Impacts of the Conductive Networks on Solid‐State Battery Operation

Abstract The micromorphology of composite cathodes is known to play a vital role in determining all‐solid‐state battery (ASSB) performance. However, much of our current understanding is derived from empirical observations, lacking a deeper mechanistic foundation. The “rocking chair” concept of battery chemistry requires maintaining charge neutrality, emphasizing the necessity of examining electrode micromorphology from the perspective of conductive networks. This study systematically investigates the microscopic electrochemical impacts of conductive network micromorphology by varying the Li + ‐to‐e − channel ratio in cathodes comprising LiNbO 3 ‐coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 6 PS 5 Cl, and carbon fibers. Utilizing multiscale synchrotron‐based spectro‐microscopy, we unravel that unbalanced Li + and e − conducting channels intensify charge polarization within active cathode particles and accelerate their degradation. A further model system with X‐ray nano‐tomography resolved e − and Li + channels indicates that spatially uniform and well‐paired Li + and e − conducting channels are highly desirable as they could promote more uniform lithiation/delithiation, mitigating microscopic electrochemical polarization. Electrode‐scale X‐ray holotomography analysis reveals that the impact of conductive networks is particle‐size‐dependent, with smaller cathode particles being more significantly affected. These findings provide mechanistic insights into the interplay between conductive networks and all‐solid‐state battery operation, laying the groundwork for rational design and optimization of cathode architectures in future solid‐state battery technologies.