Insights into Spontaneous Solid Electrolyte Interphase Formation at Magnesium Metal Anode Surface from Ab Initio Molecular Dynamics Simulations

Agarwal, Garvit; Howard, Jason D; Prabhakaran, Venkateshkumar; Johnson, Grant E.; Murugesan, Vijayakumar; Mueller, Karl T.; Curtiss, Larry A.; Assary, Rajeev S.

doi:10.1021/acsami.1c07864

Insights into Spontaneous Solid Electrolyte Interphase Formation at Magnesium Metal Anode Surface from Ab Initio Molecular Dynamics Simulations

Journal Article · Wed Aug 18 00:00:00 EDT 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c07864· OSTI ID:1821887

Agarwal, Garvit ^[1]; Howard, Jason D ^[1]; ^[2]; ^[2]; ^[2]; ^[2]; Curtiss, Larry A. ^[1]; Assary, Rajeev S. ^[1]

Argonne National Laboratory
BATTELLE (PACIFIC NW LAB)

Spontaneous chemical reactivity at multivalent (Mg, Ca, Zn, Al) electrode surfaces is critical to solid electrolyte interphase (SEI) formation, and hence, directly affects the longevity of batteries. Here, we report an investigation of the reactivity of 0.5 M Mg(TFSI)2 in 1,2-dimethoxyethane (DME) solvent at a Mg(0001) surface using ab initio molecular dynamics (AIMD) simulations and detailed Bader charge analysis. Based on the simulations, the initial degradation reactions of the electrolyte strongly depend on the structure of the Mg(TFSI)2 species near the anode surface. At the surface, the dissociation of Mg(TFSI)2 species occurs via cleavage of the N-S bond for the solvent separated ion pair (SSIP) and via cleavage of the C-S bond for the contact ion pair (CIP) configuration. In the case of the CIP, both TFSI anions undergo spontaneous bond dissociation reactions to form atomic O, C, S, F, and N species adsorbed on the surface of the Mg anode. These products indicate that the initial SEI layer formed on the surface of the pristine Mg anode consists of a complex mixture of multiple components such as oxides, carbides, sulfides, fluorides, and nitrides. We believe that the atomic level insights gained from these simulations will lay the groundwork for the rational design of tailored and functional interphases that are critical for the success of multivalent battery technology.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1821887

Report Number(s):: PNNL-SA-164872

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 32 Vol. 13

Country of Publication:: United States

Language:: English

References (59)

