Armstrong, Craig G. and Toghill, Kathryn E. (2017) Cobalt(II) complexes with azole-pyridine type ligands for non-aqueous redox-flow batteries : tunable electrochemistry via structural modification. Journal of Power Sources, 349. pp. 121-129. ISSN 0378-7753
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Abstract
Abstract A single species redox flow battery employing a new class of cobalt(II) complexes with ‘tunable’ tridentate azole-pyridine type ligands is reported. Four structures were synthesised and their electrochemical, physical and battery characteristics were investigated as a function of successive substitution of the ligand terminal pyridyl donors. The Co(II/I) and Co(III/II) couples are stable and quasi-reversible on gold and glassy carbon electrodes, however redox potentials are tunable allowing the cobalt potential difference to be preferentially increased from 1.07 to 1.91 V via pyridine substitution with weaker σ-donating/π-accepting 3,5-dimethylpyrazole groups. The charge-discharge properties of the system were evaluated using an H-type glass cell and graphite rod electrodes. The complexes delivered high Coulombic efficiencies of 89.7–99.8% and very good voltaic efficiencies of 70.3–81.0%. Consequently, energy efficiencies are high at 63.1–80.8%, marking an improvement on other similar non-aqueous systems. Modification of the ligands also improved solubility from 0.18 M to 0.50 M via pyridyl substitution with 3,5-dimethylpyrazole, though the low solubility of the complexes limits the overall energy capacity to between 2.58 and 12.80 W h L−1. Preliminary flow cell studies in a prototype flow cell are also demonstrated.