Although batteries represent a key tool for sustainable development, their working processes, in terms of reaction mechanisms, side reactions, ion transport and formation of a solid–electrolyte interface, are not yet fully understood. In this respect, operando experiments are of enormous importance for providing hints on the relevant chemical species that form ‘while a battery is working’. X-ray absorption spectroscopy (XAS) has for a long time been the standard in the investigation of local structures of materials. In this regard, applied operando can provide invaluable information on the working mechanisms of batteries. In this review, after introductory paragraphs concerning battery chemistry and the principles of XAS, some of the most important developments in operando XAS applied to battery science are considered. Emphasis is given to Li-metal, Na-ion, Li/sulfur and all solid-state batteries. Related and advanced techniques, such as resonant inelastic x-ray scattering and high-resolution fluorescence-detected x-ray absorption spectroscopy are discussed as well. Suggestions are offered for planning an XAS experiment at the synchrotron radiation source, and finally, some considerations concerning future developments are presented.

尽管电池代表了可持续发展的关键工具，但它们的工作过程，在反应机制、副反应、离子传输和固体电解质界面的形成方面，尚未完全了解。在这方面，操作实验对于提供有关“电池工作时”形成的相关化学物种的提示非常重要。X 射线吸收光谱 (XAS) 长期以来一直是研究材料局部结构的标准。在这方面，应用的操作可以提供有关电池工作机制的宝贵信息。在这篇综述中，在介绍了电池化学和 XAS 原理的段落之后，考虑了应用于电池科学的操作 XAS 的一些最重要的发展。重点是锂金属、钠离子、锂/硫和全固态电池。还讨论了相关的先进技术，例如共振非弹性 X 射线散射和高分辨率荧光检测 X 射线吸收光谱。提出了在同步辐射源上规划 XAS 实验的建议，最后提出了有关未来发展的一些考虑。