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Title: Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel

Abstract

Dissolution of Mn from lithium-manganese spinel has hindered its commercialization as a cathode material in Li-ion batteries. Disproportionation of near-surface Mn(III), in the presence of acid, has been widely thought to result in dissolved divalent Mn. To what extent stray acidic water in the cell (as opposed to the organic electrolyte) acts as the solvent for Mn ions has not been established. Simulations by Leung show that a small displacement of trivalent Mn from its equilibrium site at an LiMn2O4 (001)/ ethylene carbonate interface leads to its reduction to Mn(II). In the present work, Thermodynamic Integration is performed, based on first-principles molecular dynamics simulations within the Blue-Moon ensemble, for the detachment of Mn(III) ions at the LiMn2O4 (001)/water interface. The results show that reduction of Mn(III) to Mn(II) occurs also in the case of an aqueous interface. The simulations were performed for both neutral and acidic water (in the presence of HF), with the coordination number of the dissolving Mn ion with substrate oxygen ions taken as the reaction coordinate. The simulations indicate that an F- ion strongly binds to a surface Mn(III) ion, and weakens its adhesion to the substrate. Owing to this weakening, a surface Mn-F complex traversesmore » regions of phase space at room temperature where disproportionation becomes energetically favorable. Although this disproportionation occurs close to the substrate, where the Mn coordination number is only slightly lowered from its equilibrium value, we argue that the likelihood of reattachment after disproportionation is small (Leung arrived at a similar interpretation in the case of the LiMn2O4 (001)/ EC interface). We suggest that the critical role of F- in promoting dissolution is to weaken the Mn binding to the substrate so as to enable disproportionation. The partially detached MnF complex may then undergo additional interaction with the solvent to form, e.g., MnF2, which would enable transport away from the substrate. In conclusion, the EPR measurements by Shilina et al. which appear to show Mn(III) as the predominant solvated species are discussed.« less

Authors:
ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1416181
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 40; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; Li-ion battery; acid; cathode; disproportionation; dissolution; first principles; spinel

Citation Formats

Benedek, Roy. Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcc.7b05940.
Benedek, Roy. Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel. United States. https://doi.org/10.1021/acs.jpcc.7b05940
Benedek, Roy. Mon . "Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel". United States. https://doi.org/10.1021/acs.jpcc.7b05940. https://www.osti.gov/servlets/purl/1416181.
@article{osti_1416181,
title = {Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel},
author = {Benedek, Roy},
abstractNote = {Dissolution of Mn from lithium-manganese spinel has hindered its commercialization as a cathode material in Li-ion batteries. Disproportionation of near-surface Mn(III), in the presence of acid, has been widely thought to result in dissolved divalent Mn. To what extent stray acidic water in the cell (as opposed to the organic electrolyte) acts as the solvent for Mn ions has not been established. Simulations by Leung show that a small displacement of trivalent Mn from its equilibrium site at an LiMn2O4 (001)/ ethylene carbonate interface leads to its reduction to Mn(II). In the present work, Thermodynamic Integration is performed, based on first-principles molecular dynamics simulations within the Blue-Moon ensemble, for the detachment of Mn(III) ions at the LiMn2O4 (001)/water interface. The results show that reduction of Mn(III) to Mn(II) occurs also in the case of an aqueous interface. The simulations were performed for both neutral and acidic water (in the presence of HF), with the coordination number of the dissolving Mn ion with substrate oxygen ions taken as the reaction coordinate. The simulations indicate that an F- ion strongly binds to a surface Mn(III) ion, and weakens its adhesion to the substrate. Owing to this weakening, a surface Mn-F complex traverses regions of phase space at room temperature where disproportionation becomes energetically favorable. Although this disproportionation occurs close to the substrate, where the Mn coordination number is only slightly lowered from its equilibrium value, we argue that the likelihood of reattachment after disproportionation is small (Leung arrived at a similar interpretation in the case of the LiMn2O4 (001)/ EC interface). We suggest that the critical role of F- in promoting dissolution is to weaken the Mn binding to the substrate so as to enable disproportionation. The partially detached MnF complex may then undergo additional interaction with the solvent to form, e.g., MnF2, which would enable transport away from the substrate. In conclusion, the EPR measurements by Shilina et al. which appear to show Mn(III) as the predominant solvated species are discussed.},
doi = {10.1021/acs.jpcc.7b05940},
journal = {Journal of Physical Chemistry. C},
number = 40,
volume = 121,
place = {United States},
year = {2017},
month = {9}
}

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Works referenced in this record:

Manganese oxides for lithium batteries
journal, January 1997


Comparison of Metal Ion Dissolutions from Lithium Ion Battery Cathodes
journal, January 2006

