Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes

Hahn, Nathan T.; Driscoll, Darren M.; Yu, Zhou; Sterbinsky, George E.; Cheng, Lei; Balasubramanian, Mahalingam; Zavadil, Kevin R.

doi:10.1021/acsaem.0c01070

Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes

Journal Article · Thu Jul 23 00:00:00 EDT 2020 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.0c01070· OSTI ID:1644403

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Joint Center for Energy Storage Research, Lemont, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Joint Center for Energy Storage Research, Lemont, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States

The emergence of magnesium and calcium batteries as potential beyond Li ion energy storage technologies has generated significant interest into the fundamental aspects of alkaline earth metal cation coordination in multivalent electrolytes and the impact of coordination on application-critical electrolyte properties such as solubility, transport, and electrochemical stability. Understanding these details in calcium electrolytes is of immediate importance due to recent, unprecedented demonstrations of reversible calcium metal electrodeposition in a limited number of ethereal solvent-based systems. In this work, we provide insight connecting Ca²⁺ coordination tendencies to important calcium battery electrolyte properties. Our results demonstrate a clear solvent:Ca²⁺ coordination strength trend across a series of cyclic ether and linear glyme solvents that controls the extent of ion association in solutions of “weakly” coordinating salts. We apply understanding gained from these results to rationalize relative anion:Ca²⁺ coordination tendencies and attendant Ca²⁺ coordination structures using two oxidatively stable anions of particular interest for current battery electrolytes. Armed with this understanding of solvent and anion interactions with Ca²⁺, we demonstrate and interpret differences in electrochemical calcium deposition behavior across several electrolyte exemplars with varying solvent and anion coordination strengths. Our findings demonstrate that solvents exhibiting especially strong coordination to Ca²⁺, such as triglyme, can inhibit reversible calcium deposition despite effective elimination of anion:Ca²⁺ coordination while solvents exhibiting more modest coordination strength, such as 1,2-dimethoxyethane, may enable deposition provided anion:Ca²⁺ coordination is substantially limited. These results reveal that the strength of coordination of both anion and solvent should be considered in the design of electrolytes for calcium batteries.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1644403

Alternate ID(s):: OSTI ID: 1756838

Report Number(s):: SAND2020--7560J; 687570

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 9 Vol. 3; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

