Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes
Abstract
Ion interactions strongly determine the solvation environments of multivalent electrolytes even at concentrations below that required for practical battery-based energy storage. This statement is particularly true of electrolytes utilizing ethereal solvents due to their low dielectric constants. These solvents are among the most commonly used for multivalent batteries based on reactive metals (Mg, Ca) due to their reductive stability. Recent developments in multivalent electrolyte design have produced a variety of new salts for Mg2+ and Ca2+ that test the limits of weak coordination strength and oxidative stability. Such electrolytes have great potential for enabling full-cell cycling of batteries based on these working ions. However, the ion interactions in these electrolytes exhibit significant and non-intuitive concentration relationships. In this work, we investigate a promising exemplar, calcium tetrakis(hexafluoroisopropoxy)borate (Ca(BHFIP)2), in the ethereal solvents 1,2-dimethoxyethane (DME) and tetrahydrofuran (THF) across a concentration range of several orders of magnitude. Surprisingly, we find that effective salt dissociation is lower at relatively dilute concentrations (e.g. 0.01 M) than at higher concentrations (e.g. 0.2 M). Combined experimental and computational dielectric and X-ray spectroscopic analyses of the changes occurring in the Ca2+ solvation environment across these concentration regimes reveals a progressive transition from well-defined solvent-separated ion pairs tomore »
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Material, Physical and Chemical Sciences Center
- Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
- Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Lemont, IL (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1838182
- Alternate Identifier(s):
- OSTI ID: 1835926
- Report Number(s):
- SAND-2021-15819J
Journal ID: ISSN 1463-9076; 702247
- Grant/Contract Number:
- NA0003525; AC02-06CH11357; AC02-05CH11231; Through the Joint Center for Energy Storage Research
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 24; Journal Issue: 2; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Hahn, Nathan T., Self, Julian, Driscoll, Darren M., Dandu, Naveen, Han, Kee Sung, Murugesan, Vijayakumar, Mueller, Karl T., Curtiss, Larry A., Balasubramanian, Mahalingam, Persson, Kristin A., and Zavadil, Kevin R. Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes. United States: N. p., 2021.
Web. doi:10.1039/d1cp04370f.
Hahn, Nathan T., Self, Julian, Driscoll, Darren M., Dandu, Naveen, Han, Kee Sung, Murugesan, Vijayakumar, Mueller, Karl T., Curtiss, Larry A., Balasubramanian, Mahalingam, Persson, Kristin A., & Zavadil, Kevin R. Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes. United States. https://doi.org/10.1039/d1cp04370f
Hahn, Nathan T., Self, Julian, Driscoll, Darren M., Dandu, Naveen, Han, Kee Sung, Murugesan, Vijayakumar, Mueller, Karl T., Curtiss, Larry A., Balasubramanian, Mahalingam, Persson, Kristin A., and Zavadil, Kevin R. Wed .
"Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes". United States. https://doi.org/10.1039/d1cp04370f. https://www.osti.gov/servlets/purl/1838182.
