Diagnosing the Electrostatic Shielding Mechanism for Dendrite Suppression in Aqueous Zinc Batteries

Aqueous zinc electrolytes offer the potential for cheaper rechargeable batteries due to their safe compatibility with the high capacity metal anode; yet, they are stymied by irregular zinc deposition and consequent dendrite growth. Suppressing dendrite formation by tailoring the electrolyte is a proven approach from lithium batteries; yet, the underlying mechanistic understanding that guides such tailoring does not necessarily directly translate from one system to the other. Here, it is shown that the electrostatic shielding mechanism, a fundamental concept in electrolyte engineering for stable metal anodes, has different consequences for the plating morphology in aqueous zinc batteries. Operando electrochemical transmission electron microscopy is used to directly observe the zinc nucleation and growth under different electrolyte compositions and reveal that electrostatic shielding additive suppresses dendrites by inhibiting secondary zinc nucleation along the (100) edges of existing primary deposits and encouraging preferential deposition on the (002) faces, leading to a dense and block-like zinc morphology. The strong influence of the crystallography of Zn on the electrostatic shielding mechanism is further confirmed with Zn||Ti cells and density functional theory modeling. This work demonstrates the importance of considering the unique aspects of the aqueous zinc battery system when using concepts from other battery chemistries. The metal anode for aqueous zinc batteries is highly susceptible to dendrites and side reactions. Engineering the electrolyte with additives can combat these negative traits. Operando transmission electron microscopy is used to explore how the inclusion of LiCl additive encourages the formation of blocky Zn electroplated deposits, which it is proposed is due to an electrostatic shielding mechanism.image