New Stack Design of Micro‐tubular SOFCs for Portable Power Sources

Micro‐tubular solid oxide fuel cells (SOFCs) have high thermal stability and higher volumetric power density, which are considered to be ideal features for portable power sources and auxiliary power units for automobile. Here, we report a new stack design using anode supported micro‐tubular SOFCs with 2 mm diameter using Gd doped CeO₂ (GDC) electrolyte, NiO‐GDC anode and (La, Sr)(Co, Fe)O₃ (LSCF)‐GDC cathode. The new stack consists of three bundles with five tubular cells, sealing layers and interconnects and fuel manifolds. The performance of the stack whose volume is 1 cm³ was shown to be 2.8 V OCV and maximum power output of 1.5 W at 500 °C, applying air only by natural convection. The results also showed strong dependence of the fuel flow rates on the stack performance, which was correlated to the gas diffusion limitation.     

Progress in Microtubular Solid Oxide Fuel Cells

The benefits of microtubular solid oxide fuel cells (SOFCs) are addressed, including increased power density, rapid start-up, and cycling performance. Several international developments are discussed, especially small portable applications, which demand fast start and multiple cycles. Extrusion is the main method for making microtubular SOFCs because improved structure and properties can result from better mixing of the component particles and coextrusion can integrate several cell components in one process step. When the tubes are <3 mm in diameter, it is shown that the power density and thermal shock resistance are much increased, with start-up in a few seconds rather than hours for planar designs, as demonstrated in a single-cell hand-held system running on butane. The problems of cycling, both thermal and redox, are then considered in detail. Thermal cycling degradation follows a fatigue curve whereas redox damage is linear with the number of cycles. New results are presented on thermal and redox cycling performance.     

Thin film YSZ coatings on functionally graded freeze cast NiO/YSZ SOFC anode supports

Intermediate temperature (600–800 °C) solid oxide fuel cell (SOFC) technology is often limited by inadequate gas transport in electrodes, and high ion transport resistance electrolytes. In this study, large area filtered arc deposition (LAFAD) and hybrid filtered arc-assisted e-beam physical vapor deposition (FA-EBPVD) technologies, in combination with freeze-tape-casting, were used to fabricate SOFC anode/electrolyte bi-layers with functionally graded porous anode microstructures and thin film electrolytes favorable for both gas transport and low resistance. Traditionally-processed NiO/YSZ in addition to freeze-tape-cast NiO/YSZ anode substrates were fabricated and subsequently coated with thin film (<1–20 μm) YSZ via LAFAD and FA-EBPVD. LAFAD was found to be effective in applying thin (~1 μm) dense YSZ films on porous substrates at ~400 °C. FA-EBPVD produced relatively thick (~10–20 μm) dense YSZ coatings on porous substrates, with columnar morphology and nano-metrical grain size. A ~10 μm FA-EBPVD YSZ coating was observed to bridge NiO/YSZ surface pores of ~10 μm, which typically requires pre-filling prior to conventional thin film coating processes. Coated substrates exhibited negligible curvature, yielding flat anode/electrode bi-layers up to 2.5 cm in diameter. These results are presented with conderations for future SOFC development discussed.     

SOFC fuelled by methane without coking: optimization of electrochemical performance

In recent years, fuel cell technology has attracted considerable attention from several fields of scientific research as fuel cells produce electric energy with high efficiency, emit little noise, and are non-polluting. Solid oxide fuel cells (SOFCs) are particularly important for stationary applications due to their high operating temperature (1,073–1,273 K). Methane appears to be a fuel of great interest for SOFC systems because it can be directly converted into hydrogen by direct internal reforming (DIR) within the SOFC anode. Unfortunately, internal steam reforming in SOFC leads to inhomogeneous temperature distributions which can result in mechanical failure of the cermet anode. Moreover this concept requires a large amount of steam in the fed gas. To avoid these problems, gradual internal reforming (GIR) can be used. GIR is based on local coupling between steam reforming and hydrogen oxidation. The steam required for the reforming reaction is obtained by the hydrogen oxidation. However, with GIR, Boudouard and cracking reactions can involve a risk of carbon formation. To cope with carbon formation a new cell configuration of SOFC electrolyte support was studied. This configuration combined a catalyst layer (0.1%Ir–CeO₂) with a classical anode, allowing GIR without coking. In order to optimise the process a SOFC model has been developed, using the CFD-Ace+ software package, and including a thin electrolyte. The impact of a thin electrolyte on previous conclusions has been assessed. As predicted, electrochemical performances are higher and carbon formation is always avoided. However a sharp decrease in the electrochemical performances appears at high current densities due to steam clogging.     

