Synthetical designing of solid oxide fuel cell electrodes: Effect of particle size and volume fraction

Solid oxide fuel cell (SOFC) electrode microstructures composed of catalyst, electrolyte and pore phases with various microstructural features are synthetically generated and the effects of the mean particle size and volume fraction of each phase on three/triple phase boundaries (TPBs) are computed. For mono-sized particles with an equal volume fraction, the active and total TPB density are found to decrease with increasing the mean particle size due to decreased surface area. However, both are found to be inversely related to the square of the mean particle size. Active TPB densities of 37.62 μm μm^?3, 9.27 μm μm^?3 and 4.11 μm μm^?3 are obtained from the electrode microstructures with mono-sized particles of 0.25 μm, 0.50 μm and 0.75 μm mean particle size, respectively. Moreover, ～94% of the total TPB density is determined to be active regardless of the mean particle size. TPBs for the polydisperse particles with the same volume fraction also show a decreasing trend with the mean particle size in general. However, no significant change is observed in inactive TPB formations even for the largest particle size investigated, revealing almost fully percolated phases can be achieved when the volume fraction of each phase is equal (～33.3%). On the other, when the volume fractions are also varied, the active TPB is shown to be strongly depended on the volume fraction of the phase having the highest mean particle size. In this regard, among the related cases studied, the lowest active TPB density is computed as 0.25 μm μm^?3, whereas the highest one is measured as 26.64 μm μm^?3.     

Entropy generation analysis in a monolithic-type solid oxide fuel cell (SOFC)

The aim of the paper is to investigate possible improvements in the geometry design of a monolithic solid oxide fuel cells (SOFCs) through analysis of the entropy generation terms. The different contributions to the local rate of entropy generation are calculated using a computational fluid dynamic (CFD) model of the fuel cell, accounting for energy transfer, fluid dynamics, current transfer, chemical reactions and electrochemistry. The fuel cell geometry is then modified to reduce the main sources of irreversibility and increase its efficiency.     

Fabrication of hydrogen electrode supported cell for utilized regenerative solid oxide fuel cell application

A utilized regenerative solid oxide fuel cell (URSOFC) provides the dual function of performing energy storage and power generation, all in one unit. When functioning as an energy storage device, the URSOFC acts like a solid oxide electrolyzer cell (SOEC) in water electrolysis mode; whereby the electric energy is stored as (electrolyzied) hydrogen and oxygen gases. While hydrogen is useful as a transportation fuel and in other industrial applications, the URSOFC also acts as a solid oxide fuel cell (SOFC) in power generation mode to produce electricity when needed. The URSOFC would be a competitive technology in the upcoming hydrogen economy on the basis of its low cost, simple structure, and high efficiency. This paper reports on the design and manufacturing of its anode support cell using commercially available materials. Also reported are the resulting performance, both in electrolysis and fuel cell modes, as a function of its operating parameters such as temperature and current density. We found that the URSOFC performance improved with increasing temperature and its fuel cell mode had a better performance than its electrolysis mode due to a limited humidity inlet causing concentration polarization. In addition, there were great improvements in performance for both the SOFC and SOEC modes after the first test and could be attributed to an increase in porosity within the oxygen electrode, which was beneficial for the oxygen reaction.     

An error in solid oxide fuel cell stack modeling

This paper points out an error in the literature and analyzes its effect on electrochemical models of solid oxide fuel cell stacks. A correction is presented.     

Model based evaluation of the electrochemical reaction sites in solid oxide fuel cell electrodes

The electrode microstructure plays an important role in determining the performance of the Solid Oxide Fuel Cells (SOFCs). The conventional SOFC electrodes are based on two kinds of particles, one electron conducting and another ion conducting. Over the years, electrodes with alternative microstructures have been proposed for performance enhancement based on the developments in materials and fabrication techniques. Analytical models for the microstructure offer the scope of quick evaluation of the effect of various microstructural parameters on important microstructural properties like the triple phase boundary densities. However, validation of these models in the light of the experimental data is seldom reported. In this work, the microstructural data derived from image-based reconstruction of the electrodes is used to calibrate and validate an analytical model for the conventional SOFC electrode microstructure revealing insights into the model's applicability. This model forms the basis for the models of other modified microstructures studied in this work. Designing of improved SOFC microstructures require an understanding of the effect of controllable parameters on the reaction sites. Model based evaluation of the electrochemical reaction sites in five different SOFC microstructures is performed in this work. The results and insights will enable the selection of microstructural parameters for tailoring the electrode microstructure to achieve improved performance.     

