Stability of Ni-Fe-Layered Double Hydroxide Under Long-Term Operation in AEM Water Electrolysis.

Anion exchange membrane water electrolysis (AEMWE) is an attractive method for green hydrogen production. It allows the use of non-platinum group metal catalysts and can achieve performance comparable to proton exchange membrane water electrolyzers due to recent technological advances. While current systems already show high performances with available materials, research gaps remain in understanding electrode durability and degradation behavior. In this study, the performance and degradation tracking of a Ni3Fe-LDH-based single-cell is implemented and investigated through the correlation of electrochemical data using chemical and physical characterization methods. A performance stability of 1000 h, with a degradation rate of 84 µV h-1 at 1 A cm-2 is achieved, presenting the Ni3Fe-LDH-based cell as a stable and cost-attractive AEMWE system. The results show that the conductivity of the formed Ni-Fe-phase is one key to obtaining high electrolyzer performance and that, despite Fe leaching, change in anion-conducting binder compound, and morphological changes inside the catalyst bulk, the Ni3Fe-LDH-based single-cells demonstrate high performance and durability. The work reveals the importance of longer stability tests and presents a holistic approach of electrochemical tracking and post-mortem analysis that offers a guideline for investigating electrode degradation behavior over extended measurement periods.

In Situ Sonoactivation of Polycrystalline Ni for the Hydrogen Evolution Reaction in Alkaline Media.

In this investigation, we report on the development of a method for activating polycrystalline metallic nickel (Ni(poly)) surfaces toward the hydrogen evolution reaction (HER) in N2-saturated 1.0 M KOH aqueous electrolyte through continuous and pulsed ultrasonication (24 kHz, 44 ± 1.40 W, 60% acoustic amplitude, ultrasonic horn). It is found that ultrasonically activated Ni shows an improved HER activity with a much lower overpotential of -275 mV vs RHE at -10.0 mA cm-2 when compared to nonultrasonically activated Ni. It was observed that the ultrasonic pretreatment is a time-dependent process that gradually changes the oxidation state of Ni and longer ultrasonication times result in higher HER activity as compared to untreated Ni. This study highlights a straightforward strategy for activating nickel-based materials by ultrasonic treatment for the electrochemical water splitting reaction.

Sonoactivated polycrystalline Ni electrodes for alkaline oxygen evolution reaction.

The development of cost-effective and active water-splitting electrocatalysts is an essential step toward the realization of sustainable energy. Its success requires an intensive improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. In this work, we designed a facile and one-route strategy to activate the surface of metallic nickel (Ni) for the OER in alkaline media by ultrasound (24 kHz, 44 W, 60% acoustic amplitude, ultrasonic horn). Sonoactivated Ni showed enhanced OER activity with a much lower potential at + 10 mA cm-2 of + 1.594 V vs. RHE after 30 min ultrasonic treatment compared to + 1.617 V vs. RHE before ultrasonication. In addition, lower charge transfer resistance of 11.1 Ω was observed for sonoactivated Ni as compared to 98.5 Ω for non-sonoactivated Ni. In our conditions, ultrasound did not greatly affect the electrochemical surface area (Aecsa) and Tafel slopes however, the enhancement of OER activity can be due to the formation of free OH• radicals resulting from cavitation bubbles collapsing at the electrode/electrolyte interface.

Tuning Ni-MoO2 Catalyst-Ionomer and Electrolyte Interaction for Water Electrolyzers with Anion Exchange Membranes.

Tailoring catalyst-ionomer and electrolyte interaction is crucial for the development of anion exchange membrane (AEM) water electrolysis. In this work, the interaction of Ni-MoO2 nanosheets with ionomers and electrolyte cations was investigated. The activity of Ni-MoO2 nanosheets for the hydrogen evolution reaction (HER) increased when tested in 1 M NaOH compared to 1 M KOH; however, it decreased when tested in 0.01 M KOH compared to 1 M KOH electrolyte. The capacitance minimum associated with the potential of zero free charge (pzfc) was shifted negatively from 0.5 to 0.4 V versus RHE when KOH concentration increased from 0.1 mM to 1 M KOH, suggesting a softening of the water in the double-layer to facilitate the OH- transport and faster kinetics of the Volmer step that lead to improved HER activity. The catalyst interaction with cationic moieties in the anion ionomer (or organic electrolytes) can also be rationalized based on the capacitance minimum, because the latter indicates a negatively charged catalyst during the HER, attracting the cationic moieties leading to the blocking of the catalytic sites and lower HER performance. The HER activity of Ni-MoO2 nanosheets is lower in benzyltrimethylammonium hydroxide (BTMAOH) than in tetramethylammonium hydroxide (TMAOH). Anion fumion ionomer and electrolytes with organic cations with benzyl group adsorption (such as BTMAOH) lead to decreased HER activity in comparison with TMAOH and Nafion. By utilizing Ni-MoO2 nanosheet electrodes as a cathode in a full non-platinum group metal (PGM) AEM electrolyzer, a current density of 1.15 A/cm2 at 2 V cell voltage in 1 M KOH at 50 °C was achieved. The electrolyzer showed exceptional stability in 0.1 M KOH for 65 h at 0.5 A/cm2.

Does power ultrasound (26 kHz) affect the hydrogen evolution reaction (HER) on Pt polycrystalline electrode in a mild acidic electrolyte?

In this study, we investigated the effects of power ultrasound (26 kHz, up to ∼75 W/cm2, up to 100% acoustic amplitude, ultrasonic horn) on the hydrogen evolution reaction (HER) on a platinum (Pt) polycrystalline disc electrode in 0.5 M H2SO4 by cyclic and linear sweep voltammetry at 298 K. We also studied the formation of molecular hydrogen (H2) bubbles on a Pt wire in the absence and presence of power ultrasound using ultra-fast camera imaging. It was found that ultrasound significantly increases currents towards the HER i.e. a ∼250% increase in current density was achieved at maximum ultrasonic power. The potential at a current density of -10 mA/cm2 under silent conditions was found to be -46 mV and decreased to -27 mV at 100% acoustic amplitude i.e. a ΔE shift of ∼+20 mV, indicating the influence of ultrasound on improving the HER activity. A nearly 100% increase in the exchange current density (jo) and a 30% decrease in the Tafel slope (b) at maximum ultrasonic power, was observed in the low overpotential region, although in the high overpotential region, the Tafel slopes (b) were not significantly affected when compared to silent conditions. In our conditions, ultrasound did not greatly affect the "real" surface area (Ar) and roughness factor (R) i.e. the microscopic surface area available for electron transfer. Overall, it was found that ultrasound did not dramatically change the mechanism of HER but instead, increased currents at the Pt surface area through effective hydrogen bubble removal.