Simulation of proton exchange membrane electrolyzer: Influence of bubble covering

The bubble covering phenomenon has been considered one of the most critical factors affecting Proton Exchange Membrane Electrolysis Cell (PEMEC) at high current densities. However, the relationship between bubble dynamics and electrochemistry has not been clearly defined. This study analyzes the bubble coverage and PEMEC performance under different input conditions and develops a mathematical model of PEMEC incorporating bubble dynamics. The model successfully predicted the polarization curves and coincided with the experimental data. The results show that bubble coverage increases with increasing current density, bubble detachment radius, and temperature. It decreases with increasing pressure and water inlet velocity. Bubble coverage is influenced by temperature, pressure, wettability, current density, and water inlet velocity. Meanwhile, bubbles covering the electrode deteriorate the performance of the PEMEC, leading to higher overpotentials and lower efficiencies, which becomes more apparent with increasing current density. This paper elucidates the relationship between bubble growth/detachment, bubble coverage, and electrochemistry for the first time, and the results can provide a reference for the development and optimization of high-performance PEMEC.     

In-situ investigation of bubble dynamics and two-phase flow in proton exchange membrane electrolyzer cells

Gas bubble dynamics and two-phase flow have a significant impact on the performance and efficiency of proton exchange membrane electrolyzer cells (PEMECs). It has been strongly desired to develop an effective experimental method for in-situ observing the high-speed/micro-scale oxygen bubble dynamics and two-phase flow in an operating PEMEC. In this study, the micro oxygen bubble dynamic behavior and two-phase flow are in-situ visualized through a high-speed camera coupled with a specific designed transparent PEMEC, which uses a novel thin liquid/gas diffusion layer (LGDL) with straight-through pores. The effects of different operating conditions on oxygen bubble dynamics, including nucleation, growth, and detachment, and two-phase flow have been comprehensively investigated. The results show that temperature and current density have great effects on bubble growth rate and reaction sites while the influence of flow rate is very limited. The number, growth rate, nucleation site, and slug flow regime of oxygen gas bubbles increase as temperature and/or current density increases, which indicates that an increase in temperature and/or current density can enhance the oxygen production efficiency. Further, a mathematical model for the bubble growth is developed to evaluate the effects of temperature and current density on the bubble dynamics. A mathematical model has been established and shows a good correlation with the experimental results. The studies on two-phase flow and high-speed micro bubble dynamics in the microchannel will help to discover the true electrochemical reaction at micro-scale in an operating PEMEC.     

VOF modelling of gas–liquid flow in PEM water electrolysis cell micro-channels

In this study, the gas–liquid flow through an interdigitated anode flow field of a PEM water electrolysis cell (PEMEC) is analysed using a three-dimensional, transient, computational fluid dynamics (CFD) model. To account for two-phase flow, the volume of fluid (VOF) method in ANSYS Fluent 17.2 is used. The modelled geometry consists of the anode channels and the anode transport layer (ATL). To reduce the complexity of the phenomena governing PEMEC operation, the dependence upon electro-chemistry is disregarded. Instead, a fixed source of the gas is applied at the interface between the ATL and the catalyst layer. An important phenomenon that the model is able to capture is the gas–liquid contact angle on both the channel wall and ATL-channel interface. Particularly, the latter interface is crucial in capturing bubble entrainment into the channel. To validate the numerical simulation, photos taken of the gas–liquid flow in a transparent micro-channel, are qualitative compared against the simulation results. The experimental observations confirm the models prediction of long Taylor bubbles with small bubbles in between. From the simulation results, further intriguing details of the flow are revealed. From the bottom to the top of the outgoing channel, the film thickness gradually increases from zero to 200 μm. This increase in the film thickness is due to the particular superficial velocity field that develops in an interdigitated flow. Here both the superficial velocities change along the length of the channel. The model is capable of revealing effect of different bubble shapes/lengths in the outgoing channel. Shape and the sequence of the bubbles affect the water flow distribution in the ATL. The model presented in this work is the first step in the development of a comprehensive CFD model that comprises multiphase flow in porous media and micro-channel, electro-chemistry in catalyst layers, ion transport in membrane, hydrogen evolution, etc. The model can aid in the study of gas–liquid flow and its impact on the performance of a PEMEC.     

