Ethanol internal steam reforming in intermediate temperature solid oxide fuel cell

This study investigates the performance of a standard Ni-YSZ anode supported cell under ethanol steam reforming operating conditions. Therefore, the fuel cell was directly operated with a steam/ethanol mixture (3 to 1 molar). Other gas mixtures were also used for comparison to check the conversion of ethanol and of reformate gases (H₂, CO) in the fuel cell. The electrochemical properties of the fuel cell fed with four different fuel compositions were characterized between 710 and 860 °C by I-V and EIS measurements at OCV and under polarization. In order to elucidate the limiting processes, impedance spectra obtained with different gas compositions were compared using the derivative of the real part of the impedance with respect of the natural logarithm of the frequency.Results show that internal steam reforming of ethanol takes place significantly on Ni-YSZ anode only above 760 °C. Comparisons of results obtained with reformate gas showed that the electrochemical cell performance is dominated by the conversion of hydrogen. The conversion of CO also occurs either directly or indirectly through the water-gas shift reaction but has a significant impact on the electrochemical performance only above 760 °C.     

Reducing the operation temperature of a solid oxide fuel cell using a conventional nickel-based cermet anode on dimethyl ether fuel through internal partial oxidation

Dimethyl ether (DME)-oxygen mixture as the fuel of an anode-supported SOFC with a conventional nickel-cermet anode for operating at reduced temperatures is systematically investigated. The results of the catalytic tests indicate that sintered Ni-YSZ has high activity for DME partial oxidation, and DME conversion exceeds 90% at temperatures higher than 700 °C. Maximum methane selectivity is reached at 700 °C. Cell performance is observed between 600 and 800 °C. Peak power densities of approximately 400 and 1400 mW cm⁻² at 600 and 800 °C, respectively, are reached for the cell operating on DME-O₂ mixture. These values are comparable to those obtained using hydrogen as a fuel, and cell performance is reasonably stable at 700 °C for a test period of 340 min. SEM results demonstrate that the cell maintains good geometric integrity without any delimitation of respective layer after the stability test, and EDX results show that carbon deposition occurrs only at the outer surface of the anode. O₂-TPO analysis shows that carbon deposition over the Ni-YSZ operating on DME is greatly suppressed in the presence of oxygen. Internal partial oxidation may be a practical way to achieve high cell performance at intermediate-temperatures for SOFCs operating on DME fuel.     

A new phenomenon of a fuel-free current during intermittent fuel flow over Ni-YSZ anode in direct methane SOFCs

A solid oxide fuel cell (SOFC) test unit was constructed with YSZ electrolyte as the support, and with Ni-YSZ anode (Ni:YSZ = 3:5 in weight) and Pt cathode. Direct methane SOFC operation at 800 °C with 10% CH₄ in argon was carried out. A new phenomenon of the generation of the electrical current without the fuel was observed and termed the fuel-free current. An operation of intermittent methane supply was designed to take advantage of three driving forces, i.e. methane in the gas phase, the deposited carbon at the anode surface, and a deficiency of the bulk lattice-oxygen concentration on the anode side, for the generation of the electrical current. A continuous generation of the electrical current is obtained with a methane pulse of only one-fifth of the total operation time. The operation of intermittent methane flow can reduce or even avoid SOFC deactivation by the carbon deposition; at the same time, the deposited carbon can be fully utilized for the power generation. It was also found that hydrogen from methane has been mostly evolved to the outlet gaseous product and the amount of CO formation is much higher than that of CO₂; the operation of intermittent methane flow can further increase the amount of CO over that of CO₂; these are beneficial for the co-generation of synthesis gas.     

Study of a SOFC with a bimetallic Cu–Co–ceria anode directly fuelled with simulated biogas mixtures

The present work is focused in the study of the bimetallic Cu–Co formulation combined with CeO₂ as SOFC anode, at 750 °C, direct feed of methane and two different fuel mixtures that simulate biogas. Additionally, the sulphur tolerance of new anode material has been evaluated. Its single cell evaluation, based on a samaria doped ceria (SDC) solid electrolyte and a LSM perovskite cathode, together with the electrochemical characterisation and catalytic activity tests, have allowed to demonstrate the ability of this material to operate directly with simulated biogas mixtures without loss of single cell performance due to the formation of carbon deposits or sulphur anode poisoning. The activity of this material for the exothermic oxidation of methane reduces the energy requirement of the endothermic internal methane reforming process. The cobalt doping of basic copper–ceria formulation enhanced sulphur and carbon coking tolerance of the SOFC anode material.     

