熔融碳酸盐燃料电池（MCFC）性能研究

简要叙述了MCFC微观工作过程,然后分别详细讨论了压力,温度,反应气体的组分和利用率,电流密度,电解质板结构和电解质的成分,杂质和运动时间对MCFC性能和寿命的曩,并结合文献和实验数据对其机理进行了阐述,最后得出了为提高电池性能和瞎长其寿命的几点结论和建议。     

熔融碳酸盐燃料电池（MCFC）系统建模与控制的研究现状与发展

详细介绍了MCFC的电极,单电池、电堆,系统四个层次的建模以及MCFC控制的研究现状,指出了现有模型的不足;讨论了电堆和系统两级建模的发展方向,分析了MCFC系统的非线性,大时滞、分布参数、多输入多输出,有约束和随机干扰等特征,提出了两种适宜的控制方法。     

Decarbonizing cement plants via a fully integrated calcium looping-molten carbonate fuel cell process: Assessment of a model for fuel cell performance predictions under different operating conditions

This study is part of a comprehensive research devoted to the integration of a Calcium Looping (CaL) process with a Molten Carbonate Fuel Cell (MCFC) for the decarbonisation of a full-scale cement plant. In the proposed process, where the energy intensive oxy-combustion occurring in the CaL calciner is replaced with a conventional combustion in air. The CO₂-rich gas leaving the calciner is injected into the MCFC cathode while the anode side is fuelled by H₂-rich gases produced by a sorption-enhanced reforming (SER) process. The high CO₂-concentrated gas leaving the anode will be sent to valorisation processes and/or the CO₂ final disposal.Here we focus on modelling, simulation and characterization of the MCFC used as a device for CO₂ separation as well as electricity production, here considered as a process by-product. Polarization curves (I–V curves) and Electrochemical Impedance Spectroscopy (EIS) were measured to support the development and the calibration of a semi-empirical model obtained by theoretical consideration.The experimental campaign demonstrated that the fitted model is able to reproduce the real cell performance when varying the temperature, H₂ concentration, CO₂ concentration at anode and cathode respectively as well as CO₂ CaL capture rate.Indeed, the average difference between numerical and experimental results is always below 2%.Results also demonstrated that the MCFC can be usefully considered as an efficient CO₂ concentrator, with a CO₂ fraction at the anode outlet that is greater than 51% on a dry basis.     

A highly active Ni-Al2O3 catalyst prepared by homogeneous precipitation using urea for internal reforming in a molten carbonate fuel cell (MCFC): Effect of the synthesis temperature

Ni-Al₂O₃ catalysts for use in internal reforming in a molten carbonate fuel cell (MCFC) were prepared by homogeneous precipitation method at various synthesis temperatures. The effects of synthesis temperature on physicochemical properties and catalytic activities of the Ni-Al₂O₃ catalysts were investigated. XRD measurements exhibited that the peak intensity of NiAl₂O₄ in the calcined catalysts increased with higher synthesis temperatures. TPR measurements demonstrated that reduction peaks appeared around 670–680 °C for every synthesis temperature, indicating that the Ni particles interacted strongly with the support. Hydrogen chemisorption results showed that nickel dispersion and nickel surface area decreased in the order: K52_80C > K52_85C > K52_90C > K52_95C > K52_100C. TEM images of the reduced Ni-Al₂O₃ catalysts revealed that the average sizes of Ni particles were 13.1, 13.4 and 15.9 nm for K52_80C, K52_90C and K52_100C, respectively, which means that a higher synthesis temperature yielded a larger Ni particle. The performance of the catalysts in methane steam reforming showed that catalysts prepared at the lowest synthesis temperature (80 °C) exhibited the highest reaction rate. These results suggest that a lower synthesis temperature is favorable to prepare highly active Ni-Al₂O₃ catalysts by the homogeneous precipitation method.     

Nonlinear fuzzy modeling of a MCFC stack by an identification method

This paper reports a nonlinear fuzzy modeling study of a molten carbonate fuel cell (MCFC) stack by an identification method. MCFC is a complex nonlinear, multi-input and multi-output (MIMO) system that is hard to model by traditional methodologies. The Takagi–Sugeno (T–S) fuzzy model is suitable to model a large class of nonlinear MIMO system. In this paper, a MIMO T–S fuzzy model is used to represent MCFC. An identification method is used to determine both the nonlinear parameters of the antecedents and the linear parameters of the rules consequent in the T–S fuzzy model. The simulation tests reveal that obtained T–S fuzzy model using the identification method can efficiently approximate the static and dynamic behavior of a MCFC stack. Furthermore, based on this proposed T–S fuzzy model, valid control strategy studies such as predictive control, robust control can be developed.     