Effect of a shielded slot on a planar solid oxide fuel cell

A shielded slot was designed for use in a typical current collector/gas distributor fuel cell and was formed from a series of arches with heights suitable for providing sufficient quantities of fuel gases and reaction areas. The shielded slot was substituted in place of the interconnect and offered several advantages in terms of mechanical support and electrical contact. A three-dimensional (3-D) electrochemical reaction model and a microelectrode model of the planar solid oxide fuel cells (SOFC) were used to predict the performances of the shielded slots in planar SOFCs. Prior to analyzing the complex arrangement of the shielded slot, a variety of interconnect arrangements were simulated to understand the relationship between the gas supply and the electrical contact arrangements. The reactivity properties were examined and the most effective arrangement of shielded slots was identified in an effort to design an optimal shielded slot.     

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.     

Micro modeling of solid oxide fuel cell anode based on stochastic reconstruction

A novel modeling scheme of SOFC anode based on the stochastic reconstruction technique and the Lattice Boltzmann Method (LBM) is proposed and applied to the performance assessment and also to the optimization of anode microstructures. A cross-sectional microscopy image is exploited to obtain a two-dimensional phase map (i.e., Ni, YSZ and pore), of which two-point correlation functions are used to reconstruct a three-dimensional model microstructure. Then, the polarization resistance of the reconstructed anode is obtained by the LBM simulation. The predicted anodic polarization resistance for a given microstructure and its sintering temperature dependence are in good agreement with the literature data. Three-dimensional distributions of potential and current can be obtained, while and the effect of working temperature is discussed. The proposed method is considered as a promising tool for designing SOFC anodes.     

A study of solid oxide fuel cell stack failure by inducing abnormal behavior in a single cell test

It is well known that cell imbalance can lead to failure of batteries. Prior theoretical modeling has shown that similar failure can occur in solid oxide fuel cell (SOFC) stacks due to cell imbalance. Central to failure model for SOFC stacks is the abnormal operation of a cell with cell voltage becoming negative. For investigation of SOFC stack failure by simulating abnormal behavior in a single cell test, thin yttria-stabilized zirconia (YSZ) electrolyte, anode-supported cells were tested at 800 °C with hydrogen as fuel and air as oxidant with and without an applied DC bias. When under a DC bias with cell operating under a negative voltage, rapid degradation occurred characterized by increased cell resistance. Visual and microscopic examination revealed that delamination occurred along the electrolyte/anode interface. The present results show that anode-supported SOFC stacks with YSZ electrolyte are prone to catastrophic failure due to internal pressure buildup, provided cell imbalance occurs. The present results also suggest that the greater the number of cells in an SOFC stack, the greater is the propensity to catastrophic failure.     

Analytical investigations of varying cross section microstructures on charge transfer in solid oxide fuel cell electrodes

An extended surface modeling concept (electrochemical fin) is applied to charge transport within the SOFC electrode microstructure using an analytical modeling approach analogous to thermal fin analysis. This model is distinct from similar approaches applied to SOFC electrode microstructure in its application of a governing equation that allows for variable cross-section geometry. The model presented is capable of replicating experimentally observed electrode behavior inclusive of sensitivity to microstructural geometry, which stands in contrast to existing models that apply governing equations analogous to a constant cross-section thermal fin equation. Insights learned from this study include: the establishment of a suite of dimensionless parameters and performance metrics that can be applied to assess electrode microstructure, the definition of microstructure-related transport regimes relevant to electrode design, and correlations that allow performance predictions for electrodes that provide cell structural support. Of particular note, the variable cross-section modeling approach motivates the definition of a sintering quality parameter that quantifies the degree of constriction within the conducting network of the electrode, a phenomenon that exerts influence over electrode polarization. One-dimensional models are presented for electrochemical fins of several cross-sectional geometries with the ultimate goal of developing a general tool that enables the prompt performance evaluation of electrode microstructures. Such a tool would facilitate SOFC microstructural design by focusing more detailed modeling efforts on the most promising microstructures.     

