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000857743 0247_ $$2doi$$a10.1021/acs.jpcc.8b06560
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000857743 1001_ $$0P:(DE-HGF)0$$aBieker, Georg$$b0
000857743 245__ $$aCation-Dependent Electrochemistry of Polysulfides in Lithium and Magnesium Electrolyte Solutions
000857743 260__ $$aWashington, DC$$bSoc.66306$$c2018
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000857743 520__ $$aIn 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.
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000857743 7001_ $$0P:(DE-Juel1)169877$$aDiddens, Diddo$$b1
000857743 7001_ $$00000-0001-7852-4064$$aKolek, Martin$$b2$$eCorresponding author
000857743 7001_ $$00000-0002-9428-5291$$aBorodin, Oleg$$b3
000857743 7001_ $$0P:(DE-Juel1)166130$$aWinter, Martin$$b4$$ufzj
000857743 7001_ $$00000-0003-4378-4805$$aBieker, Peter$$b5$$eCorresponding author
000857743 7001_ $$0P:(DE-HGF)0$$aJalkanen, Kirsi$$b6
000857743 773__ $$0PERI:(DE-600)2256522-X$$a10.1021/acs.jpcc.8b06560$$gVol. 122, no. 38, p. 21770 - 21783$$n38$$p21770 - 21783$$tThe journal of physical chemistry <Washington, DC> / C C, Nanomaterials and interfaces$$v122$$x1932-7455$$y2018
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