Rationalizing Calcium Electrodeposition Behavior by Quantifying Ethereal Solvation Effects on Ca2+ Coordination in Well-Dissociated Electrolytes
Abstract
Ca-ion electrochemical systems have been pushed to the forefront of recent multivalent energy storage advances due to their use of earth-abundant redox materials and their high theoretical specific densities in relation to monovalent or even other more widely explored multivalent-charge carriers. However, significant pitfalls in metal plating and stripping arise from electrolyte decomposition and can be related to the coordination environment around Ca2+ with both the negatively charged anion and the organic–aprotic solvent. Here, we apply multiple spectroscopic techniques in conjunction with density functional theory to evaluate the coordination environment of Ca2+ across a class of ethereal solvents. Through the combination of X-ray absorption fine structure and time-dependent density functional theory, descriptive measures of the local geometry, coordination, and electronic structure of Ca–ethereal complexes provide distinct structural trends depending on the extent of the Ca2+–solvent interaction. Finally, we correlate these findings with electrochemical measurements of calcium tetrakis(hexafluoroisopropoxy)borate (CaBHFIP2) salts dissolved within this class of solvents to provide insight into the preferred structural configuration of Ca2+ electrolytic solutions for optimized electrochemical plating and stripping.
- Authors:
-
[1];
[1];
[2];
[4];
[2];
[1];
[1]
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Argonne National Lab. (ANL), Argonne, 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)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1760450
- Alternate Identifier(s):
- OSTI ID: 1766523; OSTI ID: 1777118
- Report Number(s):
- SAND-2021-0182J
Journal ID: ISSN 1945-7111; 693235
- Grant/Contract Number:
- AC04-94AL85000; AC02-06CH11357; NA0003525; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society (Online)
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society (Online); Journal Volume: 167; Journal Issue: 16; Journal ID: ISSN 1945-7111
- Publisher:
- IOP Publishing
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Driscoll, Darren M., Dandu, Naveen K., Hahn, Nathan T., Seguin, Trevor J., Persson, Kristin A., Zavadil, Kevin R., Curtiss, Larry A., and Balasubramanian, Mahalingam. Rationalizing Calcium Electrodeposition Behavior by Quantifying Ethereal Solvation Effects on Ca2+ Coordination in Well-Dissociated Electrolytes. United States: N. p., 2020.
Web. doi:10.1149/1945-7111/abc8e3.
Driscoll, Darren M., Dandu, Naveen K., Hahn, Nathan T., Seguin, Trevor J., Persson, Kristin A., Zavadil, Kevin R., Curtiss, Larry A., & Balasubramanian, Mahalingam. Rationalizing Calcium Electrodeposition Behavior by Quantifying Ethereal Solvation Effects on Ca2+ Coordination in Well-Dissociated Electrolytes. United States. https://doi.org/10.1149/1945-7111/abc8e3
Driscoll, Darren M., Dandu, Naveen K., Hahn, Nathan T., Seguin, Trevor J., Persson, Kristin A., Zavadil, Kevin R., Curtiss, Larry A., and Balasubramanian, Mahalingam. Mon .
"Rationalizing Calcium Electrodeposition Behavior by Quantifying Ethereal Solvation Effects on Ca2+ Coordination in Well-Dissociated Electrolytes". United States. https://doi.org/10.1149/1945-7111/abc8e3. https://www.osti.gov/servlets/purl/1760450.
@article{osti_1760450,
title = {Rationalizing Calcium Electrodeposition Behavior by Quantifying Ethereal Solvation Effects on Ca2+ Coordination in Well-Dissociated Electrolytes},
author = {Driscoll, Darren M. and Dandu, Naveen K. and Hahn, Nathan T. and Seguin, Trevor J. and Persson, Kristin A. and Zavadil, Kevin R. and Curtiss, Larry A. and Balasubramanian, Mahalingam},
abstractNote = {Ca-ion electrochemical systems have been pushed to the forefront of recent multivalent energy storage advances due to their use of earth-abundant redox materials and their high theoretical specific densities in relation to monovalent or even other more widely explored multivalent-charge carriers. However, significant pitfalls in metal plating and stripping arise from electrolyte decomposition and can be related to the coordination environment around Ca2+ with both the negatively charged anion and the organic–aprotic solvent. Here, we apply multiple spectroscopic techniques in conjunction with density functional theory to evaluate the coordination environment of Ca2+ across a class of ethereal solvents. Through the combination of X-ray absorption fine structure and time-dependent density functional theory, descriptive measures of the local geometry, coordination, and electronic structure of Ca–ethereal complexes provide distinct structural trends depending on the extent of the Ca2+–solvent interaction. Finally, we correlate these findings with electrochemical measurements of calcium tetrakis(hexafluoroisopropoxy)borate (CaBHFIP2) salts dissolved within this class of solvents to provide insight into the preferred structural configuration of Ca2+ electrolytic solutions for optimized electrochemical plating and stripping.},
doi = {10.1149/1945-7111/abc8e3},
journal = {Journal of the Electrochemical Society (Online)},
number = 16,
volume = 167,
place = {United States},
year = {Mon Nov 30 00:00:00 EST 2020},
month = {Mon Nov 30 00:00:00 EST 2020}
}
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