3 years ago

Ni(II)-chelated thio-crown complex as a single redox couple for non-aqueous flow batteries

Ni(II)-chelated thio-crown complex as a single redox couple for non-aqueous flow batteries
The Ni(II)-chelated thio-crown complex cation (nickel(II)-1,4,8,11-tetrathiacyclotetradecane), Ni([14]aneS4)2+ was tested as a single redox couple for non-aqueous flow batteries. The solid samples were synthesized with three different counter anions. Of the anions, bis(trifluoromethane)sulfonamide (TFSI) provides the highest solubility (0.62 M in the organic carbonate-based electrolyte solution). The anion-dependent solubility can be accounted for by the weaker cation/anion Coulombic interaction with larger anions. The complex cation participates in two redox reactions: Ni(II)Ni(III) at E 1/2 =1.11V (vs. Fc/Fc+) and Ni(II)Ni(I) at E 1/2 =0.80V (vs. Fc/Fc+), which enables the working voltage of the redox flow cell with the complex cation as a single redox couple to be 1.91V. The complex cation exhibits very stable redox behavior without any degradation. The advantage of the high working voltage and superior stability cannot, however, be fully implemented because the used electrolyte is not stable against oxidative decomposition on the positive electrode.

Publisher URL: www.sciencedirect.com/science

DOI: S1388248117302990

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