High-Rate Spinel LiMn2O4 (LMO) Following Carbonate Removal and Formation of Li-Rich Interface by ALD Treatment

Young, Matthias J.; Letourneau, Steven; Warburton, Robert E.; Dose, Wesley M.; Johnson, Christopher; Greeley, Jeffrey; Elam, Jeffrey W.

doi:10.1021/acs.jpcc.9b04418

High-Rate Spinel LiMn₂O₄ (LMO) Following Carbonate Removal and Formation of Li-Rich Interface by ALD Treatment

Journal Article · Fri Sep 06 00:00:00 EDT 2019 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.9b04418· OSTI ID:1606541

^[1]; ^[2]; Warburton, Robert E. ^[3]; ^[2]; ^[2]; ^[3]; ^[2]

Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Missouri, Columbia, MO (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Purdue Univ., West Lafayette, IN (United States)

Recent work has identified enhanced charge-storage capacity in the spinel lithium manganese oxide (LiMn₂O₄; LMO) lithium-ion battery cathode upon a single atomic layer deposition (ALD) cycle composed of one chemical exposure of trimethylaluminum (TMA) and one exposure of water (H₂O). In this paper, we report further study of the rate capability following one TMA/H₂O exposure and identify enhanced rate capability versus pristine LMO. To understand this effect, we experimentally probe the surface composition of LMO with TMA/H₂O treatment using X-ray photoelectron spectroscopy measurements with inert transfer. This includes a study of the LMO surface properties following TMA exposure before exposure to H₂O. We identify the removal of a surface carbonate layer from LMO upon TMA exposure and the formation of a Li-rich aluminum oxide surface layer upon subsequent H₂O exposure. We also observe a previously undescribed phenomenon of Li ions depleting from the LMO surface upon TMA exposure and returning upon H₂O exposure. These effects are connected with the enhanced rate capability of ALD-coated LMO and are related to a range of emerging studies on carbonate surface layers in battery cathodes, as well as the use of ALD to stabilize battery interfaces.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1606541

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 39 Vol. 123; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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High-Rate Spinel LiMn2O4 (LMO) Following Carbonate Removal and Formation of Li-Rich Interface by ALD Treatment

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High-Rate Spinel LiMn₂O₄ (LMO) Following Carbonate Removal and Formation of Li-Rich Interface by ALD Treatment