Control of a solid oxide fuel cell stack based on unmodeled dynamic compensations

To guarantee solid oxide fuel cell (SOFC) safe operation, plenty control strategies have been developed to control stack temperature and voltage within a reasonable range. However, these control approaches ignore unmodeled dynamics of the SOFC system, which may lead to unsatisfactory control results, sometimes even make the system unstable. To overcome this challenge, a unique control strategy which considers unmodeled dynamic compensations of the SOFC system is proposed in this paper. A model of the SOFC system is firstly built, which includes a known linear model and an unmodeled nonlinear dynamic estimation. A nonlinear controller based on the unmodeled dynamic compensation is then developed to force the SOFC to track desired stack temperature and voltage. To evaluate the control performance, the proposed control method is compared with a traditional sliding mode controller. The simulation results show if the unmodeled dynamics have a small effect on the SOFC, both the sliding mode controller and the proposed controller can achieve a precise tracking. If the unmodeled dynamics have a great impact on the SOFC, the temperature and voltage can be well controlled with the proposed control strategy. However, in the sliding mode controller, the temperature and voltage trajectories deviate largely from the reference values.     

Degradation behavior of anode-supported solid oxide fuel cell using LNF cathode as function of current load

We investigated the effect of current loading on the degradation behavior of an anode-supported solid oxide fuel cell (SOFC). The cell consisted of LaNi_0.6Fe_0.4O₃ (LNF), alumina-doped scandia stabilized zirconia (SASZ), and a Ni-SASZ cermet as the cathode, electrolyte, and anode, respectively. The test was carried out at 1073 K with constant loads of 0.3, 1.0, 1.5, and 2.3 A cm⁻². The degradation rate, defined by the voltage loss during a fixed period (about 1000 h), was faster at higher current densities. From an impedance analysis, the degradation depended mainly on increases in the cathodic resistance, while the anodic and ohmic resistances contributed very little. The cathode microstructures were observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM).     

Geometrical modeling of microstructure of solid oxide fuel cell composite electrodes

A model based on random packing of electron and ion conductor particles is developed to study the microstructure performance relationship of solid oxide fuel cell electrodes. This three-dimensional model takes into account special variations of triple phase boundary (TPB) by keeping track of all particles in the packing. Porosity of the media can be controlled and is set to 30%. Effect of particle size, electrode thickness, electrode composition and particle size ratio on the length of TPB line has been studied. The study shows that unlike what models based on percolation theory suggest, the electrode media is not homogeneous for electrochemical reaction. While increasing the thickness increases the length of the TPB to some extent, beyond that little or no improvement was observed. The study also revealed that adding a current collector layer made of electron conductors can increase the TPB line by at least 4%. While for particles of the same size maximum length of TPB was observed at equal volume percent of electron and ion conductor particles, for size ratio of particles other than one the maximum TPB tends to occur above or below 50% depending on the size ratio.     

Performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack fabricated by dip coating technique

A simple and feasible technique is developed successfully to fabricate the cone-shaped tubular segmented-in-series solid oxide fuel cell (SOFC) stack. The cone-shaped tubular anode substrates and yttria-stabilized zirconia (YSZ) electrolyte films are fabricated by dip coating technique. After sintering at 1400 °C for 4 h, a dense and crack-free YSZ film with a thickness of about 35.9 μm is successfully obtained. The single cell, NiO–YSZ/YSZ/LSM–YSZ, provides a maximum power density of 1.08 and 1.35 W cm⁻² at 800 and 850 °C, respectively, using moist hydrogen (75 ml/min) as fuel and ambient air as oxidant.A two-cell-stack based on the above-mentioned cone-shaped tubular anode-supported SOFC was assembled and tested. The maximum total power at 800 °C was about 3.7 W.     

Monte-Carlo simulation and performance optimization for the cathode microstructure in a solid oxide fuel cell

A 3D micro-scale model is developed to simulate the transport and electrochemical reaction in a composite cathode. This model takes into account the details of the specific cathode microstructure such as random pore structure, active TPB (three phase boundary) site distribution, particle size and composition and their interrelationship to the charge transfer and mass transport processes. Especially, the pore structure and mass diffusion were incorporated into this model. Influence of the microsturcture parameters on the performance was investigated by numerical simulations.     

