Cation Selectivity in Capacitive Deionization: Elucidating the Role of Pore Size, Electrode Potential, and Ion Dehydration

Cerón, Maira R.; Aydin, Fikret; Hawks, Steven A.; Oyarzun, Diego I.; Loeb, Colin K.; Deinhart, Amanda; Zhan, Cheng; Pham, Tuan Anh; Stadermann, Michael; Campbell, Patrick G.

doi:10.1021/acsami.0c07903

Title: Cation Selectivity in Capacitive Deionization: Elucidating the Role of Pore Size, Electrode Potential, and Ion Dehydration

Journal Article · Tue Sep 01 00:00:00 EDT 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c07903· OSTI ID:1678847

^[1]; Aydin, Fikret ^[1];

^[1]; Oyarzun, Diego I. ^[1]; Loeb, Colin K. ^[1]; Deinhart, Amanda ^[1]; Zhan, Cheng ^[1];

^[1];

^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Capacitive deionization (CDI) is a promising water desalination technology that is applicable to the treatment of low-salinity brackish waters and the selective removal of ionic contaminants. In this work, we show that by making a small change in the synthetic procedure of hierarchical carbon aerogel monolith (HCAM) electrodes, we can adjust the pore-size distribution and tailor the selectivity, effectively switching between selective adsorption of calcium or sodium ions. Ion selectivity was measured for a mixture of 5 mM NaCl and 2.5 mM CaCl₂. For the low activated flow-through CDI (fteCDI) cell, we observed extremely high sodium selectivity over calcium (S_Na/Ca $$\gg$$ 10, no Ca²⁺ adsorbed) at all of the applied potentials, while for the highly activated fteCDI cell, we observed a selectivity value of 6.6 ± 0.8 at 0.6 V for calcium over sodium that decreased to 2.2 ± 0.03 at 1.2 V. Molecular dynamics simulations indicated that the loss in Ca²⁺ selectivity over Na+ at high applied voltages could be due to a competition between ion-pore electrostatic interactions and volume exclusion (“crowding”) effects. Interestingly, we also find with these simulations that the relative sizes of the ions change due to changes in hydration at a higher voltage.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1678847

Report Number(s):: LLNL-JRNL-809022; 1015112

Journal Information:: ACS Applied Materials and Interfaces, Vol. 12, Issue 38; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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capacitive deionization
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