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

Abstract

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 materialsmore » for ion-incorporation charge storage.« less

Authors:
 [1];  [2];  [3];  [1];  [1]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. Leupold-Institut fur Angewandte Naturwissenschaften, Zwickau (Germany)
  3. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1333410
Report Number(s):
NREL/JA-5K00-67263
Journal ID: ISSN 1616-301X
Grant/Contract Number:  
AC36-08GO28308; AC36-99GO10337
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 26; Journal Issue: 43; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; atomic layer deposition; charge storage mechanism; defect theory; ion intercalation; lithium manganese oxide

Citation Formats

Young, Matthias J., Schnabel, Hans-Dieter, Holder, Aaron M., George, Steven M., and Musgrave, Charles B. Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO. United States: N. p., 2016. Web. doi:10.1002/adfm.201602773.
Young, Matthias J., Schnabel, Hans-Dieter, Holder, Aaron M., George, Steven M., & Musgrave, Charles B. Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO. United States. doi:10.1002/adfm.201602773.
Young, Matthias J., Schnabel, Hans-Dieter, Holder, Aaron M., George, Steven M., and Musgrave, Charles B. Thu . "Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO". United States. doi:10.1002/adfm.201602773. https://www.osti.gov/servlets/purl/1333410.
@article{osti_1333410,
title = {Band diagram and rate analysis of thin film spinel LiMn2O4 formed by electrochemical conversion of ALD-grown MnO},
author = {Young, Matthias J. and Schnabel, Hans-Dieter and Holder, Aaron M. and George, Steven M. and Musgrave, Charles B.},
abstractNote = {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.},
doi = {10.1002/adfm.201602773},
journal = {Advanced Functional Materials},
number = 43,
volume = 26,
place = {United States},
year = {2016},
month = {9}
}

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