Electrolyte effect on the catalytic performance of Ni-based catalysts for direct internal reforming molten carbonate fuel cell

An active and tolerant Ni-based catalyst for methane steam reforming in direct internal reforming molten carbonate fuel cells (DIR-MCFCs) was developed. Deactivation of reforming catalysts by alkali metals from the electrolyte composed of Li₂CO₃ and K₂CO₃ is one of the major obstacles to be overcome in commercialization of DIR-MCFCs. Newly developed Ni/MgSiO₃ and Ni/Mg₂SiO₄ reforming catalysts show activities of ca. 80% methane conversion. Subsequent to electrolyte addition to the catalyst, however, the activity of Ni/Mg₂SiO₄ decreases to ca. 50% of its initial value, whereas Ni/MgSiO₃ catalyst retains its initial activity. Results obtained from temperature-programmed reduction and X-ray photoelectron spectroscopy identify unreduced Ni³⁺ as a decisive factor in keeping catalytic activity from the electrolyte.     

The control strategy for a molten carbonate fuel cell hybrid system

Based on mathematical modelling and numerical simulations, the control strategy for a molten carbonate fuel cell hybrid system (MCFC-HS) is presented. Adequate maps of performances with three independent parameters are shown. The independent parameters are as follows: stack current, fuel mass flow and compressor outlet pressure. Those parameters can be controlled by external load, fuel valve and turbine–compressor shaft speed, respectively.     

The stability of molten carbonate fuel cell electrodes: A review of recent improvements

The electrode stability is a key issue for the development of conventional hydrogen fuelled and direct internal reforming (DIR) molten carbonate fuel cells (MCFCs). While for conventional MCFC anodes the stability problem has been addressed by the addition of Al or Cr to Ni, the problems of the dissolution of the NiO cathode and of the deactivation of DIR-MCFC anodes have not been fully resolved too. This review reports recent improvements in the chemical and physicochemical stability of cathode and anode materials in MCFCs and DIR-MCFCs, respectively.     

A basic model for analysis of molten carbonate fuel cell behavior

A simple mathematical model, based on the basic chemical reactions and mass transfer, was developed to predict some important characteristics of molten carbonate fuel cells (MCFC) with LiNaCO₃ and LiKCO₃ electrolytes for steady state operating conditions. The parallel and cross gas flow patterns were analyzed. Model simulates polarization characteristics, the effect of temperature, pressure and electrolyte type on the cell performance, various losses in the cell and gas flow rate changes through cell. The effect of fuel utilization on the cell potential and efficiency was also analyzed. Model predicts a better performance for the MCFC with LiNaCO₃ electrolyte and the cross flow pattern, in general. Results show a strong influence of the operating temperature on the cell potential at temperatures below 625 °C, where cell potential increases rapidly with increasing temperature. Above this temperature, however, the cell potential has almost a steady asymptotic profile. The model predicts cell efficiency steadily improving with increase in fuel utilization. The cell potential decreases almost linearly with increase in the fuel utilization percentage for both electrolytes. Models results show a stronger dependency of the cell potential on the operating pressure than that described by the Nerst equation which is in line with fact that the real variations in the cell potential can be higher due to decreased various losses.     

Optimum start-up strategies for direct internal reforming molten carbonate fuel cell systems

The study of start-up performance for a direct internal reforming molten carbonate fuel cell (DIR-MCFC) system is presented. Since a kW-class stack is assembled with an additional preheating design, the improvement of start-up behavior is conducted to find the proper operating strategy. For a cold start-up fuel cell system, both start-up delay and inverse response are strictly detected. When the optimum operating strategy is determined by solving the steady-state optimization algorithm subject to stack temperature constraint, the rapid system start-up as well as the maximum power output can be achieved simultaneously.     

