Sustainable Electrochemical Recycling of Spent Lithium-Ion Batteries: Selective Extraction of Lithium and Direct Regeneration of De-Lithiated Material

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The recycling of spent lithium-ion batteries has become an urgent imperative. In recent years, the rising demand for lithium has sparked interest in the selective extraction of lithium from spent LIBs cathode materials. This process is of interest as it can streamline processes, improve lithium recovery efficiency, and reduce processing costs. Electrochemical methods for selectively extracting lithium from spent cathode materials have gained significant attention among various selective extraction methods due to their advantages, such as low energy consumption and environmental friendliness. Despite substantial progress in improving the efficiency of lithium recovery through electrochemical methods, the economic returns from lithium salt products, to some extent, are still insufficient to offset the processing costs of the entire process, thereby limiting the further development of this technology. Therefore, it is necessary to develop reasonable strategies for the utilization of such de-lithiated materials to further enhance product yields. One promising strategy among these approaches is direct regeneration of fresh cathode materials from the de-lithiated material. However, due to a lack of clear understanding of the structural evolution of transition metal oxides during the lithium extraction process, and the lithiation mechanisms of lithium-depleted materials, there is currently no research report on the direct regeneration of such de-lithiated materials into battery materials.Herein, an electrochemical method using LiCl aqueous as electrolyte is developed to realize the selective extraction of lithium from spent polycrystal LiNi0.55Co0.15Mn0.3O2 (NCM) cathode materials, with a maximum de-lithiation rate approaching 90%. Thorough characterizations were conducted to monitor the morphological, structural, and compositional evolution of NCM during the electrochemical de-lithiation process. These findings contribute to a profound understanding of the characteristics of the de-lithiated material and inform the rational design of regeneration pathways tailored to such materials. The results reveal that the deep de-lithiation of NCM in lithium-aqueous electrolyte triggers water-molecule intercalation, leading to an unusual phase transformation beyond H1→H2→H3. This phase transformation causes substantial lattice expansion along c-axis and introduces severe lattice distortion in de-lithiated material. The over-expanded lattice and the presence of bulk defects resulted in an unstable structure, posing huge challenge for the subsequent direct regeneration of de-lithiated material using conventional calcination methods. To address this, we employ a hydrothermal re-lithiation process, characterized by a milder, lithium-rich and water-based environment. This process is able to create a “lithium-water-balance” structure for de-lithiated materials by promoting the lithium diffusion into the lithium-deficiency structure and facilitating the exchange between lithium ions and water molecules. This process effectively enhances structural stability of the de-lithiated material. As a result, subsequent calcination successfully converts the degraded structure back into the original lithium-conductive layer structure by further eliminating the remaining lattice defects in material and promoting the cation rearrangement. The regenerated material exhibits decent electrochemical performances, which delivers a capacity of 153.2 mAh g−1 at 1C and 132.5 mAh g− 1 at 5C. This work provides insights into the electrochemical de-lithiation method and fills a gap in the utilization of de-lithiated NCM, paving the way for the sustainable recycling of spent LIBs.