage devices, have experienced exponential production growth. Given their practical service life— approximately 3–5 years for electric vehicle applications and 5–8 years in stationary energy storage systems— the industry is now approaching a critical phase marked by the mass retirement of used LIBs. Projections indicate that, over the next decade, hundreds of thousands of tons of spent batteries will require recycling annually. Current recycling practices predominantly focus on recovering high-value and strategically important cathode metals such as lithium, cobalt, and nickel. In contrast, graphite— an essential anode material constituting 12%–21% of total battery mass— has long been overlooked in mainstream recycling processes. This neglect results not only in inefficient utilization of non-renewable graphite resources— 70% of global natural graphite reserves are concentrated in China, India, and Brazil— but also stems from the high energy consumption associated with synthetic graphite production. Moreover, improper disposal poses environmental risks, as residual impurities in graphite may leach into soil and water, causing contamination. Against this backdrop, this paper presents a systematic review of the primary failure mechanisms affecting graphite anodes during LIB operation and recent advances in regeneration technologies. Current research identifies three failure mechanisms driving graphite degradation: first, the dynamic "crack-regenerate-thicken" cycle of the solid electrolyte interphase(SEI) film, wherein repeated cracking and reformation during chargedischarge cycles lead to excessive SEI accumulation, significantly increasing ion transport resistance; second, the "nucleation-elongation-fracture" process of lithium dendrites, where uneven lithium deposition consumes active lithium and raises the risk of internal short circuits; and third, irreversible interlayer expansion of graphite, resulting from cumulative structural damage due to repeated lithium insertion, which cannot be restored. To address these degradation pathways, graphite regeneration strategies are categorized into three main approaches: thermal treatment(including conventional high-temperature annealing at 2 000–2 800 ℃, microwave heating, and ultrafast flash Joule heating(FJH)); elemental doping(encompassing redox pretreatment for oxide removal, heteroatom doping with N, B, S, or P to create active sites, and low-toxicity deep eutectic solvent(DES)-assisted doping); and surface coating modification(via atomic layer deposition(ALD) to form uniform Al_2O3 or carbon-based protective layers, chemical vapor deposition(CVD) for enhanced purity, or cost-effective precipitation methods for surface functionalization). Notably, emerging techniques have demonstrated exceptional performance at the laboratory scale: microwaveassisted thermal treatment reduces energy consumption to one-third of conventional high-temperature processes(from 50–80 kWh/kg to about 17–27 kWh/kg), achieves a 99.5% impurity removal rate, and produces regenerated graphite(RG) with a capacity of 354 mAh/g at 0.1 C; DES-mediated nitrogen-doped RG delivers a capacity of 406 mAh/g after 1 000 cycles at 1 C, markedly surpassing undoped RG(about 300 mAh/g); ALD-deposited Al_2O3 coatings(5–10 nm thick) enable graphite to retain 140 mAh/g after 3 000 cycles at a high current density of 3 000 mA/g; and DES-assisted doping at merely 80 ℃— far below the 800–1 200 ℃ required in traditional methods— simultaneously removes impurities and enables in-situ doping, achieving a 95.5% capacity retention after 500 cycles at 0.5 C. Despite these promising results, scaling up from lab to industrial production faces significant challenges: continuous-flow reactor systems for microwave and flash Joule heating remain underdeveloped, with most current setups operating in batch mode, severely limiting throughput; heteroatom doping often suffers from poor uniformity, leading to inconsistent material performance; and while ALD and CVD offer precise control, their high equipment costs and complex operational requirements hinder large-scale implementation in the near term. In summary, this paper provides a comprehensive overview of the failure mechanisms of graphite anodes in LIBs and the state-of-the-art in regeneration technologies. By analyzing key efficiency determinants and technical bottlenecks through the latest experimental data, it aims to guide process optimization and support the industrialization of graphite recycling, thereby promoting efficient resource recovery and advancing the sustainable development of the global lithium-ion battery industry.
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基本信息:
DOI：10.20237/j.issn.1007-7545.2026.04.005
中图分类号:TQ127.11;TM912
引用信息:
[1]曹世宇,周涵宇,董泽宇,等.锂离子电池负极石墨的失效机理和修复再生[J].有色金属(冶炼部分),2026(04):786-796.DOI:10.20237/j.issn.1007-7545.2026.04.005.
基金信息:
国家自然科学基金资助项目(52374288,52204298); 中国科学技术协会青年人才托举工程资助项目(2022QNRC001)~~
2025-10-16
2025
2025-11-02
2025-11-03
2025
1
2026-04-10
2026-04-10