Electrode reaction properties using a reactant gas addition method in a commercial 100 cm2 class solid oxide fuel cell

This work investigates the reaction characteristics of the anode and cathode by overpotential analyses in 100 cm² class planar anode-supported SOFCs. The reactant gas addition (RA) technique was applied to analyse the overpotential, which uses the reactant gas flow rate and partial pressure as parameters due to their variation upon adding a reactant species to an electrode. The anodic overpotential was determined to be made up of mass transfer-induced overpotentials of H₂ and H₂O species. The H₂O species account for the majority of the anodic overpotential at the measured current range i.e., 0–150 mA cm^?2. Thus, the anodic reaction is under an extreme H₂O-induced mass-transfer resistance compared with H₂. The RA method showed that the cathodic overpotential was mainly due to a deficiency of O₂ species in the mass transfer through the gas phase rather than the solid phase. Furthermore, both cathodic and anodic overpotentials depended on gas flow rate and utilisation, indicating a significant gas-phase mass transfer effect.     

Simply constructed highly dispersed cobalt nanoparticles in diverse N-doped graphitic carbon with remarkable performances for water electrolysis

Metal/carbon composite materials are highly promising electrocatalysts for water electrolysis. In this work, three composites of metal cobalt nanoparticles highly dispersed in N-doped carbon materials were facilely constructed by pyrolysis of different phenylenediamine based Schiff base-Co complexes (PDBs). Interestingly, the composites derived from PDBs based on different phenylenediamine exhibited different morphologies. The superior case is that rodlike composite catalyst was derived from o-phenylenediamine based PDBs. The obtained catalyst exhibited remarkable performances for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER), as well as overall water electrolysis. Only 172 and 289 mV of overpotentials and 1.57 V of cell voltage were exhibited at 10 mA cm^?2 for HER, OER and water splitting in 1.0 M KOH, respectively. The catalyst also displayed robust stability and high Faraday efficiency, and thus are potential high-performance catalyst for commercial water electrolysis.     

Lignite as a fuel for direct carbon fuel cell system

Lignite, also known as brown coal, and char derived from lignite by pyrolysis were investigated as fuels for direct carbon solid oxide fuel cells (DC-SOFC). Experiments were carried out with 16 cm² active area, electrolyte supported solid oxide fuel cell (SOFC), using pulverized solid fuel directly fed to DC-SOFC anode compartment in a batch mode, fixed bed configuration. The maximum power density of 143 mW/cm² was observed with a char derived from lignite, much higher than 93 mW/cm² when operating on a lignite fuel. The cell was operating under electric load until fuel supply was almost completely exhausted. Reloading fixed lignite bed during a thermal cycle resulted in a similar initial cell performance, pointing to feasibility of fuel cell operation in a continuous fuel supply mode. The additional series of experiments were carried out in SOFC cell, in the absence of solid fuels, with (a) simulated CO/CO₂ gas mixtures in a wide range of compositions and (b) humidified hydrogen as a reference fuel composition for all cases considered. The solid oxide fuel cell, operated with 92%CO + 8%CO₂ gas mixture, generated the maximum power density of 342 mW/cm². The fuel cell performance has increased in the following order: lignite (DC-SOFC) < char derived from lignite (DC-SOFC) < CO + CO₂ gas mixture (SOFC) < humidified hydrogen (SOFC).     

Performance and durability of metal-supported solid oxide electrolysis cells at intermediate temperatures

