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Relationship of the Molecular Structure and Transport Properties of Imide-Based Lithium Salts of “Acetonitrile/Water-in-Salt” Electrolytes

Journal Article · · Chemistry of Materials
 [1];  [2];  [3];  [3];  [4];  [5]
  1. Northern Illinois Univ., DeKalb, IL (United States)
  2. Univ. of Illinois at Urbana-Champaign, IL (United States)
  3. Argonne National Laboratory (ANL), Argonne, IL (United States)
  4. Univ. of Illinois at Urbana-Champaign, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Michigan, Ann Arbor, MI (United States)
  5. Northern Illinois Univ., DeKalb, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
+ Show Author Affiliations
“Water-in-salt” (WIS) electrolytes exhibit excellent safety and electrochemical performance. However, they possess high concentrations, relatively low diffusion coefficient, and high viscosity. “Acetonitrile/water in salt” (AWIS) electrolytes can overcome the disadvantages of WIS electrolytes. Under relatively low concentrations, AWIS electrolytes show good electrochemical performance comparable to WIS electrolytes and low conductivity. Herein, we investigate the relationship between the solvation structures and the transport properties using small-angle X-ray scattering and molecular dynamics simulation. We observed two solvation behaviors of AWIS: anions dissolved in acetonitrile forming small acetonitrile/anion clusters and additional water further dissolving the small acetonitrile/anion clusters. The introduction of acetonitrile weakens the water–solute interaction and enhances the cation–anion interaction, which results in an enhanced dynamical slowdown as the concentration increases. In conclusion, this work provides molecular-level understanding of the connection between two-stage solvation structures and transport properties for imide-based lithium salt solutions.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
AC02-06CH11357; SC0014084
OSTI ID:
2007519
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 16 Vol. 35; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (5)

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Figure 4(p. 7)figure Figure 4
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anions
electrolytes
solution chemistry
solvents
x-ray scattering