3D modeling of anode-supported planar SOFC with internal reforming of methane

Deposition of carbon on conventional anode catalysts and formation of large temperature gradients along the cell are the main barriers for implementing internal reforming in solid oxide fuel cell (SOFC) systems. Mathematical modeling is an essential tool to evaluate the effectiveness of the strategies to overcome these problems. In the present work, a three-dimensional model for a planar internal reforming SOFC is developed. A co-flow system with no pre-reforming, methane fuel utilization of 75%, voltage of 0.7 V and current density of 0.65 A cm⁻² was used as the base case. The distributions of both temperature and gas composition through the gas channels and PEN (positive electrode/electrolyte/negative electrode) structure were studied using the developed model. The results identified the most susceptible areas for carbon formation and thermal stress according to the methane to steam ratio and temperature gradients, respectively. The effects of changing the inlet gas composition through recycling were also investigated. Recycling of the anode exhaust gas, at an optimum level of 60% for the conditions studied, has the potential to significantly decrease the temperature gradients and reduce the carbon formation at the anode, while maintaining a high current density.     

Direct methane solid oxide fuel cell working by gradual internal steam reforming: Analysis of operation

A solid oxide fuel cell was designed to be operated with pure hydrocarbons, without additive or carrier gas, in order to bring technological simplifications, cost reductions and to extend the fuel flexibility limits. The cell was built-up from a conventional cell (LSM/YSZ/Ni-YSZ), to which was added a Ir-CeO₂ catalyst layer at the anode side and an original current collecting system. The cell was first operated with steam in gradual internal reforming (GIR) conditions (R = [H₂O]/[CH₄] < 1) with carrier gas at the anode. The optimal operating parameters were determined in terms of flow rates, cell potential, and fuel utilisation. The cell was finally operated with pure dry methane at 900 °C at 0.6 V yielding current density of about 0.1 A cm⁻² at max power for 120 h. Small but abrupt deterioration of the performances was observed, but no carbon deposition. Electrical and chemical analysis of this degradation are provided.At total, the fuel cell was operated for more than 200 h in pure dry methane, demonstrating that gradual internal reforming actually occurred efficiently in the anode compartment, which make possible operation without reforming agent such as H₂O or CO₂ for other hydrocarbon fuels.     

Characterization of the Ni-ScSZ anode with a LSCM-CeO2 catalyst layer in thin film solid oxide fuel cell running on ethanol fuel

Solid oxide fuel cell (SOFC) running directly on hydrocarbon fuels has attracted much attention in recent years. In this paper, a dual-layer structure anode running on ethanol is fabricated by tape casting and screen-printing method, the addition of a LSCM-CeO₂ catalyst layer to the supported anode surface yields better performance in ethanol fuel. The effect that the synthesis conditions of the catalyst layer have on the performances of the composite anodes is investigated. Single cells with this anode are also fabricated, of which the maximum power density reaches 669 mW cm⁻² at 850 °C running on ethanol steam. No significant degradation in performance has been observed after 216 h of cell testing when the Ni-ScSZ13 anode is exposed to ethanol steam at 700 °C. Very little carbon is detected on the anode, suggesting that carbon deposition is limited during cell operation. Consequently, the LSCM-CeO₂ catalyst layer on the surface of the supported anode makes it possible to have good stability for long-term operation in ethanol fuel due to low carbon deposition.     

Impact of cell design and operating conditions on the performances of SOFC fuelled with methane

An in-house-model has been developed to study the thermal and electrochemical behaviour of a planar SOFC fed directly with methane and incorporated in a boiler. The usual Ni-YSZ cermet has been considered for the anode material. It has been found that methane reforming into hydrogen occurs only at the cell inlet in a limited depth within the anode. A sensitivity analysis has allowed establishing that anode thicknesses higher than ∼400–500 μm are required to achieve both the optimal methane conversion and electrochemical performances.     