Improved molten carbonate fuel cell performance via reinforced thin anode

The effects of anode thickness on electrochemical performance and cell voltage stability of molten carbonate fuel cell (MCFC) were examined using single cell test. It was found that supported thin nickel-aluminum (Ni–Al) anode with small pore size enhanced cell performance by reducing its mass transfer resistance and crossover. The stability of cell voltage was also observed. This was achieved after 0.25 mm thick anode was reinforced with Ni 60 mesh. Unsupported 0.3 mm thick anode yielded poor performance due to deformation and cracks after a long thermal exposure. The performance was improved significantly after all the anodes were reinforced with Ni mesh.     

Analysis of a solid oxide fuel cell and a molten carbonate fuel cell integrated system with different configurations

A solid oxide fuel cell with internal reforming operation is run at partial fuel utilization; thus, the remaining fuel can be further used for producing additional power. In addition, the exhaust gas of a solid oxide fuel cell still contains carbon dioxide, which is the primary greenhouse gas, and identifying a way to utilize this carbon dioxide is important. Integrating the solid oxide fuel cell with the molten carbonate fuel cell is a potential solution for carbon dioxide utilization. In this study, the performance of the integrated fuel cell system is analyzed. The solid oxide fuel cell is the main power generator, and the molten carbonate fuel cell is regarded as a carbon dioxide concentrator that produces electricity as a by-product. Modeling of the solid oxide fuel cell and the molten carbonate fuel cell is based on one-dimensional mass balance, considering all cell voltage losses. Primary operating conditions of the integrated fuel cell system that affect the system efficiencies in terms of power generation and carbon dioxide utilization are studied, and the optimal operating parameters are identified based on these criteria. Various configurations of the integrated fuel cell system are proposed and compared to determine the suitable design of the integrated fuel cell system.     

Electrochemical performance of reversible molten carbonate fuel cells

The electrochemical performance of a state-of-the-art molten carbonate cell was investigated in both fuel cell (MCFC) and electrolysis cell (MCEC) modes by using polarization curves and electrochemical impedance spectroscopy (EIS). The results show that it is feasible to run a reversible molten carbonate fuel cell and that the cell actually exhibits lower polarization in the MCEC mode, at least for the short-term tests undertaken in this study. The Ni hydrogen electrode and the NiO oxygen electrode were also studied in fuel cell and electrolysis cell modes under different operating conditions, including temperatures and gas compositions. The polarization of the Ni hydrogen electrode turned out to be slightly higher in the electrolysis cell mode than in the fuel cell mode at all operating temperatures and water contents. This was probably due to the slightly larger mass-transfer polarization rather than to charge-transfer polarization according to the impedance results. The CO₂ content has an important effect on the Ni electrode in electrolysis cell mode. Increasing the CO₂ content the Ni electrode exhibits slightly lower polarization in the electrolysis cell mode. The NiO oxygen electrode shows lower polarization loss in the electrolysis cell mode than in the fuel cell mode in the temperature range of 600–675 °C. The impedance showed that both charge-transfer and mass-transfer polarization of the NiO electrode are lower in the electrolysis cell than in the fuel cell mode.     

Lifetime optimization of a molten carbonate fuel cell power system coupled with hydrogen production

In this paper, a biogas fuelled energy system for combined production of electricity and hydrogen is considered. The system is based on a molten carbonate fuel cell stack integrated with a micro gas turbine. Hydrogen is produced by a pressure swing absorption system. A multi-objective optimization is performed, considering the electrical efficiency and the unit cost of electricity as the objective functions.The system operation is affected by variations in fuel composition, ambient temperature and performance degradation of the components occurring during its lifetime. These effects are considered while defining the objective functions.     

