Tailoring the Electrochemical Deposition of Zn by Tuning the Viscosity of the Liquid Electrolyte

The issues during Zn deposition in rechargeable Zn-based batteries greatly hinder cycling stability. In this work, a simple and inexpensive approach to tailor the Zn electrodeposition is proposed by tuning the viscosity of the liquid electrolyte (LE). First, the growth mechanisms of Zn deposition under different electrolyte properties are investigated by numerical simulation, from which the bottom deposition tends to fuse with each other when there are more deposition sites, and the mass-transfer coefficient is lower, thus achieving uniform deposition. Besides, the whole process of Zn deposition in charging-discharging cycling is in situ observed by an optical microscope. It is found that the cause of the poor stability in the LE is due to the uneven Zn deposition, resulting in weak bonding between the deposition and the electrode surface, which is also the reason for the formation of dead Zn. In contrast, when an appropriate amount of the polymer is added to the LE to increase the viscosity, an appropriate overpotential can be created, generating more deposition sites. In addition, the viscosity reduces the mass-transfer coefficient, making the distance from the ion to the deposition sites the main controlling factor. The Zn ions are more inclined to move in the direction of electric field lines, which results in a uniform and dense deposition layer. Furthermore, the effectiveness of this method is demonstrated in a Zn-LiFePO4 battery, from which the battery with the modified electrolyte condition still works properly even in the Zn utilization of 100% and shows a capacity retention rate (35%) of nearly twice that in the original LE condition (18%) after 10 cycles. This work provides a theoretical basis for Zn deposition and provides ideas for the future development of high-performance Zn-based batteries.