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 · Wed Dec 03 23:00:00 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 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

References (21)

Die Polymerisation des Tetrahydrofurans Meerwein, H.; Delfs, D.; Morschel, H. Angewandte Chemie, Vol. 72, Issue 24 https://doi.org/10.1002/ange.19600722402	journal	December 1960
Der Chelateffekt Schwarzenbach, G. Helvetica Chimica Acta, Vol. 35, Issue 7 https://doi.org/10.1002/hlca.19520350721	journal	December 1952
Lithium-Ion Batteries Yoshio, Masaki; Brodd, Ralph J.; Kozawa, Akiya Springer New York, NY https://doi.org/10.1007/978-0-387-34445-4	book	January 2009
Electrode kinetics of the aluminium deposition from tetrahydrofuran electrolytes Eckert, J.; Galova, M. Electrochimica Acta, Vol. 26, Issue 8 https://doi.org/10.1016/0013-4686(81)85094-3	journal	August 1981
A short review on the comparison between Li battery systems and rechargeable magnesium battery technology Aurbach, D.; Gofer, Y.; Lu, Z. Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00585-7	journal	July 2001
Synthesis and crystal structure of [Mg3Cl5(Et2O)6]+[Me2SbI2]− Zhang, Wu; Hu, Ji-Ping; Ding, Xiao-Feng Inorganic Chemistry Communications, Vol. 6, Issue 9 https://doi.org/10.1016/S1387-7003(03)00221-1	journal	September 2003
Rechargeable magnesium battery: Current status and key challenges for the future Saha, Partha; Datta, Moni Kanchan; Velikokhatnyi, Oleg I. Progress in Materials Science, Vol. 66 https://doi.org/10.1016/j.pmatsci.2014.04.001	journal	October 2014
Drying of Organic Solvents: Quantitative Evaluation of the Efficiency of Several Desiccants Williams, D. Bradley G.; Lawton, Michelle The Journal of Organic Chemistry, Vol. 75, Issue 24 https://doi.org/10.1021/jo101589h	journal	December 2010
Effect of Electrolytic Properties of a Magnesium Organohaloaluminate Electrolyte on Magnesium Deposition Benmayza, Aadil; Ramanathan, Mayandi; Arthur, Timothy S. The Journal of Physical Chemistry C, Vol. 117, Issue 51, p. 26881-26888 https://doi.org/10.1021/jp4077068	journal	December 2013
Investigating the Reversibility of in Situ Generated Magnesium Organohaloaluminates for Magnesium Deposition and Dissolution Barile, Christopher J.; Spatney, Russell; Zavadil, Kevin R. The Journal of Physical Chemistry C, Vol. 118, Issue 20 https://doi.org/10.1021/jp503506c	journal	May 2014
A Single-Crystal Model for MgCl ₂ –Electron Donor Support Materials: [Mg ₃ Cl ₅ (THF) ₄ Bu] ₂ (Bu = n -Butyl) Pirinen, Sami; Koshevoy, Igor O.; Denifl, Peter Organometallics, Vol. 32, Issue 15 https://doi.org/10.1021/om400407p	journal	July 2013
Prototype systems for rechargeable magnesium batteries Aurbach, D.; Lu, Z.; Schechter, A. Nature, Vol. 407, Issue 6805, p. 724-727 https://doi.org/10.1038/35037553	journal	October 2000
Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries Doe, Robert E.; Han, Ruoban; Hwang, Jaehee Chemical Communications, Vol. 50, Issue 2, p. 243-245 https://doi.org/10.1039/C3CC47896C	journal	January 2014
Mg rechargeable batteries: an on-going challenge Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279 https://doi.org/10.1039/c3ee40871j	journal	January 2013
A facile approach using MgCl2 to formulate high performance Mg2+ electrolytes for rechargeable Mg batteries Liu, Tianbiao; Shao, Yuyan; Li, Guosheng Journal of Materials Chemistry A, Vol. 2, Issue 10 https://doi.org/10.1039/c3ta14825d	journal	January 2014
Magnesium Deposition and Dissolution Processes in Ethereal Grignard Salt Solutions Using Simultaneous EQCM-EIS and In Situ FTIR Spectroscopy Aurbach, Doron Electrochemical and Solid-State Letters, Vol. 3, Issue 1 https://doi.org/10.1149/1.1390949	journal	January 1999
Nonaqueous Electrochemistry of Magnesium Gregory, Thomas D.; Hoffman, Ronald J.; Winterton, Richard C. Journal of The Electrochemical Society, Vol. 137, Issue 3, p. 775-780 https://doi.org/10.1149/1.2086553	journal	January 1990
Electrolyte Solutions with a Wide Electrochemical Window for Rechargeable Magnesium Batteries Mizrahi, Oren; Amir, Nir; Pollak, Elad Journal of The Electrochemical Society, Vol. 155, Issue 2, p. A103-A109 https://doi.org/10.1149/1.2806175	journal	January 2008
Improving Precision and Accuracy in Coulombic Efficiency Measurements of Li-Ion Batteries Bond, T. M.; Burns, J. C.; Stevens, D. A. Journal of The Electrochemical Society, Vol. 160, Issue 3 https://doi.org/10.1149/2.014304jes	journal	January 2013
Predicting and Extending the Lifetime of Li-Ion Batteries Burns, J. C.; Kassam, Adil; Sinha, N. N. Journal of The Electrochemical Society, Vol. 160, Issue 9 https://doi.org/10.1149/2.060309jes	journal	January 2013
The challenge of developing rechargeable magnesium batteries Shterenberg, Ivgeni; Salama, Michael; Gofer, Yossi MRS Bulletin, Vol. 39, Issue 5 https://doi.org/10.1557/mrs.2014.61	journal	May 2014

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

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

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