Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.; George, Steven M.; Musgrave, Charles B.

doi:10.1002/adfm.201602773

Title: Band diagram and rate analysis of thin film spinel LiMn₂O₄ formed by electrochemical conversion of ALD-grown MnO

Journal Article · Thu Sep 22 00:00:00 EDT 2016 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.201602773· OSTI ID:1333410

Young, Matthias J. ^[1]; Schnabel, Hans-Dieter ^[2]; Holder, Aaron M. ^[3]; George, Steven M. ^[1]; Musgrave, Charles B. ^[1]

Univ. of Colorado, Boulder, CO (United States)
Leupold-Institut fur Angewandte Naturwissenschaften, Zwickau (Germany)
Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn₂O₄) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn₂O₄ thin films in electrolytes containing Li⁺, Na⁺, K⁺, and Mg²⁺ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn₂O₄ informed by screened hybrid density functional theory calculations is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn₂O₄. It is shown that the incorporation of Li⁺ or other cations into the host manganese dioxide spinel structure (λ-MnO₂) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn₂O₄. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn₂O₄ arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD)

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

Grant/Contract Number:: AC36-08GO28308; AC36-99GO10337

OSTI ID:: 1333410

Report Number(s):: NREL/JA-5K00-67263

Journal Information:: Advanced Functional Materials, Vol. 26, Issue 43; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 33 works

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