Hydrogen production from glycerol on Ni/Al2O3 catalyst

The growing demand of hydrogen needs renewable sources of raw materials to produce it. Glycerol, by-product of biodiesel synthesis, could be a bio-renewable substrate to obtain hydrogen. A Ni(5.8%)-alumina catalyst was evaluated in the steam reforming of glycerol at 600–700 °C, atmospheric pressure, 16:1 water:glycerol molar ratio, and 3.4–10.0 h⁻¹ WHSV. A glycerol aqueous solution was fed, while a nitrogen stream was co-fed. After 4 h-on-stream, conversion was 96.8% at 600 °C increasing to 99.4% at 700 °C, reaching the largest hydrogen selectivity (99.7%) at 650 °C. After 8 h, conversion decreases more significantly at 600 °C, while the hydrogen selectivity does not significantly change with temperature and increases by decreasing WHSV. After 4 h, the main by-product was methane (76–97%), increasing at higher temperature, followed by ethene, ethane, propene, and propane. At 700 °C and 10.0 h⁻¹ WHSV, the main by-products were ethene (47%) and methane (37%); it could be associated to catalyst deactivation.     

High-entropy alloy anode for direct internal steam reforming of methane in SOFC

High-entropy alloy (HEA) anode and reforming catalyst, supported on gadolinium-doped ceria (GDC), have been synthesized and evaluated for the steam reforming of methane under SOFC operating conditions using a conventional fixed-bed catalytic reactor. As-synthesized HEA catalysts were subjected to various characterization techniques including N₂ adsorption/desorption analysis, SEM, XRD, TPR, TPO and TPD. The catalytic performance was evaluated in a quartz tube reactor over a temperature range of 700–800 °C, pressure of 1 atm, gas hourly space velocity (GHSV) of 45,000 h^?1 and steam-to-carbon (S/C) ratio of 2. The conversion and H₂ yield were calculated and compared. HEA/GDC exhibited a lower conversion rate than those of Ni/YSZ and Ni/GDC at 700 °C, but showed superior stability without any sign of carbon deposition unlike Ni base catalyst. HEA/GDC was further evaluated as an anode in a SOFC test, which showed high electrochemical stability with a comparable current density obtained on Ni electrode. The SOFC reported low and stable electrode polarization. Post-test analysis of the cell showed the absence of carbon at and within the electrode. It is suggested that HEA/GDC exhibits inherent robustness, good carbon tolerance and stable catalytic activity,` which makes it a potential anode candidate for direct utilization of hydrocarbon fuels in SOFC applications.     

Catalytic steam reforming of methane,methanol, and ethanol over Ni/YSZ: The possible use of these fuels in internal reforming SOFC

This study investigated the possible use of methane, methanol, and ethanol with steam as a direct feed to Ni/YSZ anode of a direct internal reforming Solid Oxide Fuel Cell (DIR-SOFC). It was found that methane with appropriate steam content can be directly fed to Ni/YSZ anode without the problem of carbon formation, while methanol can also be introduced at a temperature as high as 1000 °C. In contrast, ethanol cannot be used as the direct fuel for DIR-SOFC operation even at high steam content and high operating temperature due to the easy degradation of Ni/YSZ by carbon deposition. From the steam reforming of ethanol over Ni/YSZ, significant amounts of ethane and ethylene were present in the product gas due to the incomplete reforming of ethanol. These formations are the major reason for the high rate of carbon formation as these components act as very strong promoters for carbon formation.     

Mini CHP based on the electrochemical generator and impeded fluidized bed reactor for methane steam reforming

The paper presents a configuration of mini CHP with the methane reformer and planar solid oxide fuel cell (SOFC) stacks. This mini CHP may produce electricity and superheated steam as well as preheat air and methane for the reformer along with cathode air used in the SOFC stack as an oxidant. Moreover, the mathematical model for this power plant has been created. The thermochemical reactor with impeded fluidized bed for autothermal steam reforming of methane (reformer) considered as the basis for the synthesis gas (syngas) production to fuel SOFC stacks has been studied experimentally as well. A fraction of conversion products has been oxidized by the air fed to the upper region of the impeded fluidized bed in order to carry out the endothermic methane steam reforming in a 1:3 ratio as well as to preheat products of these reactions. Studies have shown that syngas containing 55% of hydrogen could be produced by this reactor. Basic dimensions of the reactor as well as flow rates of air, water and methane for the conversion of methane have been adjusted through mathematical modelling.The paper provides heat balances for the reformer, SOFC stack and waste heat boiler (WHB) intended for generating superheated water steam along with preheating air and methane for the reformer as well as the preheated cathode air. The balances have formed the basis for calculating the following values: the useful product fraction in the reformer; fraction of hydrogen oxidized at SOFC anode; gross electric efficiency; anode temperature; exothermic effect of syngas hydrogen oxidation by air oxygen; excess entropy along with the Gibbs free energy change at standard conditions; electromotive force (EMF) of the fuel cell; specific flow rate of the equivalent fuel for producing electric and heat energy. Calculations have shown that the temperature of hydrogen oxidation products at SOFC anode is 850 °C; gross electric efficiency is 61.0%; EMF of one fuel cell is 0.985 V; fraction of hydrogen oxidized at SOFC anode is 64.6%; specific flow rate of the equivalent fuel for producing electric energy is 0.16 kg of eq.f./(kW·h) while that for heat generation amounts to 44.7 kg of eq.f./(GJ). All specific parameters are in agreement with the results of other studies.     

