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

Tristan J. Simons,Douglas R. MacFarlane,Maria Forsyth,Patrick C. Howlett

ChemElectroChem（2014）SCI 4区SCI 3区

ARC Ctr Excellence Elect Sci

Cited 48|Views6

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 3wt% H2O and 9mol% Zn(dca)(2) salt for their ability to support Zn0/2+ electrochemistry in the context of a rechargeable Zn battery. Despite the similarities of the two IL electrolyte systems [identical H2O and Zn(dca)(2) contents], the system based on [C(2)mim] supported much higher current densities for Zn electrochemistry at greatly reduced overpotentials [-0.23V vs. Zn pseudo-reference, 32mAcm(-2) (red) and 61mAcm(-2) (ox)] compared to the [C(4)mpyr]-based electrolyte [-0.84V vs. Zn pseudo-reference, 8mAcm(-2) (red) and 15mAcm(-2) (ox)]. The overpotential for Zn deposition is reduced by 0.13V 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 0.1mAcm(-2), whereas the [C(4)mpyr] based system could only achieve 15 cycles at the more modest current density of 0.05mAcm(-2).

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Key words

batteries,electrolytes,ionic liquids,overpotential,zinc

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