The effect of hydrogen crossover on open-circuit voltage in polymer electrolyte membrane fuel cells

Even though the measured open-circuit voltage in a H₂-O₂ PEM fuel cell is invariably about 200-250 mV lower than that predicted from thermodynamics (1.229 V at 25 °C), there is no unequivocal explanation of this phenomenon available in the literature, although several hypotheses exist. Based on a theoretical model of mixed potential with a priori parameters, it is shown here that this voltage loss under open-circuit conditions can be attributed exclusively to hydrogen crossover and the resulting oxygen reduction reaction overpotential at the cathode. The analytical model predictions agree well with available experimental results.     

Influence of catholyte pH and temperature on hydrogen production from acetate using a two chamber concentric tubular microbial electrolysis cell

Microbial electrolysis cells (MECs) could be integrated with dark fermentative hydrogen production to increase the overall system yield of hydrogen. The influence of catholyte pH on hydrogen production from MECs and associated parameters such as electrode potentials (vs Ag/AgCl), COD reduction, current density and quantity of acid needed to control pH in the cathode of an MEC were investigated. Acetate (10 mM, HRT 9 h, 24 °C, pH 7) was used as the substrate in a two chamber MEC operated at 600 mV and 850 mV applied voltage. The effect of catholyte pH on current density was more significant at an applied voltage of 600 mV than at 850 mV. The highest hydrogen production rate was obtained at 850 mV, pH 5 amounting to 200 cm³_stp/l_anode/day (coulombic efficiency 60%, cathodic hydrogen recovery 45%, H₂ yield 1.1 mol/mol acetate converted and a COD reduction of 30.5%). Within the range (18.5–49.4 °C) of temperatures tested, 30 °C was found to be optimal for hydrogen production in the system tested, with the performance of the reactor being reduced at higher temperatures. These results show that an optimum temperature (approximately 30 °C) exists for MEC and that lower pH in the cathode chamber improves hydrogen production and may be needed if potentials applied to MECs are to be minimised.     

Enzymatic biofuel cell based on electrodes modified with lipid liquid-crystalline cubic phases

Two glassy carbon electrodes modified with enzymes embedded in lyotropic liquid-crystalline cubic phase were used for the biofuel cell construction. The monoolein liquid-crystalline film allowed to avoid separators in the biofuel cell. Glucose and oxygen as fuels, and glucose oxidase and laccase as anode and cathode biocatalysts, respectively were used. The biofuel cell parameters were examined in McIlvaine buffer, pH 7 solution containing 15 mM of glucose and saturated with dioxygen. A series of mediators were tested taking into account their formal potentials, stability in the cubic phase and efficiency of mediation. Most stable was the biofuel cell based on tetrathiafulvalene (TTF) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as anode and cathode mediators, respectively. The open-circuit voltage was equal to 450 ± 40 mV. The power densities and current densities were measured for all the systems studied.     

Influence of cathode polarization on the chromium deposition near the cathode/electrolyte interface of SOFC

Chromium poisoning phenomena were compared among three SOFC cathodes using (La_0.8Sr_0.2)_0.98MnO₃ (LSM), La_0.6Sr_0.4Fe_0.8Co_0.2O₃ (LSCF) and LaNi_0.6Fe_0.4O₃ (LNF) at 700 °C by changing cathode polarization (0–400 mV). Chromium vapor deposited near the electrolyte for LSM and LNF, and the amount of the deposition increased with increasing cathode polarization. In the case of LSCF, chromium deposited near the cathode surface under smaller cathode polarization (≤200 mV). Under larger cathode polarization (≥300 mV), however, chromium deposition near the cathode/electrolyte interface similarly increased for the three cathodes. Cathode polarization facilitated the chromium deposition and there seemed to be no correlation with the current density. Microscopic distribution of the deposited chromium, which was located on the surface of LSM, LSCF, LNF grains, and also on the surface of zirconia and ceria, seemed to correspond to the distribution of oxygen vacancy by cathode polarization at the electrode reaction sites. Chromium deposition on the zirconia surface seemed to be assisted by metal oxides segregated from the cathode material, which can conduct electron required for generating oxygen vacancy continuously. Oxygen deficiency on the surface of the deposited chromium was confirmed and interdiffusion of chromium and zirconium caused by cathode polarization was also suggested.     

