Stress field and failure probability analysis for the single cell of planar solid oxide fuel cells

An analytical model is developed to predict the residual thermal stresses in a single cell of solid oxide fuel cells (SOFCs), which consists of a thick porous 8 mol% Y₂O₃ stabilized zirconia/nickel oxide (8YSZ/NiO) anode, a dense 8YSZ electrolyte and a porous lanthanum strontium manganite (LSM) cathode. The simulated stresses in the cell at room temperature, which are resulted from the contraction mismatch of its components, indicate that the major principal stress in the anode is tensile while the electrolyte and cathode are under compressive stresses. The stress in one component decreases with the increase of its thickness when the thicknesses of the other two components are fixed, and the decrease of the tensile stress in the anode will cause the increase of the compressive stresses in both the cathode and the electrolyte, and vice versa. The analysis also reveals that the anode is the part that is most susceptible to fracture since the tensile thermal stress is so high that it reaches to the fracture strength of the anode material. The Weibull statistic is employed to estimate the failure probability of the anode. The simulation results indicate that the anode failure probability decreases with the increase of the anode thickness and the decrease of the electrolyte thickness. To keep the anode failure probability less than 1E−06, the anode thickness should be greater than 0.7 mm for a cell with an electrolyte thickness of 10 μm and a cathode thickness of 20 μm.     

Three dimensional stress analysis of solid oxide fuel cell anode micro structure

One of the most common problems in solid oxide fuel cells (SOFCs) is the delamination and thus the degradation of electrode/electrolyte interface which occurs in the consequences of the stresses generated within the different layers of the cell. Nowadays, the modeling of this problem under certain conditions is one of the main issues for the researchers. The structural and thermo-physical properties of the cell materials (i.e. porosity, density, Young's modulus etc.) are usually assumed to be homogenous in the mathematical modeling of solid oxide fuel cells at macro-scale. However, during the real operation, the stresses created in the multiphase porous layers might be very different than those at macro-scale. Therefore, micro-level modeling is required for an accurate estimation of the real stresses and the performance of SOFCs. This study presents a microstructural characterization and a finite element analysis of the delamination and the degradation of porous solid oxide fuel cell anode and electrode/electrolyte interface under various operating temperatures, compressing forces and material compositions by using the synthetically generated microstructures. A multi physics computational package (COMSOL) is employed to calculate the Von Misses stresses in the anode microstructures. The maximum thermal stress in the electrode/electrolyte interface and three phase boundaries is found to exceed the yield strength at 900 °C while 800 °C is estimated as a critical temperature for the delamination and micro cracks due to thermal stress generated. The thermal stress decreases in the grain boundaries with increasing content of one of the phases (either Ni or YSZ) and the porosity of the electrode. A clamping load higher than 5 kg cm⁻² is also found to exceed the shear stress limit.     

A phase inversion/sintering process to fabricate nickel/yttria-stabilized zirconia hollow fibers as the anode support for micro-tubular solid oxide fuel cells

NiO/YSZ hollow fibers were fabricated via a combined phase inversion and sintering technique, where polyethersulfone (PESf) was employed as the polymeric binder, N-methyl-2-pyrrolidone (NMP) as the solvent and polyvinylpyrrolidone (PVP) as the additive, respectively. After reduction with hydrogen at 750 °C for 5 h, the porous Ni/YSZ hollow fibers with an asymmetric structure comprising of a microporous layer integrated with a finger-like porous layer were obtained, which can be served as the anode support of micro-tubular solid oxide fuel cells (SOFCs). As the sintering temperature was increased from 1200 to 1400 °C, the mechanical strength and the electrical conductivity of the Ni/YSZ hollow fibers increased from 35 to 178 MPa and from 30 to 772 S cm⁻¹, respectively but the porosity decreased from 64.2% to 37.0%. The optimum sintering temperature was found to be between 1350 and 1400 °C for Ni/YSZ hollow fibers applied as the anode support for micro-tubular SOFCs.     

