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Title: Electrolytic conditioning of a magnesium aluminum chloride complex for reversible magnesium deposition

Abstract

We describe in this report the electrochemistry of Mg deposition and dissolution from the magnesium aluminum chloride complex (MACC). The results define the requirements for reversible Mg deposition and definitively establish that voltammetric cycling of the electrolyte significantly alters its composition and performance. Elemental analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (SEM-EDS) results demonstrate that irreversible Mg and Al deposits form during early cycles. Electrospray ionization-mass spectrometry (ESI-MS) data show that inhibitory oligomers develop in THF-based solutions. These oligomers form via the well-established mechanism of a cationic ring-opening polymerization of THF during the initial synthesis of the MACC and under resting conditions. In contrast, MACC solutions in 1,2-dimethoxyethane (DME), an acyclic solvent, do not evolve as dramatically at open circuit potential. Furthermore, we propose a mechanism describing how the conditioning process of the MACC in THF improves its performance by both tuning the Mg:Al stoichiometry and eliminating oligomers.

Authors:
 [1];  [1];  [2];  [1];  [1]
  1. Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)
  2. 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) (SC-22)
OSTI Identifier:
1235247
Report Number(s):
SAND-2014-17888J
Journal ID: ISSN 1932-7447; 537642
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 118; Journal Issue: 48; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mg-ion battery; Mg electrodeposition; magnesium aluminum chloride complex; ring-opening polymerization

Citation Formats

Barile, Christopher J., Barile, Elizabeth C., Zavadil, Kevin R., Nuzzo, Ralph G., and Gewirth, Andrew A. Electrolytic conditioning of a magnesium aluminum chloride complex for reversible magnesium deposition. United States: N. p., 2014. Web. doi:10.1021/jp506951b.
Barile, Christopher J., Barile, Elizabeth C., Zavadil, Kevin R., Nuzzo, Ralph G., & Gewirth, Andrew A. Electrolytic conditioning of a magnesium aluminum chloride complex for reversible magnesium deposition. United States. doi:10.1021/jp506951b.
Barile, Christopher J., Barile, Elizabeth C., Zavadil, Kevin R., Nuzzo, Ralph G., and Gewirth, Andrew A. Thu . "Electrolytic conditioning of a magnesium aluminum chloride complex for reversible magnesium deposition". United States. doi:10.1021/jp506951b. https://www.osti.gov/servlets/purl/1235247.
@article{osti_1235247,
title = {Electrolytic conditioning of a magnesium aluminum chloride complex for reversible magnesium deposition},
author = {Barile, Christopher J. and Barile, Elizabeth C. and Zavadil, Kevin R. and Nuzzo, Ralph G. and Gewirth, Andrew A.},
abstractNote = {We describe in this report the electrochemistry of Mg deposition and dissolution from the magnesium aluminum chloride complex (MACC). The results define the requirements for reversible Mg deposition and definitively establish that voltammetric cycling of the electrolyte significantly alters its composition and performance. Elemental analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (SEM-EDS) results demonstrate that irreversible Mg and Al deposits form during early cycles. Electrospray ionization-mass spectrometry (ESI-MS) data show that inhibitory oligomers develop in THF-based solutions. These oligomers form via the well-established mechanism of a cationic ring-opening polymerization of THF during the initial synthesis of the MACC and under resting conditions. In contrast, MACC solutions in 1,2-dimethoxyethane (DME), an acyclic solvent, do not evolve as dramatically at open circuit potential. Furthermore, we propose a mechanism describing how the conditioning process of the MACC in THF improves its performance by both tuning the Mg:Al stoichiometry and eliminating oligomers.},
doi = {10.1021/jp506951b},
journal = {Journal of Physical Chemistry. C},
number = 48,
volume = 118,
place = {United States},
year = {2014},
month = {12}
}

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Cited by: 46 works
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Works referencing / citing this record:

The Role of MgCl 2 as a Lewis Base in ROMgCl-MgCl 2 Electrolytes for Magnesium-Ion Batteries
journal, February 2016


Electrochemical-Conditioning-Free and Water-Resistant Hybrid AlCl 3 /MgCl 2 /Mg(TFSI) 2 Electrolytes for Rechargeable Magnesium Batteries
journal, February 2019

  • He, Yishi; Li, Qi; Yang, Lanlan
  • Angewandte Chemie International Edition, Vol. 58, Issue 23
  • DOI: 10.1002/anie.201812824

Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries
journal, June 2019

  • Moss, Jared B.; Zhang, Liping; Nielson, Kevin V.
  • Batteries & Supercaps, Vol. 2, Issue 9
  • DOI: 10.1002/batt.201900029

A novel magnesium electrolyte containing a magnesium bis(diisopropyl)amide–magnesium chloride complex for rechargeable magnesium batteries
journal, January 2019

  • Yang, Yuanying; Qiu, Yixiang; NuLi, Yanna
  • Journal of Materials Chemistry A, Vol. 7, Issue 31
  • DOI: 10.1039/c9ta05769b

Electrochemical-Conditioning-Free and Water-Resistant Hybrid AlCl 3 /MgCl 2 /Mg(TFSI) 2 Electrolytes for Rechargeable Magnesium Batteries
journal, February 2019

  • He, Yishi; Li, Qi; Yang, Lanlan
  • Angewandte Chemie International Edition, Vol. 58, Issue 23
  • DOI: 10.1002/anie.201812824

Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries
journal, June 2019

  • Moss, Jared B.; Zhang, Liping; Nielson, Kevin V.
  • Batteries & Supercaps, Vol. 2, Issue 9
  • DOI: 10.1002/batt.201900029

The Role of MgCl 2 as a Lewis Base in ROMgCl-MgCl 2 Electrolytes for Magnesium-Ion Batteries
journal, February 2016


A novel magnesium electrolyte containing a magnesium bis(diisopropyl)amide–magnesium chloride complex for rechargeable magnesium batteries
journal, January 2019

  • Yang, Yuanying; Qiu, Yixiang; NuLi, Yanna
  • Journal of Materials Chemistry A, Vol. 7, Issue 31
  • DOI: 10.1039/c9ta05769b