Alkaline Water Electrolysis Research Articles

Maximizing Bifunctionality for Overall Water Splitting by Integrating H2 Spillover and Oxygen Vacancies in CoPBO/Co3O4 Composite Catalyst

In the pursuit of utilizing renewable energy sources for green hydrogen (H2) production, alkaline water electrolysis has emerged as a key technology. To improve the reaction rates of overall water electrolysis and simplify electrode manufacturing, development of bifunctional electrocatalysts is of great relevance. Herein, CoPBO/Co3O4 is reported as a binary composite catalyst comprising amorphous (CoPBO) and crystalline (Co3O4) phases as a high‐performing bifunctional electrocatalyst for alkaline water electrolysis. Owing to the peculiar properties of CoPBO and Co3O4, such as complementing Gibbs free energy values for H‐adsorption (ΔGH) and relatively smaller difference in their work functions (ΔΦ), the composite exhibits H2 spillover (HS) mechanism to facilitate the hydrogen evolution reaction (HER). The outcome is manifested in the form of a low HER overpotential of 65 mV (at 10 mA cm−2). Moreover, an abundant amount of surface oxygen vacancies (Ov) are observed in the same CoPBO/Co3O4 composite that facilitates oxygen evolution reaction (OER) as well, leading to a mere 270 mV OER overpotential (at 10 mA cm−2). The present work showcases the possibilities to strategically design non‐noble composite catalysts that combine the advantages of HS phenomenon as well as Ov to achieve new record performances in alkaline water electrolysis.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro‐Reforming Coupled with Hydrogen Production

Alkaline methanol‐water electrolysis system is regarded as an appealing strategy for electro‐reforming methanol into formate and producing hydrogen with low energy‐consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH‐, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm‐2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm‐2 for hydrogen evolution reaction (HER). Furthermore, membrane‐free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long‐term stability and FEs at high current density of 300 mA cm‐2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro‐Reforming Coupled with Hydrogen Production

Alkaline methanol‐water electrolysis system is regarded as an appealing strategy for electro‐reforming methanol into formate and producing hydrogen with low energy‐consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH‐, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm‐2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm‐2 for hydrogen evolution reaction (HER). Furthermore, membrane‐free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long‐term stability and FEs at high current density of 300 mA cm‐2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

In Situ Anodic Transition and Cathodic Contamination Affect the Overall Voltage of Alkaline Water Electrolysis

NiFe (oxy)hydroxide has been widely used as a benchmark anodic catalyst for oxygen evolution reactions (OERs) in alkaline water electrolysis devices; however, the energy saving actually takes contributions from both the anodic OER and cathodic hydrogen evolution reaction (HER). In this work, we observe the catalytic promotion upon the in situ-derived NiFe (oxy)hydroxide from the NiFe alloy monolithic electrode and also point out that the coupled nickel cathode is contaminated, leading to the loss of HER activity and a reduction in overall efficiency. It is found that Ni2+ and Fe3+ cations are inevitably detached from the anode into the electrolyte and electrodeposited on the nickel cathode after the three-month industrial simulation. This research presents the significant enhancement of the oxygen evolution catalysis using an in situ aging process and emphasizes that the catalytic application should not only be isolated on the half reaction, but a reasonable coupled electrode match to get rid of the contamination from the electrolyte is also of great significance to sufficiently present the intrinsic catalytic yielding for the real application.

FeCoNi‐based Alloy Coatings as Low Overpotential Electrocatalysts for Alkaline Water Electrolysis

