Recent Progress in Solid‐State Lithium Batteries through Cathode Microstructure Engineering

Solid‐state batteries offer transformative advancements in energy density and safety, yet they are still in the early stages of development and face significant technical challenges. Here recent advancements in cathode are explored emphasizing the challenges of developing efficient cathode/electrolyte interfaces. It delves into advancements in coating techniques, composition adjustment, cathode processing, and structural design methodologies. Abstract A high‐performance cathode is necessary to realize the great potentials of solid‐state batteries such as high energy density and long cycle life. It is also needed to validate electrolyte performance, which is lacking. Currently, cathodes for solid‐state batteries are thinner and have lower cathode active material content than their lithium‐ion battery counterpart, resulting from insufficient conductivity and limiting the battery energy density. This review article provides an overview of recent development in cathode microstructures and their impact on battery properties, including compatibility between cathode and electrolyte, cathode architecture design, interface engineering, correlation between material properties, cathode processing approaches, and performance, as well as the advanced characterization methods used to understand the above correlations. Some perspectives on future development are shared including utilizing in situ and operando characterization tools to better understand dynamic evolution of the cathode/electrolyte interface, adapting artificial intelligence and machine learning to design and optimize cathode structures. The article is aimed to promote research interest on cathode development and advance solid‐state battery technologies. Solid-state batteries offer transformative advancements in energy density and safety, yet they are still in the early stages of development and face significant technical challenges. Here recent advancements in cathode are explored emphasizing the challenges of developing efficient cathode/electrolyte interfaces. It delves into advancements in coating techniques, composition adjustment, cathode processing, and structural design methodologies. Abstract A high-performance cathode is necessary to realize the great potentials of solid-state batteries such as high energy density and long cycle life. It is also needed to validate electrolyte performance, which is lacking. Currently, cathodes for solid-state batteries are thinner and have lower cathode active material content than their lithium-ion battery counterpart, resulting from insufficient conductivity and limiting the battery energy density. This review article provides an overview of recent development in cathode microstructures and their impact on battery properties, including compatibility between cathode and electrolyte, cathode architecture design, interface engineering, correlation between material properties, cathode processing approaches, and performance, as well as the advanced characterization methods used to understand the above correlations. Some perspectives on future development are shared including utilizing in situ and operando characterization tools to better understand dynamic evolution of the cathode/electrolyte interface, adapting artificial intelligence and machine learning to design and optimize cathode structures. The article is aimed to promote research interest on cathode development and advance solid-state battery technologies. Advanced Science, Volume 12, Issue 48, December 29, 2025.