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The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions

See, Kimberly A. and Chapman, Karena W. and Zhu, Lingyang and Wiaderwek, Kamila M. and Borkiewicz, Olaf J. and Barile, Christopher J. and Chupas, Peter J. and Gewirth, Andrew A. (2016) The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions. Journal of the American Chemical Society, 138 (1). pp. 328-337. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180607-135310246

[img] PDF (Tabulated fit parameters from the Gaussian fits of the PDF data, PDF calculations of possible Mg complexes, PDF calculations of AlCl_4^– and [Mg_2(μ–Cl)_3·6THF]^+, and ^(35)Cl NMR of LiCl and TBACl in THF) - Supplemental Material
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Abstract

Mg batteries are an attractive alternative to Li-based energy storage due to the possibility of higher volumetric capacities with the added advantage of using sustainable materials. A promising emerging electrolyte for Mg batteries is the magnesium aluminum chloride complex (MACC) which shows high Mg electrodeposition and stripping efficiencies and relatively high anodic stabilities. As prepared, MACC is inactive with respect to Mg deposition; however, efficient Mg electrodeposition can be achieved following an electrolytic conditioning process. Through the use of Raman spectroscopy, surface enhanced Raman spectroscopy, ^(27)Al and ^(35)Cl nuclear magnetic resonance spectroscopy, and pair distribution function analysis, we explore the active vs inactive complexes in the MACC electrolyte and demonstrate the codependence of Al and Mg speciation. These techniques report on significant changes occurring in the bulk speciation of the conditioned electrolyte relative to the as-prepared solution. Analysis shows that the active Mg complex in conditioned MACC is very likely the [Mg_2(μ–Cl)_3·6THF]^+ complex that is observed in the solid state structure. Additionally, conditioning creates free Cl^– in the electrolyte solution, and we suggest the free Cl^– adsorbs at the electrode surface to enhance Mg electrodeposition.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/jacs.5b10987DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.5b10987PublisherSupporting Information
ORCID:
AuthorORCID
See, Kimberly A.0000-0002-0133-9693
Gewirth, Andrew A.0000-0003-4400-9907
Additional Information:© 2015 American Chemical Society. Received: October 20, 2015. Published: December 4, 2015. This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Work done at Argonne and use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Argonne National Laboratory, were supported by the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. K. A. S acknowledges postdoctoral funding from the St. Elmo Brady Future Faculty Fellowship. C. J. B. acknowledges a National Science Foundation Graduate Research Fellowship (No. NSF DGE-1144245) and a Springborn Fellowship. The authors thank Liwen F. Wan and David Prendergast for helpful discussions and providing cif files of the Mg complexes. The authors acknowledge Saul H. Lapidus for helpful discussions, Tim T. Fister for assistance with electrochemical equipment at the APS, Niya Sa for assistance with materials at the ANL, and Kevin G. Schmitt for helpful discussion regarding Raman results. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
St. Elmo Brady Future Faculty FellowshipUNSPECIFIED
NSF Graduate Research FellowshipDGE-1144245
Springborn FellowshipUNSPECIFIED
Issue or Number:1
Record Number:CaltechAUTHORS:20180607-135310246
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180607-135310246
Official Citation:The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions Kimberly A. See, Karena W. Chapman, Lingyang Zhu, Kamila M. Wiaderek, Olaf J. Borkiewicz, Christopher J. Barile, Peter J. Chupas, and Andrew A. Gewirth Journal of the American Chemical Society 2016 138 (1), 328-337 DOI: 10.1021/jacs.5b10987
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86895
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:07 Jun 2018 21:12
Last Modified:09 Mar 2020 13:18

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