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

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

Journal Article · Thu Dec 04 00:00:00 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.

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

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

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1235247

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

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

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 139 works

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

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

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