Impacts of the Conductive Networks on Solid‐State Battery Operation

Deng, Shimao; Wang, Yixian; Sun, Tianxiao; Li, Wenlong; Ge, Mingyuan; Wang, Jian; Cloetens, Peter; Pianetta, Piero; Mitlin, David; Liu, Yijin

doi:10.1002/anie.202511534

Impacts of the Conductive Networks on Solid‐State Battery Operation

Journal Article · Tue Aug 05 00:00:00 EDT 2025 · Angewandte Chemie International Edition

DOI:https://doi.org/10.1002/anie.202511534· OSTI ID:2587065

Deng, Shimao ^[1]; Wang, Yixian ^[1]; Sun, Tianxiao ^[2]; Li, Wenlong ^[2]; ^[3]; Wang, Jian ^[4]; Cloetens, Peter ^[5]; Pianetta, Piero ^[6]; Mitlin, David ^[2]; ^[2]

Materials Science and Engineering Program Walker Department of Mechanical Engineering and Texas Materials Institute The University of Texas at Austin Austin TX 78712 USA
Univ. of Texas, Austin, TX (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Univ. of Saskatchewan, Saskatoon, SK (Canada). Canadian Light Source, Inc.
European Synchrotron Radiation Facility (ESRF), Grenoble (France)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

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 LiNi_0.8Co_0.1Mn_0.1O₂, 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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); Robert A. Welch Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2587065

Report Number(s):: BNL--228577-2025-JAAM

Journal Information:: Angewandte Chemie International Edition, Journal Name: Angewandte Chemie International Edition Journal Issue: 39 Vol. 64; ISSN 1521-3773; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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