Metal-supported solid oxide electrolysis cells (MS-SOECs) operating at 600–700 °C are attractive for storage of intermittent renewable electricity from solar and wind energy due to their advantages of easy sealing and fast startup. This paper reports on the fabrication of MS-SOECs consisting of dense scandium stabilized zirconia (SSZ) electrolytes, Ce_0.8Sm_0.2O_2−δ (SDC)/Ni impregnated 430L/SSZ cathodes and SmBa_0.5Sr_0.5Co₂O_5+δ (SBSCO) impregnated SSZ anodes supported on porous 430L alloys. Such cells demonstrated excellent electrolysis performance with current densities at 650 °C as high as 0.73 A⋅cm⁻² at 1.3 V in 50% H₂O-50% H₂ and 0.95 A⋅cm⁻² at 1.5 V in 90% CO₂-10% CO. Electrochemical impedance measurements indicated that the cell performance was largely limited by the ohmic losses for steam electrolysis and by the cathodic reduction reactions for CO₂ electrolysis, especially at reduced temperatures. Pronounced degradation was observed for both steam and CO₂ electrolysis over the preliminary 90-h stability measurements at 600 °C. SEM examination and EDS mapping of measured cells showed significant aggregation and coarsening of impregnated Ni particles, resulting in smaller activities for H₂O and CO₂ reduction reactions. As evidenced by the almost unaltered ohmic resistances over the measurement durations, the 430L stainless steel substrates demonstrate excellent resistances against corrosions from H₂O and CO₂ and thus show great promise for applications in reduced-temperature MS-SOECs.     

Experimental investigation on influences of methanol reformate impurities in performances of high temperature proton exchange membrane fuel cells

Even though the methanol reformate can be fed into the high temperature proton exchange membrane fuel cell, the influences of different reformate components on the fuel cell are still unclear. This work investigates the effects of CO, CO₂, H₂O, and CH₃OH in the fuel gas on the fuel cell performances. The distribution of relaxation times and equivalent circuit model are employed for analysis. The results show the increase of anodic charge and mass transfer resistances are main factors of CO poisoning which results in 77 mV overpotential. The maximum overpotential difference between CO₂ and Ar is only 4 mV, which means the dilution effect of CO₂ is similar to Ar. H₂O decreases the Ohmic and anodic charge transfer resistances and reducing the overpotential by 10 mV. CH₃OH below 3% has slight positive effect on the fuel cell performance. However, 5% CH₃OH results in high overpotential of 36 mV.     

Nickel doped MoS2 nanoparticles as precious-metal free bifunctional electrocatalysts for glucose assisted electrolytic H2 generation

Hydrogen, as the one of clean energy source, has the advantages of high energy density and carbon-free emission. Water electrolysis is one of the most promising ways to generate hydrogen, but the rather high energy required seriously hinders its widespread applications yet. In this study, we report an alkaline electrolyzer to implement energy-saving H₂ generation by coupling cathodic hydrogen evolution reaction (HER) with anodic glucose oxidation reaction (GOR) other than oxygen evolution reaction, in which nickel-doped MoS₂ nanoparticles (Ni–MoS₂ NPs) has been developed as bifunctional electrocatalyst for HER and GOR. The electrolyzer only requires a cell voltage of 1.67 V to reach an electrolysis current density of 10 mA cm⁻², about 270 mV lower than the corresponding value in the traditional electrolyzer. Electrolytic H₂ generation with the assistance of biomass derived materials may open a new way for the future sustainable development.     

Direct electrolysis of bunsen reaction product for hydrogen production: The continuous-flow operation

Hydrogen sulfide (H₂S) emitted from oil industry's hydrotreating processes can be converted into hydrogen and used back to the same processes through a H₂S splitting cycle, where the Bunsen reaction and HI decomposition are two participating reactions. To overcome the difficulties and complications posted in the scaling up of the cycle, direct electrolysis of the Bunsen reaction product solution was proposed and has been studied in a batch electrolysis cell in our earlier work. This paper studies the direct electrolysis using a customer-made, continuous-flow electrolysis cell. The effects of the operating parameters including the current density, the entering HI concentration and flow rate of the anolyte, the toluene to aqueous phase ratio and stirring speed in anolyte cell, the H₂SO₄ concentration and circulation rate of the catholyte on the performing parameters such as the conversion of iodide ions, the yield of iodine transferred to toluene, and the anodic and cathodic current efficiencies for iodide conversion and hydrogen production were carefully investigated. The results show that the cathodic current efficiency for hydrogen production is nearly 100% for all the runs and that the anodic current efficiency for iodide ion conversion to iodine is relatively low (20%–70%) and varies with the changes in operating parameters. Running at high levels of the current density, the volumetric ratio of toluene to aqueous phase in anolyte, or the stirring speed in anolyte, and low levels of the entering concentration of I^? in anolyte or the flow rate of anolyte in electrolysis operation are in favor of having a high iodide conversion and high I₂-toluene yield. Iodide anions at a few mmol L^?1 level (a few thousandths of the entering concentration) are found in the cathodic chamber caused by its diffuse against the electric field and the proton exchange membrane. The continuous, direct electrolysis of the Bunsen product solution can be considered being adapted in the sulfur-iodine (S–I) water splitting cycle for hydrogen production.     