Fabrication of micro-tubular solid oxide fuel cells with a single-grain-thick yttria stabilized zirconia electrolyte

This study discusses the fabrication and electrochemical performance of micro-tubular solid oxide fuel cells (SOFCs) with an electrolyte consisting a single-grain-thick yttria stabilized zirconia (YSZ) layer. It is found that a uniform coating of an electrolyte slurry and controlled shrinkage of the supported tube leads to a dense, crack-free, single-grain-thick (less than 1 μm) electrolyte on a porous anode tube. The SOFC has a power density of 0.39 W cm⁻² at an operating temperature as low as 600 °C, with YSZ and nickel/YSZ for the electrolyte and anode, respectively. An examination is made of the effect of hydrogen fuel flow rate and shown that a higher flow rate leads to better cell performance. Hence a YSZ cell can be used for low-temperature SOFC systems below 600 °C, simply by optimizing the cell structure and operating conditions.     

Study on local morphological changes of nickel in solid oxide fuel cell anode using porous Ni pellet electrode

Morphological change of nickel, especially the aggregation of nickel, in solid oxide fuel cell anode is an important deactivation mechanism which results in long-period degradation of anode. In order to study the mechanisms which cause local morphological changes of nickel in solid oxide fuel cell anode, porous nickel pellet, which is mechanically pressed against dense YSZ pellet with LSM cathode, was employed as the anode of the cell. The cell was tested by static-potential method in hydrogen with different humidities environment for 60 h. The study focused on the vicinity of three phase boundary which concentrated at nickel-YSZ interface. After the discharging test, the cell performance and the microstructure at nickel-YSZ contacting point of interface were studied and correlated to nickel morphological changes. The interlocking effect and the spreading of densified nickel layer phenomena were observed between nickel and YSZ substrate after discharging with an anode to cathode terminal voltage of 0.6 V. Humidity enhanced nickel surface diffusion and humidity gradient driving vaporization-deposition mechanism, which caused the growing and merging of independent nickel droplets, were used to explain the local morphological changes and redistribution of nickel inside and along the edge of YSZ surface bonded nickel cluster, respectively. The bulk nickel morphological changes were also studied to support the humidity enhanced nickel surface diffusion mechanism. The competition of interlocking effect, nickel redistribution at TPB and bulk nickel sintering finally determined the cell performance.     

Effect of nickel-phosphorus interactions on structural integrity of anode-supported solid oxide fuel cells

An integrated experimental/modeling approach was utilized to assess the structural integrity of Ni-yttria-stabilized zirconia (YSZ) porous anode supports during the solid oxide fuel cell (SOFC) operation on coal gas containing trace amounts of phosphorus impurities. Phosphorus was chosen as a typical impurity exhibiting strong interactions with the nickel followed by second phase formation. Tests were performed using Ni-YSZ anode-supported button cells exposed to 0.5-10 ppm of phosphine in synthetic coal gas at 700-800 °C. The extent of Ni-P interactions was determined by a post-test scanning electron microscopy (SEM) analysis. Severe damage to the anode support due to nickel phosphide phase formation and extensive crystal coalescence was revealed, resulting in electric percolation loss. The subsequent finite element stress analyses were conducted using the actual anode support microstructures to assist in degradation mechanism explanation. Volume expansion induced by the Ni phase alteration was found to produce high stress levels such that local failure of the Ni-YSZ anode became possible under the operating conditions.     

Thermal stress and thermo-electrochemical analysis of a planar anode-supported solid oxide fuel cell: Effects of anode porosity

A 3D integrated numerical model is constructed to evaluate the thermal-fluid behavior and thermal stress characteristics of a planar anode-supported solid oxide fuel cell (SOFC). Effects of anode porosity on performance, temperature gradient and thermal stress are investigated. Using commercial Star-CD software with the es-sofc module, simulations are performed to obtain the current-voltage (I-V) characteristics of a fuel cell as a function of the anode porosity and the temperature distribution within the fuel cell under various operating conditions. The temperature field is then imported into the MARC finite element analysis (FEA) program to analyze thermal stresses induced within the cell. The numerical results are found to be in good agreement with the experimental data. It is shown that the maximum principal stress within the positive electrode-electrolyte-negative electrode (PEN) increases at a higher current and a higher temperature gradient. It is recommended that the temperature gradient should be limited to less than 10.6 °C mm⁻¹ to maintain the structural integrity of the PEN.     

