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首页> 外文期刊>Chemistry: A European journal >The reaction mechanism of a complex intercalation system: In situ X-ray diffraction studies of the chemical and electrochemical lithium intercalation in Cr4TiSe8
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The reaction mechanism of a complex intercalation system: In situ X-ray diffraction studies of the chemical and electrochemical lithium intercalation in Cr4TiSe8

机译：复杂插层系统的反应机理：Cr4TiSe8中化学和电化学锂插层的原位X射线衍射研究

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摘要

The intercalation reaction between Cr4TiSe8 and Li was investigated from a kinetic and an electro-chemical perspective. The structural phase transition from monoclinic to trigonal symmetry was probed by in situ energy-dispersive X-ray diffraction (in situ EDXRD) for chemical intercalation with butyllithium (BuLi). A change in the kinetic mechanism was detected for the reaction at room temperature; this was interpreted in terms of a trend from phase boundary control to diffusion control. A single diffusion-controlled mechanism is obeyed at 60 degrees C. The electrochemical measurements and the corresponding in situ Xray diffraction (in situ XRD) data revealed that the monoclinic host is intercalated up to the composition Li-x approximate to 0.1Cr4TiSe8 before the characteristic phase transition starts. The monoclinic phase undergoes complex structural changes in the following two-phase regime. Owing to the co-existence of two phases, the cell potential is constant for 0.1 < x < 0.7 and 0.9 < x < 3.0. The subsequent intercalation into the trigonal phase leads to a pronounced increase in the cell volume of the trigonal phase that stops at x approximate to 0.8. At this point, the complete reduction of Ti-IV gives rise to a voltage drop of the cell potential. XANES measurements revealed that the reduction of Ti-IV occurs prior to the reduction of Cr-III.
机译：从动力学和电化学的角度研究了Cr4TiSe8和Li之间的嵌入反应。通过原位能量色散X射线衍射（原位EDXRD）探测了从单斜对称到三角对称的结构相变，以进行丁基锂（BuLi）的化学嵌入。在室温下检测到反应的动力学机理发生了变化。这是从相位边界控制到扩散控制的趋势来解释的。在60摄氏度时遵循单一的扩散控制机制。电化学测量和相应的原位X射线衍射（原位XRD）数据表明，单斜晶主体在特征化之前嵌入了直至Li-x接近0.1Cr4TiSe8的成分。相变开始。在以下两阶段方案中，单斜晶相经历了复杂的结构变化。由于两相的共存，对于0.1

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