Solid-state cathode heterogeneity impact on utilization and fracture dynamics
Creators
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Park, Se Hwan1
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Yescas, Carlos Juarez2
- Naik, Kaustubh3
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Wang, Yingjin4
- Luo, Yuting2
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Puthusseri, Dhanya1
- Kwon, Patrick2
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Vishnugopi, Bairav S.3
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Shyam, Badri5
- Yang, Heng5
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Cook, John5
- Okasinki, John6
- Chaung, Andrew6
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Xiao, Xianghui7
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Greer, Julia4
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Mukherjee, Partha P.3
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Zahiri, Beniamin2
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Braun, Paul2
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Hatzell, Kelsey1
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1.
Princeton University
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2.
University of Illinois Urbana-Champaign
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3.
Purdue University West Lafayette
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4.
California Institute of Technology
- 5. Xerion Battery
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6.
Argonne National Laboratory
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7.
Brookhaven National Laboratory
Abstract
Structural heterogeneity in solid-state batteries can impact material utilization and fracture mechanisms. Dense crystallographically oriented lithium cobalt oxide cathodes serve as a model electrode system for exploring how density variability 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 subgrain 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. Our findings reveal the importance of materials design to alleviate stress in small-volume changing cathodes.
Copyright and License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Acknowledgement
This work was supported by the Defense Advanced Research Projects Agency (DARPA) HR00112220028. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research used resources 18-ID of the National Synchrotron Light Source II, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.
Conflict of Interest
The authors declare the following competing financial interest(s): B.S., H.Y. and J.C. are employees of Xerion Advanced Battery Corporation (XABC), and P.V.B. is a co-founder of XABC and holds an equity stake in XABC.
Contributions
S.H.P. performed XANES experiments, and analyzed XANES and EDXRD characterization experiments. D. P., Y.L., P.K., and C.J.Y. assisted with EDXRD experiments. P.M. managed and oversaw modeling efforts. K.G.N. and B.V. performed meso-scale modeling. Y.W. performed nanomechanics experiments. J.R.G. oversaw nano-indention experiments and analysis. K.B.H., P.V.B. and B.Z. advised experiments and funding. K.B.H., S.H.P., and B.Z. were involved in manuscript writing. B.S, H.Y., and J.C. provided materials and engaged in discussion on analysis. J.O., A.C. and X.X. helped with experimental set-up at the synchrotron and analysis.
Files
chemrxiv-2024-0hdbp.pdf
Additional details
Dates
- Available
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2024-04-25Version 1
Caltech Custom Metadata
- Caltech groups
- Kavli Nanoscience Institute , Division of Engineering and Applied Science (EAS)
- Publication Status
- Published