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LiMn1.5Ni0.5O4 is one of the most promising cathode materials for use in either next generation lithium-ion batteries or all solid-state batteries. However, despite the significant Research and Development (R&D) carried out throughout the last two decades the material has not made serious inroads into market. One of the major reasons is the lack of consistency in the reported intrinsic properties and electrochemical performance owing to major controversies in synthesis, crystal structure and bulk and interfacial properties of LiMn1.5Ni0.5O4, notably in contact with electrolytes. This paper is a compelling review providing an assessment on the mainstream R&D dealing with the various crystal structures of LiMn1.5Ni0.5O4 and their evolutions observed during synthesis and cycling in correlation with their electrochemical performance. Influence of electrolytes and additives along with modifications through doping and surface treatments are interrelated, and the electronic and ionic transport properties of the ordered and disordered LiMn1.5Ni0.5O4 phases are discussed. Overall, this review provides a detailed assessment on LiMn1.5Ni0.5O4 and the underlying mechanisms governing its electrochemical performance broadly providing a focused framework for further advancement towards commercialization.

The use of self-healing glass as hermetic seals is a recent advancement in sealing technology development for the planar solid oxide fuel cells (SOFCs). Because of its capability to restore mechanical properties at elevated temperatures, the self-healing glass seal is expected to provide high reliability in maintaining the long-term structural integrity and functionality of SOFCs. To accommodate the design and evaluate the effectiveness of these engineered seals under various thermomechanical operating conditions, a computational modeling framework must be developed to accurately capture and predict the healing behavior of the glass material. In the present work, a mechanistic-based, two-stage model was developed to study the stress and temperature-dependent crack healing of the self-healing glass materials. The model initially was first calibrated by experimental measurements combined with kinetic Monte Carlo (kMC) simulation results and then implemented into finite element analysis (FEA). The effects of various factors, e.g., stress, temperature, and crack morphology, on the healing behavior of the glass were investigated and discussed.

Over their designed lifetime, high-temperature electrochemical devices, such as solid oxide fuel cells (SOFCs), can experience degradation in their electrochemical performance due to environmental conditions, operating conditions, contaminants, and other factors. Understanding the different degradation mechanisms in SOFCs and other electrochemical devices is essential to reducing performance degradation and increasing the lifetimes of these devices. In this paper, SOFC degradation mechanisms are evaluated, and a damage model is presented that describes performance degradation in SOFCs due to damage or degradation in the SOFC electrodes. A degradation classification scheme is presented, dividing the various SOFC electrode degradation mechanisms into categories based on their physical effects on the SOFC. The damage model and classification method are applied both to sulfur poisoning and antimony poisoning, which occur in the SOFC anode. For sulfur poisoning, the model can calculate degradation in SOFC performance based on the operating temperature of the fuel cell and the concentration of gaseous sulfur species in the anode. For antimony poisoning, the effects of nickel consumption from the anode matrix are investigated.

Mechanical properties of solid oxide fuel cell glass-ceramic seal material, G18, are studied at high temperatures. Samples of G18 are aged for either 4 h or 100 h, resulting in samples with different crystallinity. Reduced modulus, hardness, and time-dependent behavior are measured by nanoindentation. The nanoindentation is performed at room temperature, 550, 650, and 750 °C, using loading rates of 5 mN s−1 and 25 mN s−1. Results show a decrease in reduced modulus with increasing temperature, with significant decrease above the glass transition temperature. Hardness generally decreases with increasing temperature, with a slight increase before Tg for the 4 h-aged sample. Dwell tests show that creep increases with increasing temperature, but decrease with further aging.

Statistical continuum mechanics is used to predict the coefficient of thermal expansion (CTE) for solid oxide fuel cell glass-ceramic seal materials with different morphology and crystallinity. Two-point correlation functions are utilized to represent the heterogeneous microstructure morphology and phase distribution. The model uses two-point correlation functions in conjunction with local properties to predict the effective CTE. Prediction results are comparable to experimental CTE results. The advantage of using the statistical continuum mechanics model in predicting the effective properties of anisotropic media is shown, using the ability to take the microstructure into consideration.

A self-healing glass seal has the potential to restore its mechanical properties upon being reheated to the solid oxide fuel cell (SOFC) stack operating temperature. Such a self-healing feature is desirable for achieving high seal reliability during thermal cycling. Self-healing glass is also characterized by its low mechanical stiffness and high creep rate at SOFC operating temperatures. Therefore, the geometric stability and structural integrity of the glass seal system are critical to its successful application in SOFCs. This paper describes studies of the geometric stability and structural integrity of the self-healing glass seal system and the influence of various interfacial conditions during the operating and cooling-down processes using finite element analyses. For this purpose, the test cell used in the leakage tests for compliant glass seals, conducted at Pacific Northwest National Laboratory (PNNL), was taken as the initial modeling geometry. The effect of the ceramic stopper on the geometric stability of the self-healing glass sealants was studied first. Two interfacial conditions of the ceramic stopper and glass seals, i.e., bonded (strong) or unbonded (weak), were considered. Then the influences of interfacial strengths at various interfaces, i.e., stopper/glass, stopper/PEN, as well as stopper/IC plate, on the geometric stability and reliability of glass during the operating and cooling processes were examined.

