Upgrading the performance of La2Mo2O9-based solid oxide fuel cell under single chamber conditions

Various anode-supported solid oxide fuel cells (SOFC), based on 10 mol% Dy-doped La₂Mo₂O₉ (LDM) electrolyte, are prepared analytically and operated under single chamber conditions to explore the connections between electrode and power performance. The cathode of tested SOFCs is compositionally graded with three composites of samarium strontium cobaltite and Gd-doped ceria (GDC) to relax the thermal stress, because of sizable thermal expansion differences above 400 °C. We focus the research attention on varying the anode pore structure and composition to promote the power performance in methane/air mixture at 700 °C. For the one-layer support of GDC+NiO+LDM anode, addition of 10 wt% graphite minimizes its mass transport resistance through creating 8–5 μm long and ∼1 μm wide slit-shaped pores. The graphite pore former raises the peak power value by 80 mW cm⁻². Adopting a more porous and active outer layer, the double-layer support further enhances the cell power. The peak power was first raised by 48 mW cm⁻², using an outer layer that was prepared with 63 wt% NiO. Dosing 3% Pd on this outer layer uplifts another 59 mW cm⁻². In this study, with an improved anode, the peak power value reaches 437 mW cm⁻².     

Effects of a current treatment for an in-situ sintered cathode in a Ni-supported solid oxide fuel cell

Metal-supported solid oxide fuel cells (SOFCs) are one of the most promising candidates for applications in power plants as well as in portable applications due to their good mechanical and thermal properties. A Ni-supported SOFC that consists of a metal support (Ni, ∼180 μm), an anode functional layer (Ni-yttrium stabilized zirconia YSZ, ∼15 μm), an electrolyte (YSZ, ∼5 μm), and a nanocrystalline La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathode is prepared. A nanocrystalline LSCF synthesized with ethylenediaminetetraacetic acid, citric acid, and inorganic nanodispersants, is used as an in situ sinterable cathode. The Ni-supported SOFC with nanocrystalline LSCFs is operated without a high temperature treatment for cathode sintering. The cell exhibits the maximum power density of 580 mW cm⁻² at 780 °C. A current treatment for 8 h (0.5 A cm⁻² at 780 °C) enhances the interfacial contact between the cathode and the electrolyte. After the current treatment, the maximum power density at 730 °C increase by 1.6 times from 260 mW cm⁻² to 390 mW cm⁻². The ohmic resistance (R_ohm) at 730 °C decreases from 0.43 Ω cm² to 0.21 Ω cm² and the charge transfer polarization at 0.7 V decreases from 0.42 Ω cm² to 0.30 Ω cm² due to lowered interfacial resistance between the cathode and the electrolyte. However, the mass transfer polarization increases from 0.09 Ω cm² to 0.17 Ω cm², which may result from the morphological change in the porous microstructure of the Ni support. The current treatment of the Ni-supported SOFC with in situ sintered LSCFs exhibit an increment in fuel cell performance due to the lowered ohmic resistance, which is beneficial for simple and mechanically improved fabrication and operation of metal-supported SOFCs.     

A direct-flame solid oxide fuel cell (DFFC) operated on methane,propane, and butane

This paper presents an experimental study of a direct-flame type solid oxide fuel cell (DFFC). The operation principle of this system is based on the combination of a combustion flame with a solid oxide fuel cell (SOFC) in a simple, no-chamber setup. The flame front serves as fuel reformer located a few millimeters from the anode surface while at the same time providing the heat required for SOFC operation. Experiments were performed using 13-mm-diameter planar SOFCs with Ni-based anode, samaria-doped ceria electrolyte and cobaltite cathode. At the anode, a 45-mm-diameter flat-flame burner provided radially homogeneous methane/air, propane/air, and butane/air rich premixed flames. The cell performance reaches power densities of up to 120 mW cm⁻², varying systematically with flame conditions. It shows a strong dependence on cell temperature. From thermodynamic calculations, both H₂ and CO were identified as species that are available as fuel for the SOFC. The results demonstrate the potential of this system for fuel-flexible power generation using a simple setup.     

