Dynamic modelling of an alkaline water electrolysis system and optimization of its operating parameters for hydrogen production

This work aims at developing an approach for modelling and optimizing the operation of a reference alkaline electrolysis unit operating in transient state using orthogonal collocation on finite elements (OCFE). The main goal is to define the set of operating conditions that minimize the processing cost (associated to electricity cost) given a hydrogen yield. Three components of the electrolyzer are considered: the stack of electrolytic cells and two separators that single out the hydrogen and oxygen gas streams. The dynamic behavior is considered for the mass holdup in the separators as well as the energy accumulation for these three components. The associated mathematical model is derived in the paper. Its solving allows characterizing the influence of the transient operating parameters of the system on its working and associated final hydrogen production. Mathematical optimization aims at defining the ideal operating load in order to minimize costs associated to fluctuating price of electricity consumed by the stack given a defined hydrogen yield. The model has been validated according to experimental test runs and operating conditions have been optimized under a proof of concept scenario saving 17% of electricity costs if compared to constant plant capacity.     

Influence of process conditions on gas purity in alkaline water electrolysis

In this paper the influence of operating conditions on the product gas purity of a zero-gap alkaline water electrolyzer was examined. Precise knowledge of the resulting gas purity is of special importance to prevent safety shutdown when the electrolyzer is dynamically operated using a renewable energy source. The investigation in this study involves variation of temperature, electrolyte concentration and flow rate as well as different electrolyte management concepts. The experiments were carried out in a fully automated lab-scale electrolyzer with a 150 cm² zero-gap cell and approximately 31 wt% KOH at ambient and balanced cathodic and anodic pressure. The purity of the evolved gases was measured via online gas chromatography. It can be seen from the experiments that a temperature increase and flow rate decrease reduces the gas impurity when mixing catholyte and anolyte. A further reduction of gas impurity can be achieved when both cycles are being separated and a dynamic cycling strategy is applied.     

Effect of operating parameters on hydrogen production by electrolysis of water

This paper presents an experimental study of hydrogen production by alkaline water electrolysis using Zinc alloys as materials for cathode. The aim of this study is to select the best alloy for producing hydrogen on testing the effect of some operating parameters. Experiments were conducted on a water electrolysis cell with two electrodes (anode/cathode). Throughout these experiments, we have chosen to use NaOH solution with different concentrations as an electrolyte. Binary alloys: Zn95%Fe5%, Zn90%Fe10%, Zn85%Fe15%, Zn95%Cu5%, Zn90%Cu10%, Zn85%Cu15%, Zn95%Co5%, Zn90%Co10%, Zn95%Cr5% and Zn90%Cr10% (mass %) were prepared as electrodes for the cathode. The effect of electrode composition, the electrolyte concentration, the voltage and amperage applied on volume of hydrogen produced are experimentally investigated. The results showed that the performance of alkaline water electrolysis is significantly affected by these various factors. Indeed, this preliminary study revealed that cathodes elaborated by (Zn95%Cr5%) and (Zn90%Cr10%) (mass %) produce more hydrogen gas than other alloys, in a minimum durations over the range of operating parameters tested.     

Novel alkaline water electrolysis with nickel-iron gas diffusion electrode for oxygen evolution

In the present work, a novel electrolyzer concept for alkaline water electrolysis (AEL) with a gas diffusion electrode (GDE) as anode, a conventional immersed porous cathode and a state-of-the-art Zirfon™ separator is presented and compared with a conventional electrolyzer setup. Due to the utilization of a GDE in this configuration, the electrolyte is only circulated through the cathode compartment which greatly simplifies the process. The influence of the catalyst composition and the enhanced electrode surface owing to the three-dimensional porous structure of the GDE are characterized and investigated regarding the electrode performance. Furthermore, process parameters like contact pressure and differential pressure are examined and optimized. The novel process concept with a GDE as anode reveals a similar cell potential compared to a classical electrolysis cell with a Ni/Fe-coated nickel foam anode up to 400 mA cm⁻² at 353 K and 32.5 wt% KOH and also exhibits relatively good electrochemical stability over time.     