Improved performance of molten carbonate fuel cells with (Li/Na)2CO3 electrolytes by using BYS coated cathode at low operating temperatures

In order to improve the stack life time of MCFCs, it is necessary to reduce the operating temperature of MCFCs below 600 °C, because reduced operating temperature minimizes electrolyte loss due to evaporation and corrosion. However, at the low operating temperature below 600 °C, the cell performance of MCFCs with (Li/Na)₂CO₃ electrolyte is too low to operate the fuel cell stack and system. In this study, we have performed wettability control of the liquid molten carbonate electrolyte by coating NiO cathodes with poor wetting property of the mixed ionic and electronic conductor (MIEC) such as BYS (Bi_1.5Y_0.3Sm_0.3O_3-δ). From experiments with symmetrical cells, each polarization component with various temperatures and gas conditions were studied. To investigate effects of the BYS coated cathode on the performance of MCFCs, a 100 cm² single cell of MCFCs was employed. The performance of a 100 cm² single cell with BYS coated cathode was better than that with conventional cathode by a factor of 1.84, because BYS coated cathode reduces activation polarization and mass transfer resistance greatly.     

Porous nickel MCFC cathode coated by potentiostatically deposited cobalt oxide: III. Electrochemical behaviour in molten carbonate

A cobalt oxide coating was deposited on porous nickel by a potentiostatic electrochemical technique and studied in molten (Li_0.52Na_0.48)₂CO₃ eutectics at 650 °C under an atmosphere of CO₂:Air (30:70). The structural and morphological characteristics of this coating before and after immersion in the molten electrolyte were described in a previous paper, showing that the initial Co₃O₄ layer is rapidly transformed into LiCoO₂ and afterwards probably into LiCo_1−yNi_yO₂. In the present part, the electrical and electrochemical behaviour of this promising novel MCFC cathode material was thoroughly analysed during 50 h by impedance spectroscopy. A porous nickel cathode was tested in the same conditions and taken as a reference. The oxidation and lithiation reactions are accelerated by the presence of cobalt. The charge transfer resistance is higher with the coated cathode but the diffusion resistance through this new material is lower in comparison with the state-of-the-art cathode.     

A heuristic method of variable selection based on principal component analysis and factor analysis for monitoring in a 300 kW MCFC power plant

In a commercialized 300 kW molten carbonate fuel cell (MCFC) power plant, a univariate alarm system that has only upper and lower limits is usually employed to identify abnormal conditions in the system. Even though univariate alarms have already been adopted for system monitoring, this simple monitoring system is limited for using in an extended monitoring system for fault diagnosis. Therefore, based on principal component analysis (PCA), a recursive variable grouping method for a multivariate monitoring system in a commercialized MCFC power plant is presented in this paper. In terms of development, since a principal component analysis model that contains all system variables cannot isolate a system fault, heuristic recursive variable selection method using factor analysis is presented here. To verify the performance of the fault detection, real plant operations data are used. Furthermore, comparison between type 1 and type 2 errors for four different variable groups demonstrates that the developed heuristic method works well when system faults occur. These monitoring techniques can reduce the number of false alarms occurring on site at MCFC power plant.     

Effect of CO2 partial pressure on the cathode lithiation in molten carbonate fuel cells

Nickel cathode is transformed to lithiated nickel oxide by oxidation and lithiation during the conditioning process for molten carbonate fuel cells. In the lithiation process, the amount of lithium inserted into nickel oxide depends on the oxygen and CO₂ composition and this affects the performance of nickel cathode. In this paper, CO₂ interruption technique was applied to investigate the effects of CO₂ interruption on the lithiation of nickel oxide. During the CO₂ interruption for 24 h in cathode operating at 20 mA/cm², the carbonate ion in electrolyte was decomposed into oxygen and CO₂. With the additional oxygen on cathode surface, Ni²⁺ is oxidized to Ni³⁺ with formation of cation vacancy in NiO. The lithium content of cathode increased from 3.0 at.% to 17.4 at.% (over-lithiation) and hence LiNiO₂ phase was formed in the cathode. Cathode surface area is increased by a decrease in NiO particle size with the formation of micropores. The morphological change in cathode enhanced its electrochemical performance in the single cell. Cell voltage of the single cell that has been subjected to CO₂ interruption at 120 mA/cm² was enhanced by 300 mV, due primarily to the reduction in the internal resistance from 2.0 to 0.8 Ω cm² and also in the charge transfer resistance from 3.0 to 1.1 Ω cm².     

