Dynamic energy and mass balance model for an industrial alkaline water electrolyzer plant process

This paper proposes a parameter adjustable dynamic mass and energy balance simulation model for an industrial alkaline water electrolyzer plant that enables cost and energy efficiency optimization by means of system dimensioning and control. Thus, the simulation model is based on mathematical models and white box coding, and it uses a practicable number of fixed parameters. Zero-dimensional energy and mass balances of each unit operation of a 3 MW, and 16 bar plant process were solved in MATLAB functions connected via a Simulink environment. Verification of the model was accomplished using an analogous industrial plant of the same power and pressure range having the same operational systems design. The electrochemical, mass flow and thermal behavior of the simulation and the industrial plant were compared to ascertain the accuracy of the model and to enable modification and detailed representation of real case scenarios so that the model is suitable for use in future plant optimization studies. The thermal model dynamically predicted the real case with 98.7 % accuracy. Shunt currents were the main contributor to relative low Faraday efficiency of 86 % at nominal load and steady-state operation and heat loss to ambient from stack was only 2.6 % of the total power loss.     

Hydrogen production using alkaline electrolyzer and photovoltaic (PV) module

In this paper it is presented hydrogen production using alkaline water electrolysis where a 30 W photovoltaic (PV) module was involved as a source of electric energy. Therefore, the process is without emitting CO₂. There is constructed and tested an alkaline electrolyzer with 50 × 50 × 2 mm Ni metal foam electrodes, 50 × 50 × 0.4 mm Zirphon^® membrane and 25% alkaline (KOH) solution electrolyte. Electrolyzer UI characteristics for natural and forced flow of electrolyte with PV module UI characteristics are presented. The results are in favor of forced flow circulation, and these are better if the flow velocities are higher. Calculated Energy efficiency (based on hydrogen high heating value) for both types of circulation is above 55%. There are much evidence for further improvement of the system components and consequently electrolyzer and system efficiency.     

Automized parametrization of PEM and alkaline water electrolyzer polarisation curves

A comprehensive literature review of current water electrolyzer modelling research was conducted and presented models critically evaluated. Based on the literature review this paper presents an open-source MATLAB toolbox for water electrolyzer polarisation curve parametrization and modelling. The modelling capabilities of the tooling were verified using measured PEM and alkaline water electrolyzer polarisation data. As real-world measurement data is rarely ideal, tests were also conducted using suboptimal data, first with data sets that have a low number of measurement points and secondly with data sets that have low or high current densities missing. The tooling is shown to work with a wide variety of use cases and provides an automated method for modelling and parametrization of electrolyzer polarisation curves.     

Thermal performance of a commercial alkaline water electrolyzer: Experimental study and mathematical modeling

In this paper a study of the thermal performance of a commercial alkaline water electrolyzer (HySTAT from Hydrogenics) designed for a rated hydrogen production of 1 N m³ H₂/h at an overall power consumption of 4.90 kW h/N m³ H₂ is presented. The thermal behaviour of the electrolyzer has been analyzed under different operating conditions with an IR camera and several thermocouples placed on the external surface of the main electrolyzer components. It has been found that the power dissipated as heat can be reduced by 50–67% replacing the commercial electric power supply unit provided together with the electrolyzer by an electronic converter capable of supplying the electrolyzer with a truly constant DC current. A lumped capacitance method has been adopted to mathematically describe the thermal performance of the electrolyzer, resulting in a thermal capacitance of 174 kJ °C⁻¹. The effect of the AC/DC converter characteristics on the power dissipated as heat has been considered. Heat losses to the ambient were governed by natural convection and have been modeled through an overall heat transfer coefficient that has been found to be 4.3 W m⁻² °C⁻¹. The model has been implemented using ANSYS^® V10.0 software code, reasonably describing the performance of the electrolyzer. A significant portion of the energy dissipated as heat allows the electrolyzer operating at temperatures suitable to reduce the cell overvoltages.     

