State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, School of Energy Research, Xiamen University, Xiamen 361005, China.
Acc Chem Res. 2012 Apr 17;45(4):485-94. doi: 10.1021/ar200215t. Epub 2012 Jan 20.
With their ability to convert chemical energy of fuels directly into electrical power or reversibly store electrical energy, systems such as fuel cells and lithium ion batteries are of great importance in managing energy use. In these electrochemical energy conversion and storage (EECS) systems, controlled electrochemical redox reactions generate or store the electrical energy, ideally under conditions that avoid or kinetically suppress side reactions. A comprehensive understanding of electrode reactions is critical for the exploration and optimization of electrode materials and is therefore the key issue for developing advanced EECS systems. Based on its fingerprint and surface selection rules, electrochemical in-situ FTIR spectroscopy (in-situ FTIRS) can provide real-time information about the chemical nature of adsorbates and solution species as well as intermediate/product species involved in the electrochemical reactions. These unique features make this technique well-suited for insitu studies of EECS. In this Account, we review the characterization of electrode materials and the investigation of interfacial reaction processes involved in EECS systems by using state-of-the-art in-situ FTIR reflection technologies, primarily with an external configuration. We introduce the application of in-situ FTIRS to EECS systems and describe relevant technologies including in-situ microscope FTIRS, in-situ time-resolved FTIRS, and the combinatorial FTIRS approach. We focus first on the in-situ steady-state and time-resolved FTIRS studies on the electrooxidation of small organic molecules. Next, we review the characterization of electrocatalysts through the IR properties of nanomaterials, such as abnormal IR effects (AIREs) and surface enhanced infrared absorption (SEIRA). Finally, we introduce the application of in-situ FTIRS to demonstrate the decomposition of electrolyte and (de)lithiation processes involved in lithium ion batteries. The body of work summarized here has substantially advanced the knowledge of electrode processes and represents the forefront in studies of EECS at the molecular level.
具有将燃料的化学能直接转化为电能或可逆存储电能的能力，燃料电池和锂离子电池等系统在管理能源利用方面具有重要意义。在这些电化学能量转换和存储 (EECS) 系统中，受控的电化学氧化还原反应会产生或存储电能，理想情况下是在避免或动力学抑制副反应的条件下进行。对电极反应的全面了解对于探索和优化电极材料至关重要，因此是开发先进 EECS 系统的关键问题。基于其指纹和表面选择规则，电化学原位傅里叶变换红外光谱 (原位 FTIRS) 可以提供有关电化学反应中涉及的吸附物和溶液物种以及中间/产物物种的化学性质的实时信息。这些独特的功能使该技术非常适合原位研究 EECS。在本报告中，我们通过使用最先进的原位 FTIR 反射技术（主要是外部配置）来综述原位 FTIR 对 EECS 系统中电极材料的表征和界面反应过程的研究。我们介绍了原位 FTIRS 在 EECS 系统中的应用，并描述了相关技术，包括原位显微镜 FTIRS、原位时间分辨 FTIRS 和组合 FTIRS 方法。我们首先关注原位稳态和时间分辨 FTIRS 对小分子电氧化的研究。接下来，我们通过纳米材料的 IR 特性（如异常 IR 效应 (AIREs) 和表面增强红外吸收 (SEIRA)）来综述电催化剂的表征。最后，我们介绍了原位 FTIRS 的应用，以证明电解质的分解和锂离子电池中涉及的 (脱)锂过程。这里总结的工作大大推进了电极过程的知识，并代表了分子水平上 EECS 研究的前沿。
