Graphitic materials with intercalated sites are considered as the mostly used positive electrode materials in nonaqueous Al batteries. Unlike the small‐size cations, the intercalation/de‐intercalation of large‐size anions into/out of graphite would induce large volume expansion and micro‐structure reconfiguration, leading to unexpected coulombic efficiency in the full cells (<95% within initial several cycles). For understanding the irreversible processes induced by anion intercalation/de‐intercalation (AlCl₄^–), here the kinetics of first two cycles for the Al‐graphite batteries have been systematically studied. To study kinetics behaviors at representative states, a combined method upon galvanostatic intermittent titration technique and electrochemical impedance spectroscopy has been carried out. The achieved diffusion coefficients of the positive electrodes assembled with different graphite sizes suggest that size effect also plays a critical role in determining the electrochemical kinetics in the mass transport in both electrolyte and graphitic layers as well as in interface reaction. The morphologies and micro‐structures of the post‐cycled graphite electrodes have been also experimentally studied, which also well supports the irreversible intercalation/de‐intercalation behaviors in graphite electrodes. The results offer a significant platform to well understand the essential factors in tailoring coulombic efficiency from a kinetic view, which would be helpful in promoting the graphite electrodes in Al batteries.

中文翻译：

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非水铝石墨电池中阴离子嵌入和脱嵌的初始电极动力学†

在非水铝电池中，具有插层位置的石墨材料被认为是最常用的正极材料。与小尺寸阳离子不同，大尺寸阴离子向/向石墨的嵌入/脱嵌会引起大体积膨胀和微观结构重构，从而导致全电池中出乎意料的库仑效率（在最初几个时间内<95％周期）。为了了解由阴离子插层/去插层引起的不可逆过程（AlCl ₄ ^–），此处已对铝石墨电池的前两个循环的动力学进行了系统研究。为了研究在代表性状态下的动力学行为，已经采用了基于恒电流间歇滴定技术和电化学阻抗谱的组合方法。组装有不同石墨尺寸的正极的已达到的扩散系数表明，尺寸效应在确定电解质层和石墨层的质量传输以及界面反应中的电化学动力学方面也起着至关重要的作用。还对实验后的石墨电极的形貌和微观结构进行了实验研究，这也很好地支持了石墨电极中不可逆的嵌入/脱嵌行为。