Advanced rechargeable batteries (ARBs) with the properties of green resource, safe operation and low cost, have received much attention due to the continually depletion of fossil fuels and the deterioration of global environment. The increasing pursuit of energy is pushing scientists to develop superior ARBs and it is a prerequisite to learn an in-depth understanding for components evolution and fundamental mechanism of electrode materials during charge and discharge process. As a state-of-art technique in the past few years, in situ transmission electron microscopy (TEM) presents high temporal and spatial resolutions in real-time observation, suggesting that the nonequilibrium state information can be probed during dynamic operating conditions. This powerful tool allows the direct observation of the electrode materials for the morphology change and electrochemical interface evolution during charge and discharge process. In addition, phase transformation can also be detected, and more detailed information about lattice information, crystallographic defect and element information will even be revealed. Currently, in situ TEM characterizations are initially employed for the investigation of ARBs electrode materials, which can visualize the complex electrochemical reaction at nano or even atomic scale. In this review, we conclude five kinds of classifications of in situ TEM setups for the monitoring ARBs and illuminate their detailed specific features. Besides, important imaging results from these published works within the past 10 years (2010–2020) are comprehensively analyzed. With the constant improvement of in situ TEM setups, some critical electrochemical reactions can be observed, which further facilitate the design of electrode materials for ARBs. In addition, we also propose how to utilize in situ TEM techniques to further settle the main challenges of ARBs and summarize the main challenges to further develop in situ TEM techniques in future. We believe this technique will play a vital role in investigating more underlying mechanism for ARBs.

由于矿物燃料的不断消耗和全球环境的恶化，具有绿色资源，安全操作和低成本等特性的高级可充电电池（ARB）备受关注。日益增长的对能量的追求正促使科学家们开发出卓越的ARB，这是学习深入了解充放电过程中电极材料的成分演变和基本机理的前提。作为过去几年的最先进技术，原位透射电子显微镜（TEM）在实时观察中具有很高的时间和空间分辨率，这表明可以在动态操作条件下探测非平衡状态信息。这种功能强大的工具可以直接观察电极材料在充电和放电过程中的形态变化和电化学界面的演变。此外，还可以检测到相变，甚至可以显示有关晶格信息，晶体缺陷和元素信息的更多详细信息。当前，原位TEM表征最初被用于研究ARBs电极材料，该材料可以可视化纳米级甚至原子级的复杂电化学反应。在这篇综述中，我们总结了用于监视ARB的五种现场TEM设置分类，并阐明了它们的详细特定功能。此外，对过去10年（2010-2020年）这些已发表作品的重要成像结果进行了综合分析。随着原位TEM设置的不断改进，可以观察到一些关键的电化学反应，这进一步促进了ARBs电极材料的设计。此外，我们还提出了如何利用原位TEM技术进一步解决ARB的主要挑战，并总结了将来进一步发展原位TEM技术的主要挑战。我们认为，这项技术将在研究ARB的更多潜在机制中发挥至关重要的作用。