A Photographic study of subcooled flow boiling burnout at high heat flux and velocity

The present paper reports the results of a visualization study of the burnout in subcooled flow boiling of water, with square cross section annular geometry (formed by a central heater rod contained in a duct characterized by a square cross section). The coolant velocity is in the range 3–10 m/s. High speed movies of flow pattern in subcooled flow boiling of water from the onset of nucleate boiling up to physical burnout of the heater are recorded. From video images (single frames taken with a stroboscope light and an exposure time of 1 μs), the following general behaviour of vapour bubbles was observed: when the rate of bubble generation is increasing, with bubbles growing in the superheated layer close to the heating wall, their coalescence produces a type of elongated bubble called vapour blanket. One of the main features of the vapour blanket is that it is rooted to the nucleation site on the heated surface. Bubble dimensions are given as a function of thermal-hydraulic tested conditions for the whole range of velocity until the burnout region. A qualitative analysis of the behaviour of four stainless steel heater wires with different macroscopic surface finishes is also presented, showing the importance of this parameter on the dynamics of the bubbles and on the critical heat flux.     

Experimental analysis of the unit cell approach for two-phase flow dynamics in curved flow channels

Flow behavior of gas–liquid mixtures in thin channels has become increasingly important as a result of miniaturization of fluid and thermal systems. The present empirical study investigates the use of the unit cell or periodic boundary approach commonly used in two-phase flows. This work examines the flow patterns formed in small tube diameter (<3 mm) and curved geometry flow systems for air–water mixtures at standard conditions. Liquid and gas superficial velocities were varied from 0.1 to 7.0 (～±0.01) m/s and 0.03 to 14 (～±0.2) m/s for air and water respectively to determine the flow pattern formed in three geometries and dispersed bubble, plug, slug and annular flow patterns are reported using high-frame rate videography. Flow patterns formed were plotted on the generalized two-phase flow pattern map to interpret the effect of channel size and curvature on the flow regime boundaries. Relative to a straight a channel, it is shown that a ‘C shaped’ channel that causes a directional change in the flow induces chaotic advection and increases phase interaction to enhance gas bubble or liquid slug break-up thus altering the boundaries between the dispersed bubble and plug/slug flow regimes as well as between the annular and plug/slug flow regimes.     

Two-Phase Flow Characteristics During Convective Boiling of Halocarbon Refrigerants Inside Horizontal Small-Diameter Tubes

Two-phase flow observations were performed for R134a and R245fa in 1.1- and 2.32-mm ID horizontal tubes. The tests were run for mass velocities ranging from 100 to 600 kg/m²-s and saturation temperatures of 22, 31, and 41°C. Additionally, an objective method to characterize two-phase flow patterns was developed. This method is based on simultaneous processing of signals from the following devices: a pair of diodes laser-sensors with a transparent tube between them within which the two-phase flow occurs, a micro-piezoelectric pressure transducer to determine the variation in the local pressure, and a microthermocouple within the fluid. The method was developed based on the k-means clustering algorithm, which consists of the gradual agglomeration of data of similar average characteristics. Simultaneous images of two-phase flow were obtained through a high-speed camera (10,000 frames/s) and used to identify the following flow patterns: bubbly, elongated bubbles, churn, and annular flows. The maps obtained by the objective method were compared against flow pattern results segregated based on flow visualization and a reasonable agreement was obtained between them. The vapor quality for the transition between churn and annular flow pattern decreases with decreasing the tube diameter, whereas the vapor quality for the transition between elongated bubbles and churn flow decreases with increasing tube diameter. Effects of saturation temperature and mass velocity were also verified. Additionally, elongated bubble velocities, frequencies, and lengths were determined based on the analysis of high-speed videos and the processing of signals of the diode/laser-sensor. The elongated bubble velocity was correlated as a linear function of the two-phase superficial velocity. A new image treatment method was developed to automatically identify the entrainment frequencies, which were segregated according to two groups: low and high frequency. The former group was characterized by frequencies lower than 20 Hz and the later by 50–500 Hz frequency ranges.     