Transient model of oxygen-starved proton exchange membrane fuel cell for predicting voltages and hydrogen emissions

Transfer (crossover) leaks initiated by the chemical deterioration of the PEM and the resulting performance degradation has been previously identified as one the primary life-limiting factors in fuel cells. The leaks result in reduced oxygen levels in affected cells, where a secondary factor intimately related to this is high hydrogen emissions in the cathode exhaust when some cells operate in fully-oxygen-starved conditions. This paper builds on previous work that developed a unified fuel cell model that predicts cell voltage behavior under driving (normal) and driven (oxygen-starved) conditions, where this latest analysis now explicitly includes hydrogen pumping and emissions release when operating under oxygen-depleted conditions. In addition to considering diffusion effects and electrochemical effects, the model tracks the evolution of hydrogen in the cell cathode when no oxygen remains to generate water. The voltage response of the model under normal (non-starved) conditions is first validated for steady-state and transient (current step-change) conditions against previously published experiments, and then the model is used to simulate the cell voltage and stack hydrogen emissions behavior measured from three different commercially available fuel cell stacks. In the first fuel cell stack, a 9-cell commercial short stack, only one cell was fully oxygen-starved. Excellent agreement is seen between the measured and simulated hydrogen release concentrations (where air injection was used downstream of the stack to ensure adequate oxygen levels for measurement with a catalytic hydrogen sensor and to condense water vapor in the exhaust), where the role of hydrogen pumping is seen to contribute significantly to the release behavior. The first fuel cell stack is then used transiently in comparison with testing performed where the hydrogen injection level in the cell is changed quickly, where the model gives good agreement with the measured emission response and cell voltage behavior. Further comparisons with test data from a second and third 10-cell commercial short stack models operated with stack inlet hydrogen injection show good agreement with measured emissions onset versus current, where the observed threshold of starvation and emissions occurs a few percent sooner in the third model than the simulation, but the overall behavior is well predicted.     

Porous Ni–Co surface formation and analysis of hydrogen generation by gas sensor

A Ni–Co alloy was used as the test piece. The porous Ni–Co alloy surface was prepared by Al electrodeposition at ?1.4 V and ?1.8 V and Al dissolution at ?0.5 V in a NaCl–KCl-3.5 mol% AlF₃ molten salt. The bath temperature was 750 °C and 900 °C. As a result, a porous Ni–Co alloy could be prepared by Al electrodeposition and Al dissolution on the Ni–Co alloy in the molten salt. It was clarified that a denser surface was formed at the bath temperature of 750 °C than at the bath temperature of 900 °C. Furthermore, it was clarified that the porous layer became thicker when the electrodeposition potential was ?1.8 V than when it was ?1.4 V. The formed porous Ni–Co alloy was evaluated for cathode performance in a 10 mass% KOH solution. Furthermore, the amount of generated hydrogen was measured by a constant voltage and constant current test with a gas sensor using a solid electrolyte. In the cathode polarization curve, the porous Ni–Co alloy showed a higher current density at a lower potential than the untreated Ni–Co alloy. It was shown that the Ni–Co alloy formed under the electrodeposition conditions at the electrodeposition potential of ?1.4 V and bath temperature of 750 °C is a very excellent cathode material. Furthermore, based on the constant voltage test, it was revealed that the porous treated sample generates a higher amount of hydrogen than the untreated sample.     

