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Cited by 355

The DOI matches its Crossref record; 50 of the 50 references it cites were found in a registry or an index.

Predicting Solvent Stability in Aprotic Electrolyte Li–Air Batteries: Nucleophilic Substitution by the Superoxide Anion Radical (O2•–)

Bryantsev, Vyacheslav S., Giordani, Vincent, Walker, Wesley, Blanco, Mario, Zecevic, Strahinja, Sasaki, Kenji, Uddin, Jasim, Addison, Dan, Chase, Gregory V.·2011·The Journal of Physical Chemistry A
DOI 10.1021/jp2073914
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Abstract

There is increasing evidence that cyclic and linear carbonates, commonly used solvents in Li ion battery electrolytes, are unstable in the presence of superoxide and thus are not suitable for use in rechargeable Li-air batteries employing aprotic electrolytes. A detailed understanding of related decomposition mechanisms provides an important basis for the selection and design of stable electrolyte materials. In this article, we use density functional theory calculations with a Poisson-Boltzmann continuum solvent model to investigate the reactivity of several classes of aprotic solvents in nucleophilic substitution reactions with superoxide. We find that nucleophilic attack by O(2)(•-) at the O-alkyl carbon is a common mechanism of decomposition of organic carbonates, sulfonates, aliphatic carboxylic esters, lactones, phosphinates, phosphonates, phosphates, and sulfones. In contrast, nucleophilic reactions of O(2)(•-) with phenol esters of carboxylic acids and O-alkyl fluorinated aliphatic lactones proceed via attack at the carbonyl carbon. Chemical functionalities stable against nucleophilic substitution by superoxide include N-alkyl substituted amides, lactams, nitriles, and ethers. The results establish that solvent reactivity is strongly related to the basicity of the organic anion displaced in the reaction with superoxide. Theoretical calculations are complemented by cyclic voltammetry to study the electrochemical reversibility of the O(2)/O(2)(•-) couple containing tetrabutylammonium salt and GCMS measurements to monitor solvent stability in the presence of KO(2)(•) and a Li salt. These experimental methods provide efficient means for qualitatively screening solvent stability in Li-air batteries. A clear correlation between the computational and experimental results is established. The combination of theoretical and experimental techniques provides a powerful means for identifying and designing stable solvents for rechargeable Li-air batteries.

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Metadata

Authors
Bryantsev, V. S., Giordani, V., Walker, W., Blanco, M., Zecevic, S., Sasaki, K., Uddin, J., Addison, D., & Chase, G. V.
Venue
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Published
2011-10-18
Volume
115
Issue
44
Pages
12399-12409
ISSN
  • 1089-5639 (ISSN-L)
  • 1520-5215
DOI
10.1021/jp2073914
OpenAlex
W2314331081
Cited by
355
References
50
FWCI
22.28
Type
journal article
Language
en
Open access
closed

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