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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

An intermediate-temperature direct ammonia fuel cell with a molten alkaline hydroxide electrolyte

This paper describes the development and testing of a direct ammonia fuel cell utilizing a molten alkaline hydroxide electrolyte at temperatures between 200 and 450 °C. The advantages of a molten hydroxide fuel cell include the use of a highly conductive and very low-cost electrolyte, inexpensive base metal electrocatalysts, a wide operating temperature range, fuel flexibility, and fast electrode kinetics. The direct use of ammonia in such a fuel cell, even at temperatures as low as 200 °C, is made possible due to the very chemically aggressive nature of the melt. A test cell was constructed using a KOH–NaOH eutectic mixture and produced approximately 40 mW cm⁻² of power at 450 °C while operating on a stream of pure ammonia fed to the anode and compressed ambient air fed to the cathode.     

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.     

Nanoparticle gasifier fuel cell for sustainable energy future

A new concept for production of electricity from biomass or coal using molten carbonate fuel cells is proposed. It involves feeding fine coal particles or biomass, for sustainable energy future, with steam into the anode compartment of the fuel cell in which the waste heat from the fuel cell is used to produce synthesis gas which reacts electrochemically. This concept is illustrated using carbon nanoparticles as the fuel.     

Dual ionic conductive membrane for molten carbonate fuel cell

Within this study, the electrochemically inert, molten carbonate fuel cell (MCFC) $\text{γ}$-LiAlO₂ matrix is replaced by oxygen ion conducting ceramics, typical for solid oxide fuel cell (SOFC) application. Such solution leads to synergistic ion transport both by molten carbonate mix (CO₃^2-) and yttria-stabilized zirconia (YSZ) or samaria-doped ceria (SDC) matrix (O^2-).Single unit cell tests confirm that application of hybrid ionic membrane increases the performance (power density) of the MCFC over pure $\text{γ}$-LiAlO₂ for a wide range of operating temperatures (600 °C–750 °C). Cell power density with SDC and YSZ matrices is 2% and 13% higher, respectively, compared to the $\text{γ}$-LiAlO₂ at typical 650 °C operating temperature of MCFC.     

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.     

Process analysis of molten carbonate fuel cells in carbon capture applications

Recently, Molten Carbonate Fuel Cells (MCFCs) are being increasingly investigated for carbon capture applications. The wet and low CO₂ cathode feeds of such applications can substantially affect the electrochemistry of the cell. A dual-anion mechanism has been introduced to model this electrochemical regime characterized by the parallel migration of carbonate and hydroxide ions. A model based on this mechanism has been implemented in an in-house-developed Fortran code that has been now integrated into Aspen Plus. The model is able to calculate the main performance parameters on the plane of a cell when geometry as well as feed flow rates, compositions, temperature, pressure, and current density are provided as input data. In the present work, the application of the simulation tool is presented in a process analysis aimed to optimize the formulation of the electrochemical module, further evaluate the controlling factors of the dual-anion mechanism, and discuss possible technological optimizations.     

水蒸气氛围下甘蔗渣热解气化条件的研究

在试验条件下，考察反应温度、升温速率、物料颗粒大小等因素对蔗渣在水蒸气中的热解气化特性的影响。试验结果表明，热解终温越高，物料粒径越小，越有利于产生高质量的热解气。热解终温是热解气化过程主要的决定因素，在先到达热解终温，再通入水蒸气的操作条件下，升温速率的改变对气化效果的影响并不突出。试验在最佳条件(采用粉末物料，在1000℃下进行热解)下，可以得到高热值(10MJ／m^3)合成气和较高的产气率(1．7m^3／kg)。     

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.     

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.     

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.     

Study on the levelling process of the current collector for the molten carbonate fuel cell based on curvature integration method

The current collector for the molten carbonate fuel cell (MCFC) is manufactured from the sheet metal forming process. After the forming process, the current collector is bent resulting in a specific curvature (κ_i) in the direction in which trapezoidal protrusions are formed due to springback. In the stack of the MCFC, small deformation of the current collector can bring about defects in the electrolyte, non-uniform contact and difficulties in assembling the stack. Therefore, the curvature of the current collector should be minimized in order to reduce defects which can cause critical damage in the long-term operation. In order to straighten the current collector, the levelling process using three rolls was employed. In this work, a simple and effective method for designing the levelling process was proposed. An analytic model and the finite element analysis were used in combination. The optimal curvature minimizing the resultant curvature and the resultant moment of the current collector down to zero was calculated from the bending moment–curvature relationship. The bending moment–curvature relationship of the current collector was determined from the finite element analysis of uniform bending using the simulation results of the three-stage forming process. In the analytic model based on curvature integration method, the proper roll arrangement corresponding to the optimal curvature was calculated. Experiments were conducted using the calculated roll arrangement. The current collector was levelled nearly flat using the levelling process. After the levelling process, the flattened current collector was easily assembled with a centre plate and ensuring uniform contact with the electrolyte.     

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.