Detecting and modeling oxygen bubble evolution and detachment in proton exchange membrane water electrolyzers

In this work, we discuss the effect of multiphase flow dynamics on the performance of a PEM electrolyzer. We obtained images of a flow system consisting of O₂ and water at two stages of gas production: gas evolution via bubbles and gas exiting through the channels of a flow field. We processed the obtained images of bubble evolution with a MATLAB-based bubble detection and counting algorithm, and we found that the bubble detachment sizes remained invariant within a water flow range between 0.07 and 4.65 l h⁻¹. We measured an average bubble detachment radius of 22.47 μm. We applied a bubble force balance developed by van Helden et al. [1] to model the observed effect of water flow on bubble evolution, and we found that the bubble detachment radius is a weak function of water flow when the water flow is below 60 l h⁻¹. We found that the variables that affect the bubble detachment radius the strongest were the electrode's hydrophobicity and pore size.     

Effects of photo-generated gas bubbles on the performance of tandem photoelectrochemical reactors for hydrogen production

Presence of gas bubbles in the vicinity of semiconductor electrodes interferes with their active surface areas and introduces inert voids in the electrolyte hindering its ionic conductivity. Furthermore, gas bubbles obstruct the radiation path through scattering. The aim of this work is to study the characteristic hydrogen- and oxygen-gas bubble behavior and their effects on photoelectrochemical reactor performance. Findings of gas bubble formation, electrode coverage and curtain profiles based on macroscopic bubble graphical images are reported. Effects of increased convective forces are also observed. Further, the scattering of incident light implemented through simulations based on Mie scattering theory is reported. Results show that hydrogen gas bubbles are more extensive in coverage due to formation of a froth while oxygen bubbles coalesce and rise easily. The growth of the bubble cover increases ohmic resistance reducing the current magnitude. Even at a modest current density of 10 mA/cm², the curtain thickness may rise to 2 mm or 3 mm for oxygen and hydrogen, respectively. Light scattering increases with increasing bubble size and is more pronounced for shorter wavelengths. It is also found that presence of multiple bubbles reduces light intensity by up to 2% and highest when the bubble radius is 150 μm. Increase in both photoelectrode and electrolyte resistances as well as radiation losses due to presence of bubbles hence undermine the performance of photoelectrochemical reactors.     

Bubble size distribution and electrode coverage at porous nickel electrodes in a novel 3-electrode flow-through cell

A novel 3-electrode cell type is introduced to run parametrical studies of H₂ evolution in an alkaline electrolyte on porous electrodes. Electrochemical methods combined with a high-speed optical measurement system are applied simultaneously to characterize the electrodes and the bubble dynamics in terms of bubble size distribution and coverage of the working electrode. Three different cathodes made of expanded nickel are investigated at applied current densities of |j| = 10–200 mA cm^?2 without forced flow and at a flow rate of 5 ml min^?1. The applied current density is found to significantly influence both the size of detached bubbles and the surface coverage of the working electrode. The forced flow through the cathodes is found to strongly reduce the bubble size up to current densities of about 100 mA cm^?2, whereas the initial transient until the cathode surface is completely covered by bubbles is only marginally affected by the flow-through.     

