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This work demonstrates that the ionic selectivity and ionic conductivity of nanoporous membranes can be controlled independently via layer-by-layer (LbL) deposition of polyelectrolytes and subsequent selective cross-linking of these polymer layers. LbL deposition offers a scalable, inexpensive method to tune the ion transport properties of nanoporous membranes by sequentially dip coating layers of cationic polyethyleneimine and anionic poly(acrylic acid) onto polycarbonate membranes. The cationic and anionic polymers are self-assembled through electrostatic and hydrogen bonding interactions and are chemically crosslinked to both change the charge distribution and improve the intermolecular integrity of the deposited films. Both the thickness of the deposited coating and the use of chemical cross-linking agents influence charge transport properties significantly. Increased polyelectrolyte thickness increases the selectivity for cationic transport through the membranes while adding polyelectrolyte films decreases the ionic conductivity compared to an uncoated membrane. Once the nanopores are filled, no additional decrease in conductivity is observed with increasing film thickness and, upon cross-linking, a portion of the lost conductivity is recovered. The cross-linking agent also influences the ionic selectivity of the resulting polyelectrolyte membranes. Increased selectivity for cationic transport occurs when using glutaraldehyde as the cross-linking agent, as expected due to the selective cross-linking of primary amines that decreases the net positive charge. Together, these results inform deposition of chemically robust, highly conductive, ion-selective membranes onto inexpensive porous supports for applications ranging from energy storage to water purification.

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TYPE Journal Article YEAR 2018

DOI OSTI Scopus

Electrochemistry of the NaI-AlCl3 molten salt system for use as catholyte in sodium metal batteries

Journal of the Electrochemical Society

Percival, Stephen P.; Small, Leo J.; Spoerke, Erik D.

Molten salt electrolytes show promise as safe, effective elements of emerging low to intermediate temperature molten sodium batteries. Here we investigate the NaI-AlCl3 molten salt system for its electrochemical and physical properties at 150 and 180°C, temperatures recently used to demonstrate a new NaI battery using this molten salt system. Molten salt compositions ranging from 20–75% NaI were prepared and electrochemically interrogated with carbon fiber ultramicroelectrodes utilizing cyclic voltammetry, chronoamperometry, and differential pulse voltammetry. Results indicate that at very high or very low NaI concentrations, secondary phases present hinder diffusion of the redox-active species, potentially impacting the current density of the system. Furthermore, a concentration-independent chronoamperometric analysis technique was leveraged to determine effective diffusion coefficients of active I− in the melt phase. Collectively, the physical characterization and electrochemical properties of the tested salts indicate that the catholyte composition can significantly affect the physical state, current density, ionic diffusion, and voltage window of these promising NaI-AlCl3 molten salt battery catholytes.

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TYPE Journal Article YEAR 2018

DOI OSTI Scopus