@article{osti_1838182,
title = {Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes},
author = {Hahn, Nathan T. and Self, Julian and Driscoll, Darren M. and Dandu, Naveen and Han, Kee Sung and Murugesan, Vijayakumar and Mueller, Karl T. and Curtiss, Larry A. and Balasubramanian, Mahalingam and Persson, Kristin A. and Zavadil, Kevin R.},
abstractNote = {Ion interactions strongly determine the solvation environments of multivalent electrolytes even at concentrations below that required for practical battery-based energy storage. This statement is particularly true of electrolytes utilizing ethereal solvents due to their low dielectric constants. These solvents are among the most commonly used for multivalent batteries based on reactive metals (Mg, Ca) due to their reductive stability. Recent developments in multivalent electrolyte design have produced a variety of new salts for Mg2+ and Ca2+ that test the limits of weak coordination strength and oxidative stability. Such electrolytes have great potential for enabling full-cell cycling of batteries based on these working ions. However, the ion interactions in these electrolytes exhibit significant and non-intuitive concentration relationships. In this work, we investigate a promising exemplar, calcium tetrakis(hexafluoroisopropoxy)borate (Ca(BHFIP)2), in the ethereal solvents 1,2-dimethoxyethane (DME) and tetrahydrofuran (THF) across a concentration range of several orders of magnitude. Surprisingly, we find that effective salt dissociation is lower at relatively dilute concentrations (e.g. 0.01 M) than at higher concentrations (e.g. 0.2 M). Combined experimental and computational dielectric and X-ray spectroscopic analyses of the changes occurring in the Ca2+ solvation environment across these concentration regimes reveals a progressive transition from well-defined solvent-separated ion pairs to de-correlated free ions. This transition in ion correlation results in improvements in both conductivity and calcium cycling stability with increased salt concentration. Comparison with previous findings involving more strongly associating salts highlights the generality of this phenomenon, leading to important insight into controlling ion interactions in ether-based multivalent battery electrolytes.},
doi = {10.1039/d1cp04370f},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 2,
volume = 24,
place = {United States},
year = {Wed Dec 15 00:00:00 EST 2021},
month = {Wed Dec 15 00:00:00 EST 2021}
}
Works referenced in this record:
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
Direct Contact versus Solvent-Shared Ion Pairs in NiCl 2 Electrolytes Monitored by Multiplet Effects at Ni(II) L Edge X-ray Absorption
journal, April 2007
- Aziz, Emad F.; Eisebitt, Stefan; de Groot, Frank
- The Journal of Physical Chemistry B, Vol. 111, Issue 17
Cation Solvation and Physicochemical Properties of Ca Battery Electrolytes
journal, November 2019
- Forero-Saboya, J. D.; Marchante, E.; Araujo, R. B.
- The Journal of Physical Chemistry C, Vol. 123, Issue 49
Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges
journal, February 2017
- Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C.
- Chemical Reviews, Vol. 117, Issue 5
Force Field Benchmark of Organic Liquids: Density, Enthalpy of Vaporization, Heat Capacities, Surface Tension, Isothermal Compressibility, Volumetric Expansion Coefficient, and Dielectric Constant
journal, December 2011
- Caleman, Carl; van Maaren, Paul J.; Hong, Minyan
- Journal of Chemical Theory and Computation, Vol. 8, Issue 1
The ORCA program system: The ORCA program system
journal, June 2011
- Neese, Frank
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
The Interplay between Salt Association and the Dielectric Properties of Low Permittivity Electrolytes: The Case of LiPF 6 and LiAsF 6 in Dimethyl Carbonate
journal, January 2018
- Self, Julian; Wood, Brandon M.; Rajput, Nav Nidhi
- The Journal of Physical Chemistry C, Vol. 122, Issue 4
Evaluation and Reparametrization of the OPLS-AA Force Field for Proteins via Comparison with Accurate Quantum Chemical Calculations on Peptides †
journal, July 2001
- Kaminski, George A.; Friesner, Richard A.; Tirado-Rives, Julian
- The Journal of Physical Chemistry B, Vol. 105, Issue 28
Tuning the Reversibility of Mg Anodes via Controlled Surface Passivation by H 2 O/Cl – in Organic Electrolytes
journal, October 2016
- Connell, Justin G.; Genorio, Bostjan; Lopes, Pietro Papa
- Chemistry of Materials, Vol. 28, Issue 22
Optimizing Calcium Electrolytes by Solvent Manipulation for Calcium Batteries
journal, April 2020
- Nielson, Kevin V.; Luo, Jian; Liu, T. Leo
- Batteries & Supercaps, Vol. 3, Issue 8
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers
journal, September 2015
- Abraham, Mark James; Murtola, Teemu; Schulz, Roland
- SoftwareX, Vol. 1-2
Scaling Analysis of the Screening Length in Concentrated Electrolytes
journal, July 2017
- Lee, Alpha A.; Perez-Martinez, Carla S.; Smith, Alexander M.
