Chemical composition and formation mechanisms in the cathode-electrolyte interface layer of lithium manganese oxide batteries from reactive force field (ReaxFF) based molecular dynamics

Sahithya REDDIVARI, Christian LASTOSKIE, Ruofei WU, Junliang ZHANG

Front. Energy ›› 2017, Vol. 11 ›› Issue (3) : 365-373.

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Front. Energy ›› 2017, Vol. 11 ›› Issue (3) : 365-373. DOI: 10.1007/s11708-017-0500-8
RESEARCH ARTICLE
RESEARCH ARTICLE

Chemical composition and formation mechanisms in the cathode-electrolyte interface layer of lithium manganese oxide batteries from reactive force field (ReaxFF) based molecular dynamics

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Abstract

Lithium manganese oxide (LiMn2O4) is a principal cathode material for high power and high energy density electrochemical storage on account of its low cost, non-toxicity, and ease of preparation relative to other cathode materials. However, there are well-documented problems with capacity fade of lithium ion batteries containing LiMn2O4. Experimental observations indicate that the manganese content of the electrolyte increases as an electrochemical cell containing LiMn2O4 ages, suggesting that active material loss by dissolution of divalent manganese from the LiMn2O4 surface is the primary reason for reduced cell life in LiMn2O4 batteries. To improve the retention of manganese in the active material, it is key to understand the reactions that occur at the cathode surface. Although a thin layer of electrolyte decomposition products is known to form at the cathode surface, the speciation and reaction mechanisms of Mn2+ in this interface layer are not yet well understood.

To bridge this knowledge gap, reactive force field (ReaxFF) based molecular dynamics was applied to investigate the reactions occurring at the LiMn2O4 cathode surface and the mechanisms that lead to manganese dissolution. The ReaxFFMD simulations reveal that the cathode-electrolyte interface layer is composed of oxidation products of electrolyte solvent molecules including aldehydes, esters, alcohols, polycarbonates, and organic radicals. The oxidation reaction pathways for the electrolyte solvent molecules involve the formation of surface hydroxyl species that react with exposed manganese atoms on the cathode surface. The presence of hydrogen fluoride (HF) induces formation of inorganic metal fluorides and surface hydroxyl species. Reaction products predicted by ReaxFF-based MD are in agreement with experimentally identified cathode-electrolyte interface compounds. An overall cathode-electrolyte interface reaction scheme is proposed based on the molecular simulation results.

Keywords

lithium manganese oxide batteries / reactive force field (ReaxFF) / cathode-electrolyte interface layer / molecular dynamics

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Sahithya REDDIVARI, Christian LASTOSKIE, Ruofei WU, Junliang ZHANG. Chemical composition and formation mechanisms in the cathode-electrolyte interface layer of lithium manganese oxide batteries from reactive force field (ReaxFF) based molecular dynamics. Front. Energy, 2017, 11(3): 365‒373 https://doi.org/10.1007/s11708-017-0500-8

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Acknowledgments

The authors are grateful to acknowledge sponsorship of this research from the Joint Institute of the University of Michigan and Shanghai Jiao Tong University. S.R. also received financial support for this work from the General Motors / University of Michigan Automotive Battery Consortium for the Drivetrain research center.

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2017 Higher Education Press and Springer-Verlag Berlin Heidelberg
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