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Aqueous rechargeable batteries are regarded as one of the most reliable solutions for electrochemical energy storage, and ion (e.g., H+ or OH–) transport is essential for their electrochemical performance. However, modeling and numerical simulations often fall short of depicting the actual ion transport characteristics due to deviations in model assumptions from reality. Experimental methods, including laser interferometry, Raman, and nuclear magnetic resonance imaging, are limited by the complexity of the system and the restricted detection of ions, making it difficult to detect specific ions such as H+ and OH–. Herein, in situ visualization of ion transport is achieved by innovatively introducing laser scanning confocal microscopy. Taking neutral Zn–air batteries as an example and using a pH-sensitive probe, real-time dynamic pH changes associated with ion transport processes are observed during battery operation. The results show that after immersion in the zinc sulfate electrolyte, the pH near the Zn electrode changes significantly and pulsation occurs, which demonstrates the intense self-corrosion hydrogen evolution reaction and the periodic change in the reaction intensity. In contrast, the change in the pH of the galvanized electrode plate is weak, proving its significant corrosion inhibition effect. For the air electrode, the heterogeneity of ion transport during the discharging and charging process is presented. With an increase of the current density, the ion transport characteristics gradually evolve from diffusion dominance to convection-diffusion codominance, revealing the importance of convection in the ion transport process inside batteries. This method opens up a new approach of studying ion transport inside batteries, guiding the design for performance enhancement.
Chen et al. (Thu,) studied this question.