Zinc-Catalyzed Two-Electron Nickel(IV/II) Redox Couple for Multi- Electron Storage in Redox Flow Batteries

Energy storage is a vital aspect for the successful implementation of renewable energy resources on a global scale. Herein, we investigated the redox cycle of nickel(II) bis(diethyldithiocarbamate), NiII(dtc)2, for potential use as a multielectron storage catholyte in nonaqueous redox flow batteries (RFBs). Previous studies have shown that the unique redox cycle of NiII(dtc)2 offers 2e- chemistry upon oxidation from NiII-* NiIV but 1e- chemistry upon reduction from NiIV-* NiIII-* NiII. Electrochemical experiments presented here show that the addition of as little as 10 mol % ZnII(ClO4)2 to the electrolyte consolidates the two 1e- reduction peaks into a single 2e- reduction where [NiIV(dtc)3]+ is reduced directly to NiII(dtc)2. This catalytic enhancement is believed to be due to ZnII removal of a dtc- ligand from a NiIII(dtc)3 intermediate, resulting in more facile reduction to NiII(dtc)2. The addition of ZnII also improves the 2e- oxidation, shifting the anodic peak negative and decreasing the 2e- peak separation. H-cell cycling experiments showed that 97% Coulombic efficiency and 98% charge storage efficiency was maintained for 50 cycles over 25 h using 0.1 M ZnII(ClO4)2 as the supporting electrolyte. If ZnII(ClO4)2 was replaced with TBAPF6 in the electrolyte, the Coulombic efficiency fell to 78%. The use of ZnII to increase the reversibility of 2e- transfer is a promising result that points to the ability to use nickel dithiocarbonates for multielectron storage in RFBs.

Automated summary

Energy storage plays a crucial role in the implementation of renewable energy resources globally. This study investigated the redox cycle of nickel(II) bis(diethyldithiocarbamate) for its potential use in nonaqueous redox flow batteries. The addition of ZnII to the electrolyte improved the reversibility of the multielectron transfer, leading to higher efficiency in energy storage.