Numerical modeling of three-dimensional two-phase gas–liquid flow in the flow field plate of a PEM electrolysis cell

Numerical simulations were performed for three-dimensional two-phase water/oxygen flow in the flow field plate at the anode side of a PEM electrolysis cell. The mixture model was used to simulate two phases for the purpose of examining flow features in the flow field plate in order to effectively guide the design of electrolysis cells. The water flow rate was maintained as a constant of 260 mL/min, while the flow rate of oxygen generation was assumed to change from 0 to 14 mg/s. The obtained results including the velocity, pressure, and volume fraction distributions are presented and discussed. It is found that the obtained results for single-phase flow cases cannot be linearly extrapolated into the two-phase flow cases. The irregular velocity profile (locally low velocity magnitude near the exit port section) is not observed when the flow rate of oxygen generation is relatively low. As the mass flow rate of oxygen generation increases, reverse flow develops inside the flow channels.     

Two-dimensional numerical pore-scale investigation of oxygen evolution in proton exchange membrane electrolysis cells

Oxygen blocking the porous transport layer (PTL) increases the mass transport loss, and then limits the high current density condition of proton exchange membrane electrolysis cells (PEMEC). In this paper, a two-dimensional transient mathematical model of anode two-phase flow in PEMEC is established by the fluid volume method (VOF) method. The transport mechanism of oxygen in porous layer is analyzed in details. The effects of liquid water flow velocity, porosity, fiber diameter and contact angle on oxygen pressure and saturation are studied. The results show that the oxygen bubble transport in the porous layer is mainly affected by capillary pressure and follows the transport mechanism of ‘pressurization breakthrough depressurization’. The oxygen bubble goes through three stages of growth, migration and separation in the channel, and then be carried out of the electrolysis cell by liquid water. When oxygen breaks through the porous layer and enters the flow channel, there is a phenomenon that the branch flow is merged into the main stream, and the last limiting throat affects the maximum pressure and oxygen saturation during stable condition. In addition, increasing the liquid water velocity is helpful to bubble separation; changing the porosity and fiber diameter directly affects the width of pore throat and the correlative capillary pressure; increasing porosity, reducing fiber diameter and contact angle can promote oxygen breakthrough and reduce the stable saturation of oxygen.     

Fluid flow and heat transfer characteristics of low temperature two-phase micro-channel heat sinks – Part 1: Experimental methods and flow visualization results

A new cooling scheme is proposed where the primary working fluid flowing through a micro-channel heat sink is pre-cooled to low temperature using an indirect refrigeration cooling system. Cooling performance was explored using HFE 7100 as working fluid and four different micro-channel sizes. High-speed video imaging was employed to help explain the complex interrelated influences of hydraulic diameter, micro-channel width, mass velocity and subcooling on cooling performance. Unlike most prior two-phase micro-channel heat sink studies, which involved annular film evaporation due high void fraction, the low coolant temperatures used in this study produced subcooled flow boiling conditions. Decreasing coolant temperature delayed the onset of boiling, reduced bubble size and coalescence effects, and enhanced CHF. Heat fluxes in excess of 700 W/cm² could be managed without burnout. Premature CHF occurred at low mass velocities and was caused by vapor flow reversal toward the inlet plenum. This form of CHF was eliminated by decreasing coolant temperature and/or increasing flow rate.     

Numerical investigation of PEM electrolysis cell with the new interdigitated-jet hole flow field

The flow field structure has important influences on the mass and heat transfer and the distribution uniformity in the proton exchange membrane electrolysis cell (PEMEC). In this paper, the application and operation modes and the structural parameters of the new interdigitated-jet hole flow field (JHFF) are explored, to guide the processing of the JHFF and provide references for experimental testing. A three-dimensional and two-phase model is established to simulate the effect of JHFF on the performance of PEMEC. The results demonstrate that compared with the application of JHFF only on the anode side, the application of JHFF on both sides of the anode and cathode can increase the temperature distribution uniformity and polarization performance by 41.78% and 16.25%, respectively. By increasing the number of inlet flow channels and using the counter-flow water supply mode, the temperature distribution can be more uniform. The lower the height of jet holes, the better the normal mass transfer and polarization performance, while the worse the temperature distribution uniformity. Reducing the diameter of the inlet jet holes can improve the normal mass transfer performance in the porous electrode. Synthetically, the hole height of 0.2 mm and the hole diameter of 0.4 mm are recommended. The findings provide theoretical guidance for the practical application of JHFF in PEMEC so that the positive role of JHFF in improving electrolysis performance can be fully realized.     

