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

doi:10.1007/s11708-017-0500-8

Front. Energy

2017, Vol. 11

Issue (3) : 365-373 https://doi.org/10.1007/s11708-017-0500-8

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

Sahithya REDDIVARI¹, Christian LASTOSKIE²(

), Ruofei WU³, Junliang ZHANG³

¹. Perimeter College, Georgia State University, Clarkston, GA 30021, USA
². Department of Civil and Environmental Engineering, University of Michigan, Ann Arbor, MI 48109-2125, USA
³. Institute of Fuel Cells, MOE Key Laboratory of Power & Machinery Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

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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

Corresponding Author(s): Christian LASTOSKIE

Just Accepted Date: 28 July 2017 Online First Date: 25 August 2017 Issue Date: 07 September 2017

Cite this article:

Sahithya REDDIVARI,Christian LASTOSKIE,Ruofei WU, et al. Chemical composition and formation mechanisms in the cathode-electrolyte interface layer of lithium manganese oxide batteries from reactive force field (ReaxFF) based molecular dynamics[J]. Front. Energy, 2017, 11(3): 365-373.

URL:

https://academic.hep.com.cn/fie/EN/10.1007/s11708-017-0500-8
https://academic.hep.com.cn/fie/EN/Y2017/V11/I3/365

Fig.1 Initial configuration of the simulation cell with the cathode in the center (The 100 surface is exposed to the electrolyte on both sides.)

Fig.2 The simulation snapshot for ReaxFF force field based MD simulation of LiMn₂O₄ cathode, EC/DMC electrolyte, LiPF₆ salt and FEC electrolyte additive (This snapshot shows the primary compounds present in the cathode-electrolyte interface layer after 2 ns at 330 K under NVT ensemble.)

Fig.3 Oxidation pathways of electrolyte solvent molecules on the cathode surface

Fig.4 Time evolution of primary products and reactants in the cathode-electrolyte interface layer

Fig.5 Reactions leading to the formation of the cathode-electrolyte interface (Solid lines indicate products as predicted by ReaxFF and dashed line indicates a proposed reaction pathway.)

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