This title appears in the Scientific Report :
2019
Please use the identifier:
http://dx.doi.org/10.1021/acs.jpcc.8b06560 in citations.
Please use the identifier: http://hdl.handle.net/2128/23485 in citations.
Cation-Dependent Electrochemistry of Polysulfides in Lithium and Magnesium Electrolyte Solutions
Cation-Dependent Electrochemistry of Polysulfides in Lithium and Magnesium Electrolyte Solutions
In Li/S and Mg/S batteries, the charge and discharge of the sulfur cathode proceeds through a cascade of bivalent Sx2– and radical Sy•– polysulfide intermediates. The presence of Li+ or Mg2+ cations in the electrolyte determines the type of intermediates and the overpotentials of their formation in...
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Personal Name(s): | Bieker, Georg |
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Diddens, Diddo / Kolek, Martin (Corresponding author) / Borodin, Oleg / Winter, Martin / Bieker, Peter (Corresponding author) / Jalkanen, Kirsi | |
Contributing Institute: |
Helmholtz-Institut Münster Ionenleiter für Energiespeicher; IEK-12 |
Published in: |
The journal of physical chemistry |
Imprint: |
Washington, DC
Soc.66306
2018
|
DOI: |
10.1021/acs.jpcc.8b06560 |
Document Type: |
Journal Article |
Research Program: |
Electrochemical Storage |
Link: |
OpenAccess OpenAccess |
Publikationsportal JuSER |
Please use the identifier: http://hdl.handle.net/2128/23485 in citations.
In Li/S and Mg/S batteries, the charge and discharge of the sulfur cathode proceeds through a cascade of bivalent Sx2– and radical Sy•– polysulfide intermediates. The presence of Li+ or Mg2+ cations in the electrolyte determines the type of intermediates and the overpotentials of their formation in a different manner. Based on systematic cyclic voltammetry (CV) and UV/vis investigations, this work reveals how the mutual interplay of the different cations, the electrolyte solvent, and the polysulfide anions is reflected in the electrochemical behavior of “Li2S8”/LiTFSI and “MgS8”/MgTFSI2 solutions with dimethyl sulfoxide, dimethylformamide, acetonitrile, dimethoxyethane, tetraethylene glycol dimethyl ether, or tetrahydrofuran as solvent. It was observed that the disproportionation reactions of the polysulfides are generally more pronounced and especially the S3•– radical is less stabilized in Mg2+ than in Li+ containing solutions. In contrast to their Li counterparts, the formation of S42– polysulfides during the reduction of sulfur is not observed in glyme-based Mg polysulfide solutions. Quantum chemical predictions of stability and disproportionation of the Mg/polysulfide/solvent clusters complemented the CV and UV/vis investigations. |