A symmetrical solid oxide fuel cell prepared by dry-pressing and impregnating methods

In this study, a simple and cost-effective dry-pressing method has been used to fabricate a symmetrical solid oxide fuel cell (SOFC) where the dense yttria-stabilized zirconia (YSZ) electrolyte film is sandwiched between two symmetrical porous YSZ layers in which La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) based anode and cathode are incorporated using wet impregnation techniques. The maximum power densities (P_max) of a single cell with 32 wt.% LSCM impregnated YSZ anode and cathode reach 333 and 265 mW cm⁻² at 900 °C in dry H₂ and CH₄, respectively. The cell performance is further improved with additional impregnation of a small amount of Sm-doped CeO₂ (SDC) or Ni. When 6 wt.% Ni as catalyst is added to both the anode and cathode, P_max values of 559 and 547 mW cm⁻² can be achieved, which are better than with SDC. The effect of Ni on the cathode performance is also investigated by impedance spectra analysis.     

A highly coking-resistant solid oxide fuel cell with a nickel doped ceria: Ce1−xNixO2−y reformation layer

A single phase mixed oxide ion-electron conducting electrochemical catalyst of Ce_1−xNi_xO_2−y is employed as an anode functional reformation layer for a coking-resistant solid oxide fuel cell (SOFC) based on oxide ion conducting electrolyte operated in methane and ethanol. The high catalytic activity of Ce_1−xNi_xO_2−y oxide for fuel reformation is demonstrated by the excellent cell performances in various fuels at relatively low temperatures (550–650 °C). The fast oxygen ions flux and formed steam at anode side are also found to be favorable for hydrocarbon reformation to promote the cell performance and long term stability. At 650 °C, maximum power densities of 415 and 271 mW cm⁻² are achieved in methane and ethanol respectively. The resistance against carbon deposition is significantly improved with stable voltage output in a long-term durability operation.     

Glycerol oxidation in solid oxide fuel cells based on a Ni-perovskite electrocatalyst

An investigation of the electrochemical oxidation of glycerol as alternative to hydrogen and methane in solid oxide fuel cells (SOFCs) based on a noble metal-free anode catalyst was carried out. The anode electrocatalyst consisted of a Ni-modified La_0.6Sr_0.4Fe_0.8Co_0.2O₃ (LSFCO) perovskite. After thermal activation, air treatment at 1100 °C followed by reduction at 800 °C in H₂, Ni was mainly present as ultrafine La₂NiO₄ particles homogeneously dispersed on the perovskite surface. The thermal activation also caused a modification of perovskite into a lanthanum depleted structure. The thermal reduction at 800 °C determined the occurrence of metallic Ni on the surface. These results were corroborated by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and X-ray diffraction (XRD). A suitable power density (327 mW cm⁻²) was achieved for the electrolyte supported SOFC fed with chemical-grade glycerol in almost dry condition, i.e. steam to carbon ratio (S/C) of 0.2. The highest electrical efficiency (voltage efficiency) approached 50% at the peak power under mild humidification (S/C = 0.2). Whereas an increase of water to glycerol ratio, caused a progressive decrease of voltage efficiency at the peak power down to 44% for S/C = 2.     

Improved power generation performance of solid oxide fuel cells using doped LaGaO3 electrolyte films prepared by screen printing method II. Optimization of Ni-Ce0.8Sm0.2O1.9 cermet anode support

A Ni and Sm-doped ceria (Ce_0.8Sm_0.2O_1.9, SDC) cermet anode as a porous support of doped LaGaO₃ film prepared by a wet coating and co-firing process was investigated. Different preparation methods and compositions were used to improve the power density of intermediate temperature solid oxide fuel cells. NiO-SDC precursor powder with fine particles and a porous microstructure with high surface area was synthesized by a modified impregnation method and compared with that synthesized by a ball milling method. In addition, an open circuit voltage, which is almost equal to the theoretical value of 1.1 V, and maximum power densities of 835, 277, and 67 mW cm⁻² at 700, 600, and 500 °C, respectively, were achieved on a single cell supported by a 75 wt% Ni-SDC cermet anode when a 60 μm thick Sr- and Mg-doped lanthanum gallate (LSGM) electrolyte was used. The improved power density was explained by the enlarged reaction area for the anode as a result of the low polarization resistance of the anode by high porosity and uniform distribution of Ni and SDC particles. Although a small amount of Ni diffused to the interface between the La-doped ceria (LDC) buffer layer and the LSGM electrolyte film, an adverse reaction that deteriorates cell performance seemed to be suppressed, and thus, reasonably high power density was achieved on the cell using the LSGM film prepared by the screen printing method with optimization of the anode substrate structure and composition.     

