Agricultural development, extensive industrialization, and rapid growth of the global population have inadvertently been accompanied by environmental pollution. Water pollution is exacerbated by the decreasing ability of traditional treatment methods to comply with tightening environmental standards. This review provides a comprehensive description of the principles and applications of electrochemical methods for water purification, ion separations, and energy conversion. Electrochemical methods have attractive features such as compact size, chemical selectivity, broad applicability, and reduced generation of secondary waste. Perhaps the greatest advantage of electrochemical methods, however, is that they remove contaminants directly from the water, while other technologies extract the water from the contaminants, which enables efficient removal of trace pollutants. The review begins with an overview of conventional electrochemical methods, which drive chemical or physical transformations via Faradaic reactions at electrodes, and proceeds to a detailed examination of the two primary mechanisms by which contaminants are separated in nondestructive electrochemical processes, namely electrokinetics and electrosorption. In these sections, special attention is given to emerging methods, such as shock electrodialysis and Faradaic electrosorption. Given the importance of generating clean, renewable energy, which may sometimes be combined with water purification, the review also discusses inverse methods of electrochemical energy conversion based on reverse electrosorption, electrowetting, and electrokinetic phenomena. The review concludes with a discussion of technology comparisons, remaining challenges, and potential innovations for the field such as process intensification and technoeconomic optimization.

Capacitive deionization (CDI) is a fast-emerging water desalination technology in which a small cell voltage of ~1 V across porous carbon electrodes removes salt from feedwaters via electrosorption. In flow-through electrode (FTE) CDI cell architecture, feedwater is pumped through macropores or laser perforated channels in porous electrodes, enabling highly compact cells with parallel flow and electric field, as well as rapid salt removal. We here present a onedimensional model describing water desalination by FTE CDI, and a comparison to data from a custom-built experimental cell. The model employs simple cell boundary conditions derived via scaling arguments. We show good model-to-data fits with reasonable values for fitting parameters such as the Stern layer capacitance, micropore volume, and attraction energy. Thus, we demonstrate that from an engineering modeling perspective, an FTE CDI cell may be described with simpler one-dimensional models, unlike more typical flow-between electrodes architecture where 2D models are required.

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Capacitive deionization (CDI) is an emerging water treatment technology often applied to brackish water desalination and water softening. Typical CDI cells consist of two microporous carbon electrodes sandwiching a dielectric separator, and desalt feedwater flowing through the cell by storing ions in electric double layers (EDLs) within charged micropores. CDI cells have demonstrated size-based ion selectivity wherein smaller hydrated ions are preferentially electrosorbed over larger hydrated ions. We demonstrate that such size-based selectivity can be substantially enhanced through the addition of chemical charge to micropores via surface functionalization. We develop a micropore EDL theory that includes both finite ion size effects and micropore chemical charge, which predicts such enhancements and elucidates that they result from denser counterion packing in micropores. With our experimental CDI cell, we desalted an electrolyte consisting of equimolar potassium (K+) and lithium (Li+) ions. We show that use of a surface-functionalized (oxidized) cathode significantly increased the electrosorption ratio of smaller K+ to larger Li+ compared to a cell with a pristine cathode, for example, from ∼1 to 1.84 for a charging voltage of 0.4 V. Our model predicts yet-higher electrosorption ratios are attainable, but our experimental cell suffered from significant cathode chemical charge degradation at applied voltages of ∼1 V.

Emerging water purification applications often require tunable and ion-selective technologies. For example, when treating water for direct use in irrigation, often monovalent Na+ must be removed preferentially over divalent minerals, such as Ca2+, to reduce both ionic conductivity and sodium adsorption ratio (SAR). Conventional membrane-based water treatment technologies are either largely non-selective or not dynamically tunable. Capacitive deionization (CDI) is an emerging membraneless technology that employs inexpensive and widely available activated carbon electrodes as the active element. We here show that a CDI cell leveraging sulfonated cathodes can deliver long-lasting, tunable monovalent ion selectivity. For feedwaters containing Na+ and Ca2+, our cell achieves a Na+/Ca2+ separation factor of up to 1.6. To demonstrate the cell longevity, we show that monovalent selectivity is retained over 1000 charge–discharge cycles, the highest cycle life achieved for a membraneless CDI cell with porous carbon electrodes to our knowledge, while requiring an energy consumption of ~0.38 kWh/m3 of treated water. Furthermore, we show substantial and simultaneous reductions of ionic conductivity and SAR, such as from 1.75 to 0.69 mS/cm and 19.8 to 13.3, respectively, demonstrating the potential of such a system towards single-step water treatment of brackish and wastewaters for direct use in irrigation.