Hydrogen production from photo-driven electrolysis of biomass-derived oxygenates: A case study on methanol using Pt-modified WO3 thin film electrodes

In this paper, we demonstrate the feasibility of H₂ production from biomass-derived oxygenates with photoelectrochemical cells (PECs) based on the tandem cell hybrid photoelectrode configuration. As a proof of concept, we have studied the simplest oxygenate, methanol, which is photoelectrochemically oxidized at thin film tungsten oxide (WO₃) photoelectrodes. When the methanol oxidation reaction (MOR) is coupled with the hydrogen evolution reaction (HER), this process is known as methanol electrolysis. We demonstrate that catalytic modification of the WO₃ surface by the electrodeposition of Pt particles can greatly increase MOR activity at the photoanode, resulting in a significant increase in H₂ production rates from methanol electrolysis. This improvement is greatest at low overpotentials and high Pt loadings, with the demonstrated MOR current density of Pt-WO₃ being nearly four times that of the oxygen evolution reaction (OER) on WO₃ at a potential of 0.8 V vs. the Reversible Hydrogen Electrode. We also illustrate how the increase in WO₃ photocurrent and the decrease in the oxidation onset potential, compared to the OER, make it possible to use WO₃-based photoelectrodes in a simple tandem cell configuration whereby a common PV component such as a-Si can provide the remaining voltage to achieve unassisted methanol electrolysis. Results from methanol electrolysis reveal the potential to utilize a similar approach for larger biomass-derived oxygenates, which could be a promising pathway to H₂ production from renewable feedstock using photo-driven electrolysis.     

Electroxidation of sulfur slurries: Reaction rate studies

The rates of sulfur-assisted water electrolysis can be enhanced by addition of the redox-mediators of Fe²⁺, Ce⁴⁺, V⁵⁺ and Cl⁻. Another approach to enhancing the reaction rates lies in operating the electrolysis cell at higher temperature. The anticipated advantages of high temperature operation are: (i) increase in the rates of reaction; (ii) lowering of the polarization potentials (i.e. overpotentials); and (iii) lowering of the reversible (thermodynamic) cell potentials. The energy usage for H₂ production for sulfur-assisted water electrolysis is computed and compared with that for ordinary water electrolysis.     

Samarium doped ceria-(Li/Na)2CO3 composite electrolyte and its electrochemical properties in low temperature solid oxide fuel cell

A composite of samarium doped ceria (SDC) and a binary carbonate eutectic (52 mol% Li₂CO₃/48 mol% Na₂CO₃) is investigated with respect to its morphology, conductivity and fuel cell performances. The morphology study shows the composition could prevent SDC particles from agglomeration. The conductivity is measured under air, argon and hydrogen, respectively. A sharp increase in conductivity occurs under all the atmospheres, which relates to the superionic phase transition in the interface phases between SDC and carbonates. Single cells with the composite electrolyte are fabricated by a uniaxial die-press method using NiO/electrolyte as anode and lithiated NiO/electrolyte as cathode. The cell shows a maximum power density of 590 mW cm⁻² at 600 °C, using hydrogen as the fuel and air as the oxidant. Unlike that of cells based on pure oxygen ionic conductor or pure protonic conductor, the open circuit voltage of the SDC-carbonate based fuel cell decreases with an increase in water content of either anodic or cathodic inlet gas, indicating the electrolyte is a co-ionic (H⁺/O²⁻) conductor. The results also exhibit that oxygen ionic conductivity contributes to the major part of the whole conductivity under fuel cell circumstances.     

