Efficient, Selective Sodium and Lithium Removal by Faradaic Deionization Using Symmetric Sodium Titanium Vanadium Phosphate Intercalation Electrodes.

NASICON (sodium superionic conductor) materials are promising host compounds for the reversible capture of Na+ ions, finding prior application in batteries as solid-state electrolytes and cathodes/anodes. Given their affinity for Na+ ions, these materials can be used in Faradaic deionization (FDI) for the selective removal of sodium over other competing ions. Here, we investigate the selective removal of sodium over other alkali and alkaline-earth metal cations from aqueous electrolytes when using a NASICON-based mixed Ti-V phase as an intercalation electrode, namely, sodium titanium vanadium phosphate (NTVP). Galvanostatic cycling experiments in three-electrode cells with electrolytes containing Na+, K+, Mg2+, Ca2+, and Li+ reveal that only Na+ and Li+ can intercalate into the NTVP crystal structure, while other cations show capacitive response, leading to a material-intrinsic selectivity factor of 56 for Na+ over K+, Mg2+, and Ca2+. Furthermore, electrochemical titration experiments together with modeling show that an intercalation mechanism with a limited miscibility gap for Na+ in NTVP mitigates the state-of-charge gradients to which phase-separating intercalation electrodes are prone when operated under electrolyte flow. NTVP electrodes are then incorporated into an FDI cell with automated fluid recirculation to demonstrate up to 94% removal of sodium in streams with competing alkali/alkaline-earth cations with 10-fold higher concentration, showing process selectivity factors of 3-6 for Na+ over cations other than Li+. Decreasing the current density can improve selectivity up to 25% and reduce energy consumption by as much as ∼50%, depending on the competing ion. The results also indicate the utility of NTVP for selective lithium recovery.

Linking capacity loss and retention of nickel hexacyanoferrate to a two-site intercalation mechanism for aqueous Mg2+ and Ca2+ ions.

Prussian blue analogues (PBAs) are promising cation intercalation materials for electrochemical desalination and energy storage applications. Here, we investigate the mechanism of capacity fade and degradation of nickel hexacyanoferrate (NiHCFe) during galvanostatic cycling in aqueous electrolytes that are rich in either Mg2+ or Ca2+. We combine experimental characterization, first principles electronic structure calculations, statistical mechanics and lattice-percolation modeling of electron transfer to elucidate the mechanisms responsible for the degradation of NiHCFe and its partial retention of capacity. Electrochemical characterization of porous NiHCFe electrodes suggests a two-site intercalation mechanism, while spectroscopy reveals the presence of Ni2+ and Fe(CN)63- ions in the electrolyte post cycling in Mg2+(aq). Using simple coprecipitation reactions, we show that Mg2+ and Ni2+ can coexist in the lattice framework, forming stable PBAs. Galvanostatic cycling of these PBAs shows that the presence of Mg2+ in the lattice framework results in the dissolution of Mg1.5FeIII(CN)6 in water during oxidation. We propose that Mg2+ can partially substitute Ni2+ ions in the lattice framework during galvanostatic cycling, displacing the substituted Ni2+ ions into interstitial sites. Based on differential capacitance analysis we show that Mg2+ intercalates into interstitial sites at ∼0.45 V vs. Ag/AgCl and it displaces Ni2+ in the lattice framework at ∼0.05 V vs. Ag/AgCl. Substitution of Ni2+ leads to Fe(CN)63- and Ni2+ ions being removed into the electrolyte during oxidation. Using first principles density functional theory (DFT) calculations combined with a statistical mechanics model, we verify the thermodynamic feasibility of the proposed reaction mechanism and predict the fraction of Ni2+ ions being substituted by Mg2+ during intercalation. Further, analysis of the electron density distribution and local density of states indicates that Mg2+ ions can act as insulating defects in the lattice framework that render certain Fe ions electrically inactive and likely contribute to capacity fade along with dissolution of Fe(CN)63-.

Effect of conductive additives on the transport properties of porous flow-through electrodes with insulative particles and their optimization for Faradaic deionization.

Deionization devices that use intercalation reactions to reversibly store and release cations from solution show promise for energy-efficient desalination of alternative water resources. Intercalation materials often display low electronic conductivity that results in increased energy consumption during desalination. Accordingly, we performed experiments to quantify the impact of the size and mass fraction of conductive additives and insulative active particles on the effective electronic conductivity, ionic conductivity, and hydraulic permeability of porous electrodes. We find that Ketjen black conductive additives with nodules <50 nm in diameter produce superior electronic conductivity at lower mass fractions than the larger carbon blacks commonly used in capacitive deionization. Hydraulic permeability and effective ionic conductivity depend weakly on carbon black content and size, though smaller active particles decrease hydraulic permeability. Based on these results we analyzed the energy consumption and salt removal rate of different electrode formulations by constructing an electrochemical Ashby plot predicting the variation of desalination performance with electrode transport properties. Optimized electrodes containing insulative Prussian blue analogue (PBA) particles were then fabricated and used in an experimental cation intercalation desalination (CID) cell with symmetric electrodes. For 100 mM NaCl influent energy consumption varied from 7 to 33 kJ/mol when current density increased from 1 to 8 mA/cm2, approaching ten-fold increased salt removal rate at similar energy consumption levels to past CID demonstrations. Complementary numerical and analytical modeling indicates that further improvements in energy consumption and salt removal rate are attainable by enhancing transport in solution and within PBA agglomerates.