Au-doped Ni/GDC as a new anode for SOFCs operating under rich CH4 internal steam reforming

In the present work we describe a Solid Oxide Fuel Cell (SOFC) that comprises a Ni/GDC cermet anode, doped with a potentially commercially viable concentration of gold nano-particles. Specifically, gold was applied prior to anode sintering via the deposition–precipitation method. This procedure resulted in a SOFC that allowed carbon tolerant operation at T = 850 °C under fuel rich internal steam reforming of methane, with a stable power density of 0.41 W cm⁻² at 810 mV for over 200 h.     

Steam reforming of commercial ultra-low sulphur diesel

Two main routes for small-scale diesel steam reforming exist: low-temperature pre-reforming followed by well-established methane steam reforming on the one hand and direct steam reforming on the other hand. Tests with commercial catalysts and commercially obtained diesel fuels are presented for both processes. The fuels contained up to 6.5 ppmw sulphur and up to 4.5 vol.% of biomass-derived fatty acid methyl ester (FAME). Pre-reforming sulphur-free diesel at around 475 °C has been tested with a commercial nickel catalyst for 118 h without observing catalyst deactivation, at steam-to-carbon ratios as low as 2.6. Direct steam reforming at temperatures up to 800 °C has been tested with a commercial precious metal catalyst for a total of 1190 h with two catalyst batches at steam-to-carbon ratios as low as 2.5. Deactivation was neither observed with lower steam-to-carbon ratios nor for increasing sulphur concentration. The importance of good fuel evaporation and mixing for correct testing of catalysts is illustrated. Diesel containing biodiesel components resulted in poor spray quality, hence poor mixing and evaporation upstream, eventually causing decreasing catalyst performance. The feasibility of direct high temperature steam reforming of commercial low-sulphur diesel has been demonstrated.     

Methane internal steam reforming in solid oxide fuel cells at intermediate temperatures

The internal steam reforming of methane (CH₄) on conventional solid oxide fuel cell (SOFC) anode (nickel-yttria stabilized zirconia or Ni-YSZ) offers significant advantages compared to the external reforming process. However, the technology is currently facing some major issues such as coking and oxidation of anode during operation. Here we report a low-temperature sinterable catalyst, Ce_0·77Ni_0·2Mn_0·03O_2-δ (CNMnO), applied on top of Ni-YSZ to perform the steam reforming reaction. A single cell with CNMnO/Ni-YSZ/YSZ/GDC/LSC configuration produces a peak power density of 492 mW cm^?2 in wet hydrogen and 371 mW cm^?2 in wet methane, at 600 °C. The cell also shows exceptional durability against Ni oxidation when tested in wet methane under 0.2 A cm^?2 for 100 h. The improved performance and durability of the catalyst layer has been attributed to the nanosized precipitated Ni and Mn particles distributed on the surface of individual CNMnO particles.     

Characteristics of SOFC single cells with anode active layer via tape casting and co-firing

SOFC (solid oxide fuel cell) single cells with anode active layers of various thicknesses were fabricated successfully via tape casting and co-firing in order to improve their electrochemical performance and long-term stability. The mercury porosimeter and the gas permeability were measured so as to examine the effects of the anode active layer while under a gaseous flow. It was found that the anode active layers affected the microstructural characteristics as a result of the pore distribution and the gas permeation behavior. The anode active layers improved the cell performance by increasing the number of active sites in the anode. The thickness of the anode active layer was optimized at 20 μm in this work through a combination of the power density, the ohmic ASR (area specific resistance), and the cell ASR. SOFCs with the optimized active layer showed good electrochemical performance at 600–700 °C in hydrogen or hydrocarbon fuel (methane) and excellent long-term stability for 500 h.     

