Abstract
Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies (EECSTs) like electrocatalysis and rechargeable batteries. Improving their performance relies on elucidating reaction mechanisms and structure-performance relationships via in situ studies. This review summarizes recent in situ studies of EECSTs through a variety of advanced characterization techniques aiming at mapping reaction pathways for the rational design of overall high-performance reaction systems. We outline the principles, capabilities, advantages, and limitations of various in situ techniques. Their applications in in situ studies of fuel cells, water/CO(2) electrolysis, and lithium batteries are highlighted with representative examples. These studies enable dynamic tracking of chemical and structural evolution of overall reaction systems, including materials, intermediates, products, and surroundings during operation, providing insights critical to rational system design. Future advancements will involve integrating multimodal in situ/operando approaches with artificial intelligence to enable real-time monitoring at practical scales. Such integration promises precise mechanistic insights and robust structure-performance correlations, ultimately accelerating the development of high-performance EECSTs aligned with sustainability and market requirements.