Developing efficient, stable and low‐cost electrocatalysts is a viable approach to solve the current energy crisis. It is found that increasing the surface area of the electrodes can effectively promote the electrocatalytic efficiency. Herein, the atmospheric plasma spraying (APS) technology was used to prepare FeCoNi‐Ni3C alloy coating by adding Ni3C powder to FeCoNi powder with an equal molar ratio. The atomic ratios of Ni3C in the powder are 25 %, 50 %, and 75 %, respectively. The results prove that the pores on the surface of the coating have increased after Ni3C doping, which can provide more active sites in the electrocatalytic process to promote the electrocatalytic reaction. By controlling the proportion of Ni3C, the porosity of the coating surface can be effectively regulated. In 1.0 M KOH electrolyte and 10 mA cm‐2, the 50 at.% Ni3C coating shows an overpotential of 105 mV and 212 mV for HER and OER, respectively. It is worth noting that the 50 at.% Ni3C coating has a low Tafel slope of 45.78 mV dec‐1 (HER) and 44 mV dec‐1 (OER). Furthermore, the 50 %at. Ni3C coating catalyst has a low potential of 1.664 V at 10 mA cm‐2 in a water‐splitting system.

Review of Ni-Based Materials for Industrial Alkaline Hydrogen Production.

Hydrogen has been recognized as a green energy carrier, which can relieve energy shortage and environmental pollution. Currently, alkaline water electrolysis (AWE) driven by renewable energy to produce large-scale green hydrogen is a mainstream technology. However, tardy cathodic hydrogen evolution reaction (HER) and stability issue of catalysts make it challenging to meet the industrial requirements. Ni-based materials have attracted wide attention, thanks to their low cost and rich tuning possibilities, and many efforts have focused on their activity and stability. However, due to the significant discrepancy between laboratory and industrial conditions, these catalysts have not been widely deployed in industrial AWE. In this review, we first introduce the differences between laboratory and industrial stage, especially concerning equipment, protocols and evaluation metrics. To shorten these gaps, some strategies are proposed to improve the activity and stability of the Ni-based catalysts. Besides, some key issues related to the catalysts in industrial AWE device are also emphasized, including reverse-current and foreign ions in the electrolyte. Finally, the challenges and outlooks on the industrial alkaline AWE are discussed.

Strain Effects and Crystalline-Amorphous Interface of NiFe-LDH@S-NiFeOx/NF with Heterogeneous Structure for Enhancing Electrocatalytic Oxygen Evolution Reaction of Water-Electrolysis.

Electrochemical water-electrolysis for hydrogen generation often requires more energy due to the sluggish oxygen evolution reaction (OER). This work introduces a double-layered nanoflower catalyst, NiFe-LDH@S-NiFeOx/NF, featuring a crystalline NiFe-LDH coating on amorphous S-NiFeOx on nickel foam. Strategically integrating a crystalline-amorphous (c-a) heterostructure leverages strain engineering to enhance OER activity with low overpotentials (η100 = 220 and η500 = 245mV) and stability (135 h at η100 and 80 h at η500). Theoretical density functional theory (DFT) calculations reveal that the compressive strain can optimize the adsorption of oxygen-containing intermediates to reduce the reaction energy barrier, thus improving the reaction kinetics and performance of OER. Moreover, its phosphated derivative, NiFeP@S-NiFeOx/NF, exhibits high hydrogen evolution reaction (HER) performance (η10 = 64mV, η100 = 187mV). An alkaline water-electrolysis cell of NiFeP@S-NiFeOx/NF(-)||NiFe-LDH@S-NiFeOx/NF(+) requires only a cell voltage of 1.77V at 100 mA cm-2, demonstrating excellent stability over 110 h (at both 10 and 100mA cm-2). This work highlights the benefits of integrating crystal-amorphous interfaces and strain effects, offering insights into the understanding and optimizing catalytic OER mechanism and advancing water-electrolysis technology.

Hydrogen production efficiency enhancement for alkaline water electrolyzers operating at varying temperature via an adaptive multi-mode control

The low-load efficiency performance of alkaline water electrolyzers (AWEs) is poor so its operation range is limited. It is unfeasible for AWEs to follow the fluctuant renewable energy sources (RESs). Besides, the power fluctuation will lead to the electrolyzer temperature variation. The efficiency performance is negatively influenced. Focusing on these problems, an efficiency enhancement control strategy for AWEs operating at varying temperature is introduced in this paper. First, the efficiency model of AWEs is established. Then, a multi-mode adaptive control strategy is proposed to improve the hydrogen production efficiency of AWEs. Based on the U–I curves of AWEs, parameter identification method is used to obtain the key parameters of proposed efficiency model. Finally, the feasibility of the control strategy is experimentally validated on a 10 kW AWE. The experimental outcome shows that by applying the proposed method, the low-load hydrogen production efficiency of AWEs can be improved at different temperatures. At 15% rated load, the electrolyzer efficiency increases from 21.54% to 42.73% at 80°C. The operation range of the electrolyzer can be extended from 30% to 100%–21%∼100% of rated load at 80°C.© 2024 The Authors. Published by Elsevier Ltd.

