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

Barile, Christopher J.; Barile, Elizabeth C.; Zavadil, Kevin R.; Nuzzo, Ralph G.; Gewirth, Andrew A.

doi:10.1021/jp506951b

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

Journal Article · Thu Dec 04 04:00:00 EST 2014 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp506951b· OSTI ID:1235247

Barile, Christopher J. ^[1]; Barile, Elizabeth C. ^[1]; Zavadil, Kevin R. ^[2]; Nuzzo, Ralph G. ^[1]; Gewirth, Andrew A. ^[1]

Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1235247

Report Number(s):: SAND--2014-17888J; 537642

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 48 Vol. 118; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Mg electrodeposition
Mg-ion battery
magnesium aluminum chloride complex
ring-opening polymerization

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

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References (21)

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