Chlorine-free alkaline seawater electrolysis for hydrogen production

A new process for chlorine-free seawater electrolysis is proposed in this study. The first step of the process is separation of Mg²⁺ and Ca²⁺ ions from seawater by nanofiltration. Next, the NF permeate is dosed into the electrochemical system. There it is completely split into hydrogen and oxygen gases and NaCl precipitate. The electrochemical system comprises an electrochemical cell operated at elevated temperatures (e.g. ≥ 50 °C) and a settling tank filled with aqueous NaOH solution (20–40 %wt) that operates at lower temperatures (e.g. 20–30 °C). High concentration of hydroxide ions in the electrolyzed solution prevents anodic chlorine evolution, while the accumulated NaCl precipitates in the settling tank. Batch electrolysis tests, performed in NaCl-saturated NaOH solutions, showed absolutely no chlorine formation on Ni200 and Ti/IrO₂RuO₂TiO₂ anodes at [NaOH] > 100 g/kgH₂O. Three long-term operations (9, 12 and 30 days) of the electrochemical system showed no Cl₂ or chlorate (ClO₃^?) production on both electrodes operated at current densities of 93–467 mA/cm². The Ni200 anode was corroded in the continuous operation that resulted in formation of nickel oxide on the anode surface. On the other hand, the system was successfully operated at 467 mA/cm² with Ti/IrO₂RuO₂TiO₂ electrodes in NaCl-saturated solution of NaOH (30 %wt) for 12 days. During this period no formation of Cl₂ and ClO₃^? has been observed and precipitation of NaCl occurred only in the settling tank. The performance of the system was stable during the operation as indicated by the insignificant fluctuations in the applied cell potentials and measured constant concentrations of NaOH_(aq) and NaCl_(aq) in the electrolyte solution. During 12 days of operation at ≈ 470 mA/cm² about 1.2 m³ of H₂ and ≈150 g of solid NaCl were produced in the system. Electrical energy demand of the electrolysis cell was 5.6–6.7 kWh/m³H₂ for the current density range of 187–467 mA/cm².     

Solar hydrogen production via alkaline water electrolysis

Electricity generation via direct conversion of solar energy with zero carbon dioxide emission is essential from the aspect of energy supply security as well as from the aspect of environmental protection. Therefore, this paper presents a system for hydrogen production via water electrolysis using a 960 Wp solar power plant. The results obtained from the monitoring of photovoltaic modules mounted in pairs on a fixed, a single-axis and a dual-axis solar tracker were examined to determine if there is a possibility to couple them with an electrolyzer. Energy performance of each photovoltaic system was recorded and analyzed during a period of one year, and the data were monitored on an online software service. Estimated parameters, such as monthly solar irradiance, solar electricity production, optimal angle, monthly ambient temperature, and capacity factor were compared to the observed data. In order to get energy efficiency as high as possible, a novel alkaline electrolyzer of bipolar design was constructed. Its design and operating UI characteristic are described. The operating UI characteristics of photovoltaic modules were tuned to the electrolyzer operating UI characteristic to maximize production. The calculated hydrogen rate of production was 1.138 g per hour. During the study the system produced 1.234 MWh of energy, with calculated of 1.31 MWh , which could power 122 houses, and has offset 906 kg of carbon or an equivalent of 23 trees.     

Ultrathin reinforced composite separator for alkaline water electrolysis: Comprehensive performance evaluation

Porous PPS membranes are commonly employed to separate the released gases in conventional alkaline electrolyzers. However, their poor ionic conductivity and high gas permeability bring up the issues of high energy consumption and rapidly raised safety risks when the electrolyzers operate at high-pressure levels. Therefore, it is of great significance to develop alternative membranes with superior conductivity and gas tightness. In this study, we prepared an ultrathin composite membrane with support layer via combination of hot-pressing and phase inversion precipitation techniques. The comprehensive performances of the prepared membranes, commercial PPS fabric and commercial Zirfon membrane were compared. The cell performance of the prepared membranes and commercial membranes at high current density was also evaluated. The ultrathin composite membrane exhibits lower cell voltage and ionic resistance than commercial membranes. With the introduction of support layer, the tensile strength of the prepared ultrathin composite membrane significantly increased by 19 times.     

