Faculty, Staff and Student Publications

Language

English

Publication Date

9-22-2025

Journal

Angewandte Chemie

DOI

10.1002/anie.202511534

PMID

40761037

PMCID

PMC12455428

PubMedCentral® Posted Date

8-5-2025

PubMedCentral® Full Text Version

Post-print

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 LiNbO3‐coated LiNi0.8Co0.1Mn0.1O2, Li6PS5Cl, 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.

Keywords

All‐solid‐state batteries, Li+/e− channels, Micromorphology, Microscopic electrochemical polarization, Multimodal X‐ray spectro‐microscopy

Published Open-Access

yes

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.