Ta, Kim and See, Kimberly A. and Gewirth, Andrew A. (2018) Elucidating Zn and Mg Electrodeposition Mechanisms in Nonaqueous Electrolytes for Next-Generation Metal Batteries. Journal of Physical Chemistry C, 122 (25). pp. 13790-13796. ISSN 1932-7447. doi:10.1021/acs.jpcc.8b00835. https://resolver.caltech.edu/CaltechAUTHORS:20180608-085634860
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Abstract
Cyclic voltammetry and linear sweep voltammetry with an ultramicroelectrode (UME) were employed to study Zn and Mg electrodeposition and the corresponding mechanistic pathways. CVs obtained at a Pt UME for Zn electroreduction from a trifluoromethylsulfonyl imide (TFSI^–) and chloride-containing electrolyte in acetonitrile exhibit current densities that are scan rate independent, as expected for a simple electron transfer at a UME. However, CVs obtained from three different Mg-containing electrolytes in THF exhibit an inverse dependence between scan rate and current density. COMSOL-based simulation suggests that Zn electrodeposition proceeds via a simple one-step, two-electron transfer (E) mechanism. Alternatively, the Mg results are best described by invoking a chemical step prior to electron transfer: a chemical–electrochemical (CE) mechanism. The chemical step exhibits an activation energy of 51 kJ/mol. This chemical step is likely the disproportionation of the chloro-bridged dimer [Mg_2(μ–Cl)_3·6THF]^+ present in active electrodeposition solutions. Our work shows that Mg deposition kinetics can be improved by way of increased temperature.
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| Additional Information: | © 2018 American Chemical Society. Received: January 24, 2018; Revised: February 25, 2018; Published: February 26, 2018. This work was supported as part of the Joint Center for Energy Storage, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Research. The authors thank Dr. Sang-Don Han for assistance with drying the Zn(TFSI)_2 compound, Tabitha Miller and Prof. Alison Fout for assistance with drying the solvents, and Dr. Burton H. Simpson and Dr. Zachary J. Barton for initial assistance with COMSOL simulation. K.A.S. acknowledges postdoctoral funding from the St. Elmo Brady Future Faculty Postdoctoral Fellowship. This work was carried out in part at the Visualization Laboratory in the Beckman Institute, University of Illinois at Urbana–Champaign. The authors declare no competing financial interest. | |||||||||
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| Issue or Number: | 25 | |||||||||
| DOI: | 10.1021/acs.jpcc.8b00835 | |||||||||
| Record Number: | CaltechAUTHORS:20180608-085634860 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180608-085634860 | |||||||||
| Official Citation: | Elucidating Zn and Mg Electrodeposition Mechanisms in Nonaqueous Electrolytes for Next-Generation Metal Batteries. Kim Ta, Kimberly A. See, and Andrew A. Gewirth. The Journal of Physical Chemistry C 2018 122 (25), 13790-13796. DOI: 10.1021/acs.jpcc.8b00835 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 86907 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 08 Jun 2018 16:08 | |||||||||
| Last Modified: | 15 Nov 2021 20:43 |
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