Perfect divalent cation selectivity with capacitive deionization

Capacitive deionization (CDI) is an emerging membraneless water desalination technology based on storing ions in charged electrodes by electrosorption. Due to unique selectivity mechanisms, CDI has been investigated towards ion-selective separations such as water softening, nutrient recovery, and production of irrigation water. Especially promising is the use of activated microporous carbon electrodes due to their low cost and wide availability at commercial scales. We show here, both theoretically and experimentally, that sulfonated activated carbon electrodes enable the first demonstration of perfect divalent cation selectivity in CDI, where we define "perfect" as significant removal of the divalent cation with zero removal of the competing monovalent cation. For example, for a feedwater of 15 mM NaCl and 3 mM CaCl₂, and charging from 0.4 V to 1.2 V, we show our cell can remove 127 μmol per gram carbon of divalent Ca²⁺, while slightly expelling competing monovalent Na⁺ (-13.2 μmol/g). This separation can be achieved with excellent efficiency, as we show both theoretically and experimentally a calcium charge efficiency above unity, and an experimental energy consumption of less than 0.1 kWh/m³. We further demonstrate a low-infrastructure technique to measure cation selectivity, using ion-selective electrodes and the extended Onsager-Fuoss model.