Kinetic and electrochemical analyses of a CuCI/HCl electrolyzer

An electrochemical analysis is carried out from a kinetic electrochemistry perspective of a CuCl/HCl electrolysis cell, within the CuCl thermochemical water splitting process for hydrogen production. The anolyte is a solution of 2 mol L^?1 CuCl(aq) and 10 mol L^?1 HCl(aq) while the catholyte solution is 11 mol L^?1 HCl(aq) . The cell current density of 0.5 A cm^?2 and voltage of 0.7 V are the desired working conditions for a CuCl/HCl electrolyzer. The current density of 0.5 A cm^?2 is assumed to occur at a 5% anolyte conversion degree. At 25°C , the activation overpotential of the anode half‐reaction is found to be 53 mV for a current density of 0.5 A cm^?2 while the activation overpotential of the cathode half‐reaction for the same condition is 87 mV. An increase in working temperature decreases the overpotential of the anode half‐reaction and increases the cathode half‐reaction activation overpotential. The ohmic overpotential of the cell membrane is almost 1000 times smaller than that of the activation overpotentials of the electrode half‐reactions for the same temperature and current density. A higher working temperature results in a lower membrane ohmic overpotential. The required voltage to trigger electrolysis for a current density of 0.5 A cm^?2 is found to be 0.53 V at 25°C and 0.59 V at 80°C and a higher temperature results in a higher electrochemical efficiency. The cell electrochemical efficiency increases linearly with working temperature while the voltage efficiency peaks at 75% at 60°C .     

High performance alkaline-acid direct glycerol fuel cells for portable power supplies via electrode structure design

Alkaline-acid direct glycerol fuel cells (AA-DGFC) were fabricated and primarily proven to be used as portable power generating devices. Pt/C catalyst was used as electrocatalyst for both anode and cathode. The optimal operating condition for cathode was firstly tested. Then the effects of types of backing and microporous layer on the cell performance and stability were investigated to obtain the optimal electrode structure. The cell performance was determined by using both chronoamperometry technique at a constant voltage of 0.4 V, and cell polarization with impedance measurement. The maximum peak power density obtained from the cell was 375 mW cm⁻² and the highest average current density discharged from the cell was 451 mA cm⁻². Non-wetproof carbon cloth is suitable as the backing layer for both the anode and cathode. Although MPL did not directly affect the cell performance, it greatly improved stability of the current discharged during chronoamperometric test. The cathode favors hydrophilic MPL, while hydrophobic MPL was preferred on the anode.     

Modeling and optimum design of hybrid solid oxide fuel cell-gas turbine power plants

An integrated solid oxide fuel cell-gas turbine process is modeled and analyzed. A two dimensional finite difference model is developed for planar solid oxide fuel cells (SOFCs), considering co- and counter-flow configurations. In this model, the SOFC is divided into five control volumes. Mass and heat transfer and electrochemical processes are examined and such factors as electrochemical reactions, conduction in the solid structure, convection in channels and between channels and solid structures and polarization losses are discussed. Also, the influences of temperature, pressure, current density and fuel utilization on voltage and electric power for both configurations are investigated. The results show that voltage and electric power increase as pressure and temperature rise, for both configurations. The optimum current density is determined to be 9000 A m⁻² (for co- and counter-flow). Also, the voltage in both configurations decreases as fuel utilization increases. Furthermore, an investigation of the effect of input temperature, pressure and current density on system performance and number of cells required demonstrates that the power output should be fixed at 200 kW. With increasing temperature, pressure and mole fraction of H₂, the number of cells required decreases and the electrical and overall efficiencies both increase. The optimum number of cells (co-flow) and current density are found to be 2122 and 8000 A m⁻², respectively.     

