Role of the Membrane Transport Mechanism in Electrochemical Nitrogen Reduction Experiments.

The electrochemical synthesis of ammonia through the nitrogen reduction reaction (NRR) is receiving much attention, since it is considered a promising alternative to the Haber-Bosch process. In NRR experiments, a Nafion membrane is generally adopted as a separator. However, its use is controversial since ammonia can be trapped in the membrane, to some extent, or even pass through it. We systematically investigate the interaction of a Nafion membrane with ammonia and with an electrolyte and compare it with Zirfon as a possible alternative separator. We show that Nafion containing ammonia can easily release it when immersed in a 0.1 M Na2SO4 ammonia-free electrolyte, due to the cation exchange mechanism (Na+-NH4+). Since Na2SO4 is a commonly adopted electrolyte for NRR experiments, this may cause serious measurement errors and non-reproducible results. The same experiments performed using the polysulfone Zirfon separator clearly show that it is immune to interactions with ammonia, because of its different ion conduction mechanism. The findings provide a deeper understanding of the choice of membrane and electrolyte to be adopted for NRR tests, and may allow one to obtain more accurate and reliable results.

Zirconia Toughened Alumina-Based Separator Membrane for Advanced Alkaline Water Electrolyzer.

Hydrogen is nowadays considered a favorable and attractive energy carrier fuel to replace other fuels that cause global warming problems. Water electrolysis has attracted the attention of researchers to produce green hydrogen mainly for the accumulation of renewable energy. Hydrogen can be safely used as a bridge to successfully connect the energy demand and supply divisions. An alkaline water electrolysis system owing to its low cost can efficiently use renewable energy sources on large scale. Normally organic/inorganic composite porous separator membranes have been employed as a membrane for alkaline water electrolyzers. However, the separator membranes exhibit high ionic resistance and low gas resistance values, resulting in lower efficiency and raised safety issues as well. Here, in this study, we report that zirconia toughened alumina (ZTA)-based separator membrane exhibits less ohmic resistance 0.15 Ω·cm2 and low hydrogen gas permeability 10.7 × 10-12 mol cm-1 s-1 bar-1 in 30 wt.% KOH solution, which outperforms the commercial, state-of-the-art Zirfon® PERL separator. The cell containing ZTA and advanced catalysts exhibit an excellent performance of 2.1 V at 2000 mA/cm2 at 30 wt.% KOH and 80 °C, which is comparable with PEM electrolysis. These improved results show that AWEs equipped with ZTA separators could be superior in performance to PEM electrolysis.

Importance of Hydroxide Ion Conductivity Measurement for Alkaline Water Electrolysis Membranes.

Alkaline water electrolysis (AWE) refers to a representative water electrolysis technology that applies electricity to synthesize hydrogen gas without the production of carbon dioxide. The ideal polymer electrolyte membranes for AWE should be capable of transporting hydroxide ions (OH-) quickly in harsh alkaline environments at increased temperatures. However, there has not yet been any desirable impedance measurement method for estimating hydroxide ions' conduction behavior across the membranes, since their impedance spectra are significantly affected by connection modes between electrodes and membranes in the test cells and the impedance evaluation environments. Accordingly, the measurement method suitable for obtaining precise hydroxide ion conductivity values through the membranes should be determined. For this purpose, Zirfon®, a state-of-the-art AWE membrane, was adopted as the standard membrane sample to perform the impedance measurement. The impedance spectra were acquired using homemade test cells with different electrode configurations in alkaline environments, and the corresponding hydroxide ion conductivity values were determined based on the electrochemical spectra. Furthermore, a modified four-probe method was found as an optimal measurement method by comparing the conductivity obtained under alkaline conditions.

Cerium Oxide-Polysulfone Composite Separator for an Advanced Alkaline Electrolyzer.

The intermittent and volatile nature of renewable energy sources threatens the stable operation of power grids, necessitating dynamically operated energy storage. Power-to-gas technology is a promising method for managing electricity variations on a large gigawatt (GW) scale. The electrolyzer is a key component that can convert excess electricity into hydrogen with high flexibility. Recently, organic/inorganic composite separators have been widely used as diaphragm membranes; however, they are prone to increase ohmic resistance and gas crossover, which inhibit electrolyzer efficiency. Here, we show that the ceria nanoparticle and polysulfone composite separator exhibits a low area resistance of 0.16 Ω cm2 and a hydrogen permeability of 1.2 × 10-12 mol cm-1 s-1 bar-1 in 30 wt% potassium hydroxide (KOH) electrolyte, which outperformed the commercial separator, the Zirfon PERL separator. The cell using a 100 nm ceria nanoparticle/polysulfone separator and advanced catalysts has a remarkable capability of 1.84 V at 800 mA cm-2 at 30 wt% and 80 °C. The decrease in the average pore size of 77 nm and high wettability (contact angle 75°) contributed to the reduced ohmic resistance and low gas crossover. These results demonstrate that the use of ceria nanoparticle-based separators can achieve high performance compared to commercial zirconia-based separators.