Metal-Ion Depletion Impacts the Stability and Performance of Battery Electrode Deionization over Multiple Cycles

Prussian blue hexacyanoferrate (HCF) materials, such as copper hexacyanoferrate (CuHCF) and nickel hexacyanoferrate (NiHCF), can produce higher salt removal capacities than purely capacitive materials when used as electrode materials during electrochemical water deionization due to cation intercalation into the HCF structure. One factor limiting the application of HCF materials is their decay in deionization performance over multiple cycles. By examining the performance of CuHCF and NiHCF electrodes at three different pH values (2.5, 6.3, and 10.2) in multiple-cycle deionization tests, losses in capacity (up to 73% for CuHCF and 39% for NiHCF) were shown to be tied to different redox-active centers through analysis of dissolution of electrode metals. Both copper and iron functioned as active centers for Na+ removal in CuHCF, while iron was mainly the active center in NiHCF. This interaction of Na+ and active centers was demonstrated by correlating the decrease in performance to the concentration of these metal ions in the effluent solutions collected over multiple cycles at different pHs (up to 0.86 ± 0.14 mg/L for iron and 0.42 ± 0.17 mg/L for copper in CuHCF and 0.38 ± 0.05 mg/L for iron in NiHCF). Both materials were more stable (