A novel micro protective layer applied on a simplified PEM water electrolyser

This study presents a solid polymer electrolyte (SPE) technique, using a proton exchange membrane (PEM) water electrolyser, to produce high purity hydrogen and oxygen (both 99.99%). A proposed structural design provides comprehensive sealing of the assembly while combining a current collector and a flow field plate into a single component. The titanium porous disc with a highly condensed structure compared to the carbon based gas diffusion layer plays a key role as the support for the proton exchange membrane when producing high-pressure hydrogen. The electrochemical stability is enhanced as well owing to the consolidated component. The titanium porous disc is coated with noble metal catalysts (IrO₂/Ta₂O₅ composition) as a micro protective layer (MPL) to prevent corrosion and oxidation during hydrogen production from water electrolysis. The proposed MPL can effectively transform active oxygen species (such as oxygen atoms and hydroxyl free radicals) into harmless oxygen gas during water electrolysis. In this study, it is found that the electrolytic cell can sustain up to 10 bar and its lifetime is capable of lasting over 600 h continuously while maintaining a voltage of 2.33 to 2.35 V and current density of 1 A cm⁻².     

Hydrogen production via electrolysis of aqueous formic acid solutions

Hydrogen was produced via electrolysis of aqueous formic acid solutions, and the effects of the concentrations of formic acid and NaOH on the electrolytic voltage were systematically investigated. The voltage is found to be related to the actual formic acid concentration. When the actual formic acid concentration is higher than 0.8 × 10⁻⁹ M, the initial electrolytic voltage can be as low as 0.30 V, which is much lower than the open circuit voltage in a proton exchange membrane fuel cell. The electrolytic voltage increases with the increase of the current density. Specifically at 1.0 M NaOH and 4.0 M HCOOH, the steady voltage value increases from 0.62 to 0.70 V as the current density increases from 1.0 to 6.0 mA/cm². At 3.0 M HCOOH and 2.5 M NaOH, the hydrogen production rate is 53 μmol/h under 8.0 mA/cm², which is promising for practical industrial-scale hydrogen production.     

Electrochemical characteristics of (PEM) electrolyzer under influence of charge transfer coefficient

In this paper a systematic understanding of how charge transfer coefficient (CTC) and exchange current density contributes to polarization and performance characteristics of PEM electrolyzer has been investigated. A detail discussion on the role played by charge transfer coefficient in influencing operating characteristics of PEM electrolyzer has been presented in this article. Experimental data was used to validate the accuracy of the finding of this research. Main interesting insights are that at CTC of 0.5 and 0.2 for anode and cathode respectively, the operating voltage at 1 A/cm² (current density) is around 2.0 V, however at CTC of 2 and 0.5 for anode and cathode respectively, there was significant drop in operating voltage up to 1.62 V with current density of 1 A/cm², this accounts for about 27% reduction in operating voltage. It was also discovered that with exchange current density of 1 × 10–7 for a Pt–Ir anode based electrode the CTC value for anode increase from 0.27 to 0.34 at current density of 0.05 A/cm2 to 2 A/cm2 respectively, whereas for Pt cathode catalyst with exchange current density of 1.8 × 10–3 the CTC values for cathode increased from 0.02 to 0.14 at current density of 0.1 A/cm2 to 2 A/cm2 respectively, these findings were in agreement with the CTC values reported in the literature.     

La0.75Sr0.25Cr0.5Mn0.5O3 as hydrogen electrode for solid oxide electrolysis cells

La_0.75Sr_0.25Cr_0.5Mn_0.5O₃ (LSCM) has been applied as hydrogen electrode (cathode) material in solid oxide electrolysis cells operating with different steam concentrations (20, 40, 60 and 80 vol.% absolute humidity (AH)) using 40 sccm H₂ carrier gas at 800, 850 and 900 °C, respectively. Impedance spectra and voltage-current curves were measured as a function of cell electrolysis current density and steam concentration to characterize the cell performance. The cell resistance decreased with the increase in electrolysis current density while increased with the increase in steam concentration under the same electrolysis current density. At 1.6 V applied electrolysis voltage, the maximum consumed current density increased from 431 mA cm⁻² for 20 vol.% AH to 593 mA cm⁻² for 80 vol.% AH at 850 °C. Polarization and impedance spectra experiments revealed that LSCM-YSZ hydrogen electrode played a major role in the electrolysis reaction.     

