Daily Operation Optimization of a Residential Molten Carbonate Fuel Cell Power System Using Genetic Algorithm

To decrease the cost of electricity generation of a residential molten carbonate fuel cell （MCFC） power system, multi-crossover genetic algorithm （MCGA）, which is based on ＂multi-crossover＂ and ＂usefulness-based selection rule＂, is presented to minimize the daily fuel consumption of an experimental 10kW MCFC power system for residential application. Under the operating conditions obtained by MCGA, the operation constraints are satisfied and fuel consumption is minimized. Simulation and experimental results indicate that MCGA is efficient for the operation optimization of MCFC power systems.

Study and performance test of 10 kW molten carbonate fuel cell power generation system

The use of high-temperature fuel cells as a power technology can improve the efficiency of electricity generation and achieve near-zero emissions of carbon dioxide.This work explores the performance of a 10 kW high-temperature molten carbonate fuel cell.The key materials of a single cell were characterized and analyzed using X-ray diffraction and scanning electron microscopy.The results show that the pore size of the key electrode material is 6.5 lm and the matrix material is a-LiAlO_(2).Experimentally,the open circuit voltage of the single cell was found to be 1.23 V.The current density was greater than 100 mA/cm^(2)at an operating voltage of 0.7 V.The 10 kW fuel cell stack comprised 80 single fuel cells with a total area of 2000 cm^(2)and achieved an open circuit voltage of greater than 85 V.The fuel cell stack power and current density could reach 11.7 kW and 104.5 mA/cm2 at an operating voltage of 56 V.The influence and long-term stable operation of the stack were also analyzed and discussed.The successful operation of a 10 kW high-temperature fuel cell promotes the large-scale use of fuel cells and provides a research basis for future investigations of fuel cell capacity enhancement and distributed generation in China.

Advance on Molten Carbonate Fuel Cell and Research on Some Key Problems

The paper is a summary of researches on molten carbonate fuel cell. On the same time, several key technology difficulties are discussed. Combining with our recent studies, the accessements to these problems are given out and they will be references for future works.

Numerical Simulation of Dynamic Performance of the Molten Carbonate Fuel Cell

A three dimension of dynamic mathematical model of the molten carbonate fuel cell is established,in which the heat generation, mass transfer and electrochemical characteristics are described. The performance of the fuel cell including the distributions of the temperature and the velocity is predicted numerically. Then the experimental data including the output performance of the fuel cell generation system and the temperature distributions are compared. The numerical results are in agreement with the experiment results.

Development and Experimental Research of kW-scale Molten Carbonate Fuel Cells

A kW-scale molten carbonate fuel cells stack was developed and 800-hours’ operating test and performance experimental research had been done. Utilizing domestic materials completely, we developed NiO cathode and Ni-Al anode with the active area of 336cm 2 and Υ-LiAlO 2 electrolyte tile and bipolar plate with the area of 900cm 2. The stack was composed of thirty cells, with 62%Li 2CO 3+38%K 2CO 3 as its electrolyte. During the 800 hours’ continuous operating, the performance of the stack was stable. With 99.7%(mole fraction) H 2 as fuel and O 2 from air as oxidant, the average operating voltage of a cell was about 0.72 V. The maximal current density attained to 165mA/cm 2, and the maximal output power attained to 1080 Watt. The whole performance of the stack approached to the international level in the early 90’s. This paper gives the main works and experiments results.

Nonlinear modeling of molten carbonate fuel cell stack and FGA-based fuzzy control

To improve the performance of fuel cells, the operating temperature of molten carbonate fuel cell (MCFC) stack should be controlled within a specified range. In this paper, with the RBF neural network’s ability of identifying complex nonlinear systems, a neural network identification model of MCFC stack is developed based on the sampled input-output data. Also, a novel online fuzzy control procedure for the temperature of MCFC stack is developed based on the fuzzy genetic algorithm (FGA). Parameters and rules of the fuzzy controller are optimized. With the neural network identification model, simulation of MCFC stack control is carried out. Validity of the model and the superior performance of the fuzzy controller are demonstrated.