Cobalt-impregnated La0.75Sr0.25Cr0.5Mn0.5O3−δ anodes for solid oxide fuel cells

In this study, we will report our investigation for La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) based anodes impregnated with solutions of cobalt (Co) nitrate. A YSZ supported SOFC with pure LSCrM anode and La_0.7Sr_0.3MnO₃ (LSM) cathode exhibits the maximum power density (P_max) of 58.7 and 5.2 mW cm⁻² at 850 °C in dry H₂ and dry CH₄. After the modification of anode with Co nitrate, the P_max reaches 196.2 mW cm⁻² in dry H₂ and 28.5 mW cm⁻² in dry CH₄, about 3.34 times and 5.48 times increase, respectively. These results indicate that Co is also a potential catalyst for LSCrM anode. Moreover, the effect of impregnation amount of catalyst on the cell performance is also evaluated in this study.     

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.     

Performance of an anode-supported tubular solid oxide fuel cells stack with two single cells connected by a co-sintered ceramic interconnector

Two anode-supported tubular solid oxide fuel cells (SOFCs) have been connected by a co-sintered ceramic interconnector to form a stack. This novel bilayered ceramic interconnector consists of La-doped SrTiO₃ (La_0.4Sr_0.6TiO₃) and Sr-doped lanthanum manganite (La_0.8Sr_0.2MnO₃), which is fabricated by co-sintering with green anode at 1380 °C for 3 h. La_0.4Sr_0.6TiO₃ (LST) acts as a barrier avoiding the outward diffusion of H₂ to the cathode; while La_0.8Sr_0.2MnO₃ (LSM) prevents O₂ from diffusing inward to the anode. The compatibility of LST and LSM, as well as their microstructure which co-sintered with anode are both studied. The resistances between anode and LST/LSM interconnector at different temperatures are determined by AC impedance spectra. The results have showed that the bilayered LST/LSM is adequate for SOFC interconnector application. The active area is 2 cm² for interconnector and 16 cm² for the total cathode of the stack. When operating at 900 °C, 850 °C, 800 °C with H₂ as fuel and O₂ as oxidant, the maximum power density of the stack are 353 mW cm⁻², 285 mW cm⁻² and 237.5 mW cm⁻², respectively, i.e., approximately 80% power output efficiency can be achieved compared with the total of the two single cells.     

Electrical properties of Ni-doped Sm2O3 electrolyte

Nowadays, semiconductor ionic materials have drawn significant attention for developing new electrolytes in low temperature solid oxide fuel cells (LT-SOFCs). Here we investigate the effect of nickel doping on ionic conductivity of Sm₂O₃ as an electrolyte material for low temperature SOFCs. The amount of Ni ion doping has an intense effect on the electrochemical properties and power generation. An optimized composition of 10 mol% nickel doped samarium oxide (10NSO) as an electrolyte in the fuel cell has a high open circuit voltage (OCV) of 1.09 V and a notable power output of 1080 mW cm^?2 at 520 °C. Further investigation revealed that the 10NSO displays a superior ionic conduction up to 0.26 S cm^?1 at 520 °C. Moreover, the cell demonstrates high stability up to 80 h. The high electrochemical property and good stability recommend that the NSO is a favorable candidate for symmetrical SOFC electrolyte.     