Electrooxidation study of pure ethanol/methanol and their mixture for the application in direct alcohol alkaline fuel cells (DAAFCs)

Aliphatic alcohol mainly, ethanol, methanol and their mixture were subjected to electrooxidation study using cyclic voltammetry (CV) technique in a three electrodes half cell assembly (PGSTAT204, Autolab Netherlands). A single cell set up of direct alcohol alkaline fuel cell (DAAFC) was fabricated using laboratory synthesized alkaline membrane to validate the CV results. The DAAFC conditions were kept similar as that of CV experiments. The anode and cathode electrocatalysts were Pt-Ru (30%:15% by wt.)/Carbon black (C) (Alfa Aesar, USA) and Pt (40% by wt.)/High Surface Area Carbon (C_HSA) (Alfa Aesar, USA) respectively. The CV and single cell experiments were performed at a temperature of 30 °C. The anode electrocatalyst was in the range of 0.5 mg/cm² to 1.5 mg/cm² for half cell CV analysis. The cell voltage and current density data were recorded for different concentrations of fuel (ethanol or methanol) and their mixture mixed with different concentration of KOH as electrolyte. The optimum electrocatalyst loading in half cell study was found to be 1 mg/cm² of Pt-Ru/C irrespective of fuel used. The single cell was tested using optimum anode loading of 1 mg/cm² of Pt-Ru/C which was found in CV experiment. Cathode loading was kept similar, in the order of 1 mg/cm² Pt/C_HSA. In single cell experiment, the maximum open circuit voltage (OCV) of 0.75 V and power density of 3.57 mW/cm² at a current density of 17.76 mA/cm² were obtained for the fuel of 2 M ethanol mixed with 1 M KOH. Whereas, maximum OCV of 0.62 V and power density of 7.10 mW/cm² at a current density of 23.53 mA/cm² were obtained for the fuel of 3 M methanol mixed with 6 M KOH. The mixture of methanol and ethanol (1:3) mixed with 0.5 M KOH produced the maximum OCV of 0.66 V and power density of 1.98 mW/cm² at a current density of 11.54 mA/cm².     

Performance analysis and exergoeconomic assessment of a proton exchange membrane compressor for electrochemical hydrogen storage

Electrochemical hydrogen compression (EHC) is a promising alternative to conventional compressors for hydrogen storage at high pressure, because it has a simple structure, low cost of hydrogen delivery, and high efficiency. In this study, the performance of an EHC is evaluated using a three-dimensional numerical model and finite volume method. The results of numerical analysis for a single cell of EHC are extended to a full stack of EHC. In addition, exergy and exergoeconomic analyses are carried out based on the numerical data. The effects of operating temperature, pressure, and gas diffusion layer (GDL) thickness on the energy and exergy efficiencies and the exergy cost of hydrogen are examined. The motivation of this study is to examine the performance of the EHC at different working conditions and also to determine the exergy cost of hydrogen. The results reveal that the energy and exergy efficiency of EHC stack improve by almost 3.1% when operating temperature increases from 363 K to 393 K and the exergy cost of hydrogen decreases by 0.5% at current density of 5000 A m⁻². It is concluded that energy and exergy efficiency of EHC stack decrease by 25% and 5.4% when the cathode pressure increases from 1 bar to 30 bar, respectively. Moreover, it is realized that the GDL thickness has a considerable effect on the EHC performance. The exergy cost of hydrogen decreases by 53% when the GDL thickness decreases from 0.5 mm to 0.2 mm at current density of 5000 A m⁻².     