Performance investigation of a combined MCFC system

This study investigates the performance of a combined industrial molten carbonate fuel cell (MCFC) system, including a turbo expander, which was recently installed by Enbridge Inc. in Toronto, Canada. It entails a comprehensive thermodynamic analysis regarding energy and exergy calculations, subject to varying operating conditions. Furthermore, a simplified and novel method is used for a cost analysis to assess the amortization of the system. The results from the base case study suggest that an overall energy efficiency as high as 60% is achievable while fuel cell stack energy and exergy efficiencies of 50.6% and 49.3%, respectively, are reached. The cost analysis indicates that the amortization of the system may take up to 15 years of operational time, depending on the price of electricity and natural gas. However, carbon offsets may make a paramount contribution to the overall savings and economic viability of future combined MCFC systems.     

The effect of Ni content on a highly active Ni-Al2O3 catalyst prepared by the homogeneous precipitation method

Highly active Ni-Al₂O₃ catalysts were prepared by the homogeneous precipitation method with a variety of high nickel contents ranging from 30 to 70 wt.%. The effects of nickel content on the physicochemical properties and catalytic activities of the Ni-Al₂O₃ catalysts were investigated. XRD measurements showed that the catalyst with 30 Ni wt.% only had a diffraction peak corresponding to NiAl₂O₄, whereas the catalysts of 50, 60 and 70 Ni wt.% had diffraction peaks corresponding to NiO and NiAl₂O₄. Hydrogen chemisorption results showed that the nickel surface area increased with increasing nickel content in the order: 30 < 40 < 50 < 60 < 70 Ni wt.%. Specifically, the nickel surface area increased steadily from 11 to 22 m²/g with increasing the nickel content from 30 to 50 wt.%, after which it stayed nearly constant at 22 m²/g despite the increase in nickel content from 50 to 70 wt.%. TEM images of the reduced Ni-Al₂O₃ catalysts revealed that the average sizes of the Ni particles were 12, 13 and 16 nm for the catalysts with 30, 50 and 70 Ni wt.%, respectively, suggesting that a higher nickel content yielded a larger Ni particle. The catalytic performance of methane steam reforming showed that the catalytic reaction rate increased steadily with increasing nickel content from 30 to 50 wt.%, after which it stayed nearly constant despite that the nickel content increased to over 50 wt.%. As a result, about 50 wt.% of nickel was found to be a reasonable nickel content to obtain the maximum catalytic activity.     

Degradation mechanism of molten carbonate fuel cell based on long-term performance: Long-term operation by using bench-scale cell and post-test analysis of the cell

In order to introduce molten carbonate fuel cells (MCFCs) in commercial applications, the target lifetime of a MCFC has been set at 40,000 h. We have carried out long-term operation tests on several bench-scale MCFCs, which include a 66,000-h continuous operation, and clarified the question of voltage degradation in relation to operating time. We have also carried out post-test analyses on the long-term operated cell components including the electrodes, the electrolyte matrix and the current collectors. The results of the long-term operation and the post-test analyses are described in this paper. The degradation mechanisms of voltage and components are discussed.     

