For the first time, both the electrochemical behavior as well as the solubility and stabilization of Mg polysulfides were studied. In order to reveal the influence of Li+ and Mg2+, their polysulfide solutions were systematically compared in a broad variety of solvents. At first, the polysulfide disproportionation and dissociation equilibria in solutions of “Li2S8“ and “MgS8” in DMSO, DMF, ACN, THF, DME, TEGDME, and Pyr1,4TFSI were investigated in UV/Vis spectroscopy.[2] Afterwards, the influence of additional LiTFSI and MgTFSI2, respectively, was examined and the red/ox processes of these polysulfide-containing electrolytes were studied in cyclic voltammetry experiments. In addition, quantum mechanical calculations of the stability of the individual polysulfide species were conducted.
It could be shown that Mg polysulfides form similar disproportionation and dissociation equilibria as Li polysulfides. The stabilization of different polysulfide species is not only determined by the solvents’ relative dielectric permittivity and donor number, but also depends on the coordination by either Li or Mg cations in a mutual interplay with the solvent. Adding LiTFSI/MgTFSI2 intensifies the differences between the Li and Mg polysulfide solutions. As a consequence, the red/ox behavior of these solutions differ strongly. It is demonstrated that the typically high overvoltages of Mg/S cells are related to the electrochemistry of the Mg polysulfides.
The achieved insights into the fundamentals of the Li/S and Mg/S cell chemistries might lead the way towards new electrolyte designs and play a key role in increasing the reversibility and lowering the overvoltages of Mg/S cells.
Acknowlegdements:
The authors wish to thank the BMBF for funding this work within the projects ‘ACHiLiS’ (03XP0037A) and ‘MgMeAnS’ (03XP0140). The Heinrich Böll Foundation is acknowledged for funding through a PhD scholarship.
References:
[1] G. Bieker, M. Winter, P. Bieker, Physical Chemistry Chemical Physics, 2015, 17, 8670-8679.
[2] Z. Zhao-Karger, M. Fichtner, MRS Communications, 2017, 1-15.
[3] G. Bieker, J. Wellmann, M. Kolek, K. Jalkanen, M. Winter, P. Bieker, Physical Chemistry Chemical Physics, 2017, 19, 11152-11162.