A high performance composite ionic conducting electrolyte for intermediate temperature fuel cell and evidence for ternary ionic conduction

The performance of a composite electrolyte composed of a samarium doped ceria (SDC) and a ternary eutectic carbonate melt phase was examined. The formation temperature of a continuous carbonate melt phase is crucial to the high conductivity of this material. The electrolyte contains 30 and 50 wt% carbonate exhibited a sharp increase of conductivity at a temperature close to the melting point of the eutectic carbonate, ca 400 °C, which is more than 100 °C lower than those electrolytes using binary carbonate. At around 650 °C, and with CO₂/O₂ used as the cathode gas, the fuel cell gave a power output 720 mW cm⁻² at a current density 1300 mA cm⁻². Water was measured in both the anode and cathode outlet gases and CO₂ was detected in the anode outlet gas. When discharged at 800 mA cm⁻², a stable discharge plateau was obtained. The CO₂ in the cathode gas enhances the power output and the stability of the single cell. Based on these experimental facts, a ternary ionic conducting scheme is proposed and discussed.     

Numerical studies of a separator for stack temperature control in a molten carbonate fuel cell

The use of a separator to control stack temperature in a molten carbonate fuel cell was studied by numerical simulation using a computational fluid dynamics code. The stack model assumed steady-state and constant-load operation of a co-flow stack with an external reformer at atmospheric pressure. Representing a conventional cell type, separators with two flow paths, one each for the anode and cathode gas, were simulated under conditions in which the cathode gas was composed of either air and carbon dioxide (case I) or oxygen and carbon dioxide (case II). The results showed that the average cell potential in case II was higher than that in case I due to the higher partial pressures of oxygen and carbon dioxide in the cathode gas. This result indicates that the amount of heat released during the electrochemical reactions was less for case II than for case I under the same load. However, simulated results showed that the maximum stack temperature in case I was lower than that in case II due to a reduction in the total flow rate of the cathode gas. To control the stack temperature and retain a high cell potential, we proposed the use of a separator with three flow paths (case III); two flow paths for the electrodes and a path in the center of the separator for the flow of nitrogen for cooling. The simulated results for case III showed that the average cell potential was similar to that in case II, indicating that the amount of heat released in the stack was similar to that in case II, and that the maximum stack temperature was the lowest of the three cases due to the nitrogen gas flow in the center of the separator. In summary, the simulated results showed that the use of a separator with three flow paths enabled temperature control in a co-flow stack with an external reformer at atmospheric pressure.     

Energy and exergy analyses of a hybrid molten carbonate fuel cell system

This study deals with the energy and exergy analysis of a molten carbonate fuel cell hybrid system to determine the efficiencies, irreversibilities and performance of the system. The analysis includes the operation of each component of the system by mass, energy and exergy balance equations. A parametric study is performed to examine the effect of varying operating pressure, temperature and current density on the performance of the system. Furthermore, thermodynamic irreversibilities in each component of the system are determined. An overall energy efficiency of 57.4%, exergy efficiency of 56.2%, bottoming cycle energy efficiency of 24.7% and stack energy efficiency of 43.4% are achieved. The results demonstrate that increasing the stack pressure decreases the overpotential losses and, therefore, increases the stack efficiency. However, this increase is limited by the remaining operating conditions and the material selection of the stack. The fuel cell and the other components in which chemical reactions occur, show the highest exergy destruction in this system. The compressor and turbine on the other hand, have the lowest entropy generation and, thus, the lowest exergy destruction.     

Overpotential analysis with various anode gas compositions in a molten carbonate fuel cell

The effect of anode gas composition on the overpotential in a 100 cm² class molten carbonate fuel cell is investigated. A total of five different gas compositions are used. They are applied to cross-check the effect of flow rate and composition, e.g., a given composition with different gas flow rates and a total flow rate with different gas compositions. The overpotential at the anode is analyzed via steady-state polarization, inert gas step addition and reactant gas addition methods. The analyses reveal that the anodic overpotential depends on the flow rate of the reactant species rather than the composition. Two identical gas compositions show less overpotential when a larger flow rate is applied. Compositions with large flow rates of CO₂ and H₂O also yield less overpotential due to the gas species. Overpotential analyses show that the three measurements have complementary relationships.     