油水乳化液中长气泡漂移速度的研究

建立圆管内滞止液体中长气泡漂移速度动量分析模型。用高速动态分析仪测量不同含水率β下,滞止油水乳化液中弹状流流型时Taylor气泡的漂移速度。结合前人的实验数据,依据Wallis的流动分类准则,给出了油水乳化液中长气泡漂移速度的半经验性公式,揭示了流动特性不同的液体中,长气泡的运动规律。     

Two-phase flow instability for boiling in a microchannel heat sink

The present study explores experimentally the two-phase flow instability in a microchannel heat sink with 15 parallel microchannels. The hydraulic diameter for each channel is 86.3 μm. Flow boiling in the present microchannel heat sink demonstrates significantly different two-phase flow patterns under stable or unstable conditions. For the stable cases bubble nucleation, slug flow and slug or annular flows appear sequentially in the flow direction. On the other hand, forward or reversed slug/annular flows appear alternatively in every channel. Moreover, the length of bubble slug may oscillate for unstable cases with reversed flow demonstrating the suppressing effect of pressure field for bubble growth. It is found that the magnitude of pressure drop oscillations may be used as an index for the appearance of reversed flow. A stability map on the plane of inlet subcooling number versus phase change number is established. A very narrow region for stable two-phase flow or mild two-phase flow oscillations is present near the line of zero exit quality.     

In-situ investigation and modeling of electrochemical reactions with simultaneous oxygen and hydrogen microbubble evolutions in water electrolysis

The development of water electrolyzer is challenging as we approach theoretical limits arising from electrochemical reactions and micro-scale bubble dynamics. In this research, two-phase flow and bubble dynamics are in-situ studied in a special designed single-channel electrolyzer. The devices fabricated by a 3D printer provide a whole vision of the electrochemical reaction within the channel. In-situ observations of channel-scale hydrogen and oxygen micro-bubbles dynamics are conducted, and the whole process of hydrogen evolution reactions (HERs) and oxygen evolution reactions (OERs) are simultaneously studied. The results indicate that all bubbles generate at the interface between the proton exchange membrane and the electrode wire, and the operating conditions have a great impact on the micro bubble evolution process. The bubble detachment diameter is inversely proportional to the flow velocity, but is in direct proportion to the current density. Finally, a mathematic model has been developed, and shows a good agreement with experimental data. Those results could help to better understand the bubble evolution mechanism, in order to further understand the electrochemical reaction.     

On the rise paths of single vapor bubbles after the departure from nucleation sites in subcooled upflow boiling

A photographic study was carried out for the subcooled flow boiling of water to elucidate the rise characteristics of single vapor bubbles after the departure from nucleation sites. The test section was a transparent glass tube of 20 mm in inside diameter and the flow direction was vertical upward; liquid subcooling was parametrically changed within 0–16 K keeping system pressure and liquid velocity at 120 kPa and 1 m/s, respectively. The bubble rise paths were analyzed from the video images that were obtained at the heat flux slightly higher than the minimum heat flux for the onset of nucleate boiling. In the present experiments, all the bubbles departed from their nucleation sites immediately after the inception. In low subcooling experiments, bubbles slid upward and consequently were not detached from the vertical heated wall; the bubble size was increased monotonously with time in this case. In moderate and high subcooling experiments, bubbles were detached from the wall after sliding for several millimeters and migrated towards the subcooled bulk liquid. The bubbles then reversed the direction of lateral migration and were reattached to the wall at moderate subcooling while they collapsed due to the condensation at high subcooling. It was hence considered that the mechanisms of the heat transfer from heated wall and the axial growth of vapor volume were influenced by the difference in bubble rise path. It was observed after the inception that bubbles were varied from flattened to more rounded shape. This observation suggested that the bubble detachment is mainly caused by the change in bubble shape due to the surface tension force.     

