Reducing Chloride Ion Permeation during Seawater Electrolysis Using Double-Polyamide Thin-Film Composite Membranes.

Low-cost polyamide thin-film composite membranes are being explored as alternatives to expensive cation exchange membranes for seawater electrolysis. However, transport of chloride from seawater to the anode chamber must be reduced to minimize the production of chlorine gas. A double-polyamide composite structure was created that reduced the level of chloride transport. Adding five polyamide layers on the back of a conventional polyamide composite membrane reduced the chloride ion transport by 53% and did not increase the applied voltage. Decreased chloride permeation was attributed to enhanced electrostatic and steric repulsion created by the new polyamide layers. Charge was balanced through increased sodium ion transport (52%) from the anolyte to the catholyte rather than through a change in the transport of protons and hydroxides. As a result, the Nernstian loss arising from the pH difference between the anolyte and catholyte remained relatively constant during electrolysis despite membrane modifications. This lack of a change in pH showed that transport of protons and hydroxides during electrolysis was independent of salt ion transport. Therefore, only sodium ion transport could compensate for the reduction of chloride flux to maintain the set current. Overall, these results prove the feasibility of using a double-polyamide structure to control chloride permeation during seawater electrolysis without sacrificing energy consumption.

Modeling Ion Transport across Thin-Film Composite Membranes During Saltwater Electrolysis.

Affordable thin-film composite (TFC) membranes are a potential alternative to more expensive ion exchange membranes in saltwater electrolyzers used for hydrogen gas production. We used a solution-friction transport model to study how the induced potential gradient controls ion transport across the polyamide (PA) active layer and support layers of TFC membranes during electrolysis. The set of parameters was simplified by assigning the same size-related partition and friction coefficients for all salt ions through the membrane active layer. The model was fit to experimental ion transport data from saltwater electrolysis with 600 mM electrolytes at a current density of 10 mA cm-2. When the electrolyte concentration and current density were increased, the transport of major charge carriers was successfully predicted by the model. Ion transport calculated using the model only minimally changed when the negative active layer charge density was varied from 0 to 600 mM, indicating active layer charge was not largely responsible for controlling ion crossover during electrolysis. Based on model simulations, a sharp pH gradient was predicted to occur within the supporting layer of the membrane. These results can help guide membrane design and operation conditions in water electrolyzers using TFC membranes.

Thin-Film Composite Membranes for Hydrogen Evolution with a Saline Catholyte Water Feed.

Hydrogen gas evolution using an impure or saline water feed is a promising strategy to reduce overall energy consumption and investment costs for on-site, large-scale production using renewable energy sources. The chlorine evolution reaction is one of the biggest concerns in hydrogen evolution with impure water feeds. The "alkaline design criterion" in impure water electrolysis was examined here because water oxidation catalysts can exhibit a larger kinetic overpotential without interfering chlorine chemistry under alkaline conditions. Here, we demonstrated that relatively inexpensive thin-film composite (TFC) membranes, currently used for high-pressure reverse osmosis (RO) desalination applications, can have much higher rejection of Cl- (total crossover of 2.9 ± 0.9 mmol) than an anion-exchange membrane (AEM) (51.8 ± 2.3 mmol) with electrolytes of 0.5 M KOH for the anolyte and 0.5 M NaCl for the catholyte with a constant current (100 mA/cm2 for 20 h). The membrane resistances, which were similar for the TFC membrane and the AEM based on electrochemical impedance spectroscopy (EIS) and Ohm's law methods, could be further reduced by increasing the electrolyte concentration or removal of the structural polyester supporting layer (TFC-no PET). TFC membranes could enable pressurized gas production, as this membrane was demonstrated to be mechanically stable with no change in permeate flux at 35 bar. These results show that TFC membranes provide a novel pathway for producing green hydrogen with a saline water feed at elevated pressures compared to systems using AEMs or porous diaphragms.

Relative Insignificance of Polyamide Layer Selectivity for Seawater Electrolysis Applications.

Low-cost polyamide thin-film composite (TFC) membranes are being explored as alternatives to cation exchange membranes for seawater electrolysis. An optimal membrane should have a low electrical resistance to minimize applied potentials needed for water electrolysis and be able to block chloride ions present in a seawater catholyte from reaching the anode. The largest energy loss associated with a TFC membrane was the Nernstian overpotential of 0.74 V (equivalent to 37 Ω cm2 at 20 mA cm-2), derived from the pH difference between the anolyte and catholyte and not the membrane ohmic overpotential. Based on analysis using electrochemical impedance spectroscopy, the pristine TFC membrane contributed only 5.00 Ω cm2 to the ohmic resistance. Removing the polyester support layer reduced the resistance by 79% to only 1.04 Ω cm2, without altering the salt ion transport between the electrolytes. Enlarging the pore size (∼5 times) in the polyamide active layer minimally impacted counterion transport across the membrane during electrolysis, but it increased the total concentration of chloride transported by 60%. Overall, this study suggests that TFC membranes with thinner but mechanically strong supporting layers and size-selective active layers should reduce energy consumption and the potential for chlorine generation for seawater electrolyzers.