Factors Influencing Preferential Anion Interactions during Solvation of Multivalent Cations in Ethereal Solvents Han, Kee Sung; Hahn, Nathan T.; Zavadil, Kevin R. The Journal of Physical Chemistry C, Vol. 125, Issue 11 https://doi.org/10.1021/acs.jpcc.0c09830	journal	March 2021
Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T. ACS Applied Materials & Interfaces, Vol. 7, Issue 33 https://doi.org/10.1021/acsami.5b04487	journal	August 2015
Electrode–electrolyte interfaces in lithium-based batteries Yu, Xingwen; Manthiram, Arumugam Energy & Environmental Science, Vol. 11, Issue 3 https://doi.org/10.1039/C7EE02555F	journal	January 2018
Reactivity at the Lithium–Metal Anode Surface of Lithium–Sulfur Batteries Camacho-Forero, Luis E.; Smith, Taylor W.; Bertolini, Samuel The Journal of Physical Chemistry C, Vol. 119, Issue 48 https://doi.org/10.1021/acs.jpcc.5b08254	journal	November 2015
Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries Wang, Aiping; Kadam, Sanket; Li, Hong npj Computational Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41524-018-0064-0	journal	March 2018
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Magnesium(II) Bis(trifluoromethane sulfonyl) Imide-Based Electrolytes with Wide Electrochemical Windows for Rechargeable Magnesium Batteries Ha, Se-Young; Lee, Yong-Won; Woo, Sang Won ACS Applied Materials & Interfaces, Vol. 6, Issue 6, p. 4063-4073 https://doi.org/10.1021/am405619v	journal	March 2014
Structure and dynamics in the lithium solvation shell of nonaqueous electrolytes Han, Sungho Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-42050-y	journal	April 2019
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) ₂ in Diglyme: Implications for Multivalent Electrolytes Baskin, Artem; Prendergast, David The Journal of Physical Chemistry C, Vol. 120, Issue 7 https://doi.org/10.1021/acs.jpcc.5b08999	journal	February 2016
Mg rechargeable batteries: an on-going challenge Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279 https://doi.org/10.1039/C3EE40871J	journal	January 2013
Magnesium batteries: Current state of the art, issues and future perspectives Mohtadi, Rana; Mizuno, Fuminori Beilstein Journal of Nanotechnology, Vol. 5 https://doi.org/10.3762/bjnano.5.143	journal	January 2014
The Role of MgCl ₂ as a Lewis Base in ROMgCl-MgCl ₂ Electrolytes for Magnesium-Ion Batteries Pan, Baofei; Huang, Jinhua; He, Meinan ChemSusChem, Vol. 9, Issue 6 https://doi.org/10.1002/cssc.201501557	journal	February 2016
Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode Camacho-Forero, Luis E.; Balbuena, Perla B. Physical Chemistry Chemical Physics, Vol. 19, Issue 45 https://doi.org/10.1039/C7CP06485C	journal	January 2017
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S. Angewandte Chemie International Edition, Vol. 54, Issue 27 https://doi.org/10.1002/anie.201412202	journal	May 2015
Plating and stripping calcium in an organic electrolyte Wang, Da; Gao, Xiangwen; Chen, Yuhui Nature Materials, Vol. 17, Issue 1 https://doi.org/10.1038/nmat5036	journal	November 2017
Ion Solvation Engineering: How to Manipulate the Multiplicity of the Coordination Environment of Multivalent Ions Baskin, Artem; Prendergast, David The Journal of Physical Chemistry Letters, Vol. 11, Issue 21 https://doi.org/10.1021/acs.jpclett.0c02682	journal	October 2020
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Evaluation of (CF ₃ SO ₂ ) ₂ N ⁻ (TFSI) Based Electrolyte Solutions for Mg Batteries Shterenberg, Ivgeni; Salama, Michael; Yoo, Hyun Deog Journal of The Electrochemical Society, Vol. 162, Issue 13 https://doi.org/10.1149/2.0161513jes	journal	January 2015
Tuning the Reversibility of Mg Anodes via Controlled Surface Passivation by H ₂ O/Cl ^– in Organic Electrolytes Connell, Justin G.; Genorio, Bostjan; Lopes, Pietro Papa Chemistry of Materials, Vol. 28, Issue 22 https://doi.org/10.1021/acs.chemmater.6b03227	journal	October 2016
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/B810189B	journal	January 2008
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions Lu, Z.; Schechter, A.; Moshkovich, M. Journal of Electroanalytical Chemistry, Vol. 466, Issue 2, p. 203-217 https://doi.org/10.1016/S0022-0728(99)00146-1	journal	May 1999
Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes Hahn, Nathan T.; Driscoll, Darren M.; Yu, Zhou ACS Applied Energy Materials, Vol. 3, Issue 9 https://doi.org/10.1021/acsaem.0c01070	journal	July 2020
Energy storage emerging: A perspective from the Joint Center for Energy Storage Research Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P. Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821672117	journal	June 2020
Towards a calcium-based rechargeable battery Ponrouch, A.; Frontera, C.; Bardé, F. Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4462	journal	October 2015
LiTFSI Structure and Transport in Ethylene Carbonate from Molecular Dynamics Simulations Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 110, Issue 10 https://doi.org/10.1021/jp056249q	journal	March 2006
Improving Electrodeposition of Mg through an Open Circuit Potential Hold Esbenshade, Jennifer L.; Barile, Christopher J.; Fister, Timothy T. The Journal of Physical Chemistry C, Vol. 119, Issue 41 https://doi.org/10.1021/acs.jpcc.5b07825	journal	October 2015
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Progress in development of electrolytes for magnesium batteries Deivanayagam, Ramasubramonian; Ingram, Brian J.; Shahbazian-Yassar, Reza Energy Storage Materials, Vol. 21 https://doi.org/10.1016/j.ensm.2019.05.028	journal	September 2019
