To meet future needs for industries from personal devices to automobiles, state-of-the-art rechargeable lithium-ion batteries will require both improved durability and lowered costs. To enhance battery performance and lifetime, understanding electrode degradation mechanisms is of critical importance. Various advanced in situ and operando characterization tools developed during the past few years have proven indispensable for optimizing battery materials, understanding cell degradation mechanisms, and ultimately improving the overall battery performance. Here we review recent progress in the development and application of advanced characterization techniques such as in situ transmission electron microscopy for high-performance lithium-ion batteries. Using three representative electrode systems—layered metal oxides, Li-rich layered oxides and Si-based or Sn-based alloys—we discuss how these tools help researchers understand the battery process and design better battery systems. We also summarize the application of the characterization techniques to lithium–sulfur and lithium–air batteries and highlight the importance of those techniques in the development of next-generation batteries.