Researching and adjusting the modes of joint operation of a photoelectric converter and a high pressure electrolyzer

The article describes the experimental studies of hydrogen (oxygen) generation processes by the electrolysis method that were fulfilled with the use of the energy plant model involving a solar energy photovoltaic converter (working surface area is of S = 1.5 m²) and a membrane-less high-pressure electrolyzer (capacity is of 0.002 m³ of hydrogen per hour with an operating pressure of 0.3 MPa). Under experimental studies we have adjusted the modes of joint operating the photoelectric converter and the membrane-less high pressure electrolyzer depending on the changes of solar insolation. We have determined the ways to increase the electrolyzer efficiency. It was found that the level of current density, which determines the electrolyzer efficiency by hydrogen, depends on the solar insolation level. The obtained experimental data, as to adapting an electrolyzer to be feed from a photoelectric converter, give the possibility to develop the algorithms of automatic control of the electrolyzer when it operates in composition of an autonomous energy plant.     

PEM water electrolyzer model for a power-hardware-in-loop simulator

Power-electronics-based power-hardware-in-loop (PHIL) simulator for water electrolyzer emulation with a nominal current of 405 A is developed to study the electrolyzer as part of a smart grid and to analyze the characteristics of various electrolyzer power supply electronics. A simplified model of a proton exchange membrane (PEM) electrolyzer is implemented into the PHIL simulator to describe the voltage and current characteristics of the electrolyzer stack. The model is verified comparing the current and the estimated hydrogen production of the PHIL simulator with the measured values of the commercial PEM electrolyzer following the measured solar photovoltaic (PV) system output power.     

Test of conductor and semiconductor electrocatalysts in high voltage alkaline electrolyzer as production media for green hydrogen

Despite the restricted success of conductor and semiconductor electrodes in solving hydrogen production problems, they provide a promising alternative to expensive conventional electrodes in water electrolysis investigations. Titanium dioxide (TiO₂) and silver (Ag) are widely used as photocatalysts in water splitting systems for hydrogen generation. Though TiO₂ is an inactive chemical semiconductor with poor conductivity, it has not been entirely investigated as an electrocatalyst yet. Two criteria were used to achieve this target: supplying high voltage to overcome the TiO₂ large band gap and immersing it in an alkaline solution to activate its inert surface. For comparison study, Ag noble metal nanoparticles coating was employed as a competitive electrocatalyst. In this regard, the application of Ag and TiO₂ coated on Ti electrodes in a hydrogen production system operated under high voltage was reported. The nanoparticles were synthesized using cost-effective and simple methods based on UV-deposition for Ag nanoparticles and the chemical precipitation method for TiO₂ nanoparticles. Then the synthesized nanoparticles were deposited on the Ti electrodes by simple immersion. The synthesized nanoparticles and coated electrodes were tested by XRD, SEM, and EDS to study their morphology, structure, particle size, and surface composition. Based on these results, TiO₂ nano-powder and coated electrodes exhibited homogenous spheres with a mixture of rutile and anatase phases, the majority being the anatase phase. The Ag-coated Ti substrate possessed a smaller crystallite size compared to TiO₂ coated substrate. To evaluate the performance of Ag/Ti and TiO₂/Ti electrodes toward hydrogen production, H₂ flow rates were measured in a 3.6 M KOH electrolytic solution at 6 V. Hydrogen flow rates obtained for pure Ti, Ag, and TiO₂ electrodes at a steady state were 21, 35, and 37 SCCM (standard cm³/min), respectively. Also, it was found that energy consumption was reduced when the electrodes were coated with nanoparticles. Furthermore, the electrolyzer's performance was assessed by calculating the hydrogen production efficiency and the voltage efficiency. The results showed that using TiO₂ electrodes gave the best hydrogen production and voltage efficiencies of 27% and 23%, respectively. This study brings new insights about Ag and TiO₂ coated electrodes in alkaline water electrolysis at high voltage regarding nanoparticle performance, hydrogen production, system performance, and energy consumption. In addition, minimizing the fabrication and operation costs of hydrogen production is the major enabler for the broad commercialization of water electrolysis devices.     