We present a pore-scale model of a solid oxide fuel cell (SOFC) cathode. Volatile chromium species are known to migrate from the current collector of the SOFC into the cathode where over time they decrease the voltage output of the fuel cell. A pore-scale model is used to investigate the reactive transport of chromium species in the cathode and to study the driving forces of chromium poisoning. A multi-scale modeling approach is proposed which uses a cell level model of the cathode, air channel and current collector to determine the boundary conditions for a pore-scale model of a section of the cathode. The pore-scale model uses a discrete representation of the cathode to explicitly model the surface reactions of oxygen and chromium with the cathode material. The pore-scale model is used to study the reaction mechanisms of chromium by considering the effects of reaction rates, diffusion coefficients, chromium vaporization, and oxygen consumption on chromium's deposition in the cathode. The study shows that chromium poisoning is most significantly affected by the chromium reaction rates in the cathode and that the reaction rates are a function of the local current density in the cathode.

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.

This paper examines the electrochemical and direct internal steam–methane reforming performance of the solid oxide fuel cell when subjected to pressurization. Pressurized operation boosts the Nernst potential and decreases the activation polarization, both of which serve to increase cell voltage and power while lowering the heat load and operating temperature. A model considering the activation polarization in both the fuel and the air electrodes was adopted to address this effect on the electrochemical performance. The pressurized methane conversion kinetics and the increase in equilibrium methane concentration are considered in a new rate expression. The models were then applied in simulations to predict how the distributions of direct internal reforming rate, temperature, and current density are effected within stacks operating at elevated pressure. A generic 10 cm counter-flow stack model was created and used for the simulations of pressurized operation. The predictions showed improved thermal and electrical performance with increased operating pressure. The average and maximum cell temperatures decreased by 3% (20 °C) while the cell voltage increased by 9% as the operating pressure was increased from 1 to 10 atm.

A full statistical analysis of the microstructure of glass–ceramic solid oxide fuel cell (SOFC) seal material, G18, is performed to calculate elastic properties. Predictions are made for samples aged for 4 h and 1000 h, giving different crystallinity levels. Microstructure of the glass–ceramic G18 is characterized by correlation function for each individual phase. Predicted results are compared with the Voigt and Reuss bounds in this study. The weak contrast analysis results in elastic modulus predictions between the upper and lower bounds but closer to the upper bound.

This study utilizes nanoindentation to investigate and measure creep properties of a barium calcium alumino-silicate glass–ceramic used for solid oxide fuel cell seals (SOFCs). Samples of the glass–ceramic seal material were aged for 5, 50, and 100 h to obtain different degrees of crystallinity. Instrumented nanoindentation was performed on the samples with different aging times at different temperatures to investigate the strain rate sensitivity during inelastic deformation. The temperature dependent behavior is important since SOFCs operate at high temperatures (800–1000 °C). Results show that the samples with higher crystallinity were more resistant to creep, and the creep compliance tended to decrease with increasing temperature, especially with further aged samples.

This paper discusses experimental determination of solid oxide fuel cell (SOFC) glass–ceramic seal material properties and seal/interconnect interfacial properties to support development and optimization of SOFC designs through modeling. Material property experiments such as dynamic resonance, dilatometry, flexure, creep, tensile, and shear tests were performed on PNNL's glass–ceramic sealant material, designated as G18, to obtain property data essential to constitutive and numerical model development. Characterization methods for the physical, mechanical, and interfacial properties of the sealing material, results, and their application to the constitutive implementation in SOFC stack modeling are described.

Due to mismatch of the coefficients of thermal expansion of various layers in the positive/electrolyte/negative (PEN) structures of solid oxide fuel cells (SOFC), thermal stresses and warpage on the PEN are unavoidable due to the temperature changes from the stress-free sintering temperature to room temperature during the PEN manufacturing process. In the meantime, additional mechanical stresses will also be created by mechanical flattening during the stack assembly process. In order to ensure the structural integrity of the cell and stack of SOFC, it is necessary to develop failure criteria for SOFC PEN structures based on the initial flaws occurred during cell sintering and stack assembly. In this paper, the global relationship between the critical energy release rate and critical curvature and maximum displacement of the warped cells caused by the temperature changes as well as mechanical flattening process is established so that possible failure of SOFC PEN structures may be predicted deterministically by the measurement of the curvature and displacement of the warped cells.