Silver coated cathode for molten carbonate fuel cells

Within this study, a layered cathode for use in a Molten Carbonate Fuel Cell (MCFC) has been developed. The substrate layer and reference MCFC cathode made of porous nickel was covered by a porous silver film with defined porosity and pore size. Both layers were fabricated using the tape casting method and further fired in a reductive atmosphere. The new cathode was assembled with other reference cell components to form a single MCFC, which was subjected to performance and durability tests. Scanning electron microscopy was used to analyze the microstructure of the materials before and after tests. The reference cathode was also studied for the comparison.The results show that the porous silver layer was able to enhance the electron transport between the cathode and current collector. It was also found that oxygen reduction is enhanced due to the presence of silver in the gas supply. As a result, the power density of the cell was increased by 50%. On the other hand, due to the separation from electrolyte by the NiO layer, no significant degradation of the silver layer, identified by SEM or electrochemical tests, was found after 1000 h.     

Lifetime Expectancy of molten carbonate fuel cells: Part I. Effect of temperature on the voltage and electrolyte reduction rates

Electrolyte depletion is a significant setback in the operation of molten carbonate fuel cells (MCFCs). The electrolyte loss mostly occurs as a result of the high operating temperatures of over 873 K. The effect of temperature on MCFCs was studied using several 7 cm² coin-type MCFCs operated at 873, 973 and 1073 K. Lithium-potassium carbonate (Li/K) was used as an electrolyte in this study. A decrease in cell performance with time was observed at all temperatures. The performance degradation was found to be more severe at 1073 K than at 973 K and 873 K. The electrolyte loss rate was observed by chemical means to have increased with increasing temperature. A more severe electrolyte loss rate was observed in cells operated at 1073 K, such that the electrolyte amount reduced by half after 250 h of cell operation. In this research work, a factor, F_WV, which correlates the electrolyte loss rate, voltage reduction rate, and cell life, is introduced. Its dependence on the cell electrode area and operating temperature make it a suitable parameter for simulating MCFC's lifetime.     

Integration of a molten carbonate fuel cell with a direct exhaust absorption chiller

A high market value exists for an integrated high-temperature fuel cell-absorption chiller product throughout the world. While high-temperature, molten carbonate fuel cells are being commercially deployed with combined heat and power (CHP) and absorption chillers are being commercially deployed with heat engines, the energy efficiency and environmental attributes of an integrated high-temperature fuel cell-absorption chiller product are singularly attractive for the emerging distributed generation (DG) combined cooling, heating, and power (CCHP) market. This study addresses the potential of cooling production by recovering and porting the thermal energy from the exhaust gas of a high-temperature fuel cell (HTFC) to a thermally activated absorption chiller. To assess the practical opportunity of serving an early DG-CCHP market, a commercially available direct fired double-effect absorption chiller is selected that closely matches the exhaust flow and temperature of a commercially available HTFC. Both components are individually modeled, and the models are then coupled to evaluate the potential of a DG-CCHP system. Simulation results show that a commercial molten carbonate fuel cell generating 300 kW of electricity can be effectively coupled with a commercial 40 refrigeration ton (RT) absorption chiller. While the match between the two “off the shelf” units is close and the simulation results are encouraging, the match is not ideal. In particular, the fuel cell exhaust gas temperature is higher than the inlet temperature specified for the chiller and the exhaust flow rate is not sufficient to achieve the potential heat recovery within the chiller heat exchanger. To address these challenges, the study evaluates two strategies: (1) blending the fuel cell exhaust gas with ambient air, and (2) mixing the fuel cell exhaust gases with a fraction of the chiller exhaust gas. Both cases are shown to be viable and result in a temperature drop and flow rate increase of the gases before the chiller inlet. The results show that no risk of cold end corrosion within the chiller heat exchanger exists. In addition, crystallization is not an issue during system operation. Accounting for the electricity and the cooling produced and disregarding the remaining thermal energy, the second strategy is preferred and yields an overall estimated efficiency of 71.7%.     