Self-supported hierarchical porous FeNiCo-based amorphous alloys as high-efficiency bifunctional electrocatalysts toward overall water splitting

Rationally designing an efficient and cost-effective bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is a primary matter in applying electrocatalytic water splitting. Herein, a self-supported FeNiCo-based amorphous catalyst with a hierarchical micro/nanoporous structure is fabricated by dealloying an amorphous/nanocrystalline precursor. The amorphous nanoporous framework enables the prepared electrocatalyst to afford fast reaction kinetics, abundant active sites, and enhanced electrochemical active surface areas (ECSAs). Such structural advantages and the synergistic effects of the ternary transition metals contribute to a dramatic catalytic activity of this electrocatalyst under alkaline conditions, which delivers the current density of 10 mA cm⁻² at a low overpotential of 134 mV for HER and 206 mV for OER, respectively. Furthermore, a full electrolysis apparatus constructed by the self-supported hierarchical micro/nanoporous FeNiCo-based amorphous electrocatalyst as both cathode and anode acquires a dramatically low voltage of 1.58 V operating at 10 mA cm⁻² along with stability for more than 24 h for overall water splitting.     

Construction of fuel reformer using proton conducting oxides electrolyte and hydrogen-permeable metal membrane cathode

We constructed a reformer of methane based on an electrochemical principle. This apparatus consists of the proton conducting ceramics electrolyte and the hydrogen-permeable metal membrane cathode. For methane reforming, a mixture of methane and oxygen gas is supplied to the porous Ag cathode. The hydrogen ions, which formed by the anode reaction: CH₄ + O₂ → CO₂ + 4H⁺ + 4e⁻, are transported through the proton conducting ceramics to the cathode. Then, the hydrogen is formed at the cathode by the reaction: 4H⁺ + 4e⁻ → 2H₂. The hydrogen, which permeates through the metal membrane cathode, is 100% purity.The hydrogen separation ability of the reformer was investigated at 400–650 °C by measuring the electric current through the proton conducting oxide electrolyte. Since the ionic transport number of the proton conducting oxide is nearly unity, the current through the electrolyte corresponds to the proton flux through the electrolyte.The current measurements showed that the extracted proton flux through the electrolyte increased with increasing the applied voltage as well as temperature as we expected. However, the current measurements under the low voltage revealed that the extracted current was lesser than the expected value from Ohm's law. The decrease of the current is possibly caused for the reduction of the effective voltage by the anode polarization. In order to separate the hydrogen with higher efficiency, the applied voltage must be as low as possible using the thinner electrolyte and the improved anode.     

Tailoring cation vacancies in Co,Ni phosphides for efficient overall water splitting

High-efficiency water splitting catalysts are competitive in energy conversion and clean energy production. Herein, a bifunctional water splitting catalyst CoNiP with cation vacancy defects (CoNiP–V) is constructed through defect engineering. The results show that abundant cation vacancy defects in CoNiP–V are bifunctional active centers in the process of water electrolysis, which enhance the activity of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). In 1.0 mol L^?1 potassium hydroxide, CoNiP–V requires a pretty low overpotential of 58 mV to reach a geometrical current density of 10 mA cm^?2 for HER. To deliver a current density of 100 mA cm^?2, only 137 mV and 340 mV of overpotential are needed for HER and OER, respectively. Moreover, the cell with CoNiP–V as both cathode and anode exhibits good stability, which only needs 1.61 V to achieve a current density of 100 mA cm^?2, and the cell voltage barely rises 10% after 100 h’ test under 100 mA cm^?2. Therefore, CoNiP–V is promising for the development of efficient water splitting catalysts.     

Quick-to-synthesize hybrid electrodes composed of activated carbon cloth with Co/Fe-based films as bifunctional electrocatalysts for water splitting

Hybrid electrodes have recently been investigated as attractive alternatives to noble-metal-based electrocatalysts for hydrogen production by water splitting. Herein, we propose an electrode composed of an oxidized carbon cloth with an electrodeposited bimetallic Co/Fe-based film. By optimizing the electrodeposition conditions and applying electrochemically activated carbon cloth as a substrate, one can prepare a free-standing noble-metal-free electrocatalytic electrode with high bifunctional electrocatalytic activity in hydrogen and oxygen evolution from alkaline solution. The developed Fe_0.25Co_0.75 electrode requires overpotentials of 245 mV for HER and 360 mV for OER at high current densities of −100 and 100 mA cm⁻², respectively. Furthermore, its overall synthesis time from commercially available raw materials is only approximately 20 min. The electrode material was used as both a cathode and an anode in the model electrolyzer, which can deliver 10 mA cm⁻² of current density at 1.66 V without loss of activity during 100 h of performance.     