Separators for alkaline water electrolysis prepared by plasma-initiated grafting of acrylic acid on microporous polypropylene membranes

Highly hydrophilic separators for alkaline water electrolysis were prepared by plasma-initiated grafting of acrylic acid on porous polypropylene (PP) membranes. The membranes were activated in a low-pressure radio-frequency discharge in oxygen and subsequently graft polymerization of acrylic acid was performed in aqueous solution. The membranes were characterized by gravimetric grafting degree (GD), SEM, FTIR, critical wetting surface tension (CWST) test, mechanical strength, and electrolytic conductivity. Moreover, the membranes were applied as separators in alkaline electrolysis cell, and content of hydrogen in the produced oxygen was measured to determine membrane permeability to hydrogen dissolved in the electrolyte. It was observed that increasing GD improves performance of membranes as separators in alkaline electrolysis, although the particular effects on the electrolytic conductivity and hydrogen permeability strongly depend on structure the of initial PP substrate. Ageing test conducted in 30 wt% KOH at 60 °C revealed that although considerable degrafting took place at beginning of the test, the remaining polyacrylic acid provided highly hydrophilic character to membrane for 7000 h of the test.     

An analysis of PEM water electrolysis cells operating at elevated current densities

Recent developments related to the operation of PEM water electrolysis cells at elevated current density are reported. First, a cost analysis has been performed to discuss the interest of extending the range of operating current density of these cells, towards the 10 A cm⁻² range and above. Then the technical impact this may have on the cell design has been analyzed, and the practical conditions required to remove the extra-heat and to facilitate fluid transport across the porous transport layers have been identified. Experimental current-voltage polarization curves have been measured using a pressurized laboratory cells equipped with PFSA (perfluoro-sulfonic acid) membranes of various thicknesses, operating at 80 °C and current densities up to 10 A cm⁻². These experimental polarization curves have been fitted using model equations. Key cell parameters such as internal cell resistance, charge transfer exchange current densities and roughness factors have been determined from these fits. The impact of the cell design on the performance and efficiency of PEM water electrolysis cells operated in the multi A cm⁻² range of current density has been analyzed, with a focus on the situation that prevails above 5 A cm⁻².     

Modeling alkaline water electrolysis for power-to-x applications: A scheduling approach

The flexible operation of alkaline water electrolyzers enables power-to-x plants to react efficiently to different energy scenarios. In this work, a novel scheduling model for alkaline water electrolysis is formulated as a mixed-integer linear program. The model is constructed by implementing operational states (production, standby, idle) and transitions (cold/full startup, shutdown) as integer variables, while the power loading and hydrogen flowrate are set as continuous variables. The operational characteristics (load range, startup time, ramp rates) are included as model constraints. The proposed model allows finding optimal number of electrolyzers and production schedules when dealing with large data sets of intermittent energy and electricity price. The optimal solution of the case study shows a balance between hydrogen production, energy absorption, and operation and investment costs. The optimal number of electrolyzers to be installed corresponds to 54% of the ones required to absorb the highest energy peak, being capable of loading 89.7% of the available energy during the year of operation, with an overall plant utilization of 93.7% and 764 startup/shutdown cycles evenly distributed among the units.     

Electrochemically fabricated NiCu alloy catalysts for hydrogen production in alkaline water electrolysis

NiCu alloy catalysts for alkaline water electrolysis were prepared by an electrodeposition method varying the alloy composition. When the deposition potential became more positive, the bulk and surface Cu content in NiCu alloys as well as the catalyst particle size gradually increased, which were confirmed by various spectroscopic and electrochemical techniques. The surface coverage of the catalysts was found to be a function of the deposition potential, as well. The catalytic activities of the prepared NiCu alloys to hydrogen evolution reaction (HER) were investigated with cyclic voltammetry in a 6.0 M KOH electrolyte at 298 K, and the mass activities of NiCu alloys were correlated with bulk and surface Cu contents to investigate the Cu alloying effect.     

Multidimensional and transient modeling of an alkaline water electrolysis cell

A three-dimensional (3-D) transient numerical model of an alkaline water electrolysis (AWE) cell with potassium hydroxide solution is developed by rigorously accounting for the hydrogen and oxygen evolution reactions and resulting species and charge transport through various AWE components. First, the AWE model is experimentally validated against a polarization curve corresponding to a wide range of currents as high as 2.0 A·cm^?2. In general, the simulation results compare well with the measured data and further reveal the operating characteristics of AWE cells, showing key distributions of solid/electrolyte potentials and multidimensional contours of reactant and product concentrations at various current densities. In particular, the contribution of hydroxide ion (OH^?) diffusion to the ohmic losses through porous electrodes and a porous separator are quantitatively examined at low and high electrolyte flow rates. The present full 3-D AWE model provides a basic understanding of the electrochemical and transport phenomena and can be further applied to practical large-scale AWE cell and stack geometries for grid-scale hydrogen production.     