  • Choi, W.; Manthiram, A.
  • Journal of The Electrochemical Society, Vol. 153, Issue 9
  • DOI: 10.1149/1.2219710

Preparation of a new crystal form of manganese dioxide: λ-MnO2
journal, September 1981


First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li x Mn 2 O 4 (100) Surfaces
journal, April 2012

  • Leung, Kevin
  • The Journal of Physical Chemistry C, Vol. 116, Issue 18
  • DOI: 10.1021/jp212415x

Electronic and Bonding Properties of LiMn 2 O 4 Spinel with Different Surface Orientations and Doping Elements and Their Effects on Manganese Dissolution
journal, January 2016

  • Lee, Yoon Koo; Park, Jonghyun; Lu, Wei
  • Journal of The Electrochemical Society, Vol. 163, Issue 7
  • DOI: 10.1149/2.0991607jes

On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions
journal, January 2017

  • Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch
  • Journal of the American Chemical Society, Vol. 139, Issue 5
  • DOI: 10.1021/jacs.6b10781

Soluble Mn(III) in Suboxic Zones
journal, September 2006


Molecular Dynamics Simulations of Solvation and Kink Site Formation at the {001} Barite−Water Interface
journal, November 2008

  • Stack, Andrew G.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 6
  • DOI: 10.1021/jp8062993

A Truncated Manganese Spinel Cathode for Excellent Power and Lifetime in Lithium-Ion Batteries
journal, February 2012

  • Kim, Joo-Seong; Kim, KyungSu; Cho, Woosuk
  • Nano Letters, Vol. 12, Issue 12
  • DOI: 10.1021/nl303619s

Revealing the Reconstructed Surface of Li[Mn 2 ]O 4
journal, April 2016


Electrochemical dissolution of Mn3O4 in acid solutions
journal, January 2007

  • Fetisov, Vadim B.; Kozhina, Galina A.; Ermakov, Alexander N.
  • Journal of Solid State Electrochemistry, Vol. 11, Issue 9
  • DOI: 10.1007/s10008-007-0269-5

Simulation of the surface structure of lithium manganese oxide spinel
journal, May 2011


Transport Processes at α-Quartz–Water Interfaces: Insights from First-Principles Molecular Dynamics Simulations
journal, May 2008

  • Adeagbo, Waheed A.; Doltsinis, Nikos L.; Klevakina, Ksenia
  • ChemPhysChem, Vol. 9, Issue 7
  • DOI: 10.1002/cphc.200700819

Simulation of Aqueous Dissolution of Lithium Manganate Spinel from First Principles
journal, February 2012

  • Benedek, R.; Thackeray, M. M.; Low, J.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 6
  • DOI: 10.1021/jp208793k

Reaction Energy for LiMn[sub 2]O[sub 4] Spinel Dissolution in Acid
journal, January 2006

  • Benedek, R.; Thackeray, M. M.
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 6
  • DOI: 10.1149/1.2188071

Surface structure and equilibrium particle shape of the LiMn 2 O 4 spinel from first-principles calculations
journal, February 2013


Thermodynamic Stability of Low- and High-Index Spinel LiMn 2 O 4 Surface Terminations
journal, April 2016

  • Warburton, Robert E.; Iddir, Hakim; Curtiss, Larry A.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 17
  • DOI: 10.1021/acsami.6b01069

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


Ab initio calculations of free-energy reaction barriers
journal, January 2008


Network equilibration and first-principles liquid water
journal, January 2004

  • Fernández-Serra, M. V.; Artacho, Emilio
  • The Journal of Chemical Physics, Vol. 121, Issue 22
  • DOI: 10.1063/1.1813431

    Works referencing / citing this record:

    Theoretical Insights into Oxidation States of Transition Metals at (001) and (111) LiNi 0.5 Mn 1.5 O 4 Spinel Surfaces
    journal, January 2018

    • Intan, Nadia N.; Klyukin, Konstantin; Alexandrov, Vitaly
    • Journal of The Electrochemical Society, Vol. 165, Issue 5
    • DOI: 10.1149/2.1251805jes

    Deciphering the Cathode-Electrolyte Interfacial Chemistry in Sodium Layered Cathode Materials
    journal, October 2018


    Investigation of various layered lithium ion battery cathode materials by plasma- and X-ray-based element analytical techniques
    journal, October 2018

    • Evertz, Marco; Kasnatscheew, Johannes; Winter, Martin
    • Analytical and Bioanalytical Chemistry, Vol. 411, Issue 1
    • DOI: 10.1007/s00216-018-1441-8