Formation of porous Ni surface by electrodeposition and dissolution in molten salt

In a NaCl–KCl-3.5 mol%AlF3 molten salt bath, Al deposition and Al dissolution were performed at the bath temperatures of 750 °C and 900 °C to form a porous Ni surface. Furthermore, in order to investigate the hydrogen evolution behavior of the prepared porous Ni, the cathode polarization curve was measured in 10% KOH.When the Al was dissolved after the Al deposition, a porous layer was formed on the Ni surface of the substrate. When the electrodeposition potential of Al was lowered, it formed a thicker layer. Observations of the porous surface showed that the sample at 900 °C had a finer morphology than at 750 °C.The cathode polarization curve in an alkaline aqueous solution was measured. The porous Ni showed a higher cathode current density at a potential higher than the untreated Ni. The cathode current density increased in the order of untreated Ni, 750 °C treatment, and 900 °C treatment. Therefore, it was found that the 900 °C treatment generated the most hydrogen. The sample with the higher porosity showed a higher cathode current density based on the cathode polarization curve.The activation energies for the hydrogen evolution reaction were 10.3 kJ/mol for the untreated Ni, 10.1 kJ/mol at 750 °C, and 11 kJ/mol at 900 °C. There is no difference in the reaction mechanism, and it is considered that the performance was improved by increasing the surface area.     

Online health monitoring of a fuel cell using total harmonic distortion analysis

The present work aims to show the nonlinear behavior of a PEM fuel cell under different mass transport conditions. Understanding this behavior helps in online state-of-health monitoring and control of a fuel cell stack. To analyze the health of an operating stack, a total harmonic distortion analysis (THDA) system requires only the sum of voltages or currents of the stack to be monitored. A low-frequency current or voltage signal is impressed on the fuel cell stack, and the resulting voltage or current signal is measured. To determine any change in harmonics, the measured signal is processed with a harmonic analyzer. The operational states of individual cells of the fuel cell stack may be inferred from at least one change in the harmonic content of the impressed signal. The mass transport problem related to the cathode and anode is distinguished using mixed-frequency signals. The present study found experimentally that hydrogen starvation is dominantly observed in the harmonic analysis only below a frequency of 15 Hz, whereas air starvation showed harmonic changes at frequencies below 100 Hz. Total harmonic distortions were observed to rise to 2–2.5% under both the starvation conditions but with different frequency signals.     

Study of cell voltage uniformity of proton exchange membrane fuel cell stack with an optimized artificial neural network model

The cell voltage uniformity of the proton exchange membrane fuel cell stack, which may consist of tens or hundreds of cells in series, plays a significant role in the stack's lifetime and performance. But it is challenging to predict the multi-cell voltages and the uniformity with a physics-based model due to complex stack geometry and huge computation efforts. In this work, we develop an artificial neural network model to estimate the steady-state cell voltage distributions of a 60 kW 140-cell stack. The optimized and well-trained model can efficiently reproduce the 140-cell voltages at different operating conditions with the error of less than 2 mV. The increased cathode gas pressure improves the cell voltage consistency and stack performance, while the voltage uniformity worsens with ascending load current. The efficient model prediction of cell voltages is beneficial for accurate evaluation of fuel cell performance, health state, and reliability.     