Optimizing Alkaline Water Electrolysis: A Dual-Model Approach for Enhanced Hydrogen Production Efficiency

This study develops a semi-empirical model of an alkaline water electrolyzer (AWE) based on thermodynamic and electrochemical principles to investigate cell voltage behavior during electrolysis. By importing polarization curve test data under specific operational conditions, eight undefined parameters are precisely fitted, demonstrating the model’s high accuracy in describing the voltage characteristics of alkaline electrolyzers. Additionally, an AWE system model is introduced to examine the influence of various operational parameters on system efficiency. This innovative approach not only provides detailed insights into the operational dynamics of AWE systems but also offers a valuable tool for optimizing performance and enhancing efficiency, advancing the understanding and optimization of AWE technologies.

A Well‐Advanced High‐Throughput Test System for Electrocatalytic Screening Applications Under Industrial Relevant Conditions – A Perspective to Accelerate Electrolysis Research and Development

ABSTRACTElectrolysis is a dynamic research area in which both mature and new promising processes, such as alkaline water electrolysis and electrochemical CO2 reduction, are under enormous development pressure due to their high relevance for the energy sector. High‐throughput (HT) technologies are efficient screening platforms that can accelerate research activities and significantly shorten development times. Over the past 25 years, various HT platforms have found their way into electrochemical research. These typically have one or more major disadvantages: they are characterized by abstract experimental conditions, designed for a specific application or process, or generate insufficiently comparable data. In this publication, we present a newly developed HT test system that enables the parallel operation of 16 electrochemical bench‐scale flow cells under industry‐relevant test conditions. The specially developed modular flow cell can be operated variably in the fully automated system and allows research into the most common applications in electrochemistry for many different processes with a focus on all relevant variants of water electrolysis and electrochemical CO2 reduction. Both the HT system and the developed flow cell are designed to accelerate the generation of reliably reproducible data with high comparability in order to strengthen scientific exchange. The fully automated process control, online analysis and programmable feedback loops of the HT test system provide great potential for the design of experiment strategies. The implementation of Design of Experiment strategies will maximize the testing efficiency of this innovative research system.

Optimization of chemical engineering control for large-scale alkaline electrolysis systems based on renewable energy sources

In the context of renewable energy, dynamic control is crucial for large-scale alkaline water electrolysis systems. Under traditional Proportional-Integral-Derivative (PID) control, the system's temperature and impurity levels may exceed safe limits during sudden load changes, compromising system safety. Therefore, this study proposes a control strategy based on mathematical models of system temperature and impurities, including Model Predictive Control (MPC) for temperature and Optimal Curve Tracking (OCT) for impurities. The MPC controller offsets the disturbances in temperature caused by current fluctuations through state prediction, while the OCT controller ensures that impurity levels remain within safe limits. Real-time application of these control strategies is achieved through MATLAB-PLC communication, validating controller performance. Experimental results show that the MPC controller exhibits excellent dynamic response and stability in controlling the stack temperature, with a maximum temperature peak deviation of only 2.9 K and a temperature fluctuation range of 5.9 K. This represents a reduction of 1.6 K in peak deviation compared to traditional PID controllers and significantly decreases the temperature fluctuation range. The OCT controller also demonstrates good safety and stability in controlling hydrogen to oxygen (HTO) impurity levels, consistently maintaining the HTO content at the set upper limit of 1.5%, thereby expanding the safe operational range of the system and reducing the need for frequent adjustments to the system setpoints.

