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First-principles calculations of oxidation potentials of electrolytes in lithium–sulfur batteries and their variations with changes in environment

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c8cp02912a· OSTI ID:1868507
 [1];  [2]
  1. Texas A & M Univ., College Station, TX (United States); Texas A&M University
  2. Texas A & M Univ., College Station, TX (United States)
+ Show Author Affiliations
In this work, oxidation potentials of electrolyte molecules in Li–sulfur (Li/S) batteries and their variations in various solvent environments are investigated using first-principles calculations in order to understand oxidative decomposition reactions of electrolytes for cathode passivation. Electrolyte solvents, Li salts, and various additives in Li/S batteries along with some Li-ion battery additives are studied. Oxidation potentials of isolated electrolyte molecules are found to be out of the operating range of typical Li/S batteries. The complexation of electrolyte molecules with Li+, salt anion, salt, S8, and pyrene alters oxidation potentials compared to those of the isolated systems. The salt anion lowers oxidation potentials of electrolyte molecules by at least 4.7% while the complexes with Li+ have higher oxidation potentials than the isolated molecules by at least 10.4%. S8 and pyrene, used as model compounds for sulfur and sulfur/ carbon composite cathode materials, also affect oxidation potentials of electrolyte molecules, but their influence is negligible and the oxidation trends differ from those of the Li+ and salt anion. Although complexations change the oxidation potentials of electrolyte molecules, they are still higher than the operating voltage range of Li/S batteries, which indicates that oxidation of the studied electrolytes in Li/S batteries is not expected under ambient conditions.
Research Organization:
Texas A & M Univ., College Station, TX (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
Grant/Contract Number:
EE0007766
OSTI ID:
1868507
Alternate ID(s):
OSTI ID: 1540013
OSTI ID: 1458587
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 27 Vol. 20; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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