- Physical Review Letters, Vol. 119, Issue 2
Reversible Calcium Plating and Stripping at Room Temperature Using a Borate Salt
journal, August 2019
- Shyamsunder, Abhinandan; Blanc, Lauren E.; Assoud, Abdeljalil
- ACS Energy Letters, Vol. 4, Issue 9
A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 2
Stability of Calcium Ion Battery Electrolytes: Predictions from Ab Initio Molecular Dynamics Simulations
journal, March 2021
- Yamijala, Sharma S. R. K. C.; Kwon, Hyuna; Guo, Juchen
- ACS Applied Materials & Interfaces, Vol. 13, Issue 11
Understanding the Effects of Concentration on the Solvation Structure of Ca 2+ in Aqueous Solution. I: The Perspective on Local Structure from EXAFS and XANES
journal, June 2003
- Fulton, John L.; Heald, Steve M.; Badyal, Yaspal S.
- The Journal of Physical Chemistry A, Vol. 107, Issue 23
Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes
journal, April 2018
- Wildman, Andrew; Martinez-Baez, Ernesto; Fulton, John
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 10
Widening Electrochemical Window of Mg Salt by Weakly Coordinating Perfluoroalkoxyaluminate Anion for Mg Battery Electrolyte
journal, January 2019
- Lau, Ka-Cheong; Seguin, Trevor J.; Carino, Emily V.
- Journal of The Electrochemical Society, Vol. 166, Issue 8
A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics
journal, August 1997
- Cancès, E.; Mennucci, B.; Tomasi, J.
- The Journal of Chemical Physics, Vol. 107, Issue 8
Interactions and dynamics in electrolyte solutions by dielectric spectroscopy
journal, January 2009
- Buchner, Richard; Hefter, Glenn
- Physical Chemistry Chemical Physics, Vol. 11, Issue 40
Achievements, Challenges, and Prospects of Calcium Batteries
journal, October 2019
- Arroyo-de Dompablo, M. Elena; Ponrouch, Alexandre; Johansson, Patrik
- Chemical Reviews
Plating and stripping calcium in an organic electrolyte
journal, November 2017
- Wang, Da; Gao, Xiangwen; Chen, Yuhui
- Nature Materials, Vol. 17, Issue 1
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008
- Chai, Jeng-Da; Head-Gordon, Martin
- Physical Chemistry Chemical Physics, Vol. 10, Issue 44
Natural transition orbitals
journal, March 2003
- Martin, Richard L.
- The Journal of Chemical Physics, Vol. 118, Issue 11
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
- Weigend, Florian; Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996
- Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian
- Journal of the American Chemical Society, Vol. 118, Issue 45
Polarizable continuum model: Polarizable continuum model
journal, January 2012
- Mennucci, Benedetta
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 3
Canonical sampling through velocity rescaling
journal, January 2007
- Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
- The Journal of Chemical Physics, Vol. 126, Issue 1
Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries
journal, January 2019
- Li, Zhenyou; Fuhr, Olaf; Fichtner, Maximilian
- Energy & Environmental Science, Vol. 12, Issue 12
Ion Pairing and Redissociaton in Low-Permittivity Electrolytes for Multivalent Battery Applications
journal, February 2020
- Self, Julian; Hahn, Nathan T.; Fong, Kara D.
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 6
Microelectrode studies of reversible Mg deposition in THF solutions containing complexes of alkylaluminum chlorides and dialkylmagnesium
journal, March 2005
- Viestfrid, Yu.; Levi, M. D.; Gofer, Y.
- Journal of Electroanalytical Chemistry, Vol. 576, Issue 2, p. 183-195
Molecular dynamics with coupling to an external bath
journal, October 1984
- Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
- The Journal of Chemical Physics, Vol. 81, Issue 8
Quantifying Species Populations in Multivalent Borohydride Electrolytes
journal, April 2021
- Hahn, Nathan T.; Self, Julian; Han, Kee Sung
- The Journal of Physical Chemistry B, Vol. 125, Issue 14
Composition of complex aluminum hydrides and borohydrides, as inferred from conductance, molecular association, and spectroscopic studies
journal, May 1973
- Ashby, E. C.; Dobbs, Frank R.; Hopkins, Harry P.