Planar Solid Oxide Fuel Cells Using PSZ,Processed by Sequential Aqueous Tape Casting and Constrained Sintering

A process for obtaining planar anode‐supported solid oxide fuel cells was developed. Aqueous‐based slurries were prepared and sequentially deposited via tape casting to form half cell tapes consisting of the electrolyte, functional, and structural anode. Sintering of the three‐layered tapes was done in two stages: presintering circular samples of 25 mm diameter in free conditions first, and then sintering them using zirconium disks as light loads (90 Pa), to obtain half cells having 20 mm and 3.8 m^?1 in diameter and curvature, respectively. Active materials for the electrolyte, anode, and cathode were partially stabilized zirconia (PSZ), Ni and LSM, respectively. Finally, thicknesses of complete cells were 400, 30, 30, and 80 μm for the structural anode, functional anode, electrolyte, and cathode, respectively. The cells were tested in a no‐chamber (direct‐flame) setup evaluating electrochemical performance and shock thermal resistance. Open circuit voltage was 830 mV at 560°C using methanol as fuel in a burner with porous media to modify the shape of the flame. Cells were also strong enough to resist the rapid temperature changes during several no‐chamber tests.     

Evaluation of extruded cathode honeycomb monolith-supported SOFC under rapid start-up operation

The electrochemical properties of a novel honeycomb solid oxide fuel cell (SOFC), supported by an extruded cathode monolith and capable of generating high-volumetric power density under intermediate temperature operation, are reported. The SOFC was fabricated via the extrusion of a cathode honeycomb support and channel surface coating with electrolyte/anode bilayers using a wet chemical process. Under humidified H₂ fuel flow, high-volumetric power density above 2 and 3 W cm⁻³ at 0.7 V was exhibited at 700 and 750 °C, respectively. In addition, microstructure observation and electrochemical analyses confirmed that the honeycomb SOFC has structural durability for the rapid start-up operation with a heating rate of 100 °C min⁻¹.     

Wet Atomisation of Gd‐doped CeO2 Electrolyte Slurries for Intermediate Temperatures' Microtubular SOFC Applications

A wet atomising system has been employed as a novel method to prepare ultrafine Gd‐doped CeO₂ (GDC) electrolyte slurries. By changing the fluid flow pressure and repeating the atomisation process several times for the same atomised slurries, we have obtained optimised ultrafine GDC slurry with high‐dispersed and homogeneous distribution. The sizes of the particles of GDC were in the range of tens of nanometres. A highly dense electrolyte layer (membrane) was prepared using the ultrafine GDC slurries for intermediate temperatures microtubular solid oxide fuel cell (SOFC) applications. The SOFC was fabricated by using supporting porous anode tubes of NiO and GDC, and the cathode consisted of La_0.6Sr_0.4Co_0.2Fe_0.8O_3–y and GDC. A dense 10 μm GDC electrolyte layer was obtained at a lower sintering temperature of 1,250 °C for 1 h. The SOFC was tested with humidified (3% H₂O) hydrogen as a fuel and the static air as an oxidant, and the tubular cell maintained its high performance even at 500 °C.     