Enhanced Oxygen Evolution Reaction in Alkaline Water Electrolysis Using Bimetallic NiFe Metal-Organic Frameworks Integrated with Carbon Nanotubes

Hydrogen is considered a very clean and highly available renewable energy resource for the future. Water electrolysis (WE) is a conspicuous promising technology to produce hydrogen on a large scale, without generating carbon dioxide. In this study, we prepared bimetallic NiFe-based metal–organic frameworks (MOFs) integrated with CNTs (NiFe–BTC@CNTs) as highly efficient electrocatalysts for the oxygen evolution reaction (OER) in alkaline water electrolysis. Combining NiFe MOFs and CNTs significantly enhanced the electrochemical performance and structural integrity of the catalyst. The NiFe–BTC@CNT (30 wt.% CNTs) demonstrates a significant low overpotential of 230 mV at 10 mA·cm⁻2, superior catalytic activity with a Tafel slope of 36 mV·dec⁻1, and excellent stability under both constant and dynamic operating conditions. These unique characteristics are attributed to the high surface area and abundant active sites provided by the bimetallic MOF structure, combined with the exceptional electrical conductivity and mechanical strength of CNTs. Furthermore, the integration of CNTs improves the dispersion while preventing the agglomeration of MOF particles, ensuring a more uniform and accessible active surface area. This research highlights the potential of the NiFe–BTC@CNT catalysts as high-performance durable electrocatalysts for sustainable hydrogen production, offering a significant advance in the development of advanced materials for energy conversion and storage applications.

Insights over the in-situ grown copper sulfide/NiFe-LDH composites for alkaline and urea water electrolysis

Insights over the in-situ grown copper sulfide/NiFe-LDH composites for alkaline and urea water electrolysis

Catalyst coated diaphragms for enhanced alkaline water electrolysis

Catalyst coated diaphragms for enhanced alkaline water electrolysis

Influence of Annealing Temperature on the OER Activity of NiO(111) Nanosheets Prepared via Microwave and Solvothermal Synthesis Approaches.

Earth-abundant transition metal oxides are promising alternatives to precious metal oxides as electrocatalysts for the oxygen evolution reaction (OER) and are intensively investigated for alkaline water electrolysis. OER electrocatalysis, like most other catalytic reactions, is surface-initiated, and the catalyst performance is fundamentally determined by the surface properties. Most transition metal oxide catalysts show OER activities that depend on the predominantly exposed crystal facets/surface structure. Therefore, the design of synthetic strategies to obtain the most active crystal facets is of significant research interest. In this work, rock salt NiO OER catalysts with (111) predominantly exposed facets were synthesized by a solvothermal (ST) method either heated under supercritical or microwave-assisted (MW) conditions. Particular emphasis was placed on the influence of the post annealing temperature on the structural configuration and OER activity to compare their catalytic performances. The as-prepared electrocatalysts are pure α-Ni hydroxides which were converted to rock salt NiO (111) nanosheets with hexagonal pores after heat treatment at different temperatures. The OER activity of the electrodes has been evaluated in 0.1 M KOH using geometric and intrinsic current densities via normalization by the disk area and BET area, respectively. The lowest overpotential at a geometric current density of 10 mA/cm2 is found for samples pretreated by heating between 400 and 500 °C with a catalyst loading of 115 μg/cm2. Despite the very similar nature of the catalysts obtained from the two methods, the ST electrodes show a higher geometric and intrinsic current density for 500 °C pretreatment. The MW electrodes, however, achieve an optimal geometric current density for 400 °C pretreatment, while their intrinsic current density requires pretreatment over 600 °C. Interestingly, pretreated electrodes show consistently higher OER activity as compared to the poorly crystalline/less ordered hydroxide as-prepared electrocatalysts. Thus, our study highlights the importance of the synthesis method and pretreatment at an optimal temperature.

