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Utilization of heavy alkali dopants as a beacon to study the cathode electrolyte decomposition layer in lithium-ion batteries

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Abstract

We introduce low levels of CsClO4 and RbClO4 into the electrolyte of LiCoO2 electrochemical half-cells to probe the composition of the passivation film on the surface of the cathode, the electrolyte decomposition layer (EDL). The advantages of these heavy alkali dopants lie in their large ionic radii, which limit intercalation, yet their strong light scattering cross-section creates a beacon that highlights the formation of products near the cathode surface. Detailed surface analysis and depth profiling with X-ray photoelectron spectroscopy, and bulk analysis utilizing X-ray absorption spectroscopy, show evidence for the formation of Cs/Rb compounds, such as carbonates, halides, and perchlorates, similar to those formed by lithium in previous studies, but also reveal the significantly reduced mobility of the Cs/Rb relative to Li in the non-uniform EDL. This unique approach could open several presently untapped techniques to gather new information on the EDL in Li-ion batteries.

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Acknowledgments

The authors are grateful to the Office of Naval Research for support of this work through the Naval Research Laboratory. CP would like to thank the National Research Council for financial support and Dr. Bradford Pate for assistance and guidance in collecting and analyzing the XPS measurements. The synchrotron measurements were successful due to the help of Dr. Kumi Pandya. The National Synchrotron Light Source is supported by the U.S. Department of Energy, Division of Material Sciences and Division of Chemical Sciences, under contract number DE-AC02-98CH10886. The X11 beamline is supported by the U.S. Naval Research Laboratory and contributions from Participating Research Team (PRT) members.

Supporting information

XPS elemental scans, electrochemical data, XANES spectra, and XANES standards.

Funding sources

This work was funded by the Office of Naval Research through the Naval Research Laboratory.

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Author notes

  1. Christopher J. Patridge

    Present address: Department of Chemistry, D’Youville College, Buffalo, NY, USA

Authors and Affiliations

  1. Chemistry Division, U.S. Naval Research Laboratory, Washington, DC, 20375, USA

    Christopher J. Patridge, Corey T. Love & David E. Ramaker

  2. NRC/NRL Cooperative Research Associate, U.S. Naval Research Laboratory, Washington, DC, 20375, USA

    Christopher J. Patridge

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  1. Christopher J. Patridge
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Correspondence to Corey T. Love.

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Patridge, C.J., Love, C.T. & Ramaker, D.E. Utilization of heavy alkali dopants as a beacon to study the cathode electrolyte decomposition layer in lithium-ion batteries. Ionics 22, 51–62 (2016). https://doi.org/10.1007/s11581-015-1519-7

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