Solid Oxide Fuel Cells: Technology Status

In its most common configuration, a solid oxide fuel cell (SOFC) uses an oxygen-ion conducting ceramic electrolyte membrane, perovskite cathode, and nickel cermet anode electrode. Cells operate in the 600–1000°C temperature range and utilize metallic or ceramic current collectors for cell-to-cell interconnection. Recent developments in engineered electrode architectures, component materials chemistry, cell and stack designs, and fabrication processes have led to significant improvements in the electrical performance and performance stability as well as reduction in the operating temperature of such cells. Large kW-size power-generation systems have been designed and field demonstrated. This paper reviews the status of SOFC power-generation systems with emphasis on cell and stack component materials, electrode reactions, materials reactions, and corrosion processes.     

Analysis of a solid oxide fuel cell system for combined heat and power applications under non-nominal conditions

In this paper, a model for a solid oxide fuel cell (SOFC) system for decentralized electricity production is developed and studied. The proposed system, operated on natural gas, consists of a planar anode supported fuel cell section and a balance of plant (BoP) which includes gases supply, a fuel processor, a heat management system, an after-burner and a power conditioning system. A reference case is defined and evaluated taking into account the state of the art of the technology and the related technical constrains. Electrical and thermal efficiency of the system, for non-reference conditions are evaluated. In particular, the effect of the deviation from the reference conditions of fuel utilization, gas temperature spring in fuel cell stack, anode off-gas recirculation rate, air inlet temperature and external pre-reforming reaction extent is analyzed. The present study revealed to be a powerful tool for evaluating the SOFC system performance under a wide range of operation and paves the way for defining control strategies in order to maintain high system efficiency under part-load operations.     

Synthesis and characterisation of macroporous Yttria Stabilised Zirconia (YSZ) using polystyrene spheres as templates

Yttria Stabilised Zirconia (YSZ) is commonly used as an oxygen sensor and an oxygen pump in automotive and industrial applications, and is a choice electrolyte for Solid Oxide Fuel Cell (SOFC) technology. YSZ is also a major component of the SOFC electrodes, and is commonly mixed with 50% volume NiO to create a Ni/YSZ cermet anode. In both the adsorption and fuel cell applications homogeneous control of the porosity of YZS is important. Templating methods provide well ordered macroporous structures and have been used to prepare ordered, macroporous YSZ from metal nitrate precursors using polystyrene spheres of 1 μm as templates. Ordered three-dimensional structures were synthesised and the effects of sintering temperatures of 650–1400 °C on pore size, particle size and pore wall thickness were examined. Ordered porosity was maintained at all temperatures, though some structural degradation and sintering was observed at 1400 °C. This study demonstrated that templated porosity is maintained well above the conventional sintering temperature of the electrodes, and higher than previous studies reported. The stability of these structures at high temperatures makes this fabrication technique a promising alternative to conventional methods of synthesising porous materials.     

Electrochemical Performance of a Ni and YSZ Composite Synthesised by Ultrasonic Spray Pyrolysis as an Anode for SOFCs

The electrochemical performance of an anode material for a solid oxide fuel cell (SOFC) depends highly on microstructure in addition to composition. In this study, a NiO–yttria‐stabilised zirconia (NiO–YSZ) composite with a highly dispersed microstructure and large pore volume/surface area has been synthesised by ultrasonic spray pyrolysis (USP) and its electrochemical characteristics has been investigated. For comparison, the electrochemical performance of a conventional NiO–YSZ is also evaluated. The power density of the zirconia electrolyte‐supported SOFC with the synthesised anode is ∼392 mW cm^–2 at 900 °C and that of the SOFC with the conventional NiO–YSZ anode is ∼315 mW cm^–2. The improvement is ∼24%. This result demonstrates that the synthesised NiO–YSZ is a potential alternative anode material for SOFCs fabricated with a zirconia solid electrolyte.     

