Morphology control of zinc electrodeposition by surfactant addition for alkaline-based rechargeable batteries†
The development of Zn–air batteries with a high energy density of 1350 W h kg−1 is one of the breakthroughs required to achieve a low carbon society. However, morphology control of the Zn negative electrode during charge/discharge (Zn-deposition/stripping) is essential for practical application. Considering the manufacturing process, a simple strategy is preferable. Herein, we employed surfactants as an inhibitor of the formation of mossy and dendrite Zn structures, and studied electrochemical Zn growth from the perspective of the electric charge of the surfactant. Even by using an additive free electrolyte of 0.25 M ZnO + 4 M KOH and with 1 mM sodium dodecyl sulfate (SDS: anionic surfactant) or polyacrylic acid (PAA: non-ionic surfactant), mossy and dendrite formations were unavoidable irrespective of the current density. On the other hand, a cationic surfactant, trimethyloctadecylammonium chloride (STAC), suppressed the shape change and resulted in a smooth and dense morphology. Zeta potential measurements, kinetic current densities observed from Tafel plots, and constant potential electrolysis indicate that quaternary ammonium cations (STAC) with bulky size adsorb onto protrusions which are the cause of shape change and suppress Zn deposition in the region to promote lateral growth. Although the adsorption of STAC increased the average overvoltage for Zn-deposition/stripping in a symmetric Zn|Zn cell under a current density of 10 mA cm−2, significantly stable behavior continued for 200 h. In contrast, the overvoltage of the additive free system suddenly increased after 156 h, associated with the accumulation of insulating ZnO and Zn(OH)2 formed on the Zn surface. In charge–discharge tests using an asymmetric Cu|Zn cell, the coulombic efficiency in the additive free electrolyte was less than 95%, whereas the addition of STAC at 1 mM achieved superior cycling performance without any capacity loss originating from the generation of dead Zn (electrical isolation). These results demonstrate that the addition of STAC is a promising method of controlling the Zn morphology.