Molecular Structure and Electron Affinity of Metal-Solvent Complexes: Insights from Density Functional Theory Simulations Agarwal, Garvit; Doan, Hieu A.; Assary, Rajeev S. Journal of The Electrochemical Society, Vol. 167, Issue 10 https://doi.org/10.1149/1945-7111/ab9c7b	journal	June 2020
Improved grid-based algorithm for Bader charge allocation Sanville, Edward; Kenny, Steven D.; Smith, Roger Journal of Computational Chemistry, Vol. 28, Issue 5 https://doi.org/10.1002/jcc.20575	journal	January 2007
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Probing Conformational Evolution and Associated Dynamics of Mg(N(SO ₂ CF ₃ ) ₂ ) ₂ ·Dimethoxyethane Adduct Using Solid-State ¹⁹ F and ¹ H NMR Chen, Ying; Jaegers, Nicholas R.; Han, Kee Sung The Journal of Physical Chemistry C, Vol. 124, Issue 9 https://doi.org/10.1021/acs.jpcc.9b10212	journal	February 2020
Ethylene Carbonate-Based Electrolyte Decomposition and Solid–Electrolyte Interphase Formation on Ca Metal Anodes Young, Joshua; Smeu, Manuel The Journal of Physical Chemistry Letters, Vol. 9, Issue 12 https://doi.org/10.1021/acs.jpclett.8b01261	journal	June 2018
Effects of High and Low Salt Concentration in Electrolytes at Lithium–Metal Anode Surfaces Camacho-Forero, Luis E.; Smith, Taylor W.; Balbuena, Perla B. The Journal of Physical Chemistry C, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpcc.6b10774	journal	December 2016
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420 https://doi.org/10.1021/jacs.5b01004	journal	February 2015
Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W. The Journal of Physical Chemistry B, Vol. 119, Issue 4 https://doi.org/10.1021/jp508184f	journal	January 2015
Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization Tian, Yaosen; Zeng, Guobo; Rutt, Ann Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00767	journal	December 2020
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
Effects of charged interfaces on electrolyte decomposition at the lithium metal anode Camacho-Forero, Luis E.; Balbuena, Perla B. Journal of Power Sources, Vol. 472 https://doi.org/10.1016/j.jpowsour.2020.228449	journal	October 2020
Theoretical Studies of Lithium Perchlorate in Ethylene Carbonate, Propylene Carbonate, and Their Mixtures Li, Tao Journal of The Electrochemical Society, Vol. 146, Issue 10 https://doi.org/10.1149/1.1392523	journal	January 1999
Reaction Pathways for Solvent Decomposition on Magnesium Anodes Lowe, Jeffrey S.; Siegel, Donald J. The Journal of Physical Chemistry C, Vol. 122, Issue 20 https://doi.org/10.1021/acs.jpcc.8b01752	journal	April 2018
Theoretical Insights into Solid Electrolyte Interphase Formation in an Al Anode Dual-Ion Battery Das, Sandeep; Bhauriyal, Preeti; Pathak, Biswarup The Journal of Physical Chemistry C, Vol. 124, Issue 14 https://doi.org/10.1021/acs.jpcc.9b11421	journal	March 2020
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Computational Design of New Magnesium Electrolytes with Improved Properties Qu, Xiaohui; Zhang, Yong; Rajput, Nav Nidhi The Journal of Physical Chemistry C, Vol. 121, Issue 30 https://doi.org/10.1021/acs.jpcc.7b04516	journal	July 2017
Role of Inorganic Surface Layer on Solid Electrolyte Interphase Evolution at Li-Metal Anodes Kamphaus, Ethan P.; Angarita-Gomez, Stefany; Qin, Xueping ACS Applied Materials & Interfaces, Vol. 11, Issue 34 https://doi.org/10.1021/acsami.9b07587	journal	August 2019
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Anion Association Strength as a Unifying Descriptor for the Reversibility of Divalent Metal Deposition in Nonaqueous Electrolytes Connell, Justin G.; Zorko, Milena; Agarwal, Garvit ACS Applied Materials & Interfaces, Vol. 12, Issue 32 https://doi.org/10.1021/acsami.0c09404	journal	July 2020
Atoms in molecules Bader, R. F. W. Accounts of Chemical Research, Vol. 18, Issue 1 https://doi.org/10.1021/ar00109a003	journal	January 1985
Comparative Study of Ethylene Carbonate-Based Electrolyte Decomposition at Li, Ca, and Al Anode Interfaces Young, Joshua; Kulick, Peter M.; Juran, Taylor R. ACS Applied Energy Materials, Vol. 2, Issue 3 https://doi.org/10.1021/acsaem.8b01707	journal	February 2019
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Role of Chloride for a Simple, Non-Grignard Mg Electrolyte in Ether-Based Solvents Sa, Niya; Pan, Baofei; Saha-Shah, Anumita ACS Applied Materials & Interfaces, Vol. 8, Issue 25 https://doi.org/10.1021/acsami.6b03193	journal	June 2016
Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries Thackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D. Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/C2EE21892E	journal	January 2012
Rechargeable magnesium battery: Current status and key challenges for the future Saha, Partha; Datta, Moni Kanchan; Velikokhatnyi, Oleg I. Progress in Materials Science, Vol. 66 https://doi.org/10.1016/j.pmatsci.2014.04.001	journal	October 2014
PACKMOL: A package for building initial configurations for molecular dynamics simulations Martínez, L.; Andrade, R.; Birgin, E. G. Journal of Computational Chemistry, Vol. 30, Issue 13 https://doi.org/10.1002/jcc.21224	journal	October 2009
Anion-Assisted Delivery of Multivalent Cations to Inert Electrodes Baskin, Artem; Lawson, John W.; Prendergast, David The Journal of Physical Chemistry Letters, Vol. 12, Issue 18 https://doi.org/10.1021/acs.jpclett.1c00943	journal	April 2021

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