Electrophoretic Deposition of Zirconia Thin Film on Nonconducting Substrate for Solid Oxide Fuel Cell Application

Electrophoretic deposition (EPD) of 8 mol% yttria‐stabilized zirconia (YSZ) electrolyte thin film has been carried out onto nonconducting porous NiO‐YSZ cermet anode substrate using a fugitive and electrically conducting polymer interlayer for solid oxide fuel cell (SOFC) application. Such polymer interlayer burnt out during the high‐temperature sintering process (1400°C for 6 h) leaving behind a well adhered, dense, and uniform ceramic YSZ electrolyte film on the top of the porous anode substrate. The EPD kinetics have been studied in depth. It is found that homogeneous and uniform film could be obtained onto the polymer‐coated substrate at an applied voltage of 15 V for 1 min. After the half‐cell (anode + electrolyte) is co‐fired at 1400°C, a suitable cathode composition (La_0.65Sr_0.3MnO₃) thick film paste is screen printed on the top of the sintered YSZ electrolyte. A second stage of sintering of such cathode thick film at 1100°C for 2 h finally yield a single cell SOFC. Such single cell produced a power output of 0.91 W/cm² at 0.7 V when measured at 800°C using hydrogen and oxygen as fuel and oxidant, respectively.     

New Fabrication Technique for Series‐Connected Stack With Micro Tubular SOFCs

Solid oxide fuel cell (SOFC) is highly efficient and is a promising candidate for future power systems. Among the many types of SOFCs which have been reported, the micro tubular design offers improved thermal robustness, with the possibility of rapid start‐up/shut‐down. In this study, a new stack structure for anode‐supported micro tubular SOFCs was developed in which porous MgO matrices were used to position the micro tubular cell elements. This arrangement allowed for electrical interconnection of each cell in a series, using a silver paste and a connecting LSCF paste for the anode and the cathode, respectively, in the MgO support structure. With this technique, the bundle size could be easily increased towards the kW class module design.     

A new and simple way to prepare monolithic solid oxide fuel cell stack by stereolithography 3D printing technology using 8 mol% yttria stabilized zirconia photocurable slurry

Yttria (8 mol%) stabilized zirconia (8YSZ) photocurable slurry is the basis for stereolithography-based 3D (SLA) printed structured electrolyte support for monolithic solid oxide fuel cell (SOFC) stack. The curing resin with trifunctional trimethylolpropane triacrylate and 1,6-hexanediol diacrylate (TMPTA/HDDA) mass ratio of 1.5:8.5 and 1 wt% of photoinitiator provided excellent curing performance and low viscosity of 2.1 mPa·s. Stable 8YSZ photocurable slurry possessing high solid content of 43 vol% and low viscosity of 3.6 Pa·s at 30 s^?1 shear rate were obtained, without particle sedimentation after 180-day stability test. The activation energy of 8YSZ fabricated by 3D printing method was 0.87 eV, similar to that by dry-pressing method. The 3D printed monolithic 3-tube SOFC stack exhibited a peak power density of 230 mW·cm^?2 at 850 °C. This research proves the great potential of 3D printing technology to prepare monolithic SOFC stack, paving the way to develop SOFCs for practical applications.     

Novel Design of Microchanneled Tubular Solid Oxide Fuel Cells and Synthesis Using a Multipass Extrusion Process

A novel, microchanneled tubular solid oxide fuel cell was fabricated using a multipass extrusion process, with an outside diameter of 2.7 mm that contained 61 cells. Cell materials used in this work were 8 mol% yttria-stabilized zirconia (8YSZ), La_0.8Sr_0.2MnO₃ (LSM), and NiO–8YSZ (50:50 vol%) as electrolyte, cathode, and anode, respectively. Three stages of heat-treatment processes were applied, at 700°C in N₂ condition, at 1000°C in air, and then sintered at 1300°C for 2 h, respectively. The X-ray diffraction analysis confirmed that no reaction phases appeared after sintering. The microstructures of anode and cathode were fairly porous while the electrolyte had a dense microstructure (relative density >96%). The thickness of electrolyte, anode, and cathode were 20, 30, and 40 μm, respectively, and the diameter of the continuous channels was 150 μm.     