Carbon monoxide-fueled solid oxide fuel cell

This study explored CO as a primary fuel in anode-supported solid oxide fuel cells (SOFCs) of both tubular and planar geometries. Tubular single cells with active areas of 24 cm² generated power up to 16 W. Open circuit voltages for various CO/CO₂ mixture compositions agreed well with the expected values. In flowing dry CO, power densities up to 0.67 W cm⁻² were achieved at 1 A cm⁻² and 850 °C. This performance compared well with 0.74 W cm⁻² measured for pure H₂ in the same cell and under the same operating conditions. Performance stability of tubular cells was investigated by long-term testing in flowing CO during which no carbon deposition was observed. At a constant current of 9.96 A (or, 0.414 A cm⁻²) power output remained unchanged over 375 h of continuous operation at 850 °C. In addition, a 50-cell planar SOFC stack was operated at 800 °C on 95% CO (balance CO₂), which generated 1176 W of total power at a power density of 224 mW cm⁻². The results demonstrate that CO is a viable primary fuel for SOFCs.     

Predictive control of solid oxide fuel cell based on an improved Takagi-Sugeno fuzzy model

Thermal management of a solid oxide fuel cell (SOFC) stack essentially involves control of the temperature within a specific range in order to maintain good performance of the stack. In this paper, a nonlinear temperature predictive control algorithm based on an improved Takagi-Sugeon (T-S) fuzzy model is presented. The improved T-S fuzzy model can be identified by the training data and becomes a predictive model. The branch-and-bound method and the greedy algorithm are employed to set a discrete optimization and an initial upper boundary, respectively. Simulation results show the advantages of the model predictive control (MPC) based on the identified and improved T-S fuzzy model for an SOFC stack.     

High performance praseodymium nickelate oxide cathode for low temperature solid oxide fuel cell

The praseodymium nickelate oxide Pr₂NiO_4+δ, a mixed conducting oxide with the K₂NiF₄-type structure, was evaluated as cathode for low temperature solid oxide fuel cells (T = 873 K). The electrochemical performance of the cathode has been improved by optimization of the microstructure of the porous cathode combined with the use of a ceria barrier layer in between the cathode and zirconia electrolyte. Both low polarization and ohmic resistances were obtained using Pr₂NiO_4+δ-powders with a median particle size of 0.4 μm, and sintering the screen printed layer at a sintering temperature of about 1353 K for 1 h. These manufacturing conditions resulted in a cathode microstructure with well established connections between the cathode particles and good adhesion of the cathode on the electrolyte. Full-sized anode supported cells have been manufactured using the same process conditions for the Pr₂NiO_4+δ cathode and tested. The best results were obtained when using a dense Ce_0.8Gd_0.2O_1.9 (20CGO) barrier layer. While a complete optimization of the cell preparation has not yet been achieved, the electrochemical performances of anode supported cells with Pr₂NiO_4+δ are higher than those with the well known state-of-the-art La_0.6Sr_0.4Fe_0.8Co_0.2O_3−δ (LSFC) material.     

Parametric study on interfacial crack propagation in solid oxide fuel cell based on electrode material

Interfacial delamination is one of the typical failure modes of solid oxide fuel cell, which is caused by interfacial crack propagation. In order to improve the stability, durability and mechanical integrity of the cell, the influence of electrode material properties on the interfacial crack propagation is studied. Based on a large number of experimental data, the material model of anode and cathode adopts approximate linear model and the different material optimization schemes are set by changing the material parameters, i.e., the ratio of elastic modulus and thermal expansion coefficient between electrode and electrolyte. The crack energy release rate and crack propagation length are taken as important objective functions to compare the extent of interfacial crack propagation under different material optimization schemes. The internal relationship between electrode material parameters and interfacial crack propagation behavior is analyzed, and the optimization scheme of electrode material is obtained to reduce the possibility of delamination in the cell. This research provides guidance for the improvement of stability and integrity of solid oxide fuel cell.