Performance analysis of new cathode materials for molten carbonate fuel cells

The slow dissolution of the lithiated nickel oxide cathode represents one of the main causes of performance degradation in molten carbonate fuel cells (MCFC). Two main approaches were studied in ENEA laboratories to overcome this problem: protecting the nickel cathode covering it by a thin layer of a material with a low solubility in molten carbonate and stabilizing the nickel cathode doping it with iron and magnesium.Among several materials, due to its low solubility and good conductivity, lithium cobaltite was chosen to cover the nickel cathode and slow down its dissolution. A nickel electrode covered with a thin layer of lithium cobaltite doped with magnesium, was fabricated by complex sol-gel process. To simplify electrode preparation, no thermal treatments were made after covering to produce lithium cobaltite, and during the cell start-up LiMg_0.05Co_0.95O₂ was obtained in situ.To stabilize the nickel cathode, metal oxides Fe₂O₃ and MgO were chosen as dopant additives to be mixed with NiO powder in a tape-casting process (Mg_0.05Fe_0.01Ni_0.94O).On the prepared materials TGA analysis, morphological analysis by scanning electron microscopy (SEM-EDS) and electrical conductivity measurements were carried out.A conventional nickel cathode, the nickel cathode covered by lithium cobaltite precursors and the nickel cathode stabilized by iron and magnesium oxides were each tested in a 100 cm² fuel cell.Polarization curves and internal resistance (iR) measurements were acquired during the cell lifetime (1000 h) and the effect of gas composition variation on the cell performance was studied.From a comparison with the conventional nickel cathode it can be observed that the new materials have similar performance and show a good potential stability during the cell operating time. From the post-test analysis both the nickel cathode covered by lithium cobaltite and the nickel cathode doped with iron and magnesium seem to succeed in reducing nickel dissolution.     

Study of PEM fuel cell performance by electrochemical impedance spectroscopy

Electrochemical impedance spectroscopy is a suitable and powerful diagnostic testing method for fuel cells because it is non-destructive and provides useful information about fuel cell performance and its components. This paper presents the diagnostic testing results of a 120 W single cell and a 480 W PEM fuel cell short stack by electrochemical impedance spectroscopy. The effects of clamping torque, non-uniform assembly pressure and operating temperature on the single cell impedance spectrum were studied. Optimal clamping torque of the single cell was determined by inspection of variations of high frequency and mass transport resistances with the clamping torque. The results of the electrochemical impedance analysis show that the non-uniform assembly pressure can deteriorate the fuel cell performance by increasing the ohmic resistance and the mass transport limitation. Break-in procedure of the short stack was monitored and it is indicated that the ohmic resistance as well as the charge transfer resistance decrease to specified values as the break-in process proceeds. The effect of output current on the impedance plots of the short stack was also investigated.     

The impact of air contaminants on PEMFC performance and durability

The impact of air contaminants such as sulfur compounds (SO₂, H₂S) and nitrogen compounds (NO_x and NH₃) was investigated using subscale fuel cells. The severity of the effect of these impurities varies depending on the contaminants. Among air contaminants, sulfur compounds cause the most severe performance loss due to decrease of available Pt sites for oxygen reduction reaction (ORR). We found that sulfur compounds adsorbed on Pt surface tend to be oxidized to sulfate at 0.9 V and higher potentials. The cell performance can be recovered partially by excursions to high potentials due to increase of available Pt sites. Furthermore, flushing the cathode with high humidity gases results in almost complete recovery of the cell performance. We conclude that these recovery effects are due to oxidation/removal of the contaminants from the Pt surface.     

Effect of equivalent and non-equivalent Al substitutions on the structure and electrochemical properties of LiNi0.5Mn0.5O2

Pristine, equivalently and non-equivalently Al substituted LiNi_0.5Mn_0.5O₂ materials were prepared by a combination of co-precipitation and solid-state reaction. As shown by XRD and XPS, lattice volume shrinkage of LiNi_0.5(Mn_0.45Al_0.05)O₂ was attributed to the presence of Ni in both 2+ and 3+, while the lattice volume expansion of Li(Ni_0.45Al_0.05)Mn_0.5O₂ was caused by lowering the average oxidation state of Mn. Electrochemical performance of LiNi_0.5Mn_0.5O₂ materials can be greatly affected by the change of oxidation states of the transition metals by Al substitution. Non-equivalent substitution of Al for Ni leads to deteriorated discharge performance and cyclic stability due to the reduction of the electrochemical active Ni²⁺ and structure supported Mn⁴⁺, while an increase in the amount of Ni²⁺ in LiNi_0.5(Mn_0.45Al_0.05)O₂ brings obvious improvement of the electrochemical properties. EIS analyses of the electrode materials at pristine and charged states indicate that the poor electrochemical performance of Li(Ni_0.45Al_0.05)Mn_0.5O₂ material can be ascribed to the higher charge transfer resistance and surface film resistance, and the observed higher current rate capability of LiNi_0.5(Mn_0.45Al_0.05)O₂ can be understood due to the better charge transfer kinetics.     