Experimental study on the external electrical thermal and dynamic power characteristics of alkaline water electrolyzer

As hydrogen production with a water electrolyzer is an effective way for renewable energy consumption, understanding the external electrical characteristics of water electrolyzer is of great significance for the modeling and simulation, system configuration, and control strategy of the system for hydrogen production by renewable energy. However, there are relatively fewer studies in this area. This paper presents the establishment of an experimental platform to conduct an experimental study on the static and dynamic voltage‐current characteristics and analyze the adjustability of the electric power of the traditional alkaline water electrolyzer, the relationship between the electrical characteristics and the electrolyte temperature, and operating point of the alkaline water electrolyzer. In addition, the mathematical fitting problem of the electrical characteristics of the alkaline water electrolyzer is discussed. The work could supply a reference to alkaline water electrolyzer intergrated application in renewable energy.     

Ni alloy nanowires as high efficiency electrode materials for alkaline electrolysers

The fabrication and characterization of nickel-alloy electrodes for alkaline electrolysers is reported. Three different alloys (Ni–Co, Ni–Zn and Ni–W) at different composition were studied in order to determine the optimum condition. Nanostructured electrodes were obtained by template electrodeposition into a nanoporous membrane, starting from aqueous solution containing the two elements of the alloy at different concentrations. Composition of alloys can be tuned by electrolyte composition and also depends on the difference of the redox potential of elements and on the presence of complexing agents in deposition bath. Electrochemical and electrocatalytic tests, aimed at establishing the best alloy composition, were carried out for hydrogen evolution reaction. Then, test conducted at a constant current density in potassium hydroxide (30% w/w) aqueous solution were also performed. For all investigated alloys, very encouraging results were obtained and in particular Ni–Co alloys richer in Co showed the best performance.     

Performance of nickel electrode for alkaline water electrolysis prepared by high pressure cold spray

To promote Ni electrode performance during water splitting, a novel coating process, High pressure cold spray, is applied to prepare electrodes from blended Ni + Al powder. By controlling Al fraction, electrodes are obtained with varied microstructure. SEM and EDX are implemented to check the micromorphology of electrodes. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) are performed to estimate the effect of Al addition on electrode performance. Resultantly, significant improvement of electrode performance is achieved by increasing the fraction of Al from 10 vol% to 20 vol%. The obtained coatings are found with numerous pores owing to the removal of Al during the activation. By applying electrochemical test, the HER of all samples are dominated by Volmer step, and sample N20A is found with the highest active surface area. Thus, sample N20A exhibits the highest electro-catalytic activity to HER of alkaline water electrolysis.     

Mathematical modeling and simulation for external electrothermal characteristics of an alkaline water electrolyzer

The water electrolyzer is a key device in the direct energy interaction between the hydrogen production system and the fluctuation power supply. Therefore, to understand its external electrothermal characteristics and modeling, an efficient simulation method is not only theoretically significant but also of great value in engineering applications for the key techniques, such as the study of control strategy and optimum configuration of renewable energy generation. Currently, research studies on the electrothermal characteristics of the alkaline water electrolyzer (AWE) are focused mainly on the microcosmic mechanism, without sufficient emphasis on the modeling and simulation technique of the external macroscopic electrothermal characteristics. Based on relevant theories in electrochemistry and test results of the electrothermal characteristics, this paper establishes a mathematical model of the equivalent impedance characteristics, electrothermal characteristics, and power regulation characteristics of AWE. Then, a simulation model of the external electrothermal characteristics is built with Matlab/Simulink. Finally, the accuracy of the established mathematical model and the functionality of the simulation model are verified. The research can provide some reference for the modeling and simulation of the electrical characteristics of AWE.     

Synthesis of nickel-based skeletal catalyst for an alkaline electrolyzer

A method for preparing Nickel-based skeletal catalyst as well as its characterization is reported. The catalyst has an intended use as a cathode in alkaline electrolysis. Skeletal catalyst electrodes were synthesized from equal weights (50% each) of aluminum and nickel powders. The catalyst was prepared with metal powders which were melted in an induction oven, allowing the alloy to solidify at room temperature to obtain the thermodynamically-stable phases of the alloy. Samples from the resulting alloy went through a leaching process in an alkaline solution using two different leaching times. After leaching, porous and amorphous electrodes were obtained and then subjected to a slow oxidative stage to avoid ignition. The structure, composition, morphology and electrochemical characteristics of the electrodes were studied. The leached samples showed a high exchange current density indicating that are good catalysts for the Hydrogen Evolution Reaction (HER), a property enhanced by the adsorption of hydrogen during the leaching process which facilitated the hydrogen reduction overall reaction.     