Predicting the transient response of a serpentine flow-field PEMFC: II: Normal to minimal fuel and AIR

The three-dimensional (3D) transient model presented in part I is used to study the overshoot and undershoot behavior observed in a PEMFC during operation with fixed normal stoichiometic flow rates of hydrogen and air for a 1.0 V s⁻¹ change in the load. In contrast to the behavior with excess flow shown in part I, the predictions show second-order responses for both decreases and increases in the load. That is, there is current overshoot when the load cell is decreased from 0.7 V to 0.5 V and there is current undershoot when the cell voltage is increased from 0.5 V to 0.7 V. The simulation of a 10 cm² reactive area with a serpentine flow path is used to explain this behavior in terms of the reacting gas concentrations, the flow through the gas diffusion media, the movement of water through the MEA by electro-osmotic and back diffusion forces, and the variation in the distributions of current density. The operating conditions correspond to 101 kPa, 70 °C cell temperature, anode and cathode dew-points and stoichiometries of 65 °C and 57 °C and 1.45 and 2.42 at an initial operating voltage of 0.7 V and current density of 0.33 A cm⁻². The fixed flow rates correspond to stoichiometries of 1.05 and 1.73 at 0.5 V for the 0.46 A cm⁻² predicted current density. The predictions illustrate regions where the MEA may alternate between wet and dry conditions and this may be useful to explain stability and durability of the MEA during transient operation.     

Two-dimensional multi-physics modeling of porous transport layer in polymer electrolyte membrane electrolyzer for water splitting

Polymer electrolyte membrane (PEM) electrolyzers have received increasing attention for renewable hydrogen production through water splitting. In present work, a two-dimensional (2-D) multi-physics model is established for PEM electrolyzer to describe the two-phase flow, electron/proton transfer, mass transport, and water electrolysis kinetics with focus on the porous transport layer (PTL) and the channel-land structure. After comparing four sets of experimental data, the model is employed to investigate PTL thickness impact on liquid water saturation and local current density. It is found that the PTL under the land may have much lower liquid saturation than that under the channel due to land blockage. The PTL thickness may significantly impact liquid water access to the catalyst layer (CL) under the land. Specifically, the 100 μm thick PTL shows less than 1% liquid saturation at the CL-PTL interface under 4–5 A/cm², leading to water starvation and electrolyzer voltage increase. As the operating current density decreases under 2–3.5 A/cm², the liquid saturation recovers and increases to about 10–20%. In thicker PTLs, the liquid saturation is higher under the land reaching 30–40% at the CL-PTL interface under 5 A/cm² for 200 and 500 μm thick PTLs. For the 100 μm thick PTL, the local current density drops to below 0.5 A/cm² under the land with 5 A/cm² average current density. For the 200 and 500 μm thick PTLs, the local current is almost uniform in the in-plane direction. The numerical model is extremely valuable to investigate PTL properties and dimensions to optimize channel-land design and configuration for high performing electrolyzers.     

High voltage and self-healing zwitterionic double-network hydrogels as electrolyte for zinc-ion hybrid supercapacitor/battery

The hydrogel electrolyte is an important part of safety and development potential in zinc-based energy storage equipment due to its inherent low mechanical strength and voltage decomposition. However, hydrogel electrolytes possess a reduced working life for zinc dendrites growth and a narrow voltage window. In this study, a hydrogel electrolyte prepares by the zwitterionic monomer [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) (MS) and sodium alginate (SA) alleviate these problems. The zwitterionic double-network hydrogel has good mechanical strength, inhibits the growth of zinc dendrites, enhances practicability, greatly increases the voltage window (0–2.4 V), and has self-healing properties to its rich functional groups. The assembled zinc-ion hybrid supercapacitors (ZHSs) have a high-power density of 172.33 W kg^?1 and an energy density of 88.56 Wh·kg^?1 at 0.5 A g^?1. The assembled zinc-ion battery also has good electrochemical performance. Flexible ZHSs and batteries provide power to the timer stably under different bending angles. The zwitterionic double-network hydrogel can be applied to both zinc-based supercapacitors and batteries.     