MICROSTRUCTURE CHARACTERIZATION OF LiCoO_2 COATINGS FOR MOLTEN CARBONATE FUEL CELLS COMPONENTS

The sol-gel process, sing aqueous solutions, is used for dip coating ontosubstrates of 316L stainless steel. A suitable coating of Li CoO_2 is achieved by varying thethickness and heat treating at 650 deg C for 3 h. Thermal analysis, X-ray diffraction analysis andSEM are carried out to characterize the microstructure of the coatings. The results show that thecoating transforms from an amorphous gel to crystalline phases above 350 deg C, and show a porousstructure. The phase transition mechanism is discussed.

Performance Evaluation of a Molten Carbonate Fuel Cell-Graphene Thermionic Converter-Thermally Regenerative Electrochemical Cycles Hybrid System

A combined system model is proposed including a molten carbonate fuel cell(MCFC),a graphene thermionic converter(GTIC)and thermally regenerative electrochemical cycles(TRECs).The expressions for power output,energy efficiency of the subsystems and the couple system are formulated by considering several irreversible losses.Energy conservation equations between the subsystems are achieved leaned on the first law of thermodynamics.The optimum operating ranges for the combined system are determined compared with the MCFC system.Results reveal that the peak power output density(POD)and the corresponding energy efficiency are 28.22%and 10.76%higher than that of the single MCFC system,respectively.The effects of five designing parameters on the power density and energy efficiency of the MCFC/GTIC/TRECs model are also investigated and discussed.

Hybrid Dynamic Modeling and Control of Molten Carbonate Fuel Cell Stack Shutdown

A hybrid automaton modeling approach that incorporates state space partitioning, phase dynamic modeling and control law synthesis by control strategy is utilized to develop a hybrid automaton model of molten carbonate fuel cell (MCFC) stack shutdown. The shutdown operation is divided into several phases and their boundaries are decided according to a control strategy, which is a set of specifications about the dynamics of MCFC stack during shutdown. According to the control strategy, the specification of increasing stack temperature is satisfied in a phase that can be modeled accurately. The model for phase that has complex dynamic is approximated. The duration of this kind of phase is decreased to minimize the error caused by model approximation.

Al^(3+) doped CeO_(2) for proton conducting fuel cells

Developing high ionic conducting electrolytes is crucial for applying proton-conducting fuel cell(PCFCs)practically.The cur-rent study investigates the effect of alumina on the structural,morphological,electrical,and electrochemical properties of CeO_(2).Lattice oxygen vacancies are induced in CeO_(2) by a general doping concept that enables fast ionic conduction at low-temperature ranges(300-500℃)for PCFCs.Rietveld refinement of the X-ray diffraction(XRD)patterns established the pure cubic fluorite structure of Al-doped CeO_(2)(ADC)samples and confirmed Al ions’fruitful integration in the CeO_(2) lattice.The electronic structure of the alumina-doped ceria of the materials(10ADC,20ADC,and 30ADC)has been investigated.As a result,it was found that the best composition of 30ADC-based electrolytes induced maximum lattice oxygen vacancies.The corresponding PCFC exhibited a maximum power output of 923 mW/cm^(2)at 500℃.Moreover,the investigation proves the proton-conducting ability of alumina-doped ceria-based fuel cells by using an oxide ion-blocking layer.

Probing the Efficiency of PPMG-Based Composite Electrolytes for Applications of Proton Exchange Membrane Fuel Cell

PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.

Recent progresses in the development of tubular segmented-in-series solid oxide fuel cells:Experimental and numerical study

Solid oxide fuel cells(SOFCs)have attracted a great deal of interest because they have the highest efficiency without using any noble metal as catalysts among all the fuel cell technologies.However,traditional SOFCs suffer from having a higher volume,current leakage,complex connections,and difficulty in gas sealing.To solve these problems,Rolls-Royce has fabricated a simple design by stacking cells in series on an insulating porous support,resulting in the tubular segmented-in-series solid oxide fuel cells(SIS-SOFCs),which achieved higher output voltage.This work systematically reviews recent advances in the structures,preparation methods,perform-ances,and stability of tubular SIS-SOFCs in experimental and numerical studies.Finally,the challenges and future development of tubular SIS-SOFCs are also discussed.The findings of this work can help guide the direction and inspire innovation of future development in this field.