Ni/YSZ and Ni–CeO2/YSZ anodes prepared by impregnation for solid oxide fuel cells

In this paper, Ni/YSZ and Ni–CeO₂/YSZ anodes for a solid oxide fuel cell (SOFC) were prepared by tape casting and vacuum impregnation. By this method, the Ni content in the anode could be reduced compared to the traditional tape casting method. It was found that adding CeO₂ into the Ni/YSZ anode by a Ni(NO₃)₂ and Ce(NO₃)₃ mixed impregnation could further enhance cell performance. This was investigated in H₂ at 1073 K. XRD patterns indicated that CeO₂ and Ni were separate phases, and the CeO₂ addition could enhance the Ni dispersion on the YSZ framework surface which was observed by SEM images. It was shown that adding CeO₂ into the Ni anodes could decrease the cell polarization resistance. The maximum power density for cells with 25 wt.% Ni, 5 wt.% CeO₂–25 wt.% Ni/YSZ, or 10 wt.% CeO₂–25 wt.% Ni/YSZ anode was 230 mW cm⁻², 420 mW cm⁻² and 530 mW cm⁻², respectively, in H₂ at 1073 K. The OCV for these cells was 1.05–1.09 V, indicating that a dense electrolyte film was obtained by co-firing porous YSZ layer and dense YSZ layer.     

New ionic diffusion strategy to fabricate proton-conducting solid oxide fuel cells based on a stable La2Ce2O7 electrolyte

A composite of NiO–BaZr_0.1Ce_0.7Y_0.2O_3−δ (NiO-BZCY) was successfully prepared by a simple one-step-combustion process and applied as an anode for solid oxide fuel cells based on stable La₂Ce₂O₇ (LCO) electrolyte. A high open circuit voltage of 1.00 V and a maximum power density of 315 mW cm⁻² were obtained with NiO-BZCY anode and LCO electrolyte when measured at 700 °C using humidified hydrogen fuel. SEM-EDX and Raman results suggested that a thin BaCeO₃-based reaction layer about 5 μm in thickness was formed at the anode/electrolyte interface for Ba cations partially migrated from anode into the electrolyte film. Impedance spectra analysis showed that the activation energy for LCO conductivity differed with the anode materials, about 52.51 kJ mol⁻¹ with NiO-BZCY anode and 95.08 kJ mol⁻¹ with NiO-LCO anode. The great difference in these activation energies might suggest that the formed BaCeO₃ reaction layer could promote the proton transferring numbers of LCO electrolyte.     

A promising Ni–Fe bimetallic anode for intermediate-temperature SOFC based on Gd-doped ceria electrolyte

Anode supported solid oxide fuel cells (SOFC) based on Ni–Fe bimetal and gadolinia-doped ceria (GDC) composite anode were fabricated and evaluated in the intermediate- and low-temperature range. Ni_0.75Fe_0.25-GDC anode substrate and GDC electrolyte bilayer were prepared by the multi-layered aqueous tape casting method. The single cell performance was characterized with La_0.6Sr_0.4Co_0.2Fe_0.8O₃-GDC (LSCF-GDC) composite cathode. The maximum power density reached 330, 567, 835 and 1333 mW cm⁻² at 500, 550, 600 and 650 °C, respectively. Good long-term performance stability has been achieved at 600 °C for up to 100 h. The improved single cell performance was achieved in the reduced temperature after the long-term stability test. The maximum power density registered 185 and 293 mW cm⁻² at 400 and 450 °C, respectively. The impedance spectra fitting results of the test cell revealed that the improved cell performance was attributed to the much lower electrochemical reaction resistance. XRD and SEM examination indicated that the outstanding performance of the single cell seemed to arise from the optimized composition and excellent microstructure of Ni_0.75Fe_0.25-GDC anode, as well as the improved stability of the anode microstructure with prolonged testing time.     

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.     

Direct carbon solid oxide Fuel Cell—a potential high performance battery

Tubular cone-shaped Ni-based anode-supported solid oxide fuel cells (SOFCs), with yttria-stabilized zirconia (YSZ) electrolyte and La_0.8Sr_0.2MnO₃ (LSM) cathode, were investigated with Fe catalyst-loaded activated carbon directly filled in as fuel. Three identical single cells were operated at different current and it turned out that larger current resulted in shorter operation life and smaller carbon utilization. A 3-cell-stack, with the segmented cone-shaped cells connected in series, was assembled and tested. A peak power density of 465 mW cm⁻² and a volumetric power density of 710 mW cm⁻³ were achieved at 850 °C. The degradation performance was analyzed according to the electrochemical characterization and SEM-EDX measurement. Based on the experimental results, the potential of developing such direct carbon SOFC into a high performance battery was proposed.     