Recent progress in alkaline water electrolysis for hydrogen production and applications

Alkaline water electrolysis is one of the easiest methods for hydrogen production, offering the advantage of simplicity. The challenges for widespread use of water electrolysis are to reduce energy consumption, cost and maintenance and to increase reliability, durability and safety. This literature review examines the current state of knowledge and technology of hydrogen production by water electrolysis and identifies areas where R&D effort is needed in order to improve this technology. Following an overview of the fundamentals of alkaline water electrolysis, an electrical circuit analogy of resistances in the electrolysis system is introduced. The resistances are classified into three categories, namely the electrical resistances, the reaction resistances and the transport resistances. This is followed by a thorough analysis of each of the resistances, by means of thermodynamics and kinetics, to provide a scientific guidance to minimising the resistance in order to achieve a greater efficiency of alkaline water electrolysis. The thermodynamic analysis defines various electrolysis efficiencies based on theoretical energy input and cell voltage, respectively. These efficiencies are then employed to compare different electrolysis cell designs and to identify the means to overcome the key resistances for efficiency improvement. The kinetic analysis reveals the dependence of reaction resistances on the alkaline concentration, ion transfer, and reaction sites on the electrode surface, the latter is determined by the electrode materials. A quantitative relationship between the cell voltage components and current density is established, which links all the resistances and manifests the importance of reaction resistances and bubble resistances. The important effect of gas bubbles formed on the electrode surface and the need to minimise the ion transport resistance are highlighted. The historical development and continuous improvement in the alkaline water electrolysis technology are examined and different water electrolysis technologies are systematically compared using a set of the practical parameters derived from the thermodynamic and kinetic analyses. In addition to the efficiency improvements, the needs for reduction in equipment and maintenance costs, and improvement in reliability and durability are also established. The future research needs are also discussed from the aspects of electrode materials, electrolyte additives and bubble management, serving as a comprehensive guide for continuous development of the water electrolysis technology.     

Three-dimensional coupling numerical simulation of two-phase flow and electrochemical phenomena in alkaline water electrolysis

Alkaline water electrolysis has the advantage of scalability for industrial-scale mass production of hydrogen; however, it is operated under a lower current density than other methods of water electrolysis because a high overpotential resulting from ion transport limitations will occur at high current density. Bubble dynamics can both prevent ion transport by its existence and accelerate it by bubble-induced flow. In this study, we conduct three-dimensional coupling numerical simulations of two-phase flow and electrochemical phenomena to elucidate the mechanisms by which microscale bubble dynamics influence ion transport and the cell overpotential. We find that the flow induced by rising microbubbles enhances ion transport to the anode and suppresses the cell overpotential. Moreover, bubble atomization further suppresses the overpotential because smaller bubbles approach the anode more closely than larger ones and accelerate ion transport to the anode surface.     

Effect of pulse potential on alkaline water electrolysis performance

In this study, the effect of pulse potential on alkaline water electrolysis energy consumption is investigated. A specially designed electrical circuit is used to observe the effect of different duty cycles and frequency values on water electrolysis energy consumption in different concentration values of alkaline solution. The results show that using pulse potential enhances the mass transport of oxygen and hydrogen bubbles due to the pumping effect. This provides less contact with oxygen bubbles to improve corrosion resistance of anode electrodes. Moreover, decreasing mass transfer losses on the electrode surface resulted in a 20–25% lower energy consumption to produce 1 mol of hydrogen in the cell. The optimum frequency for 10% and 50% duty cycle and 10% and 15% concentration are investigated. For 10% duty cycle, the optimum frequency is specified around 140–200 kHz and for 50% duty cycle, it is around 380–400 kHz for all concentration values.     

Ultrashort pulse laser-structured nickel surfaces as hydrogen evolution electrodes for alkaline water electrolysis

In this study, we report on micro- and nanostructured Ni surfaces produced by an ultrashort pulse laser process as cathode materials for the alkaline electrolysis of water. We studied the influence of the laser-induced microstructure and surface morphology as well as a cyclic voltammetric activation process on the electrochemical activity of the hydrogen evolution reaction. Galvanostatic techniques, steady-state polarization curves to attain Tafel parameters and capacitance calculations via electrochemical impedance spectroscopy were used to analyze the electrodes. The analyses reveal that the ultrashort pulse laser process increases the specific surface on formerly flat Ni surfaces. Further, the cyclic voltammetric activation process gives rise to an increased intrinsic activity. Both effects lead to a strongly reduced overpotential value. This work demonstrates that different processes can be combined to dramatically boost the activity of Ni electrodes for the hydrogen evolution reaction.     

