Revealing the Design Principles of Ni‐Rich Cathodes for All‐Solid‐State Batteries

Abstract Electrode microstructure is one of the primary factors determining the electrochemical properties of all‐solid‐state batteries (ASSBs). However, the key principles of electrode design to realize fast ionic/electronic transport pathways are not well elucidated. Herein, the correlation between electrode microstructure and electrochemical behaviors is studied through different electrode design in terms of energy‐density‐related electrode composition and Ni‐rich layered oxides particle size distribution. A positive relation between particle size and mass fraction in electrode design is revealed, that is, as the particle size increases, more cathode materials are required to enable the fast reaction kinetics. The well interconnected active particles and solid electrolytes construct the highly percolated ionic/electronic transfer networks, which determines the overall electrochemical properties. The findings in this work give a new insight into electrode design to promote the development of high‐energy and high‐power ASSBs.