The formation of solid electrolyte interphase on graphite anodes plays a key role in the efficiency of Li-ion batteries. However, to date, fundamental understanding of the formation of LiF as one of the main solid electrolyte interphase components in hexafluorophosphate-based electrolytes remains elusive. Here, we present experimental and theoretical evidence that LiF formation is an electrocatalytic process that is controlled by the electrochemical transformation of HF impurity to LiF and H2. Although the kinetics of HF dissociation and the concomitant production of LiF and H2 is dependent on the structure and nature of surface atoms, the underlying electrochemistry is the same. The morphology, and thus the role, of the LiF formed is strongly dependent on the nature of the substrate and HF inventory, leading to either complete or partial passivation of the interface. Our finding is of general importance and may lead to new opportunities for the improvement of existing, and design of new, Li-ion technologies.
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This research was sponsored by BMW Technology Corporation. The research was conducted at Argonne National Laboratory—a US Department of Energy Office of Science laboratory operated by UChicago Argonne under contract number DE-AC02-06CH11357 and in part at the Technische Universität, München. We acknowledge support from the Office of Science, Office of Basic Energy Sciences and Materials Sciences and Engineering Division. We also thank C. Thompson and H. You for help with the AFM and crystal truncation rod measurements.
The authors declare no competing interests.
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Strmcnik, D., Castelli, I.E., Connell, J.G. et al. Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries. Nat Catal 1, 255–262 (2018). https://doi.org/10.1038/s41929-018-0047-z
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