Fabrication of solid oxide fuel cell anode electrode by spray pyrolysis

Large triple phase boundaries (TPBs) and high gas diffusion capability are critical in enhancing the performance of a solid oxide fuel cell (SOFC). In this study, ultrasonic spray pyrolysis has been investigated to assess its capability in controlling the anode microstructure. Deposition of porous anode film of nickel and Ce_0.9Gd_0.1O_1.95 on a dense 8 mol.% yttria stabilized zirconia (YSZ) substrate was carried out. First, an ultrasonic atomization model was utilized to predict the deposited particle size. The model accurately estimated the deposited particle size based on the feed solution condition. Second, effects of various process parameters, which included the precursor solution feed rate, precursor solution concentration and deposition temperature, on the TPB formation and porosity were investigated. The deposition temperature and precursor solution concentration were the most critical parameters that influenced the morphology, porosity and particle size of the anode electrode. Ultrasonic spray pyrolysis achieved homogeneous distribution of constitutive elements within the deposited particles and demonstrated capability to control the particle size and porosity in the range of 2-17 μm and 21-52%, respectively.     

Analysis of the three-dimensional microstructure of a solid-oxide fuel cell anode using nano X-ray tomography

The visualization of three-dimensional (3D) microstructures of solid oxide fuel cells helps to understand the efficiency of the electrochemical conversion process, study the device's reliability, and improve manufacturing processes. Here, we used X-ray nanotomography to investigate a porous nickel-yttria-stabilized zirconia (Ni-YSZ) composite anode. These results were used to characterize and quantify the key structural parameters, such as the volume ratio of the three phases (Ni, YSZ, and pore), connected porosity, surface area of each phase, interface of Ni/YSZ, volume-specific three-phase boundary length (TPB where the Ni, YSZ and fuel gas phases come together), and electrical conductivity of the anode.     

A study of the process parameters for yttria-stabilized zirconia electrolyte films prepared by screen-printing

Screen-printing technology was developed to fabricate gas-tight yttria-stabilized zirconia (YSZ) electrolyte films on porous NiO–YSZ anode substrates for use in solid oxide fuel cells (SOFCs). Several key process parameters such as the starting YSZ powder, printing ink composition, printing time and sintering temperature were studied and reported in detail. SEM results revealed that the selected process parameters exerted obvious influences on the microstructure of the screen-printed YSZ films. Open-circuit voltages (OCVs) were used to evaluate the usage feasibility of screen-printed YSZ films in SOFCs. Cell performance test results showed that the above-mentioned parameters had crucial effects on the OCVs and power density of the prepared cells. Based on appropriate parameters, an OCV value of 1.081 V and a power density of 0.96 Wcm⁻² were obtained at 800 °C using hydrogen as fuel and ambient air as oxidant.     

Applications of nano-composite materials for improving the performance of anode-supported electrolytes of SOFCs

In order to improve the performance of the anode-supported electrolyte of solid oxide fuel cells (SOFCs), the anode electrode is modified by inserting an anode functional layer of nano-composite powders between a Ni–YSZ electrode and YSZ electrolyte. The NiO–YSZ nano-composite powders are fabricated by coating nano-sized Ni and YSZ particles on the YSZ core particle by the Pechini process. The reduction of the polarization resistance of a single cell that is applied to the anode functional layer is attributed to the increasing reaction of three-phase boundaries (TPBs) within the layer and the micro-structured uniformity in the electrode. Two methods were used, namely tape-casting/dip-coating and tape-casting/co-firing, for studying the performance. It can be concluded that the cell with an anode functional layer thickness (15–20 μm) and a microstructure of NiO–YSZ nano-composite materials which was fabricated by the tape-casting/dip-coating method improved the output power (to 1.3 W cm⁻²) at 800 °C using hydrogen as fuel and air as an oxidant.     

Evaluation of carbon deposition behavior on the nickel/yttrium-stabilized zirconia anode-supported fuel cell fueled with simulated syngas

The nickel/yttrium-stabilized zirconia (Ni/YSZ) anode-supported solid oxide fuel cells (SOFCs) have been operated under various simulated syngases at different temperatures to investigate the degradation behavior of the cells caused by carbon deposition. The results show that the carbon morphology and the cell performance degradation are influenced significantly by the operation temperature. The stability of the cell fueled with syngas can be improved by applying a constant current, but the cell degraded quickly after carbon deposition. The microstructure damage is close to the anode surface and leads to a conductivity decrease, which is an important reason for the cell degradation and failure at 750 °C. Conversely, the degradation behavior at 650 °C is mainly due to solid carbon deposits inside of the anode that impede fuel diffusion and electrochemical reactions on the anodic side. The effect of carbon deposition on the microstructure degradation is also investigated using transmission electron microscope.     

