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Understanding the Surprising Ionic Conductivity Maximum in Zn(TFSI)2 Water/Acetonitrile Mixture Electrolytes

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [3];  [2];  [4];  [5];  [5];  [4];  [1];  [2]
  1. University of Notre Dame, IN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
  4. Univ. of Colorado, Boulder, CO (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
  5. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
+ Show Author Affiliations

Aqueous electrolytes composed of 0.1 M zinc bis-(trifluoromethyl-sulfonyl)-imide (Zn-(TFSI)2) and acetonitrile (ACN) were studied using combined experimental and simulation techniques. The electrolyte was found to be electrochemically stable when the ACN V% is higher than 74.4. In addition, it was found that the ionic conductivity of the mixed solvent electrolytes changes as a function of ACN composition, and a maximum was observed at 91.7 V% of ACN although the salt concentration is the same. This behavior was qualitatively reproduced by molecular dynamics (MD) simulations. Detailed analyses based on experiments and MD simulations show that at high ACN composition the water network existing in the high water composition solutions breaks. As a result, the screening effect of the solvent weakens and the correlation among ions increases, which causes a decrease in ionic conductivity at high ACN V%. Furthermore, this study provides a fundamental understanding of this complex mixed solvent electrolyte system.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC02-06CH11357; NA0003525
OSTI ID:
2281691
Alternate ID(s):
OSTI ID: 2311271
OSTI ID: 2377139
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 50 Vol. 14; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Diffusion
Electrolytes
Ionic conductivity
Solution chemistry
Transport properties