The demand for lithium-ion batteries (LIBs) has increased rapidly. However, commercial inorganic-based cathode materials have a low theoretical capacity and inherent disadvantages, such as high cost and toxicity. Redox-active organic cathodes with a high theoretical capacity, eco-friendly properties, and sustainability have been developed to overcome these limitations. Herein, perylene diimide derivatives N-substituted with 1,2,4-triazol-3-yl rings (PDI-3AT) were developed to apply as a cathode material for LIBs. The PDI-3AT cathode exhibited discharge capacities of 85.2 mAh g^–1 (50 mA g^–1 over 100 cycles) and 64.5 mAh g^–1 (500 mA g^–1 over 1000 cycles) with ratios to the theoretical capacities of 84 and 64%, respectively. Electrochemical kinetics analysis showed capacitive behaviors of the PDI-3AT cathode with efficient pathways for lithium-ion transport. Also, the activation step of the PDI-3AT cathode was demonstrated by improving the charge transfer resistance and lithium-ion diffusion coefficient during the initial few charge–discharge cycles. Furthermore, DFT calculations at the B3LYP/6-311+G** level and ex situ analysis of various charge states of the PDI-3AT electrode using attenuated total reflection Fourier transform infrared (ATR FT-IR) analysis, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were conducted for the further study of the lithium-ion storage mechanism. The results showed that the lithiation process formed the lithium enolate (═C–O–Li) coordinated with the N atoms of the 1,2,4-triazole ring. It is expected that our study results will encourage the production and use of redox-active perylene diimide derivatives as next-generation cathode materials.

中文翻译：

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储锂机理：1,2,4-三唑-3-基环N-取代苝二酰亚胺有机正极材料研究进展

锂离子电池（LIB）的需求迅速增长。然而，商业无机基正极材料具有较低的理论容量和固有的缺点，例如成本高和毒性。具有高理论容量、环保特性和可持续性的氧化还原活性有机阴极已经被开发出来以克服这些限制。在此，开发了被1,2,4-三唑-3-基环N-取代的苝二酰亚胺衍生物（PDI-3AT）作为LIB的正极材料。PDI-3AT 正极的放电容量为 85.2 mAh g ^–1（50 mA g ^–1，超过 100 次循环）和 64.5 mAh g ^–1（500 mA g ^–1，超过 1000 次循环），与理论容量的比率为 84 和 64 ％， 分别。电化学动力学分析表明 PDI-3AT 阴极的电容行为具有有效的锂离子传输途径。此外，PDI-3AT 正极的活化步骤通过在最初的几次充放电循环中改善电荷转移电阻和锂离子扩散系数得到证明。此外，在 B3LYP/6-311+G** 水平上进行了 DFT 计算，并使用衰减全反射傅立叶变换红外 (ATR FT-IR) 分析、X 射线衍射 ( XRD）和X射线光电子能谱（XPS）用于进一步研究锂离子存储机制。结果表明，锂化过程形成与1,2,4-三唑环的N原子配位的烯醇锂(=C-O-Li)。预计我们的研究结果将鼓励氧化还原活性苝二酰亚胺衍生物作为下一代正极材料的生产和使用。