Low porosity, high areal-capacity Prussian blue analogue electrodes enhance salt removal and thermodynamic efficiency in symmetric Faradaic deionization with automated fluid control.

Prussian blue analogues (PBAs) show great potential for low-energy Faradaic deionization (FDI) with reversible Na-ion capacity approaching 5 M in the solid-state. However, past continuous-flow demonstrations using PBAs in FDI were unable to desalinate brackish water to potable levels using single-pass architectures. Here, we show that recirculation of effluent from a symmetric cation intercalation desalination cell into brine/diluate reservoirs enables salt removal exceeding 80% at thermodynamic efficiency as high as 80% when cycled with 100 mM NaCl influent and when controlled by a low-volume, automated fluid circuit. This exceptional performance is achieved using a novel heated, alkaline wet phase inversion process that modulates colloidal forces to increase carbon black aggregation within electrode slurries to solidify crack-free, high areal-capacity PBA electrodes that are calendered to minimize cell impedance and electrode porosity. The results obtained demonstrate the need for co-design of auxiliary fluid-control systems together with electrode materials to advance FDI beyond brackish salinity.

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.

Reducing impedance to ionic flux in capacitive deionization with Bi-tortuous activated carbon electrodes coated with asymmetrically charged polyelectrolytes.

Capacitive deionization (CDI) with electric double layers is an electrochemical desalination technology in which porous carbon electrodes are polarized to reversibly store ions. Planar composite CDI electrodes exhibit poor energetic performance due the resistance associated with salt depletion and tortuous diffusion in the macroporous structure. In this work, we investigate the impact of bi-tortuosity on desalination performance by etching macroporous patterns along the length of activated carbon porous electrodes in a flow-by CDI architecture. Capacitive electrodes were also coated with thin asymmetrically charged polyelectrolytes to improve ion-selectivity while maintaining the bitortuous macroporous channels. Under constant current operation, the equivalent circuit resistance in CDI cells operating with bi-tortuous electrodes was approximately 2.2 times less than a control cell with unpatterned electrodes, leading to significant increases in working capacitance (20-22 to 26.7-27.8 F g-1), round-trip efficiency (52-71 to 71-80%), and charge efficiency (33-59 to 35-67%). Improvements in these key performance indicators also translated to enhanced salt adsorption capacity, rate, and most importantly, the thermodynamic efficiency of salt separation (1.0-2.0 to 2.2-4.1%). These findings demonstrate that the use of bi-tortuous electrodes is a novel approach of reducing impedance to ionic flux in CDI.

Poroelasticity-driven lubrication in hydrogel interfaces.

It is widely accepted that hydrogel surfaces are slippery, and have low friction, but dynamic applied stresses alter the hydrogel composition at the interface as water is displaced. The induced osmotic imbalance of compressed hydrogel which cannot swell to equilibrium should drive the resistance to slip against it. This paper demonstrates the driving role of poroelasticity in the friction of hydrogel-glass interfaces, specifically how poroelastic relaxation of hydrogels increases adhesion. We translate the work of adhesion into an effective surface energy density that increases with the duration of applied pressure from 10 to 50 mJ m-2, as measured by micro-indentation. A model of static friction coefficient is derived from an area-based rules of mixture for the surface energies, and predicts the friction coefficient changes upon initiation of slip. For kinetic friction, the competition between duration of contact and relaxation time is quantified by a contacting Péclet number, PeC. A single length parameter on the scale of micrometers fits these two models to experimental micro-friction data. These models predict how short durations of applied pressure and faster sliding speeds, do not disrupt interfacial hydration; this prevailing water maintains low friction. At low speeds where interface drainage dominates, the osmotic suction works against slip for higher friction. The prediction of friction coefficients after adhesion characterization by micro-indentation makes use of the interplay between poroelasticity, adhesion, and friction. This approach provides a starting point for prediction of, and design for, hydrogel interfacial friction.