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Title: Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li–air batteries

Superoxide reacts with carbonate solvents in Li–air batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. As a result, the reactions are found to be first order and the rate constants are 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1]
  1. Univ. of Massachusetts Boston, Boston, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
OSTI Identifier:
1177851
Report Number(s):
BNL--107735-2015-JA
Journal ID: ISSN 0378-7753; R&D Project: MA453MAEA; VT1201000
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 274; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE superoxide disproportionation; Lewis acid catalyst; Li–air battery; reaction rate constant