Performance evaluation of La0.4Sr0.6Co0.2Fe0.7Nb0.1O3−δ as both anode and cathode material in solid oxide fuel cells

Solid oxide fuel cell (SOFC) has experienced a growing interest in the last few decades because of generating energy more efficiently than the conventional combustion of fossil fuels. By using the same material as anode and cathode of SOFC (symmetric fuel cell), the production of reliable and repeatable cells would be simpler. In this work, La_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3−δ (LSCFN) perovskite has been prepared and evaluated as both cathode and anode material of symmetric fuel cell. The results of symmetric fuel cell show that a maximum peak power density of 500 mW cm⁻² has been achieved and the total electrode polarization resistances of the cell is only 0.22 Ω cm² at 850 °C which is much lower than that of typical symmetric fuel cell with La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ as electrode material. All of these results indicate that LSCFN can potentially be a promising candidate for the electrode material of symmetric fuel cell.     

The study of Au/MoS2 anode catalyst for solid oxide fuel cell (SOFC) using H2S-containing syngas fuel

Au/MoS₂ is a promising anode catalyst for conversion of all components of H₂S-containing syngas in solid oxide fuel cell (SOFC). MoS₂-supported nano-Au particles have catalytic activity for conversion of CO when syngas is used as fuel in SOFC systems, thus preventing poisoning of MoS₂ active sites by CO. In contrast to use of MoS₂ as anode catalyst, performance of Au/MoS₂ anode catalyst improves when CO is present in the feed. Current density over 600 mA cm⁻² and maximum power density over 70 mW cm⁻² were obtained at 900 °C, showing that Au/MoS₂ could be potentially used as sulfur-tolerant catalyst in fuel cell applications.     

Solid oxide fuel cell with compositionally graded cathode functional layer deposited by pressure assisted dual-suspension spraying

In this work, the benefit of compositionally grading a cathode functional layer (CFL) for solid oxide fuel cells (SOFCs) is explored. Cells are prepared wherein either a standard cathode functional layer (SCFL) or a linearly compositionally graded cathode functional layer (CGCFL) is placed between the cell electrolyte and cathode current collecting regions. The electrochemical performance of these cells is compared with a SOFC cell containing no CFL. All cells are fabricated using a pressurized dual-suspension spraying system. Electrolytes, cathode functional layer, and cathode current collecting materials are deposited on a powder compacted anode support. SEM and EDAX area maps are taken to study the resulting micro-structures and to verify that the desired CFL profiles are produced. The EDAX area map verifies that a compositionally graded CFL and a SCFL are obtained. The cells are analyzed using impedance spectroscopy to evaluate the electrochemical performances of each cell. The open circuit voltage (OCV) and peak power densities of all three cells are 1.04 V with 80 mW cm⁻², 1.12 V with 108 mW cm⁻², and 1.08 V with 193 mW cm⁻² at 850 °C for the SCFL cell, the cell without a CFL, and the compositionally graded CFL cell respectively. The results show that this approach is a viable means for producing SOFC functional layers with unique composition and interfacial properties.     

Nano Ni layered anode for enhanced MCFC performance at reduced operating temperature

Nanoparticles of Ni and Ni–Al₂O₃ were coated on a molten carbonate fuel cell (MCFC) anode by spray method to enlarge the electrochemical reaction sites at triple phase boundaries (TPBs). Both nano Ni coated anode and nano Ni–Al₂O₃ anode exhibited significant reduction of anode polarization, thanks to smaller charge transfer resistance. The maximum power density of nano Ni coated anode was 159 mW cm⁻² at current density of 300 mA cm⁻² operating at 600 °C. This is about 7% increase from the standard cell performance tested and compared in the study. Although low performance of nano coated Ni–Al₂O₃ cell is observed due to electrolyte consumption, the stability of cell performance during operation time is more favorable in MCFCs operation.