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Title: First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li xMn 2O 4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from Li xMn 2O 4 (100) surfaces]

Abstract

Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (100) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is necessary but far from sufficient. Key steps that facilitate Mn(II) ion migration include concerted liquid/solid-state motions, proton-induced weakening of Mn-O bonds forming mobile OH - surface groups; and chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI component facilitates electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.

Authors:
 [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1335668
Report Number(s):
SAND-2016-10062J
Journal ID: ISSN 1932-7447; 649565
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 116; Journal Issue: 18; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; lithium ion batteries; lithium manganese oxide; solid electrolyte interface; ab initio molecule dynamics; computational electrochemistry

Citation Formats

Leung, Kevin. First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on LixMn2O4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from LixMn2O4 (100) surfaces]. United States: N. p., 2012. Web. doi:10.1021/jp212415x.
Leung, Kevin. First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on LixMn2O4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from LixMn2O4 (100) surfaces]. United States. doi:10.1021/jp212415x.
Leung, Kevin. Fri . "First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on LixMn2O4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from LixMn2O4 (100) surfaces]". United States. doi:10.1021/jp212415x. https://www.osti.gov/servlets/purl/1335668.
@article{osti_1335668,
title = {First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on LixMn2O4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from LixMn2O4 (100) surfaces]},
author = {Leung, Kevin},
abstractNote = {Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel LixMn2O4 (100) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is necessary but far from sufficient. Key steps that facilitate Mn(II) ion migration include concerted liquid/solid-state motions, proton-induced weakening of Mn-O bonds forming mobile OH- surface groups; and chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li2CO3 and organic lithium ethylene dicarbonate (LEDC) anode SEI component facilitates electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.},
doi = {10.1021/jp212415x},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 18,
volume = 116,
place = {United States},
year = {2012},
month = {4}
}

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