Hydrogen production by a low-cost electrolyzer developed through the combination of alkaline water electrolysis and solar energy use

Electrolysis is a relatively simple process for obtaining hydrogen and can be combined with use of renewable energy sources, such as solar photovoltaic energy, for clean, sustainable gas production. This study designed a cylindrical electrolytic cell made of acrylic and 304 stainless steel electrodes to produce hydrogen. The electrolyte used was sodium hydroxide (NaOH 2–5 mol L^?1), and the direct current voltages applied were 2.0, 2.7, and 3.4 V. The maximum hydrogen production was achieved with 5.0 mol L^?1 NaOH and 3.4 V electric voltage. The system was connected to a photovoltaic panel of 20 W and exposed to solar radiation from 10 a.m. to 2 p.m. Approximately 2 L of hydrogen was produced within a period, and an average irradiance of 800.0 W m^?2 ± 60 W m^?2 was achieved. The system was stable throughout the tests.     

Reducing the hydrogen production cost by operating alkaline electrolysis as a discontinuous process in the French market context

The possible reduction of the hydrogen production cost when operating alkaline electrolysers in a discontinuous way, in order to benefit from low electricity prices, is investigated. Beside the insights about the electricity market (prices do not correlate the demand; they are related to the supply-and-demand hardness), advances in modelling discontinuous operation are proposed. An optimum production cost is found that induces a profit of 4%, with regard to a plant that would work continuously. Specific attention should be given to related overcosts: additional degradation due to frequent transitions from the minimum electrolyser load to the nominal one, higher maintenance needs, and hydrogen storage costs. Such an operating mode would also greatly benefit from a reduction of the electrolyser prices. However, the state-of-the-art as regards the electrolyser minimum loads and transition time appears satisfactory.     

Electrochemical investigations on amorphous Fe-base alloys for alkaline water electrolysis

In this work different amorphous melt-spun Fe-alloys (Fe₈₂B₁₈, Fe₈₀Si₁₀B₁₀, Fe₆₀Co₂₀Si₁₀B₁₀) were investigated as cathode materials for the alkaline electrolysis of water. In particular, the influence of cobalt as well as the metalloids boron and silicon on the activity for the hydrogen evolution reaction (HER) was studied in 1 M KOH at 298 K using cyclic voltammetric, galvanostatic and polarization techniques. The electrocatalytic activity was evaluated in the view of the overpotential. It was found that cyclic voltammetric techniques can be used to activate the melt-spun Fe-alloys strongly. Different cyclic voltammetric activation procedures are discussed and the influence of the sweep rate and the potential window on the HER activity was elucidated. The experimental data indicate that the addition of metalloids and, most importantly, of cobalt improves the HER activity of the materials. Thus, the overpotential can be reduced by 200 mV compared to polycrystalline Ni.     

Development and testing of a novel catalyst-coated membrane with platinum-free catalysts for alkaline water electrolysis

A stable, platinum-free catalyst-coated anion-exchange membrane with a promising performance for alkaline water electrolysis as an energy conversion technology was prepared and tested. A hot plate spraying technique used to deposit electrodes 35 or 120 μm thick on the surface of an anion-selective polymer electrolyte membrane. These thicknesses of 35 and 120 μm corresponding to the catalyst load of 2.5 and 10 mg cm⁻². The platinum free catalysts based on NiCo₂O₄ for anode and NiFe₂O₄ for cathode were used together with anion selective polymer binder in the catalyst/binder ratio equal to 9:1. The performance of the prepared membrane-electrode assembly was verified under conditions of alkaline water electrolysis using different concentrations of liquid electrolyte ranging from 1 to 15 wt% KOH. The electrolyser performance was compared to a cell utilizing a catalyst-coated Ni foam as the electrodes. The prepared membrane-electrode assembly stability at a current load of 0.25 A cm⁻² was verified by a 72-hour electrolysis test. The results of the experiments indicated the possibility of a significant reduction of the catalyst loading compared to a catalyst-coated substrate approach.