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Role of a Multivalent Ion–Solvent Interaction on Restricted Mg2+ Diffusion in Dimethoxyethane Electrolytes

Journal Article · · Journal of Physical Chemistry. B
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  1. Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
  2. Stony Brook Univ., NY (United States)
  3. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
+ Show Author Affiliations
The diffusion behavior of Mg2+ in electrolytes is not as readily accessible as that from Li+ or Na+ utilizing PFG NMR, due to the low sensitivity, poor resolution, and rapid relaxation encountered when attempting 25Mg NMR. In MgTFSI2/DME solutions, “bound” DME (coordinating to Mg2+) and “free” DME (bulk) are distinguishable from 1H NMR. With the exchange rates between them obtained from 2D 1H EXSY NMR, we can extract the self-diffusivities of free DME and bound DME (which are equal to that of Mg2+) before the exchange occurs using PFG diffusion NMR measurements coupled with analytical formulas describing diffusion under two-site exchange. Further, the high activation enthalpy for exhange (65–70 kJ/mol) can be explained by the structural change of bound DME as evidenced by its reduced C–H bond length. Comparison of the diffusion behaviors of Mg2+, TFSI–, DME, and Li+ reveals a relative restriction to Mg2+ diffusion that is caused by the long-range interaction between Mg2+ and solvent molecules, especially those with suppressed motions at high concentrations and low temperatures.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2479913
Alternate ID(s):
OSTI ID: 1988980
Report Number(s):
PNNL-SA--161192
Journal Information:
Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 45 Vol. 125; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Diffusion
Ions
Molecules
Solvents
Transport properties