In this paper, we present an integrated experimental and modeling methodology in predicting the life of coated and uncoated metallic interconnect (IC) for solid oxide fuel cell (SOFC) applications. The ultimate goal is to provide cell designer and manufacture with a predictive methodology such that the life of the IC system can be managed and optimized through different coating thickness to meet the overall cell designed life. Crofer 22 APU is used as the example IC material system. The life of coated and uncoated Crofer 22 APU under isothermal cooling was predicted by comparing the predicted interfacial strength and the interfacial stresses induced by the cooling process from the operating temperature to room temperature, together with the measured oxide scale growth kinetics. It was found that the interfacial strength between the oxide scale and the Crofer 22 APU substrate decreases with the growth of the oxide scale, and that the interfacial strength for the oxide scale/spinel coating interface is much higher than that of the oxide scale/Crofer 22 APU substrate interface. As expected, the predicted life of the coated Crofer 22 APU is significantly longer than that of the uncoated Crofer 22 APU.

The interfacial adhesion strength between the oxide scale and the substrate is crucial to the reliability and durability of metallic interconnects in solid oxide fuel cell (SOFC) operating environments. It is necessary, therefore, to establish a methodology to quantify the interfacial adhesion strength between the oxide scale and the metallic interconnect substrate, and furthermore to design and optimize the interconnect material as well as the coating materials to meet the design life of an SOFC system. In this paper, we present an integrated experimental/analytical methodology for quantifying the interfacial adhesion strength between the oxide scale and a ferritic stainless steel interconnect. Stair-stepping indentation tests are used in conjunction with subsequent finite element analyses to predict the interfacial strength between the oxide scale and Crofer 22 APU substrate.

In this research, a Simulink model of a standalone vehicular solid-oxide fuel cell (SOFC) auxiliary power unit (APU) is developed. The SOFC APU model consists of three major components: a controller model; a power electronics system model; and an SOFC plant model, including an SOFC stack module, two heat exchanger modules, and a combustor module. This paper discusses the development of the nonlinear dynamic models for the SOFC stacks, the heat exchangers and the combustors. When coupling with a controller model and a power electronic circuit model, the developed SOFC plant model is able to model the thermal dynamics and the electrochemical dynamics inside the SOFC APU components, as well as the transient responses to the electric loading changes. It has been shown that having such a model for the SOFC APU will help design engineers to adjust design parameters to optimize the performance. The modeling results of the SOFC APU heat-up stage and the output voltage response to a sudden load change are presented in this paper. The fuel flow regulation based on fuel utilization is also briefly discussed.

A 3D simulation tool for modeling solid oxide fuel cells is described. The tool combines the versatility and efficiency of a commercial finite element analysis code, MARC®, with an in-house developed robust and flexible electrochemical (EC) module. Based upon characteristic parameters obtained experimentally and assigned by the user, the EC module calculates the current density distribution, heat generation, and fuel and oxidant species concentration, taking the temperature profile provided by MARC® and operating conditions such as the fuel and oxidant flow rate and the total stack output voltage or current as the input. MARC® performs flow and thermal analyses based on the initial and boundary thermal and flow conditions and the heat generation calculated by the EC module. The main coupling between MARC® and EC is for MARC® to supply the temperature field to EC and for EC to give the heat generation profile to MARC®. The loosely coupled, iterative scheme is advantageous in terms of memory requirement, numerical stability and computational efficiency. The coupling is iterated to self-consistency for a steady-state solution. Sample results for steady states as well as the startup process for stacks with different flow designs are presented to illustrate the modeling capability and numerical performance characteristic of the simulation tool.

The gas transport in the porous electrode is treated by a phenomenological approach such that the gas concentration at the three-phase boundary (TPB) region is the additive superposition of that transported from the source, i.e. the gas channels. With plausible approximations and elemental algebra, analytical expressions are obtained to estimate the effects of ribs on the concentration polarization of planar fuel cell operations. It is shown that the model can closely reproduce the experimental concentration polarization curve for small and medium current density (up to about 2 A/cm 2 ), providing a simple and effective method for engineering application. The concentration polarization caused by the presence of a rib is discussed and the concentration profiles with varying rib widths are illustrated. In connection with the electrical resistance, the determination of the optimal rib width for minimizing the overall polarization is also shown.

A simulation tool for modeling planar solid oxide fuel cells is demonstrated. The tool combines the versatility of a commercial computational fluid dynamics simulation code with a validated electrochemistry calculation method. Its function is to predict the flow and distribution of anode and cathode gases, temperature and current distributions, and fuel utilization. A three-dimensional model geometry, including internal manifolds, was created to simulate a generic, cross-flow stack design. Similar three-dimensional geometries were created for simulation of co-flow, and counterflow stack designs. Cyclic boundary conditions were imposed at the top and bottom of the model domains, while the lateral walls were assumed adiabatic. The three cases show that, for a given average cell temperature, similar fuel utilizations can result irrespective of the flow configuration. Temperature distributions however, which largely determine thermal stresses during operation, are dependent on the chosen design geometry/flow configuration. The co-flow case had the most uniform temperature distribution and the smallest thermal gradients, thus offers thermo-structural advantages over the other flow cases.