Development and preliminary testing of a unitized regenerative fuel cell based on PEM technology

Results related to the development and testing of a unitized regenerative fuel cell (URFC) based on proton-exchange membrane (PEM) technology are reported. A URFC is an electrochemical device which can operate either as an electrolyser for the production of hydrogen and oxygen (water electrolysis mode) or as a H₂/O₂ fuel cell for the production of electricity and heat (fuel cell mode). The URFC stack described in this paper is made of seven electrochemical cells (256 cм² active area each). The nominal electric power consumption in electrolysis mode is of 1.5 kW and the nominal electric power production in fuel cell mode is 0.5 kW. A mean cell voltage of 1.74 V has been measured during water electrolysis at 0.5 A cm⁻² (85% efficiency based on the thermoneutral voltage of the water splitting reaction) and a mean cell voltage of 0.55 V has been measured during fuel cell operation at the same current density (37% electric efficiency based on the thermoneutral voltage). Preliminary stability tests are satisfactory. Further tests are scheduled to assess the potentialities of the stack on the long term.     

Effect of the CeO2 nanoparticles in microporous layers on the durability of proton exchange membrane fuel cells

In this work, the effect of the CeO₂ in the microporous layer (MPL) on the durability of proton exchange membrane (PEM) fuel cells is investigated. The 400 h dry-wet accelerated stress test (AST) and the open-circuit voltage (OCV) holding testing were used to identify the function of CeO₂ in the microporous layer (MPL) on the durability and performance of MEA. The results show that the performance decay of the sample with CeO₂ is much smaller than the sample without CeO₂ (e.g., 24 mV vs. 140 mV@ 1200 mA cm⁻²). More importantly, the OCV decrease rate for sample without CeO₂ is as high as 7.250μV/cycle, which is 9.6 times as the value of 0.752μV/cycle for sample with CeO₂. And it is interesting that the addition of CeO₂ in MPL does not increase the inner resistance in the cell. Therefore, the addition of CeO₂ to the MPL not only can significantly improve the cell durability but also can effectively alleviate the negative impact of Ce ions on the proton conductivity in proton exchange membrane.     

A novel experimental study on discharge characteristics of an aluminum‐air battery

In order to explore the discharge characteristics of aluminum‐air battery and find out the best discharge performance of aluminum‐air battery under the optimum working conditions, this paper studies discharge performances of an aluminum‐air battery under various ambient temperature and battery discharge conditions. The relationship between the temperature rise of the battery electrolyte and the discharge current density was studied by an experimental method. Effects of the electrolyte concentration and the ambient temperature on the battery discharge voltage were investigated. In addition, a novel method for calculating the efficiency of the aluminum‐air battery was proposed. Results show that the temperature of the aluminum‐air battery electrolyte gradually increases as its discharge current density increases and the electrolyte temperature rise could reach as high as 10°C after 60 minutes with a constant 35 mA cm^?2 discharge current density. The specific energy and the specific capacity of the aluminum‐air battery first increase and then decrease as the current density increases. When the current density is 25 mA cm^?2, the specific energy has a peak of 3105 Wh kg^?1 for the condition of the chamber temperature 40°C and the electrolyte concentration 2 mol L^?1 (2 M), while the specific capacity has a peak of 2207 Ah kg^?1; furthermore, its efficiencies under various conditions increase first with the current density, reach a peak range of 19.6% to approximately 36% at 25 mA cm^?2, and then decrease. These experimental results could be used as a technical guidance for the optimization in thermal management designs of the aluminum‐air battery under various operating conditions.     

A two-phase model for studying the role of microporous layer and catalyst layer interface on polymer electrolyte fuel cell performance

In this work, a two-phase, two-dimensional model is developed to investigate the role of interfacial voids at the microporous layer (MPL) and catalyst layer (CL) interface on the polymer electrolyte fuel cell (PEFC) performance. The model incorporates the MPL|CL interfacial region as a separate domain and simulates two-phase transport within the interfacial voids. Different case studies, including the experimentally-measured MPL|CL interface and a perfect contact interface, are conducted. Model simulations indicate that the MPL|CL interfacial morphology has a significant effect on performance, particularly in the high current density region (>1.0 A/cm²). The interfacial voids at the MPL|CL interface are found to retain liquid water during operation and induce mass transport resistance, resulting in nearly a 20% reduction in the limiting current density when compared to perfect interfacial contact. The liquid water saturation retained at the interface and the magnitude of the mass and charge transport resistance induced by the interface are found to be highly dependent upon the geometry and size of the interfacial voids. Finally, simulations indicate that the morphology of the MPL|CL interface affects the location where reactions tend to occur in the CL, and also has a direct impact on the temperature distribution within the cathode.     