Impact of applied cell voltage on the performance of a microbial electrolysis cell fully catalysed by microorganisms

The effect of the operating voltage on the performance of a microbial electrolysis cell (MEC) equipped with both a bioanode and a biocathode for hydrogen production is reported. Chronoamperometry tests ranged between 0.3 and 2.0 V were carried out after both bioelectrodes were developed. A maximum current density up to 1.6 A m⁻² was recorded at 1.0 V with hydrogen production rate of nearly 6.0 ± 1.5 L m⁻² cathode day⁻¹. Trace amounts of methane, acetone and formate were detected in cathode's headspace and catholyte which followed the same trend as hydrogen production rate. Meanwhile substrate consumption in anolyte also followed the trend of hydrogen production and current density changes. The bioanode could utilise up to 95% of acetate in the tested voltage ranges, however, at a cell voltage of 2.0 V the bioanode's activity stopped due to oxygen evolution from water hydrolysis. Cyclic voltammograms revealed that the bioanode activity was vital to maintain the functionality of the whole system. The biocathode relied on the bioanode to maintain its potential during the hydrogen evolution. The overall energy efficiency recovered from both bioanode and external power in terms of hydrogen production at the cathode was determined as 29.4 ± 9.0%, within which substrate oxidation contributed up to nearly 1/3 of the total energy marking the importance of bioanode recovering energy from wastewater to reduce the external power supply.     

Dependence of polarization in anode-supported solid oxide fuel cells on various cell parameters

The performance of solid oxide fuel cells (SOFCs) is affected by various polarization losses, namely, ohmic polarization, activation polarization and concentration polarization. Under given operating conditions, these polarization losses are largely dependent on cell materials, electrode microstructures, and cell geometric parameters. Solid oxide fuel cells (SOFC) with yttria-stabilized zirconia (YSZ) electrolyte, Ni–YSZ anode support, Ni–YSZ anode interlayer, strontium doped lanthanum manganate (LSM)–YSZ cathode interlayer, and LSM current collector, were fabricated. The effect of various parameters on cell performance was evaluated. The parameters investigated were: (1) YSZ electrolyte thickness, (2) cathode interlayer thickness, (3) anode support thickness, and (4) anode support porosity. Cells were tested over a range of temperatures between 600 and 800 °C with hydrogen as fuel, and air as oxidant. Ohmic contribution was determined using the current interruption technique. The effect of these cell parameters on ohmic polarization and on cell performance was experimentally measured. Dependence of cell performance on various parameters was rationalized on the basis of a simple analytical model. Based on the results of the cell parameter study, a cell with optimized parameters was fabricated and tested. The corresponding maximum power density at 800 °C was ∼1.8 W cm⁻².     

Interface engineering of NiTe@CoFe LDH for highly efficient overall water-splitting

Design and synthesis of highly active, inexpensive and durable catalyst for simultaneous hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is highly desired for green hydrogen generation. In this work, high conductivity NiTe nanorods are coupled with amorphous CoFe layered double hydroxide (LDH) to achieve a hierarchical NiTe@CoFe LDH heterostructure via a hydrothermal reaction and a subsequent electrodeposition process. The as-prepared three-dimensional (3D) self-supported NiTe@CoFe LDH nanorods endow highly efficient electron transfer and mass diffusion, and this architecture with abundant electrode/electrolyte interfaces can provide more active sites. Consequently, with the synergistic effect of NiTe and CoFe LDH, the as-prepared NiTe@CoFe LDH electrocatalyst achieved a current density of 10 mA cm^?2 with low overpotentials of 218 mV and 103 mV for OER and HER, respectively, and showing a robust stability for 50 h. Furthermore, an alkaline electrolyzer with NiTe@CoFe LDH serving as both the anode and cathode requires a cell voltage of 1.56 V to yield 10 mA cm^?2 current density, and can sustain for more than 50 h, with a slightly current density increase of 5%, showing potential for practical industrial application to generate hydrogen. This work highlights the construction low cost highly efficient 3D rods electrode for promising applications in green hydrogen generation.     

