Unravelling the convoluted and dynamic interphasial mechanisms on Li metal anodes

Tan, Sha; Kim, Ju-Myung; Corrao, Adam; Ghose, Sanjit; Zhong, Hui; Rui, Ning; Wang, Xuelong; Senanayake, Sanjaya; Polzin, Bryant J.; Khalifah, Peter; Xiao, Jie; Liu, Jun; Xu, Kang; Yang, Xiao-Qing; Cao, Xia; Hu, Enyuan

doi:10.1038/s41565-022-01273-3

Unravelling the convoluted and dynamic interphasial mechanisms on Li metal anodes

Journal Article · Mon Dec 05 00:00:00 EST 2022 · Nature Nanotechnology

DOI:https://doi.org/10.1038/s41565-022-01273-3· OSTI ID:1906171

Tan, Sha ^[1]; Kim, Ju-Myung ^[2]; ^[3]; Ghose, Sanjit ^[4]; Zhong, Hui ^[3]; Rui, Ning ^[5]; Wang, Xuelong ^[5]; Senanayake, Sanjaya ^[5]; Polzin, Bryant J. ^[6]; ^[1]; ^[7]; ^[7]; ^[8]; ^[5]; ^[2]; ^[5]

Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook University, NY (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Stony Brook University, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); University of Washington, Seattle, WA (United States)
Army Research Laboratory, Adelphi, MD (United States)

Accurate understanding of the chemistry of solid-electrolyte interphase (SEI) is key to developing new electrolytes for high-energy batteries using lithium metal (Li⁰) anodes. SEI is generally believed to be formed by the reactions between Li⁰ and electrolyte. 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 Li⁰, 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 Li⁰. 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 Li⁰ to form LiH and Li₂O. While the desired anion-derived LiF-rich SEI is typically found in the concentrated electrolytes or their derivatives, here 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; SC0012704

OSTI ID:: 1906171

Alternate ID(s):: OSTI ID: 2356831
OSTI ID: 2460529
OSTI ID: 2202275

Report Number(s):: BNL--223812-2022-JAAM; PNNL-SA--179646

Journal Information:: Nature Nanotechnology, Journal Name: Nature Nanotechnology Journal Issue: 3 Vol. 18; ISSN 1748-3387

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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