Correlating Buffering Agents' Premier pH with Interface Stability Toward Long-Term Zn Metal Anodes

Aqueous solvents in Zn metal batteries inevitably induces hydrogen evolution reactions (HER) due to fluctuating pH levels in electrolytes, leading to severe side reactions and dendrite growth. To address these challenges, buffering agents have been recently proposed as a solution to maintain constant electrolyte pH values upon cycling. Nonetheless, the critical role of buffering additives' premier pH in determining interface stability is largely overlooked. Herein, two types of buffering agents, single amphoteric and conjugate acid-base pairs, are employed to correlate their initial pHs with the interface stability. Based on the observations, the lifetime of Zn metal anodes initially increases and then decreases as the initial pH level goes up from 2.0 to 5.0, with an optimal lifetime at pH 3.3 for both buffering agent categories. This phenomenon lies in ample H⁺ in low pH and rich OH^- in high pH, leading to either severe HER or by-products passivation layer. The optimized pH allows cells to deliver a high average Coulombic efficiency of 99.61% over 1500 cycles at a large current density of 5 mA cm^-2, which is significantly superior to 345 cycles achieved in the pristine electrolyte. Furthermore, this enhanced interface enables stable Zn/activated carbon full batteries over 15 000 cycles.