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@ARTICLE{Bieker:857743,
author = {Bieker, Georg and Diddens, Diddo and Kolek, Martin and
Borodin, Oleg and Winter, Martin and Bieker, Peter and
Jalkanen, Kirsi},
title = {{C}ation-{D}ependent {E}lectrochemistry of {P}olysulfides
in {L}ithium and {M}agnesium {E}lectrolyte {S}olutions},
journal = {The journal of physical chemistry / C C, Nanomaterials and
interfaces},
volume = {122},
number = {38},
issn = {1932-7455},
address = {Washington, DC},
publisher = {Soc.66306},
reportid = {FZJ-2018-06711},
pages = {21770 - 21783},
year = {2018},
abstract = {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.},
cin = {IEK-12},
ddc = {530},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {131 - Electrochemical Storage (POF3-131)},
pid = {G:(DE-HGF)POF3-131},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000446141900009},
doi = {10.1021/acs.jpcc.8b06560},
url = {https://juser.fz-juelich.de/record/857743},
}