SOFC氧离子导体电解质材料的研究进展及性能优化策略

典型的固体氧化物燃料电池(SOFC)由致密电解质、多孔阴极和阳极三部分构成。其中,电解质介于阴极和阳极之间,是一种具有全固态结构的氧化物陶瓷材料。电解质是SOFC的核心部件之一,是电池工作温度和电池性能的决定性因素。目前,对于高温电解质材料的研究与应用已经相对成熟。但是,在电池高温运行条件下,会导致电极和电解质界面反应、密封困难及使用寿命变短等问题。因此,SOFC电解质的发展逐渐趋向于中温化。但随着工作温度的降低,电解质欧姆阻抗(Ro)势必增大,使得电池的电导率下降。基于此,电解质在中温下的性能提升以及优化近年来备受关注。文中综述了几种不同类型的氧离子导体电解质最新研究进展,并论述了SOFC中低温运行条件下电解质性能提升的主要优化策略。     

Analysis of the Ripple Current in a 5 kW Polymer Electrolyte Membrane Fuel Cell Stack

Polymer electrolyte fuel cell systems are increasingly being used in applications requiring an inverter to convert the direct current (DC) output of the stack to an alternating current (AC). These inverters, and other time‐varying inputs to the stack such as the anode feed pressure, cause deviations from the average stack current, or ripple currents, which are undesirable for reasons of performance and durability. A dynamic fuel cell model has been developed and validated against experimental data for a 5 kW fuel cell stack, examining in detail the ripple current behaviour. It was shown that the ripple currents exceed the 2% maximum recommended value, and may lead to long‐term degradation of the fuel cell stack.     

Portable Size DMFC‐Stack

A small, low temperature, direct methanol fuel cell stack for portable applications has been developed. Several flow field designs were investigated with respect to stable operation and high performance. Due to carbon dioxide and water production on the anode and cathode, respectively, methanol and oxygen access to the electrodes is hindered. During single cell operation the effect of both carbon dioxide evolution and water production on the current output was observed. The difference between parallel and serial feeding of both fuel and oxidant to the DMFC stack was also investigated. It was found that it is very important to remove reaction products from the active cell surface in order to ensure stable stack operation at low temperatures. The maximal power realised with the 12‐cell direct methanol fuel cell stack was 30 W.     

Boosting intermediate temperature performance of solid oxide fuel cells via a tri-layer ceria–zirconia–ceria electrolyte

Using cost-effective fabrication methods to manufacture a high-performance solid oxide fuel cell (SOFC) is helpful to enhance the commercial viability. Here, we report an anode-supported SOFC with a three-layer Gd_0.1Ce_0.9O_1.95 (gadolinia-doped-ceria [GDC])/Y_0.148Zr_0.852O_1.926 (8YSZ)/GDC electrolyte system. The first dense GDC electrolyte is fabricated by co-sintering a thin, screen-printed GDC layer with the anode support (NiO–8YSZ substrate and NiO–GDC anode) at 1400°C for 5 h. Subsequently, two electrolyte layers are deposited via physical vapor deposition. The total electrolyte thickness is less than 5 μm in an area of 5 × 5 cm², enabling an area-specific ohmic resistance as low as 0.125 Ω cm⁻² at 500°C (under open circuit voltage), and contributing to a power density as high as 1.2 W cm⁻² at 650°C (at an operating cell voltage of 0.7 V, using humidified [10 vol.% H₂O] H₂ as fuel and air as oxidant). This work provides an effective strategy and shows the great potential of using GDC as an electrolyte for high-performance SOFC at intermediate temperature.     

Design and Fabrication of a Novel Electrode-Supported Honeycomb SOFC

We report the design and fabrication of a novel electrode-supported honeycomb solid oxide fuel cell (SOFC), that can generate high volumetric power density. Among various cell designs, honeycomb SOFCs are suitable for compact SOFC modules because they have a large surface electrode area per unit volume. We have succeeded in fabricating a cathode-supported honeycomb SOFC via extrusion of a LaSrMnO₃ honeycomb monolith and through the use of a new slurry injection method for the channel surface coating using electrolyte/anode bi-layers. The fabricated honeycomb SOFCs exhibited high volumetric power densities of approximately 1.2 W/cm³ at 600°C under a wet H₂ fuel flow.