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Prussian blue analogs (PBAs) are used as electrode materials in energy storage and water deionization cells due to their reversible cation intercalation capability. Despite extensive research on their performance and intercalation mechanisms, little attention has been given to their behavior under open-circuit conditions. Recent studies using symmetrical PBA electrodes in two electrode deionization cells reported that after constant current cycling in dilute NaCl (<0.2 M), the cell voltage dropped under open-circuit conditions, which substantially increased the amount of energy consumed for deionization. However, it remains unclear which electrode (anode/cathode) experienced potential drift and if it was influenced by the low salinity of the electrolyte. Here, we performed a series of electrochemical experiments under different charging and discharging regimes and electrolyte compositions to determine the processes that contributed most significantly to open-circuit potential drift. The data indicated that charge redistribution within the electrode was the main contributor to open circuit potential drift, with electrode dissolution and parasitic reactions playing negligible roles. A one-dimensional finite element model was constructed to simulate charge redistribution by accounting for cation diffusion under open-circuit conditions. The open-circuit potential profiles generated by the model were validated against experimental trends, confirming the occurrence of charge redistribution. A Monte Carlo analysis of the model was conducted to determine the relationship of potential drift to key factors such as applied current, electrode thickness, diffusion coefficient of intercalating ions, and intercalation capacity. Subsequently, a dimensionless number (Da) was developed based on the Dahmköhler number to relate the extent of potential drift resulting from combinations of these factors. The analyses revealed a strong positive correlation between simulated potential drift andDa. Among the key factors studied here, the diffusion coefficient and applied current had the largest impact onDaand, consequently, on potential drift.

 

Several capacitive deionization (CDI) cell architectures employ ion-exchange membranes to control the chemistry of the electrolyte contacting the electrodes. Here, we experimentally examined how exposing carbon electrodes to either a saline electrolyte or an electrolyte containing a soluble redox-active compound influenced deionization energy demands and long-term stability over ∼50 hours. We specifically compared the energy demands (W h L −1 ) required to deionize 20 mM NaCl to 15 mM with a 50% water recovery as a function of productivity (L m −2 h −1 ). Relative to a conventional membrane capacitive deionization (MCDI) cell, flowing saline electrolyte over the electrodes did not affect energy demands but increased electrode salt adsorption capacities and capacity retention over repeated cycles. Exposing the electrodes to an electrolyte containing a redox-active compound, which made the cell behave similarly to an electrodialysis system, dramatically reduced energy demands and showed remarkable stability over 50 hours of operation. These experimental results indicate that using a recirculated soluble redox-active compound in the electrolyte contacting the electrodes to balance charge leads to far more energy efficient brackish water deionization than when charge is balanced by the electrodes undergoing capacitive charging/discharging reactions.