- Journal of the American Chemical Society, Vol. 95, Issue 9
Dielectric Relaxation of Aqueous NaCl Solutions
journal, January 1999
- Buchner, Richard; Hefter, Glenn T.; May, Peter M.
- The Journal of Physical Chemistry A, Vol. 103, Issue 1
Ion Pairing and Diffusion in Magnesium Electrolytes Based on Magnesium Borohydride
journal, December 2017
- Samuel, Devon; Steinhauser, Carl; Smith, Jeffrey G.
- ACS Applied Materials & Interfaces, Vol. 9, Issue 50
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998
- Barone, Vincenzo; Cossi, Maurizio
- The Journal of Physical Chemistry A, Vol. 102, Issue 11
Electrolyte Solutions with a Wide Electrochemical Window for Rechargeable Magnesium Batteries
journal, January 2008
- Mizrahi, Oren; Amir, Nir; Pollak, Elad
- Journal of The Electrochemical Society, Vol. 155, Issue 2, p. A103-A109
Properties of Electrolytic Solutions. IV. The Conductance Minimum and the Formation of Triple Ions Due to the Action of Coulomb Forces 1
journal, June 1933
- Fuoss, Raymond M.; Kraus, Charles A.
- Journal of the American Chemical Society, Vol. 55, Issue 6
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics
journal, February 2015
- Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya
- Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420
A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries
journal, January 2017
- Zhao-Karger, Zhirong; Gil Bardaji, Maria Elisa; Fuhr, Olaf
- Journal of Materials Chemistry A, Vol. 5, Issue 22
The Possible Presence of Triple Ions in Electrolyte Solutions of Low Dielectric Permittivity
journal, May 2008
- Petrucci, Sergio; Masiker, Marilyn C.; Eyring, Edward M.
- Journal of Solution Chemistry, Vol. 37, Issue 7
PACKMOL: A package for building initial configurations for molecular dynamics simulations
journal, October 2009
- Martínez, L.; Andrade, R.; Birgin, E. G.
- Journal of Computational Chemistry, Vol. 30, Issue 13
Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes
journal, December 2003
- Staroverov, Viktor N.; Scuseria, Gustavo E.; Tao, Jianmin
- The Journal of Chemical Physics, Vol. 119, Issue 23
Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes
journal, July 2020
- Hahn, Nathan T.; Driscoll, Darren M.; Yu, Zhou
- ACS Applied Energy Materials, Vol. 3, Issue 9
Effect of Concentration Changes on Permittivity of Electrolyte Solutions
journal, February 1968
- Cavell, E. A. S.; Knight, P. C.
- Zeitschrift für Physikalische Chemie, Vol. 57, Issue 3_6
Investigation of Fundamental Transport Properties and Thermodynamics in Diglyme−Salt Solutions
journal, November 2006
- Petrowsky, Matt; Frech, Roger; Suarez, Sophia N.
- The Journal of Physical Chemistry B, Vol. 110, Issue 46
Rationalizing Calcium Electrodeposition Behavior by Quantifying Ethereal Solvation Effects on Ca 2+ Coordination in Well-Dissociated Electrolytes
journal, December 2020
- Driscoll, Darren M.; Dandu, Naveen K.; Hahn, Nathan T.
- Journal of The Electrochemical Society, Vol. 167, Issue 16
A Fluorinated Alkoxyaluminate Electrolyte for Magnesium-Ion Batteries
journal, November 2016
- Herb, Jake T.; Nist-Lund, Carl A.; Arnold, Craig B.
- ACS Energy Letters, Vol. 1, Issue 6
Complexity in “Simple” Electrolyte Solutions: Ion Pairing in MgSO 4 (aq)
journal, February 2004
- Buchner, Richard; Chen, Ting; Hefter, Glenn
- The Journal of Physical Chemistry B, Vol. 108, Issue 7