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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.
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Effects of interstitial water and alkali cations on the expansion, intercalation potential, and orbital coupling of nickel hexacyanoferrate from first principles
Prussian blue analogs (PBAs) are an important material class for aqueous electrochemical separations and energy storage owing to their ability to reversibly intercalate monovalent cations. However, incorporating interstitial [Formula: see text] molecules in the ab initio study of PBAs is technically challenging, though essential to understanding the interactions between interstitial water, interstitial cations, and the framework lattice that affect intercalation potential and cation intercalation selectivity. Accordingly, we introduce and use a method that combines the efficiency of machine-learning models with the accuracy of ab initio calculations to elucidate mechanisms of (1) lattice expansion upon intercalation of cations of different sizes, (2) selectivity bias toward intercalating hydrophobic cations of large size, and (3) semiconductor–conductor transitions from anhydrous to hydrated lattices. We analyze the PBA nickel hexacyanoferrate [[Formula: see text]] due to its structural stability and electrochemical activity in aqueous electrolytes. Here, grand potential analysis is used to determine the equilibrium degree of hydration for a given intercalated cation (Na[Formula: see text], K[Formula: see text], or Cs[Formula: see text]) and [Formula: see text] oxidation state based on pressure-equilibrated structures determined with the aid of machine learning and simulated annealing. The results imply new directions for the rational design of future cation-intercalation electrode materials that optimize performance in various electrochemical applications, and they demonstrate the importance of choosing an appropriate calculation framework to predict the properties of PBA lattices accurately.
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- Award ID(s):
- 1931659
- PAR ID:
- 10363845
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- Journal of Applied Physics
- Volume:
- 131
- Issue:
- 10
- ISSN:
- 0021-8979
- Page Range / eLocation ID:
- Article No. 105101
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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