Process modelling of an alkaline water electrolyzer

In this paper a model for the prediction of the product gas purity in alkaline water electrolysis is proposed. For the estimation of the exhaust gas compositions the operating conditions, such as current density, electrolyte flow rate, concentration and temperature as well as process management possibilities are considered. The development of the model relies on a classical process engineering approach and depicts the electrolysis cell through coupled continuously stirred-tank reactors. Furthermore, the mass transport phenomena between the phases are considered through the application of Reynolds and Sherwood correlations. Finally, the validation of the model is performed through experiments, which are carried out in a lab-scale electrolyzer with a 150 cm² zero-gap cell and KOH electrolyte at atmospheric pressure. This investigation reveals that gas purity in alkaline water electrolysis is mainly affected by mixing the anodic and cathodic electrolyte cycles, which transport dissolved electrolysis products into the opposite half cell compartments. However, this transport mechanism can be significantly reduced by adjustment of the operating conditions of the electrolyzer.     

New multi-physics approach for modelling and design of alkaline electrolyzers

This work presents a multi-physics model used for the design and diagnosis of the alkaline electrolyzers. The model is based on a new approach that allows to choose precisely the design parameters of a new electrolyzer even if it is not commercially available and predicting energy consumption, efficiency and rate of hydrogen production, taking into account to their physical state and various operating conditions. The approach differs from those of conventional models of the following: It allows the characterization of the electrolyzer based on its structural parameters in a relatively short time (few minutes) compared with the conventional approach which need experimental data collected for few weeks (Ulleberg). The approach allows describing a range of alkaline electrolyzers, while semi-empirical models found in literature are inherent to a specific electrolyzer. In addition, the model takes into account the variation of all structural parameters (geometry, materials and their evolution depending on operating conditions) and operational parameters of the electrolyzer (temperature, pressure, concentration, bulk bubbling and recovery rate of electrode surface by the bubble), while the models in the literature involve only the temperature. The developed multi-physics model was programmed in a Matlab Simulink^® environment and an alkaline electrolyzer’s simulation tool was developed. The simulation tool was validated using two industrial (Stuart and Phoebus) electrolyzers with different structures and power rates. Simulation results reproduced experimental data with good accuracy (less than 0.9%). The simulation tool was also used to compare the energy efficiency of two hydrogen production systems. The first one is based on atmospheric electrolyzer with a compressor for hydrogen storage and the second one is a barometric electrolyzer (under pressure) with its auxiliary devices to identify the effective mode of hydrogen production according to the physical state and operating conditions of the electrolyzer. The analysis of results revealed that the second mode of hydrogen production is more efficient and confirms the results of the literature based solely on the thermodynamic approach (K. Onda et al) without the input of the power consumed by power overvoltages.     

Performance assessment of gas crossover phenomenon and water transport mechanism in high pressure PEM electrolyzer

To improve proton exchange membrane (PEM) electrolyzes’ performance the voltage loss through them should be avoided. In this work, it is intended to analyze losses including of diffusion loss, ohmic loss due to electrode, bipolar plate (BP), and membrane resistances, and gas crossover associated with the water transferring mechanisms. All of the losses are associated with water transferring mechanisms, which is created due to electro-osmoic drag, pressure differential between the anode and cathode sides, and diffusion. Furthermore, the effect of membrane thickness, cathode pressure, and operating temperature on the hydrogen crossover is examined. In addition, the contribution of ohmic loss due to electrode bipolar plate (BP), and membrane resistances is studied and, the contribution of different losses on the cell performance is discussed. Results show that raising cathode pressure from 1 to 40 bar lead to the increment of anodic hydrogen content from 1.038% to 21% at the specific current density of 10,000 A/m2. Enhancing the thickness of membrane has considerable impact on decrementing anodic hydrogen content, but the mass transfer loss rises from 0.022 to 0.027 V with enhancing membrane thickness from 50 to 300 μm, respectively. Furthermore, the contribution of voltage losses, assigned to each of losses are equal to 85%, 3%, and 12% for activation, diffusion and ohmic losses, respectively. It is found that, from the reported contribution for ohmic loss, the contribution of electrode BP, and membrane resistances are 31% and 69%, respectively.     

