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Unraveling the convoluted and dynamic interphasial mechanisms on Li metal anode

Journal Article · · Nature Nanotechnology

Accurate understanding of the chemistry of solid-electrolyte interphase (SEI) is key to developing new electrolytes for high-energy batteries using lithium metal (Li-0) anodes(1). SEI is generally believed to be formed by the reactions between Li-0 and electrolyte(2,3). However, our new study shows this is not the whole story. Through synchrotron-based X-ray diffraction and pair distribution function analysis, we reveal a much more convoluted formation mechanism of SEI, which receives considerable contributions from electrolyte, cathode, moisture and native surface species on Li-0, with highly dynamic nature during cycling. Using isotope labelling, we traced the origin of LiH to electrolyte solvent, moisture and a new source: the native surface species (LiOH) on pristine Li-0. When lithium accessibility is very limited as in the case of anode-free cells, LiOH develops into plate-shaped large crystals during cycling. Alternatively, when the lithium source is abundant, as in the case of Li||NMC811 cells, LiOH reacts with Li-0 to form LiH and Li2O. While the desired anion-derived LiF-rich SEI is typically found in the concentrated electrolytes or their derivatives, we found it can also be formed in low-concentration electrolyte via the crosstalk effect, emphasizing the importance of formation cycle protocol and opening up opportunities for low-cost electrolyte development.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science - Office of Basic Energy Sciences - Joint Center for Energy Storage Research (JCESR); USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Vehicle Technologies Office
DOE Contract Number:
AC02-06CH11357
OSTI ID:
2202275
Journal Information:
Nature Nanotechnology, Vol. 18, Issue 3
Country of Publication:
United States
Language:
English

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