Water transport characteristics in the gas diffusion media of proton exchange membrane fuel cell - Role of the microporous layer

Water transport through the gas diffusion media of a proton exchange membrane fuel cell (PEMFC) was investigated with a focus on the role of the microporous layer (MPL) coated on the cathode gas diffusion layer (GDL). The capillary pressure of the MPL and GDL, which plays a significant role in water transport, is derived as a function of liquid saturation using a pore size distribution (PSD) model. PSD functions are derived with parameters that are determined by fitting to the measured total PSD data. Computed relations between capillary pressure and liquid saturation for a GDL and a double-layered GDL (GDL + MPL) show good agreement with the experimental data and proposed empirical functions. To investigate the role of the MPL, the relationship between the water withdrawal pressure and liquid saturation are derived for a double-layered GDL. Water transport rates and cell voltages were obtained for various feed gas humidity using a two-dimensional cell model, and are compared with the experimental results. The calculated results for the net drag with application of the capillary pressure derived from the PSD model show good agreement with the experimental values. Furthermore, the results show that the effect of the MPL on the cell output voltage is significant in the range of high humidity operation.     

Highly active and stable A-site Pr-doped LaSrCrMnO-based fuel electrode for direct CO2 solid oxide electrolyzer cells

Direct CO₂ electrolysis has been explored as a means to store renewable energy and produce renewable fuels. La chromate-based perovskite oxides have attracted great attention as fuel electrode materials for solid oxide electrolyzer cells. However, the electrochemical catalytic activity of such oxides is relatively low, and their stability has not been confirmed. In this study, Pr is doped into La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ (LSCM) and the applicability of the resulting fuel electrode to direct CO₂ electrolysis is investigated. The polarization resistance of the resulting electrode at 800 °C is decreased by 25%. Distribution function of relaxation times analysis indicates that the observed improvements may be attributed to increased oxygen ion conductivity. A full cell of Pr-doped LSCM-gadolinium-doped ceria (GDC)|scandia-stabilized zirconia|La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ-GDC achieves an electrolysis current of 0.5 A cm⁻² at 1.36 V and a Faradaic efficiency close to 100%. Short-term (210 h) stability testing of the cell under an electrolysis current of 0.5 A cm⁻² at 800 °C with pure CO₂ as the feedstock reveals a decrease in applied voltage at a rate of 7 mV kh⁻¹, thereby indicating excellent stability. Thus, given its satisfactory performance and stability, the Pr-doped LSCM electrode may be considered a promising candidate material for direct CO₂ electrolysis.     

Optimization of blocked flow field performance of proton exchange membrane fuel cell with auxiliary channels

The flow field optimization design is one of the important methods to improve the performance of proton exchange membrane fuel cell (PEMFC). In this study, a new structure with staggered blocks on the parallel flow channels of PEMFC and auxiliary flow channels under the ribs is proposed. Through numerical calculation method, the effect of blocks auxiliary flow field (BAFF) on pressure drop, reactant distribution and liquid water removal in the fuel cells are investigated. The results show that when the operating voltage is 0.5 V, the current density of BAFF is 21.74% higher than that of the straight parallel flow field (SPFF), and the power density reaches 0.65 W cm^?2. BAFF improves performance by equalizing the pressure drop across sub-channels, promoting the uniform distribution of reactant, and enhancing transport across the ribs. In addition, through parameter analysis, it is found that BAFF can discharge liquid water in time at the conditions of high humidification, high current density and low temperature, which ensures the output performance of the fuel cell and improves the durability of the fuel cell. This paper provides new ideas for the improvement of PEMFC flow field design, which is beneficial to the development of PEMFC with high current density.