From concept to commercialization:A review of tubular solid oxide fuel cell technology

The reduced sealing difficulty of tubular solid oxide fuel cells(SOFCs)makes the stacking of tubular cell groups relatively easy,and the thermal stress constraints during stack operation are smaller,which helps the stack to operate stably for a long time.The special design of tubular SOFC structures can completely solve the problem of high-temperature sealing,especially in the design of multiple single-cell series integrated into one tube,where each cell tube is equivalent to a small electric stack,with unique characteristics of high voltage and low current output,which can significantly reduce the ohmic polarization loss of tubular cells.This paper provides an overview of typical tubular SOFC structural designs both domestically and internationally.Based on the geometric structure of tubular SOFCs,they can be divided into bamboo tubes,bamboo flat tubes,single-section tubes,and single-section flat tube structures.Meanwhile,this article provides an overview of commonly used materials and preparation methods for tubular SOFCs,including commonly used materials and preparation methods for support and functional layers,as well as a comparison of commonly used preparation methods for microtubule SOFCs,It introduced the three most important parts of building a fuel cell stack:manifold,current collector,and ceramic adhesive,and also provided a detailed introduction to the power generation systems of different tubular SOFCs,Finally,the development prospects of tubular SOFCs were discussed.

Model reduction of fractional impedance spectra for time–frequency analysis of batteries, fuel cells, and supercapacitors

Joint time–frequency analysis is an emerging method for interpreting the underlying physics in fuel cells,batteries,and supercapacitors.To increase the reliability of time–frequency analysis,a theoretical correlation between frequency-domain stationary analysis and time-domain transient analysis is urgently required.The present work formularizes a thorough model reduction of fractional impedance spectra for electrochemical energy devices involving not only the model reduction from fractional-order models to integer-order models and from high-to low-order RC circuits but also insight into the evolution of the characteristic time constants during the whole reduction process.The following work has been carried out:(i)the model-reduction theory is addressed for typical Warburg elements and RC circuits based on the continued fraction expansion theory and the response error minimization technique,respectively;(ii)the order effect on the model reduction of typical Warburg elements is quantitatively evaluated by time–frequency analysis;(iii)the results of time–frequency analysis are confirmed to be useful to determine the reduction order in terms of the kinetic information needed to be captured;and(iv)the results of time–frequency analysis are validated for the model reduction of fractional impedance spectra for lithium-ion batteries,supercapacitors,and solid oxide fuel cells.In turn,the numerical validation has demonstrated the powerful function of the joint time–frequency analysis.The thorough model reduction of fractional impedance spectra addressed in the present work not only clarifies the relationship between time-domain transient analysis and frequency-domain stationary analysis but also enhances the reliability of the joint time–frequency analysis for electrochemical energy devices.

Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.

Critical role of carbon support in metal nanoaggregate facilitating Fe-N-C catalyst for PEM fuel cell application

Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct interaction between FeN_(4)active sites and metal nanoaggregates.However,the role of carbon support that hosts metal nanoaggregates and active sites has been overlooked.Here,a Fe-N-C catalyst encapsulating inactive gold nanoparticles is prepared as a model catalyst to investigate the electronic tuning of Au nanoparticles(NPs)towards the carbon support.Au NPs donate electrons to carbon support,making it rich inπelectrons,which reduces the work function and regulates the electronic configuration of the FeN_(4)sites for an enhanced ORR activity.Meanwhile,the electron-rich carbon support can mitigate the electron depletion of FeN_(4)sites caused by carbon support oxidation,thereby preserving its high activity.The yield and accumulation of H_(2)O_(2)are thus alleviated,which delays the oxidation of the catalyst and benefits the stability.Due to the electron-rich carbon support,the composite catalyst achieves a top-level peak power density of 0.74 W/cm^(2) in a 1.5 bar H_(2)-air PEMFC,as well as the improved stability.This work elucidates the key role of carbon support in the performance enhancement of the FeN-C/metal nanoaggregate composite catalysts for fuel cell application.