Modeling of molten carbonate fuel cell based on the volume-resistance characteristics and experimental analysis

The real-time dynamic simulation of MCFC is still difficult up to now. This work presents a one-dimensional mathematical model for MCFC considering the variation of local gas properties, and the experimental analysis for the validation of model. The volume-resistance (V-R) characteristic modeling method has been introduced. Using the V-R modeling method and the modular modeling idea, the partial differential equations for cell mass, energy and momentum balance can be modified in order to develop a model for quick simulation. Experiments have been carried out at Shanghai Jiaotong University Fuel Cell Research Institute. The experiments have been done under different operating pressures, and the results are used to validate the model. A good agreement between simulation and experimental results has been observed. Steady- and dynamic-state simulation results are analyzed. The results indicate that the V-R characteristic modeling method is feasible and valuable. The model can be used in the real-time dynamic simulation.     

An analysis for a molten carbonate fuel cell of complex geometry using three-dimensional transport equations with electrochemical reactions

A three-dimensional (3D) analysis has been developed and applied to obtain performance characteristics of a molten carbonate fuel cell (MCFC) of complex geometry. The equations are solved to obtain the velocity, temperature, pressure, and concentration distributions in the cathode/anode channel. The channel with uniformly distributed trapezoidal supports, is approximated by an anisotropic porous medium, and the effective permeability and conductivity are obtained by separate three-dimensional finite volume method (FVM) calculations for a single periodic module. The current density distribution for a given cell voltage is calculated iteratively by coupling it to the local chemical reaction rate. Thus, the current–voltage relation can be successfully obtained. Here, the cell characteristics for various operating conditions are presented and discussed. The calculation is carried out by increasing the electric load until the fuel-depleted region appears on the electrode surface. This procedure is capable of predicting essential cell features and may be used in finding the optimal cell design and/or operating conditions.     

Life cycle analysis and cost of a molten carbonate fuel cell prototype

The LCA is a method enabling the performance of a complete study on the environmental impacts of the product, taking into consideration all its life cycle (“from the cradle to the tomb” or, better “from the cradle to the cradle” when also the maximum recycling/reusing of the materials is provided. There are many procedures to perform an LCA of the consumers’ products. In particular, the SUMMA method (Sustainability Multi-criteria Multi-scale Assessment) allows obtaining a number of indices of efficiency and environmental sustainability which make the LCA assessment much more complete and significant. LCA method often represents the basis for an additional assessment of industrial products and processes, the LCC (Life Cycle Costing) which, allowing the association of economic variables to any phase of the life cycle, represents a useful tool for financial planning and management. The case study analysed in the present work concerns an LCA analysis, using the SUMMA method and the LCC of one small size molten carbonate fuel cell, 2.5 kW, assembled in the Fuel Cells Laboratory within the Educational Pole of Terni at the Università degli Studi di Perugia. For sake of completeness of the results, the methods Ecoindicator99 and Impact2002 + were used in the analysis, as implemented in the used calculation software, the SimaPro 7.1 by PRè Consultants. From the registered results, it emerges that the environmental energy sustainability of the analysed element enables its widespread and in-depth employment in the phase subsequent to the optimisation of the connected economic frame; the scenarios opened by the present work envisage great margins of improvements of said aspects in the future experiments.     

Stirling based fuel cell hybrid systems: An alternative for molten carbonate fuel cells

This paper presents a new design for high temperature fuel cell and bottoming thermal engine hybrid systems. Now, instead of the commonly used gas turbine engine, an externally fired - Stirling - piston engine is used, showing outstanding performance when compared to previous designs.Firstly, a comparison between three thermal cycles potentially usable for recovering waste heat from the cell is presented, concluding the interest of the Stirling engine against other solutions used in the past.Secondly, the interest shown in the previous section is confirmed when the complete hybrid system is analyzed. Advantages are not only related to pure thermal and electrochemical parameters like specific power or overall efficiency. Additionally, further benefits can be obtained from the atmospheric operation of the fuel cell and the possibility to disconnect the bottoming engine from the cell to operate the latter on stand alone mode. This analysis includes on design and off design operation.