Morphological Heterogeneity Impact of Film Solid-State Cathode on Utilization and Fracture Dynamics

Park, Se Hwan; Juarez-Yescas, Carlos; Naik, Kaustubh G.; Wang, Yingjin; Luo, Yuting; Puthusseri, Dhanya; Kwon, Patrick; Vishnugopi, Bairav S.; Shyam, Badri; Yang, Heng; Cook, John; Okasinski, John; Chuang, Andrew C.; Xiao, Xianghui; Greer, Julia R.; Mukherjee, Partha P.; Zahiri, Beniamin; Braun, Paul V.; Hatzell, Kelsey B.

doi:10.1021/acsnano.5c06799

Morphological Heterogeneity Impact of Film Solid-State Cathode on Utilization and Fracture Dynamics

Journal Article · Wed Jun 04 00:00:00 EDT 2025 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.5c06799· OSTI ID:2568504

^[1]; ^[2]; Naik, Kaustubh G. ^[3]; Wang, Yingjin ^[4]; Luo, Yuting ^[2]; Puthusseri, Dhanya ^[1]; Kwon, Patrick ^[2]; Vishnugopi, Bairav S. ^[3]; Shyam, Badri ^[5]; Yang, Heng ^[5]; Cook, John ^[5]; Okasinski, John ^[6]; ^[6]; Xiao, Xianghui ^[7]; ^[4]; Mukherjee, Partha P. ^[3]; ^[2]; ^[2]; ^[1]

Princeton Univ., NJ (United States)
Univ. of Illinois at Urbana-Champaign, IL (United States)
Purdue Univ., West Lafayette, IN (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)
Xerion Advanced Battery Corp., Kettering, OH (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Structural heterogeneity in solid-state batteries can impact material utilization and fracture mechanisms. Crystallographically oriented lithium cobalt oxide film cathodes serve as a model electrode system for exploring how void distribution contributes to stress relief and build up during cycling. Real- and reciprocal-space operando and ex situ synchrotron based experiments are utilized to understand structural changes across multiple length scales contribute to stress generation and fracture. Nanotomography uncovers a depth-dependent porosity variation in the pristine electrode and highlights preferential fracture in regions of lower porosity during delithiation. Energy-dispersive X-ray diffraction and 3D X-ray absorption near-edge spectroscopy (XANES) reveal the underutilization of cathode material in these regions. 3D XANES also confirms preferential delithiation near the sub-grain boundaries. Chemo-mechanical modeling coupled with site-specific mechanical characterization demonstrate how stress accumulation in dense regions of the electrode leads to fracture and underutilization of active material. In conclusion, our findings reveal the importance of materials design to alleviate stress in small-volume changing cathodes.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Defense Advanced Research Projects Agency (DARPA)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 2568504

Alternate ID(s):: OSTI ID: 2570251

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 23 Vol. 19; ISSN 1936-086X; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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