Ali Hemmatifar

Energy breakdown in capacitive deionization

We explored the energy loss mechanisms in capacitive deionization (CDI). We hypothesize that resistive and parasitic losses are two main sources of energy losses. We measured contribution from each loss mechanism in water desalination with constant current (CC) charge/discharge cycling. Resistive energy loss is expected to dominate in high current charging cases, as it increases approximately linearly with current for fixed charge transfer (resistive power loss scales as square of current and charging time scales as inverse of current). On the other hand, parasitic loss is dominant in low current cases, as the electrodes spend more time at higher voltages. We built a CDI cell with five electrode pairs and standard flow between architecture. We performed a series of experiments with various cycling currents and cut-off voltages (voltage at which current is reversed) and studied these energy losses. To this end, we measured series resistance of the cell (contact resistances, resistance of wires, and resistance of solution in spacers) during charging and discharging from voltage response of a small amplitude AC current signal added to the underlying cycling current. We performed a separate set of experiments to quantify parasitic (or leakage) current of the cell versus cell voltage. We then used these data to estimate parasitic losses under the assumption that leakage current is primarily voltage (and not current) dependent. Our results confirmed that resistive and parasitic losses respectively dominate in the limit of high and low currents. We also measured salt adsorption and report energy-normalized adsorbed salt (ENAS, energy loss per ion removed) and average salt adsorption rate (ASAR). We show a clear tradeoff between ASAR and ENAS and show that balancing these losses leads to optimal energy efficiency.

Self similarities in desalination dynamics and performance using capacitive deionization

Charge transfer and mass transport are two underlying mechanisms which are coupled in desalination dynamics using capacitive deionization (CDI). We developed simple reduced-order models based on a mixed reactor volume principle which capture the coupled dynamics of CDI operation using closed-form semi-analytical and analytical solutions. We use the models to identify and explore self-similarities in the dynamics among flow rate, current, and voltage for CDI cell operation including both charging and discharging cycles. The similarity approach identifies the specific combination of cell (e.g. capacitance, resistance) and operational parameters (e.g. flow rate, current) which determine a unique effluent dynamic response. We here demonstrate self-similarity using a conventional flow between CDI (fbCDI) architecture, and we hypothesize that our similarity approach has potential application to a wide range of designs. We performed an experimental study of these dynamics and used well-controlled experiments of CDI cell operation to validate and explore limits of the model. For experiments, we used a CDI cell with five electrode pairs and a standard flow between (electrodes) architecture. Guided by the model, we performed a series of experiments that demonstrate natural response of the CDI system. We also identify cell parameters and operation conditions which lead to self-similar dynamics under a constant current forcing function and perform a series of experiments by varying flowrate, currents, and voltage thresholds to demonstrate self-similarity. Based on this study, we hypothesize that the average differential electric double layer (EDL) efficiency (a measure of ion adsorption rate to EDL charging rate) is mainly dependent on user-defined voltage thresholds, whereas flow efficiency (measure of how well desalinated water is recovered from inside the cell) depends on cell volumes flowed during charging, which is determined by flowrate, current and voltage thresholds. Results of experiments strongly support this hypothesis. Results show that cycle efficiency and salt removal for a given flowrate and current are maximum when average EDL and flow efficiencies are approximately equal. We further explored a range of CC operations with varying flowrates, currents, and voltage thresholds using our similarity variables to highlight trade-offs among salt removal, energy, and throughput performance.

Thermodynamics of Ion Separation by Electrosorption

We present a simple, top-down approach for the calculation of minimum energy consumption of electrosorptive ion separation using variational form of the (Gibbs) free energy. We focus and expand on the case of electrostatic capacitive deionization (CDI). The theoretical framework is independent of details of the double-layer charge distribution and is applicable to any thermodynamically consistent model, such as the Gouy-Chapman-Stern and modified Donnan models. We demonstrate that, under certain assumptions, the minimum required electric work energy is indeed equivalent to the free energy of separation. Using the theory, we define the thermodynamic efficiency of CDI. We show that the thermodynamic efficiency of current experimental CDI systems is currently very low, around 1% for most existing systems. We applied this knowledge and constructed and operated a CDI cell to show that judicious selection of the materials, geometry, and process parameters can lead to a 9% thermodynamic efficiency and 4.6 kT per removed ion energy cost. This relatively high thermodynamic efficiency is, to our knowledge, by far the highest thermodynamic efficiency ever demonstrated for traditional CDI. We hypothesize that efficiency can be further improved by further reduction of CDI cell series resistances and optimization of operational parameters.