High performance anode with dendritic porous structure for low temperature solid oxide fuel cells

A dendritic porous supported microstructure simultaneously creates small pore size and broad gas diffusion pathways in a solid oxide fuel cell anode membrane. This microstructure also achieves pore sizes that reduce with increasing depth within the membrane without increasing the structure tortuosity. Such a microstructure supplies high triple phase boundary density, fast gas diffusion and low polarization resistance. Here we characterise the performance of a porous anode with such a dendritic microstructure. The solid oxide fuel cell with this high performance anode achieved 0.92 W cm^?2 power density at 600 °C.     

Fabrication and characterization of Cu–Ni–YSZ SOFC anodes for direct use of methane via Cu-electroplating

The Cu–Ni–YSZ cermet anodes for direct use of methane in solid oxide fuel cells have been fabricated by electroplating Cu into a porous Ni–YSZ cermet anode. The uniform distribution of Cu in the Ni–YSZ anode was obtained by electroplating in an aqueous solution mixture of CuSO₄·5H₂O and H₂SO₄ for 30 min with 0.1 A of applied current. When the Cu–Ni–YSZ anode was exposed to methane at 700 °C, the amount of carbon deposited on the anode decreased as the amount of Cu in the Cu–Ni solid solution increased. The power density (0.24 W/cm²) of a single cell with a Cu–Ni–YSZ anode was slightly lower in methane at 700 °C than the power density (0.28 W/cm²) of a single cell with a Ni–YSZ anode. However, the performance of the Ni–YSZ anode-supported single cell degraded steeply over 21 h because of carbon deposition, whereas the Cu–Ni–YSZ anode-supported single cell showed enhanced durability up to 200 h.     

High performance solid oxide fuel cells based on tri-layer yttria-stabilized zirconia by low temperature sintering process

Performance of solid oxide fuel cells (SOFCs) depends critically on the composition and microstructure of the electrodes. It is fabricated a dense yttria-stabilized zirconia (YSZ) electrolyte layer sandwiched between two porous YSZ layers at low temperature. The advantages of this structure include excellent structural stability and unique flexibility for evaluation of new electrode materials for SOFC applications, which would be difficult or impossible to be evaluated using conventional cell fabrication techniques because of incompatibility with YSZ under processing conditions. The porosity of porous YSZ increases from 65.8% to 68.6% as the firing temperature decreased from 1350 to 1200 °C. The open cell voltages of the cells based on the tri-layers of YSZ, co-fired using a two-step sintering at 1200 °C, are above 1.0 V at 700-800 °C, and the peak power densities of cells infiltrated LSCF and Pd-SDC electrodes are about 525, 733, and 935 mW cm⁻² at 700, 750, and 800 °C, respectively.     

Microstructural analysis of a solid oxide fuel cell anode using focused ion beam techniques coupled with electrochemical simulation

Porous composite electrodes play a critical role in determining the performance and durability of solid oxide fuel cells, which are now emerging as a high efficiency, low emission energy conversion technology for a wide range of applications.In this paper we present work to combine experimental electrochemical and microstructural characterisation with electrochemical simulation to characterise a porous solid oxide fuel cell anode. Using a standard, electrolyte supported, screen printed Ni-YSZ anode, electrochemical impedance spectroscopy has been conducted in a symmetrical cell configuration. The electrode microstructure has been characterised using FIB tomography and the resulting microstructure has been used as the basis for electrochemical simulation. The outputs from this simulation have in turn been compared to the results of the electrochemical experiments.A sample of an SOFC anode of 6.68 μm × 5.04 μm × 1.50 μm in size was imaged in three dimensions using FIB tomography and the total triple phase boundary density was found to be 13 μm⁻². The extracted length-specific exchange current for hydrogen oxidation (97% H₂, 3% H₂O) at a Ni-YSZ anode was found to be 0.94 × 10⁻¹⁰, 2.14 × 10⁻¹⁰, and 12.2 × 10⁻¹⁰ A μm⁻¹ at 800, 900 and 1000 °C, respectively, consistent with equivalent literature data for length-specific exchange currents for hydrogen at geometrically defined nickel electrodes on YSZ electrolytes.     

