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.
Capacitive deionization (CDI) is a promising technique for salt removal and may have potential for highly selective removal of ion species. In this work, we take advantage of functional groups usually used with ionic exchange resins and apply these to CDI. To this end, we functionalize activated carbon with a quaternary amines surfactant and use this surface to selectively and passively (no applied field) trap nitrate ions. We then set the cell voltage to a constant value to regenerate these electrodes, resulting in an inverted capacitive deionization (i-CDI) operation. Unlike resins, we avoid use of concentrated chemicals for regeneration. We measure the selectivity of nitrate versus chloride ions as a function of regeneration voltage and initial chloride concentration. We experimentally demonstrate up to about 6.5-fold (observable) selectivity in a cycle with a regeneration voltage of 0.4 V. We also demonstrate a novel multi-pass, air-flush i-CDI operation to selectively enrich nitrate with high water recovery. We further present a dynamic, multi-species electrosorption and equilibrium solution-to-surface chemical reaction model and validate the model with detailed measurements. Our i-CDI system exhibits higher nitrate selectivity at lower voltages; making it possible to reduce NaNO 3 concentrations from ∼170 ppm to below the limit of maximum allowed values for nitrate in drinking water of about 50 ppm NaNO 3 .
The volume thermal expansion of powdered natural orthoenstatite [(Mg 0.994 Fe 0.002 Al 0.004) 2 (Si 0.996 Al 0.004) 2 O 6 ] has been measured to 1473 K using energy dispersive synchrotron X-ray diffraction. Over the temperature range examined, the data are consistent with a volume thermal expansion, , that linearly increases with temperature as given by the expression (T) = 29.7(16) x 10-6 K-1 + 5.7(11) x 10-9 K-2 T. An analysis in terms of the often-used constant expansion coefficient yields 0 = 34.5(17) x 10-6 K-1 , which is in good agreement with several previous experimental results on orthoenstatite (Mg 2 Si 2 O 6) over a similar temperature range. Our results do not support the extreme upper and lower bounds reported in earlier studies for the thermal expansivity of Fe-rich orthoenstatite, but rather suggest that the thermal expansion of this phase is approximately midway between those extreme values.
Ion adsorption and equilibrium between electrolyte and microstructure of porous electrodes are at the heart of capacitive deionization (CDI) research. Surface functional groups are among the factors which fundamentally affect adsorption characteristics of the material and hence CDI system performance in general. Current CDI-based models for surface charge are mainly based on a fixed (constant) charge density, and do not treat acid-base equilibria of electrode microstructure including so-called micropores. We here expand current models by coupling the modified Donnan (mD) model with weak electrolyte acid-base equilibria theory. In our model, surface charge density can vary based on equilibrium constants (pK's) of individual surface groups as well as micropore and electrolyte pH environments. In this initial paper, we consider this equilibrium in the absence of Faradaic reactions. The model shows the preferential adsorption of cations versus anions to surfaces with respectively acidic or basic surface functional groups. We introduce a new parameter we term "chemical charge efficiency" to quantify efficiency of salt removal due to surface functional groups. We validate our model using well controlled titration experiments for an activated carbon cloth (ACC), and quantify initial and final pH of solution after adding the ACC sample. We also leverage inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography (IC) to quantify the final background concentrations of individual ionic species. Our results show a very good agreement between experiments and model. The model is extendable to a wide variety of porous electrode systems and CDI systems with applied potential.
We demonstrate capillary fed porous copper structures capable of dissipating over 1200 W cm À2 in boiling with water as the working fluid. Demonstrated superheats for this structure are dramatically lower than those previously reported at these high heat fluxes and are extremely insensitive to heat input. We show superheats of less than 10 K at maximum dissipation and varying less than 5 K over input heat flux ranges of 1000 W cm À2. Fabrication of the porous copper layers using electrodeposition around a sacrificial template allows fine control of both microstructure and bulk geometry, producing structures less than 40 lm thick with active region lateral dimensions of 2 mm  0.3 mm. The active region is volumetrically Joule heated by passing an electric current through the porous copper bulk material. We analyze the heat transfer performance of the structures and suggest a strong influence of pore size on superheat. We compare performance of the current structure to existing wick structures. V
A framework is presented for understanding carrier generation and recombination mechanisms in irradiated silicon devices. Data obtained by many workers for irradiated bulk material and devices are analyzed and summarized, and key damagefactor dependences are identified. Measurements, simulations, and analyses support the conclusion that correlation of displacement damage effects with the rate of nonionizing energy loss (NIEL) for proton, neutron, pion, and heavy-ion bombardment is due to the dominant influence of defect subclusters. At low NIEL values ( 5 10 5 MeV-cm 2 /g), isolated defects dominate the electrical properties. At relatively high NIEL ( 2 10 4 MeV-cm 2 /g), subclusters dominate. Enhanced carrier generation and recombination produced by those small disordered regions is considered. Modeling results are presented for behavior observed in the transition region between domination by isolated defects and by clusters. The model presented in this paper simultaneously accommodates defect cluster models and NIEL scaling phenomena in the same framework.
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