The Crucial Role of Vacancy Concentration in Enabling Superatomic Diffusion in Lithium Intermetallics

Behara, Sesha Sai; Van der Ven, Anton

doi:10.1021/acsenergylett.5c00266

The Crucial Role of Vacancy Concentration in Enabling Superatomic Diffusion in Lithium Intermetallics

Journal Article · Mon Mar 17 00:00:00 EDT 2025 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.5c00266· OSTI ID:2531280

^[1]; Van der Ven, Anton ^[1]

University of California, Santa Barbara, CA (United States)

Anode-free solid-state Li batteries promise significant increases in energy densities compared to current commercial batteries that rely on liquid electrolytes. Major challenges persist in controlling morphological evolution during the plating and stripping of lithium metal at the anode current collector. Elemental additives that alloy with lithium have been found to modify the plating and stripping behavior of lithium. Many alloying elements form intermetallics with lithium and the mobility of Li through these intermetallics is believed to have an important effect on morphological evolution. This study shows that Li transport coefficients through intermetallics span a wide range in values, with the B32 LiAl intermetallic predicted to have a Li tracer diffusion coefficient as high as 10^–6 cm²/s at room temperature, which is 8 orders of magnitude larger than that of isostructural B32 LiZn. This work demonstrates the crucial role of vacancy concentration in controlling the mobility of Li atoms through intermetallics. While the migration barriers for Li-vacancy exchanges in both LiAl and LiZn are remarkably low, the superatomic conductivity in LiAl is shown to arise from the unique electronic structure of the B32 LiAl compound, which favors high concentrations of vacancies.

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Research Organization:: University of California, Santa Barbara, CA (United States)

Sponsoring Organization:: National Energy Research Scientific Computing Center (NERSC); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2531280

Alternate ID(s):: OSTI ID: 2555807

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 4 Vol. 10; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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