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失效鋰離子電池石墨負極回收利用研究進展

Progress on recycling graphite cathode from spent lithium-ion batteries

  • 摘要: 新能源汽車產業發展是實現我國“雙碳”戰略的重要舉措. 石墨因其高導電率、高容量和高穩定性等優點,成為當前主流的負極材料,其需求量和報廢量增長迅速. 廢石墨負極因含多種金屬、黏結劑、電解液等,具有污染性和資源性雙重特點,其高效清潔回收利用成為人們研究的熱點與重點問題. 首先介紹了全球石墨礦產資源分布及其消費結構,表明我國石墨資源較為豐富(約占全球15.7%),但產量與消費量全球第一,分別達到65.4%和86.6%,且電池負極消費比重日益增長. 為提高石墨負極利用水平,系統綜述了石墨負極回收利用研究進展,闡述了石墨負極的再生方法,包括物理法、濕法浸出、火法及其他方法. 為進一步提高再生石墨負極的電化學性能,改性技術(如元素摻雜、碳包覆、復合等方法)也受到人們的廣泛關注. 此外,還概括了石墨負極合成的其他新型功能材料,如石墨烯及氧化石墨烯、電容器、吸附劑和催化劑等,為石墨負極高值利用提供了新的選擇. 最后,總結了負極石墨材料回收利用的技術瓶頸和面臨的挑戰,為其綠色高效循環利用提供了研究思路和發展方向.

     

    Abstract: The rapid development of the new energy vehicle industry promotes the achievement of “dual-carbon” goals. Graphite has become the mainstream cathode material because of its high conductivity, capacity, and stability. Demand for graphite and the importance of end-of-life issues have grown rapidly with the booming of the Li-battery vehicle industry. Waste graphite cathodes are important resources of valuable materials, including Li, Cu, and graphite. However, they are also classified as solid wastes and cause potential environmental issues owing to the presence of binders, electrolytes, fluoride, etc. Hence, efficient and clean recycling of spent graphite has recently attracted considerable attention. In this review, the global distribution of mineral resources and the consumption structure of graphite are introduced. The graphite mineral reserve in China is quite abundant, approximately 15.7% of the world’s reserves. Meanwhile, the production and consumption of graphite in China is 65.4% and 86.6% of the global total, respectively. Its use in batteries as anodic materials is increasing. To improve the recycling technology of graphite cathodes, the progress in recycling them from spent lithium-ion batteries is reviewed systematically. Recycling methods, including physical separation, hydrometallurgical leaching, pyrometallurgy, and other methods, are elaborated. Graphite modification methods (e.g., element doping, carbon coating, and material compositing) used to enhance the electrochemical properties of regenerated graphite are summarized. Furthermore, the preparation of new functional materials from waste graphite has attracted considerable attention, for example, its reuse as graphene and graphene oxide, capacitors, adsorbents, and catalysts. However, because of the differences in graphite anode material manufacturers and various situations of failures and damage levels, obtaining uniform high-performance graphite products is highly challenging. The environmental issues arising from the disposal of electrolytes, organic binders, and hazardous metal ions in wastewater cannot be ignored. Currently, recovery technologies are complex and can only achieve a single goal, such as the purification of graphite by acid leaching. Therefore, a short, low-cost, and efficient process must be developed to achieve high-performance graphite products. More importantly, for graphite anode regeneration and reuse, the corresponding product standard system must be established to promote the industrial application of waste graphite anode recycling.

     

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