Zn Electrochemistry in 1‐Ethyl‐3‐Methylimidazolium and N‐Butyl‐N‐Methylpyrrolidinium Dicyanamides: Promising New Rechargeable Zn Battery Electrolytes

Abstract We have studied both 1‐ethyl‐3‐methylimidazolium (C 2 mim) and N ‐butyl‐ N ‐methylpyrrolidinium (C 4 mpyr) dicyanamide (dca) ionic liquids (ILs) containing 3 wt % H 2 O and 9 mol % Zn(dca) 2 salt for their ability to support Zn 0/2+ electrochemistry in the context of a rechargeable Zn battery. Despite the similarities of the two IL electrolyte systems identical H 2 O and Zn(dca) 2 contents, the system based on C 2 mim supported much higher current densities for Zn electrochemistry at greatly reduced overpotentials −0.23 V vs. Zn pseudo‐reference, 32 mA cm −2 (red) and 61 mA cm −2 (ox) compared to the C 4 mpyr‐based electrolyte −0.84 V vs. Zn pseudo‐reference, 8 mA cm −2 (red) and 15 mA cm −2 (ox). The overpotential for Zn deposition is reduced by 0.13 V on Zn metal surfaces compared to glassy carbon (GC), regardless of the electrolyte used. The morphologies of the Zn deposits on both GC and Zn surfaces were also studied. The Zn surfaces promote a deposition that displays a smooth morphology, resulting from an instantaneous nucleation mechanism demonstrated by chronoamperometric experiments. Finally, both C 2 mim and C 4 mpyr electrolytes were tested in symmetrical Zn|Zn cells, where it was determined that the C 2 mim system could sustain over 90 cycles at 0.1 mA cm −2 , whereas the C 4 mpyr based system could only achieve 15 cycles at the more modest current density of 0.05 mA cm −2 .