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Enhancing the Ion-Size-Based Selectivity of Capacitive Deionization Electrodes

  • Eric N. Guyes
    Eric N. Guyes
    Faculty of Mechanical Engineering, Technion − Israel Institute of Technology, Haifa 3200003, Israel
  • Tahel Malka
    Tahel Malka
    Faculty of Chemical Engineering, Technion − Israel Institute of Technology, Haifa 3200003, Israel
    More by Tahel Malka
  • , and 
  • Matthew E. Suss*
    Matthew E. Suss
    Faculty of Mechanical Engineering, Technion − Israel Institute of Technology, Haifa 3200003, Israel
    *E-mail: [email protected]
Cite this: Environ. Sci. Technol. 2019, 53, 14, 8447–8454
Publication Date (Web):June 12, 2019
Copyright © 2019 American Chemical Society

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    Abstract Image

    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.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.8b06954.

    • Predictions of micropore selectivity for pristine and oxidized cathodes; electrode material characterization; titration protocol and chemical charge determination; CDI cell and experiment details; conductivity and K+ electrode calibration details; additional details for nonmonotonic electrosorption ratio are shown in Figure S6 (PDF)

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