Optimization of the electrode-supported tubular solid oxide cells for application on fuel cell and steam electrolysis

Hydrogen electrode-supported tubular solid oxide cells (SOCs) were fabricated by dip-coating and co-sintering method. The electrochemical properties of tubular SOCs were investigated both in fuel cell and electrolysis modes. Ni-YSZ was employed as hydrogen electrode support. The pore ratio of Ni-YSZ support strongly affected the performance of tubular SOCs, especially in steam electrolysis mode. The pore ratio was adjusted by the content of pore-former in support slurry. The results showed that 3 wt.% pore former content is the proper value to produce high performance both in fuel cell and electrolysis modes. In fuel cell mode, the maximum power density reached 743.1 mW cm⁻² with H₂ (105 sccm) and O₂ (70 sccm) as working gases at 850 °C. In electrolysis mode, as the electrolysis voltage was 1.3 V, the electrolysis current density reached 425 mA cm⁻² with H₂ (35 sccm) and N₂ (70 sccm) adsorbed 47% steam as working gases in hydrogen electrode at 850 °C. The stability of tubular SOCs was related to the ratio of NiO/YSZ in the support. The sample with NiO/YSZ = 60/40 shows a better performance than the sample with NiO/YSZ = 50/50.     

Application of CuNi–CeO2 fuel electrode in oxygen electrode supported reversible solid oxide cell

The oxygen electrode-supported reversible solid oxide cell (RSOC) has demonstrated distinguishing advantages of fuel flexibility, shorter gas diffusion path and more choices for fuel electrode materials. However, there are serious drawbacks including the difficulty of co-firing the oxygen electrode and electrolyte, and the inefficient electrochemical performance. In this study, a (La_0.8Sr_0.2)_0.95MnO_3-δ (LSM) supported RSOC with the configuration of La_0.6Sr_0.4Fe_0.9Sc_0.1O_3-δ (LSFSc)-YSZ/YSZ/CuNi–CeO₂-YSZ is fabricated by tape casting, co-sintering and impregnation technologies. The single cell is evaluated at both fuel cell (FC) and electrolysis cell (EC) mode. Significant maximum power density of 436.0 and 377 mW cm^?2 is obtained at 750 °C in H₂ and CH₄ fuel atmospheres, respectively. At electrolysis voltage of 1.3 V and 50% steam content, current density of ?0.718, ?0.397, ?0.198 and ?0.081 A cm^?2 is obtained at 750, 700, 650 and 600 °C respectively. Much higher electrolysis performance than FC mode is exhibited probably due to the optimized electrodes with increased triple phase boundary (TPB) area and faster gas diffusion (oxygen and steam) and electrochemical reactions for water splitting. Additionally, the short-term stability of single cell in H₂ and CH₄ are also studied.     

Niobium diffusion modified austenitic stainless steel bipolar plate for direct methanol fuel cell

An austenitic stainless steel with a niobium diffusion protective layer is evaluated for bipolar plate of direct methanol fuel cell (DMFC). Corrosion resistance of niobium diffusion modified AISI 304 stainless steel (niobized 304 SS) is investigated in simulated DMFC cathodic environment (0.5 M H₂SO₄ + 2 ppm HF + 0.1 M methanol solution at 50 °C) and anodic environment (0.5 M H₂SO₄ + 2 ppm HF + (1 M, 10 M and 20 M) methanol solution at 50 °C), respectively. Potentiodynamic, potentiostatic as well as electrochemical impedance spectroscopy tests show that, comparing with a bare 304 SS, the corrosion current density of niobized 304 SS is reduced greatly while the polarization resistance is raised in the simulated DMFC cathodic environment. Corrosion tests in the simulated anodic environment are applied to examine the effect of methanol on the corrosion behaviour of niobized 304 SS. It is interesting to find that the niobized 304 SS shows better corrosion resistance in the higher methanol concentration solutions.     

