Interfacial and Kinetic Origins of Voltage Loss in Neutral Zinc‐Air Batteries

ABSTRACT Rechargeable zinc‐air batteries are promising candidates for grid‐scale energy storage; however, their practical deployment is limited by oxygen electrocatalysis inefficiencies and interfacial instabilities, particularly outside conventional alkaline electrolytes. In this work, zinc‐air batteries operating under neutral electrolyte conditions using ZnCl ₂ soaked KC‐PAA‐PAM gel polymer electrolytes and electrochemically synthesized Ni/Fe layered double hydroxide electrocatalysts is investigated. Ni/Fe‐LDH is intentionally employed as an OER‐biased benchmark catalyst to diagnose electrolyte and interface driven limitations rather than as a bifunctional ORR/OER solution. Full cells exhibit highly stable cycling over hundreds of hours, yet operate at substantially suppressed charge and discharge voltages relative to the thermodynamic value. Electrochemical impedance analysis shows that ohmic losses contribute only minimally to this voltage suppression. Post‐mortem X‐ray photoelectron spectroscopy reveals metallic zinc accumulation on the air cathode and chloride‐containing species on the anode, indicating parasitic interfacial processes. Synchrotron‐based soft X‐ray absorption spectroscopy confirms stable Ni ²⁺ and Fe ³⁺ oxidation states during cycling, consistent with OER‐biased catalytic behavior, while neutral‐electrolyte oxygen evolution measurements demonstrate strong electrolyte‐induced suppression of oxygen kinetics. Together, these results show that electrolyte chemistry and cathode‐side parasitic processes, rather than catalyst identity alone, dominate voltage losses in neutral zinc‐air batteries, providing mechanistic insight into the fundamental challenges associated with neutral electrolyte operation.