Electrode performance of a new La0.6Sr0.4Co0.2Fe0.8O3 coated cathode for molten carbonate fuel cells

To improve the cathode performance in molten carbonate fuel cells (MCFCs), Lanthanum Strontium Cobalt Ferrite (La_0.6Sr_0.4Co_0.2Fe_0.8O₃, LSCF) of perovskite structure was coated on a porous Ni plate by a vacuum suction method. The electrochemical performance of modified cathode was examined and compared with that of uncoated conventional cathode via single cell operation and electrochemical impedance analysis (EIS). The cell voltage of the single cell using the LSCF coated cathode, measured at 650 °C with current density of 150 mA/cm² is 0.837 V and it is higher than that of the cell with uncoated conventional cathode, 0.805 V. The higher performance and the lower charge transfer resistance were obtained at 600–700 °C after LSCF coating. The lower activation energy of oxygen reduction reaction was also obtained. The lower activation energy of oxygen reduction reaction after LSCF coating shows that LSCF on lithiated NiO cathode plays a role of catalyst on the oxygen reduction reaction in cathode.     

Hydrogen pumping effect induced by fuel starvation in a single cell of a PEM fuel cell stack at galvanostatic operation

In a proton exchange membrane fuel cell stack, a single cell is potentially subjected to voltage reversal under fuel starvation conditions, which is extremely harmful to its durability. In this work, we develop a two-dimensional computational model to investigate the current and potential distributions in a single cell under these voltage reversal conditions. It is found that most of hydrogen under these conditions is oxidized in a narrow region close to the fuel-inlet, and the anode area before hydrogen depletion can be characterized into an activation limited region and a mass-transport limited region. Meanwhile, an unexpected hydrogen evolution phenomenon is discovered in the cathode catalyst layer (CCL) adjacent to the fuel inlet, owing to the imbalance between the localized ultrahigh hydrogen oxidation current density in the anode and the lower limiting current density of oxygen reduction reaction in the adjacent CCL. Furthermore, the evolved hydrogen gas is also found to be oxidized nearby due to the steep variation of electrolyte potential in the CCL, indicating the coexistence of hydrogen evolution, hydrogen oxidation and oxygen reduction within the micron-scale thickness of CCL, which significantly adds to the complexity of the coupled phenomena in the voltage-reversal single cell.     

Highly durable,Pt free and large-area Ni–B film synthesized by SILAR as a bifunctional electrode for electrochemical water splitting

A search for efficient, durable, large-area, and economic catalyst material for low-cost production of hydrogen and oxygen is currently a high priority in the field of electrocatalysis (EC). In view of this, a cost-effective, earth abundant, highly stable, Pt free, and large-area (8 cm × 8 cm) bifunctional Ni–B electrocatalyst is reported via simple and economic SILAR method. A highly porous surface of Ni–B film with high surface wettability indicated better electrochemical water-splitting properties for the films and is obtained at 100 cycles. A Low over-potential value to obtain HER (49 mV) and OER (340 mV) at 10 mA/cm² current suggested that they are comparable to the well-known Pt and RuO electrodes in alkaline medium (1M KOH), respectively. In actual water-splitting setup having Ni–B film (as cathode) and stainless steel (as anode), the hydrogen production of 612 ml/h is obtained at constant potential, which was enhanced by 18% i.e., 726 ml/h when a Ni–B film as both cathode and anode electrode was used. Both the electrodes are highly stable for over 15 days and interestingly they showed 7% increment in the EC performance.     

Partially oxidized cobalt species in nitrogen-doped carbon nanotubes: Enhanced catalytic performance to water-splitting

It's still an ongoing research challenge to explore non-precious metal-based catalysts for substituting precious metal catalysts during full water electrocatalysis. Herein, we reported the partially oxidized cobalt species in nitrogen-doped carbon nanotubes hierarchical structures to produce dual-functionality towards oxygen/hydrogen evolution reactions. The in situ transformation of carbon nanotubes and well-exposed metal-oxide contributes to mass diffusion and greater electrolyte-accessible surface area. The as-synthesized catalyst displays low overpotentials of 287 mV and 171 mV for oxygen and hydrogen evolution reactions at 10 mA cm^?2 of current density with remarkable performance during long-term stability. Furthermore, when employed as cathode and anode, a respectable performance of 1.68 V demonstrated our catalyst as an efficient bifunctional material for conducting water-splitting operation.