Mechanism of oxygen electrode delamination in solid oxide electrolyzer cells

An electrochemical model for degradation of solid oxide electrolyzer cells is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. It is shown that electronic conduction   through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, μ_O2${\mu }_{{\mathrm{O}}_2}$, within the electrolyte. The μ_O2${\mu }_{{\mathrm{O}}_2}$ within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accord with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte.     

Performance of a PEM electrolyzer using RuIrCoOx electrocatalysts for the oxygen evolution electrode

The Proton Exchange Membrane Water Electrolyzer (PEMWE) can be coupled to renewable energy sources (solar radiation and wave energy), which produce the necessary electricity for splitting the water. In this work the performance of a PEMWE using RuIrCoO_x as anodic electrocatalyst had been examined. The oxide powder was synthesized using a chemical reduction method, followed by thermal oxidation. The electrochemical properties of the electrocatalysts were examined by cyclical and lineal voltammetry in 0.5 M H₂SO₄. It was found that RuIrCoO_x oxide electrodes present a stable performance for OER. The PEMWE was designed and in-home built. Chrono-potentiometric experiments were recorded in the current range of 0.25 mA cm⁻² to 75 mA cm⁻² at 300 s. The current pulses length is chosen to be sufficiently long so that the voltage remains constant. Their intrinsic electrocatalytic activity in combination with their large surface area and stability are quite promising for the development of economically feasible electrocatalysts for (PEMWE).     

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.     

Numerical simulation and exergoeconomic analysis of a high temperature polymer exchange membrane electrolyzer

In this paper, a finite volume numerical method is developed to investigate a high temperature polymer exchange membrane (PEM) electrolyzer cell using a three-dimensional and non-isothermal model. The results that are obtained for the single cell are generalized to a full stack of electrolyzer and an exergoeconomic analysis is performed based on the numerical data. The effects of operating temperature, the pressure of cathode, gas diffusion layer (GDL) thickness, and membrane thickness on the energy and exergy efficiencies and exergy cost of the electrolyzer are examined. This study reveals that by increasing the working temperature from 363 K to 393 K, the exergy cost of hydrogen decreases from 23.16 $/GJ to 22.39 $/GJ, and the exergy efficiency of PEM electrolyzer stack at current density of 10,000 A/m² increases from 0.56 to 0.59. The results indicate that increase of pressure deteriorates the system performance at voltages below 1.4 V. It is concluded that operation of the electrolyzer at higher pressures results in decrease of the exergy cost of hydrogen. Increase of membrane thickness from 50 μm to 183 μm leads to increase of the exergy cost of hydrogen from 23.24 $/GJ to 35.99 $/GJ.     

Performance assessment of solar-powered high pressure proton exchange membrane electrolyzer: A case study for Erzincan

In this study, a performance assessment of a solar-powered high-pressure proton exchange membrane (PEM) electrolyzer for hydrogen production is conducted. The feasibility analysis of photovoltaic systems equipped with a high pressure PEM electrolyzer is presented for a university campus-scale community in Erzincan- Turkey. Variable solar irradiance data sets are utilized to assess the performance of the proposed system. A parametric study is conducted in order to evaluate the influence of some design parameters as well as operating conditions on the efficiency of the system. Efficiency of the overall system in the case of relevant inverter sizing is in the range of 11–12%. An ascent of the number of stacks leads to an increase in production rate which is almost linear by photovoltaic (PV) array size. The results shows that in order to have a higher efficiency, the inverter size should be higher than 0.75% of maximum excess power. The proposed system investigated in this study shows great promise of opening up opportunity to develop the high pressure PEM electrolyzer.