Development of trimetallic Ni–Cu–Zn anode for low temperature solid oxide fuel cells with composite electrolyte

Trimetallic alloys of Ni_0.6Cu_0.4−xZn_x (x = 0, 0.1, 0.2, 0.3, 0.4) have been investigated as promising anode materials for low temperature solid oxide fuel cells (SOFCs) with composite electrolyte. The alloys have been obtained by reduction of Ni_0.6Cu_0.4−xZn_xO oxides, which are synthesized by using the glycine–nitrate process. Increasing the Zn content x decreases the particle sizes of the oxides at a given sintering temperature. Fuel cells have been constructed using lithiated NiO as cathode and as-prepared alloys as anodes based on the composite electrolyte. Peak power densities are observed to increase with the increasing Zn addition concentration into the anode. The maximum power density of 624 mW cm⁻² at 600 °C, 375 mW cm⁻² at 500 °C has been achieved for the fuel cell equipped with Ni_0.6Zn_0.4 anode. A.c. impedance results show that the resistances dramatically decrease with increasing temperatures under open circuit voltage state. Both cathodic and anodic interfacial polarization resistances increase with the amplitude of applied DC voltage. Possible reaction process for H₂ oxidation reaction at anode based on composite electrolyte has been proposed for the first time. The stability of the fuel cell with Ni_0.6Cu_0.2Zn_0.2 composite anode has been investigated. The results indicate that the trimetallic Ni_0.6Cu_0.4−xZn_x anodes are considerable for low temperature SOFCs.     

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.     

Pd/Hemin-rGO as a bifunctional electrocatalyst for enhanced ethanol oxidation reaction in alkaline media and hydrogen evolution reaction in acidic media

H₂ generation needs a cost-effective, robust, stable, long-durable, and super-active electrocatalyst. This study reveals a rapid and facile method for fabricating Pd NPs on Hemin-rGO as novel support. The obtained electrocatalyst was characterized by UV–Vis, XPS, FESEM, EDS, HRTEM, and AFM. The electrochemical measurements reveal the superb effect of Hemin-rGO for enhancing the catalytic activity of Pd as bifunctional electrocatalysts for hybrid water electrolysis (hydrogen evolution reaction (HER) and ethanol electrooxidation reaction (EOR)). Pd/Hemin-rGO displays a low peak potential (−210 V) with remarkable current density (1.95 A mg⁻¹ Pd) in 0.1 M EtOH and 0.1 M NaOH. The ratio of j_f/j_b of Pd/Hemin-rGO compared with Pd electrocatalyst reveals this novel support's ani-poisoning effect. Besides, it shows the Tafel slope of 26 mV dec⁻¹ and overpotentials of 47 and 131 mV were obtained at 10 and 100 mA cm⁻² in acidic media toward HER. Exploring and designing new electrocatalysts may be enhanced by this research, which can use Hemin as a novel support for noble metals such as Pt, Pd, Rh, Au, and Ru for diverse energy-related applications.     

Elementary reaction modeling and experimental characterization of solid oxide fuel-assisted steam electrolysis cells

A one-dimensional elementary reaction kinetic model for solid oxide fuel-assisted steam electrolysis cell (SOFEC) is developed coupling heterogeneous elementary reactions, electrochemical reaction kinetics, electrode microstructure and transport processes of charge and mass. This model is calibrated and validated by experimental data from a button cell with anode gases of H₂, CO and CH₄ at 800 °C. After comparisons with solid oxide electrolysis cell (SOEC), the energy demands, performance and efficiency of CO-assisted SOFEC and CH₄-assisted SOFEC are investigated numerically. One important finding is that over 80% of electricity can be saved by SOFEC at a current density of 3000 A m⁻². SOFEC assisted by CO or CH₄ for steam electrolysis has better performance than SOEC, especially by CH₄. The efficiencies of 12% CO-SOFEC and 12% CH₄-SOFEC are at least, respectively, 7% and 30% higher than that of SOEC at 800 °C with the current density of below 2500 A m⁻². Finally, the effects of type of assisting-fuel, fuel composition and applied voltage are studied. It is found that CO-SOFEC shows higher anode polarization and thus lower performance than CH₄-SOFEC with the same molar fraction of fuel. It is also found that the performance of SOFEC increases with increasing proportion of assisted fuel in anode at high current density.     