Enhancing layered perovskite ferrites with ultra-high-density nanoparticles via cobalt doping for ceramic fuel cell anode

Nanoparticles anchored on the perovskite surface have gained considerable attention for their wide-ranging applications in heterogeneous catalysis and energy conversion due to their robust and integrated structural configuration.Herein,we employ controlled Co doping to effectively enhance the nanoparticle exsolution process in layered perovskite ferrites materials.CoFe alloy nanoparticles with ultra-high-density are exsolved on the(PrBa)_(0.95)(Fe_(0.8)Co_(0.1)Nb_(0.1))2O_(5+δ)(PBFCN_(0.1))surface under reducing atmosphere,providing significant amounts of reaction sites and good durability for hydrocarbon catalysis.Under a reducing atmosphere,cobalt facilitates the reduction of iron cations within PBFCN_(0.1),leading to the formation of CoFe alloy nanoparticles.This formation is accompanied by a cation exchange process,wherein,with the increase in temperature,partial cobalt ions are substituted by iron.Meanwhile,Co doping significantly enhance the electrical conductivity due to the stronger covalency of the Cosingle bondO bond compared with Fesingle bondO bond.A single cell with the configuration of PBFCN_(0.1)-Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)|SDC|Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF)-SDC achieves an extremely low polarization resistance of 0.0163Ωcm^(2)and a high peak power density of 740 mW cm^(−2)at 800℃.The cell also shows stable operation for 120 h in H_(2)with a constant current density of 285 mA cm^(−2).Furthermore,employing wet C_(2)H_(6)as fuel,the cell demonstrates remarkable performance,achieving peak power densities of 455 mW cm^(−2)at 800℃and 320 mW cm^(−2)at 750℃,marking improvements of 36%and 70%over the cell with(PrBa)_(0.95)(Fe_(0.9)Nb_(0.1))_(2)O_(5+δ)(PBFN)-SDC at these respective temperatures.This discovery emphasizes how temperature influences alloy nanoparticles exsolution within doped layered perovskite ferrites materials,paving the way for the development of high-performance ceramic fuel cell anodes.

Recent progress on mechanisms,principles,and strategies for high-activity and high-stability non-PGM fuel cell catalyst design

The commercialization of a polymer membrane H2-O2 fuel cell and its widespread use call for the development of cost-effective oxygen reduction reaction(ORR)nonplatinum group metal(NPGM)catalysts.Nevertheless,to meet the requests for the real-world fuel cell application and replacing platinum catalysts,it still needs to address some challenges for NPGM catalysts regarding the sluggish ORR kinetics in the cathode and their poor durability in acidic environment.In response to these issues,numerous efforts have been made to study NPGM catalysts both theoretically and experimentally,developed these into the atomically dispersed coordinated metal-nitrogen-carbon(M-N-C)form over the past decades.In this review,we present a comprehensive summary of recent advancements on NPGM catalysts with high activity and durability.Catalyst design strategies in terms of optimizing active-site density and enhancing catalyst stability against demetalization and carbon corrosion are highlighted.It is also emphasized the importance of understanding the mechanisms and principles behind those strategies through a combination of theoretical modeling and experimental work.Especially,further understanding the mechanisms related to the active-site structure and the formation process of the single-atom active site under pyrolysis conditions is critical for active-site engineering.Optimizing the active-site distance is the basic principle for improving catalyst activity through increasing the catalyst active-site density.Theoretical studies for the catalyst deactivation mechanism and modeling stable active-site structures provide both mechanisms and principles to improve the NPGM catalyst durability.Finally,currently remained challenges and perspectives in the future on designing high-performance atomically dispersed NPGM catalysts toward fuel cell application are discussed.

Boost the Utilization of Dense FeN_(4) Sites for High-Performance Proton Exchange Membrane Fuel Cells

Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site density(SD)and site utilization.Herein,we reported a melamine-assisted vapor deposition approach to overcome these hindrances.The melamine not only compensates for the loss of nitrogen caused by high-temperature pyrolysis but also effectively etches the carbon substrate,increasing the external surface area and mesoporous porosity of the carbon substrate.These can provide more useful area for subsequent vapor deposition on active sites.The prepared 0.20Mela-FeNC catalyst shows a fourfold higher SD value and site utilization than the FeNC without the treatment of melamine.As a result,0.20Mela-FeNC catalyst exhibits a high ORR activity with a half-wave potential(E_(1/2))of 0.861 V and 12-fold higher ORR mass activity than the FeNC in acidic media.As the cathode in a H_(2)-O_(2)PEMFCs,0.20Mela-FeNC catalyst demonstrates a high peak power density of 1.30 W cm^(-2),outstripping most of the reported Fe-N-C catalysts.The developed melamine-assisted vapor deposition approach for boosting the SD and utilization of Fe-N-C catalysts offers a new insight into high-performance ORR electrocatalysts.