Magnesium Borohydride: From Hydrogen Storage to Magnesium Battery Mohtadi, Rana; Matsui, Masaki; Arthur, Timothy S. Angewandte Chemie International Edition, Vol. 51, Issue 39, p. 9780-9783 https://doi.org/10.1002/anie.201204913	journal	August 2012
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
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
Effect of viscosity and volume on the specific conductivity of lithium salts in solvent mixtures Brouillette, Dany; Perron, Gérald; Desnoyers, Jacques E. Electrochimica Acta, Vol. 44, Issue 26 https://doi.org/10.1016/S0013-4686(99)00267-4	journal	September 1999
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi Computer Physics Communications, Vol. 167, Issue 2 https://doi.org/10.1016/j.cpc.2004.12.014	journal	April 2005
A review of electrolytes for lithium–sulphur batteries Scheers, Johan; Fantini, Sébastien; Johansson, Patrik Journal of Power Sources, Vol. 255 https://doi.org/10.1016/j.jpowsour.2014.01.023	journal	June 2014
Advanced rechargeable zinc-based batteries: Recent progress and future perspectives Li, Hongfei; Ma, Longtao; Han, Cuiping Nano Energy, Vol. 62 https://doi.org/10.1016/j.nanoen.2019.05.059	journal	August 2019
Achievements, Challenges, and Prospects of Calcium Batteries Arroyo-de Dompablo, M. Elena; Ponrouch, Alexandre; Johansson, Patrik Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00339	journal	October 2019
Determination of Mg ²⁺ Speciation in a TFSI ^– -Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy Watkins, Tylan; Buttry, Daniel A. The Journal of Physical Chemistry B, Vol. 119, Issue 23 https://doi.org/10.1021/acs.jpcb.5b00339	journal	June 2015
Solvation of Magnesium Ion in Triglyme-Based Electrolyte Solutions Kimura, Toshiki; Fujii, Kenta; Sato, Yoshiki The Journal of Physical Chemistry C, Vol. 119, Issue 33 https://doi.org/10.1021/acs.jpcc.5b04626	journal	August 2015
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
Role of Coordination Structure of Magnesium Ions on Charge and Discharge Behavior of Magnesium Alloy Electrode Hattori, Masashi; Yamamoto, Kentaro; Matsui, Masaki The Journal of Physical Chemistry C, Vol. 122, Issue 44 https://doi.org/10.1021/acs.jpcc.8b08558	journal	October 2018
Cation Solvation and Physicochemical Properties of Ca Battery Electrolytes Forero-Saboya, J. D.; Marchante, E.; Araujo, R. B. The Journal of Physical Chemistry C, Vol. 123, Issue 49 https://doi.org/10.1021/acs.jpcc.9b07308	journal	November 2019
Confession of a Magnesium Battery Bucur, Claudiu B.; Gregory, Thomas; Oliver, Allen G. The Journal of Physical Chemistry Letters, Vol. 6, Issue 18 https://doi.org/10.1021/acs.jpclett.5b01219	journal	August 2015
“Ion Solvation Spectra”: Free Energy Analysis of Solvation Structures of Multivalent Cations in Aprotic Solvents Baskin, Artem; Prendergast, David The Journal of Physical Chemistry Letters, Vol. 10, Issue 17 https://doi.org/10.1021/acs.jpclett.9b01569	journal	July 2019
Asymmetric Composition of Ionic Aggregates and the Origin of High Correlated Transference Number in Water-in-Salt Electrolytes Yu, Zhou; Curtiss, Larry A.; Winans, Randall E. The Journal of Physical Chemistry Letters, Vol. 11, Issue 4 https://doi.org/10.1021/acs.jpclett.9b03495	journal	January 2020
Understanding Ca Electrodeposition and Speciation Processes in Nonaqueous Electrolytes for Next-Generation Ca-Ion Batteries Ta, Kim; Zhang, Ruixian; Shin, Minjeong ACS Applied Materials & Interfaces, Vol. 11, Issue 24 https://doi.org/10.1021/acsami.9b04926	journal	May 2019
A Fluorinated Alkoxyaluminate Electrolyte for Magnesium-Ion Batteries Herb, Jake T.; Nist-Lund, Carl A.; Arnold, Craig B. ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00356	journal	November 2016
Reversible Calcium Plating and Stripping at Room Temperature Using a Borate Salt Shyamsunder, Abhinandan; Blanc, Lauren E.; Assoud, Abdeljalil ACS Energy Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsenergylett.9b01550	journal	August 2019
Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500049y	journal	October 2014
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
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
Enhanced Stability of the Carba- closo -dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design Hahn, Nathan T.; Seguin, Trevor J.; Lau, Ka-Cheong Journal of the American Chemical Society, Vol. 140, Issue 35 https://doi.org/10.1021/jacs.8b05967	journal	July 2018
Electrolyte Reactivity in the Double Layer in Mg Batteries: An Interface Potential-Dependent DFT Study Kopač Lautar, Anja; Bitenc, Jan; Rejec, Tomaž Journal of the American Chemical Society, Vol. 142, Issue 11 https://doi.org/10.1021/jacs.9b12474	journal	February 2020
Complex Nature of Ionic Coordination in Magnesium Ionic Liquid-Based Electrolytes: Solvates with Mobile Mg ²⁺ Cations Giffin, Guinevere A.; Moretti, Arianna; Jeong, Sangsik The Journal of Physical Chemistry C, Vol. 118, Issue 19 https://doi.org/10.1021/jp502354h	journal	May 2014
Solvate Structures and Spectroscopic Characterization of LiTFSI Electrolytes Seo, Daniel M.; Boyle, Paul D.; Sommer, Roger D. The Journal of Physical Chemistry B, Vol. 118, Issue 47 https://doi.org/10.1021/jp505006x	journal	September 2014
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
A Highly Reversible Lithium Metal Anode Park, Min Sik; Ma, Sang Bok; Lee, Dong Joon Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep03815	journal	January 2014
A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries Zhao-Karger, Zhirong; Gil Bardaji, Maria Elisa; Fuhr, Olaf Journal of Materials Chemistry A, Vol. 5, Issue 22 https://doi.org/10.1039/C7TA02237A	journal	January 2017
Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries Li, Zhenyou; Fuhr, Olaf; Fichtner, Maximilian Energy & Environmental Science, Vol. 12, Issue 12 https://doi.org/10.1039/C9EE01699F	journal	January 2019
The critical role of configurational flexibility in facilitating reversible reactive metal deposition from borohydride solutions Hahn, Nathan T.; Self, Julian; Seguin, Trevor J. Journal of Materials Chemistry A, Vol. 8, Issue 15 https://doi.org/10.1039/D0TA02502J	journal	January 2020
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
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
Escaping free-energy minima Laio, A.; Parrinello, M. Proceedings of the National Academy of Sciences, Vol. 99, Issue 20 https://doi.org/10.1073/pnas.202427399	journal	September 2002
A molecular dynamics method for simulations in the canonical ensemble Nosé, Shūichi Molecular Physics, Vol. 52, Issue 2 https://doi.org/10.1080/00268978400101201	journal	June 1984
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Separable dual-space Gaussian pseudopotentials Goedecker, S.; Teter, M.; Hutter, J. Physical Review B, Vol. 54, Issue 3 https://doi.org/10.1103/PhysRevB.54.1703	journal	July 1996
Relativistic separable dual-space Gaussian pseudopotentials from H to Rn Hartwigsen, C.; Goedecker, S.; Hutter, J. Physical Review B, Vol. 58, Issue 7 https://doi.org/10.1103/PhysRevB.58.3641	journal	August 1998
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
Efficient Exploration of Reactive Potential Energy Surfaces Using Car-Parrinello Molecular Dynamics Iannuzzi, Marcella; Laio, Alessandro; Parrinello, Michele Physical Review Letters, Vol. 90, Issue 23 https://doi.org/10.1103/PhysRevLett.90.238302	journal	June 2003
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Electrolyte Solutions with a Wide Electrochemical Window for Rechargeable Magnesium Batteries Mizrahi, Oren; Amir, Nir; Pollak, Elad Journal of The Electrochemical Society, Vol. 155, Issue 2, p. A103-A109 https://doi.org/10.1149/1.2806175	journal	January 2008
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
Electrolyte Solvation and Ionic Association II. Acetonitrile-Lithium Salt Mixtures: Highly Dissociated Salts Seo, Daniel M.; Borodin, Oleg; Han, Sang-Don Journal of The Electrochemical Society, Vol. 159, Issue 9 https://doi.org/10.1149/2.035209jes	journal	January 2012
Widening Electrochemical Window of Mg Salt by Weakly Coordinating Perfluoroalkoxyaluminate Anion for Mg Battery Electrolyte Lau, Ka-Cheong; Seguin, Trevor J.; Carino, Emily V. Journal of The Electrochemical Society, Vol. 166, Issue 8 https://doi.org/10.1149/2.0751908jes	journal	January 2019
Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles Seguin, Trevor J.; Hahn, Nathan T.; Zavadil, Kevin R. Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00175	journal	April 2019

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