Mechanical strength improvement of aluminum foam-reinforced matrix for molten carbonate fuel cells

During the cell operation of molten carbonate fuel cells (MCFCs), matrix cracks caused by poor mechanical strength accelerate cell performance degradation. Therefore, for a stable long-term cell operation, the improvement of mechanical properties of matrix is highly required. In this study, aluminum foam was used to enhance the mechanical strength of the matrix as a 3D (three dimensional) support structure. Unlikely conventional matrix (pure α-LiAlO₂ matrix) which has paste-like structure at the MCFC operating temperature, Al foam-reinforced α-LiAlO₂ matrix has significantly strong mechanical strength because the 3D network structure of Al foam can form the harden alumina skin layer during a cell operation. As a result, the mechanical strength of the Al foam-reinforced α-LiAlO₂ matrix was enhanced by 9 times higher than the pure α-LiAlO₂ matrix in a 3-point bending test. In addition, thermal cycle test showed notable cell stability due to strong mechanical strength of Al foam-reinforced α-LiAlO₂ matrix. The Al foam-reinforced α-LiAlO₂ matrix shows appropriate microstructure to preserve the liquid electrolyte when performing the mercury porosimeter analysis and differential pressure test between anode and cathode. Moreover, evaluation of stability and durability for a long-term cell operation were demonstrated by single cell test for 1,000 h.     

Electrochemical impedance study of the poisoning behaviour of Ni-based anodes at low concentrations of H2S in an MCFC

The effect was investigated of low H₂S concentrations, simulating biogas impurity, on the poisoning behaviour of a Ni-based, molten carbonate fuel cell anode. A conventional Ni–Cr anode was coated with ceria using dip coating to form a rare earth metal oxide thin layer on the surface of the anode. Electrochemical studies of the Ni-based samples were performed in symmetric cells under anode atmosphere (H₂, CO₂, H₂O and N₂ as balance) with 2, 6, 12, and 24 ppm of H₂S by means of electrochemical impedance spectroscopy.     

The effect of ambient contamination on PEMFC performance

The effect of environmental contamination (NO_x, SO₂) on the performance of proton exchange membrane fuel cells (PEMFC) was studied. The performance of PEMFCs was tested for 100 h with different cathode reactants. According to the Ambient Air Quality Standard of PRC, three kinds of cathode gases were applied to operate the fuel cells, which were 1 ppm NO₂/air, 1 ppm SO₂/air and a mixture of contaminant gases. The gas mixture contained 0.8 ppm NO₂, 0.2 ppm NO and 1 ppm SO₂. Finally, the poisoning behavior and the mechanisms were analyzed by constant-current discharging and cycle voltammetry (CV). During the 100 h test, the potentials of the fuel cell degraded by 65%, 77% and 90% with 1 ppm SO₂/air, a gas mixture and 1 ppm NO₂/air, respectively.     

Effects of temperature and humidity on the cell performance and resistance of a phosphoric acid doped polybenzimidazole fuel cell

Performance and electrochemical impedance spectroscopy (EIS) tests were performed at different temperatures and humidity levels to understand the effects of temperature and humidity on the performance and resistance of a PBI/H₃PO₄ fuel cell.The results of the performance tests indicated that increasing the temperature significantly improved the cell performance. In contrast, no improvement was observed when the gas humidity was increased. On the other hand, the EIS results showed that the membrane resistance was reduced for elevated temperatures. This development can be interpreted by the increase in membrane conductivity, as reflected by the Arrhenius equation. As the formation of H₄P₂O₇ and the self-dehydration of H₃PO₄ start around 130-140 °C, in PBI, they increase the membrane resistance at temperatures that are higher than 130 °C. In addition, the membrane resistance was reduced for elevated gas humidity levels. This is because an increase in humidity leads to an increase of the membrane hydration level.The resistance of the catalyst kinetics mainly contributes to the charge transfer resistance. However, under certain conditions, the interfacial charge transfer resistance is also important. It was concluded that the gas diffusion is the main contributor to the mass transfer resistance under dry conditions while it is the gas concentration under humid conditions.