Corrosion properties and contact resistance of TiN, TiAlN and CrN coatings in simulated proton exchange membrane fuel cell environments

In this study, the contact resistance (CR) and electrochemical properties of TiN, CrN and TiAlN electron beam physical vapor deposition (EBPVD) coatings and their stainless steel 316L (SS316L) substrate were investigated in a simulated proton exchange membrane (PEM) fuel cell environment. The potentiodynamic polarization corrosion tests were conducted at 70 °C in 1 M H₂SO₄ purged with either O₂ or H₂, and the potentiostatic corrosion tests were performed under both simulated cathodic (+0.6 V vs. Ag/AgCl reference electrode purged with O₂) and anodic conditions (−0.1 V vs. Ag/AgCl reference electrode purged with H₂) for a long period (4 h). SEM was used to observe the surface morphologies of the samples after corrosion testing. All the TiN-, TiAlN- and CrN-coated SS316L showed a lower CR than the uncoated SS316L. While the corrosion performance of the coatings was dependent on the cathodic and anodic conditions, the CrN coating exhibited a higher (in the anodic environment) or similar (in the cathodic environment) corrosion resistance to the uncoated SS316L. Thus, the CrN-coated SS316L could potentially be used as a bipolar plate material in the PEM fuel cell environment. Although the EBPVD process greatly reduced number of pinholes in the coatings compared to other plasma enhanced reactive evaporations, future research efforts should be directed to eliminate the pinholes in the coatings for long-term durability in fuel cell applications.     

Syngas production at intermediate temperature through H2O and CO2 electrolysis with a Cu-based solid oxide electrolyzer cell

Solid Oxide Electrolyzer Cells (SOECs) are promising energy devices for the production of syngas (H₂/CO) by H₂O and/or CO₂ electrolysis. Here we developed a Cu–Ce_0.9Gd_0.1O_2−δ/Ce_0.8Gd_0.2O_2−δ/Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ-Ce_0.8Gd_0.2O_2−δ cell and performed H₂O and CO₂ electrolysis experiments in the intermediate temperature range (600°C–700 °C). As a baseline, the cell was first tested in fuel cell operation mode; the sample shows a maximum power density peak of 104 mW cm⁻² at 700 °C under pure hydrogen and air. H₂O electrolysis testing revealed a steady production of hydrogen with a Faraday's efficiency of 32% at 700 °C at an imposed current density of −78 mA cm⁻². CO production was observed during CO₂ electrolysis but higher cell voltages were required. A lower efficiency of about 4% was obtained at 700 °C at an imposed current density of −660 mA cm⁻². These results confirm that syngas production is feasible by water and carbon dioxide electrolysis but further improvements from both the manufacturing and the electrocatalytic aspects are needed to reach higher yields and efficiencies.     

Polybenzimidazole-membrane-based PEM fuel cell in the temperature range of 120–200 °C

Phosphoric acid-doped polybenzimidazole-membrane-based PEM fuel cells were tested in the temperature range of 120–200 °C, with ambient backpressure and 0% RH. AC impedance spectroscopy, surface cyclic voltammetry and fuel cell performance simulation were used to obtain the exchange current densities for the cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR) on platinum-based catalysts at such high temperatures. The activation energies for ORR, HOR and membrane conductivity were also obtained separately. The results showed that temperature significantly affects the charger transfer and gas (O₂ and H₂) diffusion resistances. The effect of O₂ stoichiometry (ST_air) on fuel cell performance was also investigated. Increasing ST_air can effectively increase the O₂ partial pressure in the feed air, leading to improvements in both the thermodynamics and the kinetics of the fuel cell reactions. In addition, it was observed that increasing ST_air could also improve the gas diffusion processes.