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Title: Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

Abstract

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures,more » exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [3];  [2];  [1];  [3];  [1];  [1]
  1. Univ. of Illinois, Urbana, IL (United States)
  2. Univ. of Bielefeld, Bielefeld (Germany)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1235306
Report Number(s):
SAND-2015-4340J
Journal ID: ISSN 1944-8244; 590456
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 7; Journal Issue: 33; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; rechargeable magnesium battery; magnesium anode; passivation; corrosion; columnar growth

Citation Formats

Wetzel, David J., Malone, Marvin A., Haasch, Richard T., Meng, Yifei, Vieker, Henning, Hahn, Nathan, Golzhauser, Armin, Zuo, Jian-Min, Zavadil, Kevin R., Gewirth, Andrew A., and Nuzzo, Ralph G. Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling. United States: N. p., 2015. Web. doi:10.1021/acsami.5b04487.
Wetzel, David J., Malone, Marvin A., Haasch, Richard T., Meng, Yifei, Vieker, Henning, Hahn, Nathan, Golzhauser, Armin, Zuo, Jian-Min, Zavadil, Kevin R., Gewirth, Andrew A., & Nuzzo, Ralph G. Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling. United States. https://doi.org/10.1021/acsami.5b04487
Wetzel, David J., Malone, Marvin A., Haasch, Richard T., Meng, Yifei, Vieker, Henning, Hahn, Nathan, Golzhauser, Armin, Zuo, Jian-Min, Zavadil, Kevin R., Gewirth, Andrew A., and Nuzzo, Ralph G. 2015. "Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling". United States. https://doi.org/10.1021/acsami.5b04487. https://www.osti.gov/servlets/purl/1235306.
@article{osti_1235306,
title = {Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling},
author = {Wetzel, David J. and Malone, Marvin A. and Haasch, Richard T. and Meng, Yifei and Vieker, Henning and Hahn, Nathan and Golzhauser, Armin and Zuo, Jian-Min and Zavadil, Kevin R. and Gewirth, Andrew A. and Nuzzo, Ralph G.},
abstractNote = {Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.},
doi = {10.1021/acsami.5b04487},
url = {https://www.osti.gov/biblio/1235306}, journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 33,
volume = 7,
place = {United States},
year = {Mon Aug 10 00:00:00 EDT 2015},
month = {Mon Aug 10 00:00:00 EDT 2015}
}

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Works referencing / citing this record:

Morphology evolution of magnesium facets: DFT and KMC simulations
journal, January 2019


Fervent Hype behind Magnesium Batteries: An Open Call to Synthetic Chemists-Electrolytes and Cathodes Needed
journal, August 2017


Mg Cathode Materials and Electrolytes for Rechargeable Mg Batteries: A Review
journal, January 2019