Abstract
Zinc-based aqueous battery systems are attractive for grid storage applications due to the inherent electrolyte safety, material non-toxicity, low cost, high volumetric capacity of zinc and the low polarizability of the zinc anode in aqueous solutions. Despite these key features, they possess lower energy density when compared to lithium-ion batteries primarily due to the limited working potential range for aqueous electrolytes. In addition, zinc hosts a slew of problems such as inhomogeneous material distribution upon cycling and the formation of inactive zinc species and dendrites, all of which contribute to capacity loss and ultimately, cell failure. Water-in-salt electrolytes (WiSE) have been found to be an effective strategy to expand the electrochemical window of aqueous electrolytes for high energy density aqueous-based batteries, including zinc batteries. There is a growing amount of literature on highly concentrated acetate-based electrolytes as low-cost and non-toxic WiSE for lithium, potassium, sodium and magnesium and zinc battery systems. However, work is scarce on the nature of zinc electrochemistry, morphology and reversibility in these concentrated electrolytes at realistic current densities (> 1 mA/cm2) and higher zinc utilization. Understanding the electrochemical behavior of zinc in this electrolyte system will significantly aid in the development of a high voltage zinc aqueous battery.In this work, the zinc electrochemical performance and surface morphology is studied in highly concentrated bi-salt potassium acetate (KOAc)-zinc acetate (Zn(OAc)2) electrolytes. The impact of the high concentration on the electrochemical working window of the electrolytes is measured using potential sweep and constant-current techniques. As the acetate concentration is varied from 1 m to 32 m, the largest electrochemical window is measured at 3.33 V for 31 m KOAc+ 1 m Zn(OAc)2. Zinc half cells are cycled at current densities of 1-5 mA/cm2 to examine zinc reversibility with respect to zinc depth-of-discharge (DOD) in these electrolytes. The zinc discharge product is visualized by in-operando optical microscopy as a function of the potential and is observed to be a zinc plating/stripping phenomenon in contrast to zinc dissolution/precipitation typically observed in alkaline media. Energy dispersive X-ray spectroscopy and X-ray diffraction studies display the minor presence of zinc oxide and zinc hydroxide after repeated cycling. Cloud point measurements are performed to measure the phase stability of these electrolytes at 5-25ºC as a function of acetate concentration, which show that concentrations below (and including) 27 m KOAc + 1 m Zn(OAc)2 does not induce crystallization at these temperatures. Preliminary measurements using spectroscopic techniques such as Raman and nuclear magnetic resonance (NMR) spectroscopy are conducted to elucidate ion solvation structures as a function of acetate concentration. Overall, the current and proposed studies are fruitful in understanding the relationship between zinc anode and the concentrated acetate-based electrolytes in the pursuit of a high-voltage aqueous zinc battery.
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