Two-phase flow in a proton exchange membrane electrolyzer visualized in situ by simultaneous neutron radiography and optical imaging

In proton exchange membrane (PEM) electrolyzers, oxygen evolution in the anode and flooding due to water cross-over in the cathode yields two distinct two-phase transport conditions which strongly affect the performance. Two-phase transport in an electrolyzer cell is visualized by simultaneous neutron radiography and optical imaging. Optical and neutron data are used in a complementary manner to aid in understanding the two-phase flow behavior. Two different patterns of gas-bubble evolution and departure are identified: periodic growth/removal of small bubbles vs. prolonged blockage by stagnant large bubbles. In addition, the bubble distribution across the active area is not uniform due to combined effects of buoyancy and proximity to the inlet. The effects of operating parameters such as current density, temperature and water flow rate on the two-phase distribution are investigated. Higher water accumulation is detected in the cathode chamber at higher current density, even though the cathode is purged with a high flow rate of N₂.     

Investigation of the bubble behaviour at the free surface of a large three-dimensional gas fluidized bed

Gas fluidization is generally associated with the formation of bubbles that critically influence the performance of fluidized bed processes (FBPs). Therefore, in the design, simulation and operation of FBPs, it is very essential to know the behaviour of the bubbles at the free surface. The size and growth of bubbles play an important role for determining properties such as bed expansion, solids entraiment, in-bed heat transfer and solid mixing. This paper presents a study on the behaviour of bubbles at the free surface of a large three dimensional gas-fluidized bed with square section of 61×61 cm². Measurements were carried out to determine the effects of bed height and excess air velocity on the bubble eruption diameter, frequency and bubble fraction. All experiments were performed at freely bubbling mode and the flow characteristics of bubbles were recorded by a video camera. Bed materials used were 593 μm raw perlite and 1233 μm sand falling within the categories of Geldarts Groups B and D, respectively. The fixed bed height ranged from about 8–18 cm for raw perlite and 9–26 cm for sand. The excess air velocity was varied between 0·5 and 1·75 cm s⁻¹ for raw perlite and 13 and 25 cm s⁻¹ for sand. Equations related to the bubble count, frequency, flow area shape factor and through-flow coefficient were given using a modified form of two-phase theory of fluidisation. Observations were made to validate the two-phase theory for two different particles. The flow area shape factor was in the range of 0·47–0·81 for raw perlite and 0·20 to 0·57 for sand, with mean values of 0·6 and 0·4, respectively. The through-flow coefficient was found to be between −0·68 and 2·82 for raw perlite and between 3·27 to 15·87 for sand, and was larger than predicted values of classical bubble models. © 1998 John Wiley & Sons, Ltd.     

The characteristics and visualization of critical heat flux of R-134a flowing in a vertical annular geometry with spacer grids

In the present paper, critical heat flux (CHF) experiments of forced convection boiling were performed to investigate the CHF characteristics of a vertical annular channel with one heated rod and four spacer grids for new refrigerant R-134a. The experiments were conducted under outlet pressure of 11.6, 13, 16 and 20 bar, mass fluxes of 100–600 kg/m² s, and inlet temperatures of 25–40 °C. The parametric trend of the CHF data was well consistent with previous understanding in water. The comparison between the present results with effect of the flow obstacle enhancing CHF and water data in similar geometry shows R-134a can be a modeling fluid for simulating water CHF in high pressure and high temperature condition even for annular geometry. The direct observation of flowing bubble behaviors contributes to enhancing our understanding on the effect of flow obstacles for flow boiling heat transfer.