Yttria-stabilized zirconia (YSZ) supported Ni–Co alloys (precursor of SOFC anodes) as catalysts for the steam reforming of ethanol

Bioethanol is an attractive fuel for direct internal reforming SOFC (DIR-SOFC). The aim of this work is to investigate the activity of Ni–YSZ, used as precursor for the preparation of SOFC anodes and as catalyst of the ethanol steam reforming reaction. The effect of the addition of cobalt is also studied, as the best performance is given by Ni–Co (25:25)/YSZ catalyst. This achieves total conversion of ethanol around 670 K, at which temperature the H₂ yield is 65%. The addition of Co results in the inhibition of the dehydration reaction as well as of methane production. Furthermore, Co also has an effect on the hydrogen yield, by increasing it and thus apparently favouring methane steam reforming.     

Internal reforming characteristics of cermet supported solid oxide fuel cell using yttria stabilized zirconia fed with partially reformed methane

In order to investigate the internal reforming characteristics in a cermet supported solid oxide fuel cell (SOFC) using YSZ as the electrolyte, the concentration profiles of the gaseous species along the gas flow direction in the anode were measured. Partially reformed methane using a pre-reformer kept at a constant temperature is supplied to the center of the cell which is operated with a seal-less structure at the gas outlet. The anode gas is sucked in via silica capillaries to the initially evacuated gas tanks. The process is simultaneously carried out using five sampling ports. The sampled gas is analyzed by a gas chromatograph. Most of the measurements are made at the cell temperature (T_cell) of 750 °C and at various temperatures of the pre-reformer (T_ref) with various fuel utilizations (U_f) of the cell. The composition of the fuel at the inlet of the anode was confirmed to be almost the same as that theoretically calculated assuming equilibrium at the temperature of the pre-reformer. The effect of internal reforming in the anode is clearly observed as a steady decrease in the methane concentration along the flow axis. The effect of the water-gas shift reaction is also observed as a decrease in the CO₂ concentration and an increase of CO concentration around the gas inlet region, as the water-gas shift reaction inversely proceeds when T_cell is higher than T_ref. The diffusion of nitrogen from the seal-less outermost edge is observed, and the diffusion is confirmed to be more significant as U_f decreases. The observations are compared with the results obtained by the SOFC supported by lanthanum gallate electrolyte. With respect to the internal reforming performance, the cell investigated here is found to be more effective when compared to the previously reported electrolyte supported cell.     

Performance and life-time behaviour of NiCu–CGO anodes for the direct electro-oxidation of methane in IT-SOFCs

An anodic cermet of NiCu alloy and gadolinia doped ceria has been investigated for CH₄ electro-oxidation in IT-SOFCs. Polarization curves have been recorded in the temperature range from 650 to 800 °C. A maximum power density of 320 mW cm⁻² at 800 °C has been obtained in the presence of dry methane in an electrolyte-supported cell. The electrochemical behaviour during 1300 h operation in dry methane and in the presence of redox-cycles has been investigated at 750 °C; variation of the electrochemical properties during these experiments have been interpreted in terms of anode morphology modifications. The methane cracking process at the anode catalyst has been investigated by analysing the oxidative stripping of deposited carbon species.     

Externally reformed solid oxide fuel cell–micro-gas turbine (SOFC–MGT) hybrid systems fueled by methanol and di-methyl-ether (DME)

Solid oxide fuel cell–micro-gas turbine (SOFC–MGT) hybrid power plants integrate a solid oxide fuel cell and a micro-gas turbine and can achieve efficiencies of over 60% even for small power outputs (200–500 kW). The SOFC–MGT systems currently developed are fueled with natural gas, which is reformed inside the same stack, but the use of alternative fuels can be an interesting option. In particular, as the reforming temperature of methanol and di-methyl-ether (DME) (200–350 °C) is significantly lower than that of natural gas (700–900 °C), the reformer can be sited outside the stack. External reforming in SOFC–MGT plants fueled by methanol and DME enhances efficiency due to improved exhaust heat recovery and higher voltage produced by the greater hydrogen partial pressure at the anode inlet. The study carried out in this paper shows that the main operating parameters of the fuel reforming section (temperature and steam-to-carbon ratio (SCR)) must be carefully chosen to optimise the hybrid plant performance. For the stoichiometric SCR values, the optimum reforming temperature for the methanol fueled hybrid plant is approximately 240 °C, giving efficiencies of about 67–68% with a SOFC temperature of 900 °C (the efficiency is about 72–73% at 1000 °C). Similarly, for DME the optimum reforming temperature is approximately 280 °C with efficiencies of 65% at 900 °C (69% at 1000 °C). Higher SCRs impair stack performance. As too small SCRs can lead to carbon formation, practical SCR values are around one for methanol and 1.5–2 for DME.