Integration of Multifunctionality in a Colloidal Self‐Repairing Catalyst for Alkaline Water Electrolysis to Achieve High Activity and Durability

Integration of Multifunctionality in a Colloidal Self‐Repairing Catalyst for Alkaline Water Electrolysis to Achieve High Activity and Durability

Accurately prepared the large-area and efficiently 3D electrodes for overall seawater splitting

How to achieve accurately regulation of catalytic electrodes is the challenge of designing high-performance catalytic electrodes. In this work, large area, high stability and excellent conductivity electrode are prepared via one-step mild (298 K) electroplating method and precise control of electroplating parameters on nickel foam (FeNi@NF). The FeNi@NF electrode catalyst the hydrogen/oxygen evolution reaction (HER/OER) in simulate seawater (1.0 M KOH + 0.5 M NaCl), and achieves the current density of 100 mA cm−2 with only 287 mV and 323 mV overpotential. The alkaline electrolyzer drives 100 mA cm−2 for overall water splitting at a low voltage of 1.73 V. More importantly, the catalytic performance durable for more than 5 days at the industrial current density (1000 mA cm−2), and the designed large-area 25.0 cm2 catalytic electrode can achieve stable operation of industrial proton exchange membrane electrolyser. This preparation strategy provides a new idea for the current research of energy engineering and energy storage.

Biomass-Driven Polygeneration Coupled to Power-to-X: An Energy and Economic Comparison Between On-Site Electric Vehicle Charging and Hydrogen Production

The power-to-X strategy for passenger car applications offers a viable solution for using the surplus electrical power from renewable energy sources instead of exporting it to the grid. The innovative system proposed in this study allocates surplus electrical power from a building-integrated biomass-based Combined Cooling Heating and Power (CCHP) system to on-site applications and evaluates the energetic and economic benefits. The system comprises two key components: a 50 kW electric vehicle (EV) charging station for EVs and a 50 kW alkaline electrolyzer system for on-site hydrogen production, which is later dispensed to fuel cell electric vehicles (FCEVs). The primary goal is to decrease the surplus of electricity exports while simultaneously encouraging sustainable transportation. The system’s economic viability is assessed through two scenarios of fuel (e.g., biomass) supply costs (e.g., with and without fuel market costs) and compared to the conventional approach of exporting the excess power. The key findings of this work include a substantial reduction in surplus electricity exports, with only 3.7% allocated for EV charging and 31.5% for hydrogen production. The simple payback period (SPB) is notably reduced, enhancing economic viability. Sensitivity analysis identifies the optimal hydrogen system, featuring a 120 kW electrolyzer and a 37 kg daily hydrogen demand. The results underscore the importance of prioritizing self-consumed energy over exports to the national grid, thereby supporting integrated renewable energy solutions that enhance local energy utilization and promote sustainable transportation initiatives.

A nanoporous nickel–iron alloy seamlessly anchored into hierarchical porous nickel for efficient and extremely stable water splitting

The development of a robust, low-cost electrode for electrochemical water splitting is a challenging, but essential task for realizing hydrogen production under industrial conditions. Here, we seamlessly anchor nanoporous nickel–iron into a hierarchical porous nickel foam (npNi–Fe/HPNF) by a designed gaseous oxidation–reduction engineering for a commercial nickel foam. The three-dimensional hierarchical porous structure considerably enhances the specific surface area of the electrode, yielding abundant electrocatalytic sites that promote the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Moreover, owing to its mechanically robust, seamlessly anchored architecture, and remarkable superhydrophilicity/superaerophobicity, the electrolyzer composed of self-standing npNi–Fe/HPNF and its electro-activation derivative displays a current density of 10 mA cm−2 at 1.54 V, ultralong durability of more than 2000 h at 500 mA cm−2 in a 1 M KOH electrolyte, and high performance of 2 V at 1 A cm−2 in a quasi-industrial environment (5 M KOH and 70 °C), outperforming most alkaline electrolyzers based on state-of-the-art electrodes. Exceptional electrochemical performance and the ability to be prepared at a large scale (2500 cm2) make npNi–Fe/HPNF a promising candidate for industrial water splitting applications.

Dual-objective Optimization of Solar Driven Alkaline Electrolyzer System for On-Site Hydrogen Production and Storage: Current and Future Scenarios

Dual-objective Optimization of Solar Driven Alkaline Electrolyzer System for On-Site Hydrogen Production and Storage: Current and Future Scenarios