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Title: Preferential solvation of lithium cations and impacts on oxygen reduction in lithium–air batteries

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [3];  [3];  [1]
  1. Univ. of Wisconsin Milwaukee, Milwaukee, WI (United States)
  2. Wuhan Univ. of Technology, Wuhan (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
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The solvation of Li⁺ with eleven non-aqueous solvents commonly used as the electrolytes for Li batteries were studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li⁺ was determined. The Lewis acidity of the solvated Li⁺ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O₂⁻ depends on the relative Lewis acidity of the solvated Li⁺ ion. The impact of the solvated Li⁺ cation on the O₂ redox reaction was also investigated.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-98CH10886
OSTI ID:
1214540
Report Number(s):
BNL-108382-2015-JA; R&D Project: MA453MAEA; VT1201000
Journal Information:
ACS Applied Materials and Interfaces, Vol. 7, Issue 36; ISSN 1944-8244
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

References (24)

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Raman Spectra and Transport Properties of Lithium Perchlorate in Ethylene Carbonate Based Binary Solvent Systems for Lithium Batteries journal June 1998
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Electrolyte Solvation and Ionic Association II. Acetonitrile-Lithium Salt Mixtures: Highly Dissociated Salts journal January 2012
Empirical parameters for donor and acceptor properties of solvents journal September 1976
Stability of superoxide radicals in glyme solvents for non-aqueous Li–O2 battery electrolytes journal January 2013
Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium−Air Battery journal April 2010
Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li–air batteries journal January 2015
Solvation of Lithium Ions in Mixed Organic Electrolyte Solutions by Electrospray Ionization Mass Spectroscopy journal January 2002
Studies on Solvation of Lithium Ions in Organic Electrolyte Solutions by Electrospray Ionization-Mass Spectroscopy journal January 2001
Infrared Spectroscopy Studies on Stability of Dimethyl Sulfoxide for Application in a Li–Air Battery journal August 2013
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Predicting Solvent Stability in Aprotic Electrolyte Li–Air Batteries: Nucleophilic Substitution by the Superoxide Anion Radical (O 2 •– ) journal November 2011
Molecular Oxygen Electroreduction at Pt and Au Electrodes in Acetonitrile Solutions journal June 1983
Preferential Solvation of Li+ Directs Formation of Interphase on Graphitic Anode journal January 2011
Chemical Instability of Dimethyl Sulfoxide in Lithium–Air Batteries journal August 2014

Cited By (2)

Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents journal July 2019
The Progress of Li-S Batteries-Understanding of the Sulfur Redox Mechanism: Dissolved Polysulfide Ions in the Electrolytes journal June 2018

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Related Subjects

25 ENERGY STORAGE
superoxide
solvation
lithium ion
ESI/MS
oxygen reduction