Fabrication and evaluation of a Ni/La0.75Sr0.25Cr0.5Fe0.5O3−δ co-impregnated yttria-stabilized zirconia anode for single-chamber solid oxide fuel cells

In this study, an anode-supported solid oxide fuel cell (SOFC) has been prepared using a porous yttria-stabilized zirconia (YSZ) anode matrix. The anode was prepared by impregnating the sintered porous YSZ matrix with a nitrate aqueous containing La³⁺, Sr²⁺, Cr³⁺, Fe³⁺, Ni²⁺ and urea. The formed anode exhibited high surface area and porosity, and had fast path for the transportation of oxygen ion and electron, as well as resulting in high three-phase boundaries (TPBs). Single-chamber fuel cell test was conducted in a methane-oxygen gas mixture using an YSZ membrane as the electrolyte and La_0.8Sr_0.2MnO_3−δ (LSM) as the cathode. The influences of environmental temperature and gas composition on the cell performance were also investigated. Under the optimized gas composition (CH₄/O₂ = 2/1) and furnace temperature (800 °C) conditions, a maximum power density of 214 mW cm⁻² was achieved. The test results demonstrated good cell stability and indicated that the perovskite oxide-based anodes were quite robust with redox cycling.     

Effects of anode and electrolyte microstructures on performance of solid oxide fuel cells

To improve the performance of anode-supported solid oxide fuel cells (SOFCs), various types of single cells are manufactured using a thin-film electrolyte of Yttria stabilized zirconia (YSZ) and an anode functional layer composed of a NiO–YSZ nano-composite powder. Microstructural/electrochemical analyses are conducted. Single-cell performances are highly dependent on electrolyte thickness, to the degree that the maximum power density increases from 0.74 to 1.12 W cm⁻² according to a decrease in electrolyte thickness from 10.5 to 6.5 μm at 800 °C. The anode functional layer reduced the polarization resistance of a single cell from 1.07 to 0.48 Ω cm² at 800 °C. This is attributed to the provision by the anode layer of a highly reactive and uniform electrode microstructure. It is concluded that optimization of the thickness and homogeneity of component microstructure improves single-cell performances.     

Effect of alumina on the curvature, Young's modulus, thermal expansion coefficient and residual stress of planar solid oxide fuel cells

Planar solid oxide fuel cells (SOFCs) are composites consisting of porous and dense functional layers as electrodes and electrolytes, respectively. Because of the thermo-elastic mismatch between the individual layers, residual stresses develop during manufacturing and cause unconstrained cells to warp. The addition of alumina decreases the thermal expansion coefficient (TEC) of the NiO and yttria-stabilized zirconia (YSZ) anode-support material. Correspondingly, the lower TECs have flattened the half cells during fabrication. In addition, the residual stress at room temperature (RT) for samples with more than 4 wt% alumina is only 20% of the residual stress of the samples without alumina, at approximately 100 MPa. The effects of Al₂O₃ on the curvature, Young's modulus, TEC and residual stress of the SOFC with (NiO-YSZ)_1−x(Al₂O₃)_x (x = 1-5 wt%) anode support are discussed in this work.     

The effect of electrode infiltration on the performance of tubular solid oxide fuel cells under electrolysis and fuel cell modes

The electrochemical performance of two different anode supported tubular cells (50:50 wt% NiO:YSZ (yttria stabilized zirconia) or 34:66 vol.% Ni:YSZ) as the fuel electrode and YSZ as the electrolyte) under SOFC (solid oxide fuel cell) and SOEC (solid oxide electrolysis cell) modes were studied in this research. LSM (La_0.80Sr_0.20MnO_3−δ) was infiltrated into a thin porous YSZ layer to form the oxygen electrode of both cells and, in addition, SDC (Sm_0.2Ce_0.8O_1.9) was infiltrated into the fuel electrode of one of the cells. The microstructure of the infiltrated fuel cells showed a suitable distribution of fine LSM and SDC particles (50–100 nm) near the interface of electrodes and electrolyte and throughout the bulk of the electrodes. The results show that SDC infiltration not only enhances the electrochemical reaction in SOFC mode but improves the performance even more in SOEC mode. In addition, LSM infiltrated electrodes also boost the SOEC performance in comparison with standard LSM–YSZ composite electrodes, due to the well-dispersed LSM nanoparticles (favouring the electrochemical reactions) within the YSZ porous matrix.