Ultrafine ordered L1_(2)-Pt-Co-Mn ternary intermetallic nanoparticles as high-performance oxygen-reduction electrocatalysts for practical fuel cells

The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.

Particle Swarm Optimization based predictive control of Proton Exchange Membrane Fuel Cell (PEMFC)

Proton Exchange Membrane Fuel Cells (PEMFCs) are the main focus of their current development as power sources because they are capable of higher power density and faster start-up than other fuel cells. The humidification system and output performance of PEMFC stack are briefly analyzed. Predictive control of PEMFC based on Support Vector Regression Machine (SVRM) is presented and the SVRM is constructed. The processing plant is modelled on SVRM and the predictive control law is obtained by using Particle Swarm Optimization (PSO). The simulation and the results showed that the SVRM and the PSO re-ceding optimization applied to the PEMFC predictive control yielded good performance.

Simulation of the Internal Transport Phenomena for PEM Fuel Cells with Different Modes of Flow

A numerical model for proton exchange membrane (PEM) fuel cell is developed, which can simulate such basic transport phenomena as gas-liquid two-phase flow in a working fuel cell. Boundary conditions for both the conventional and the interdigitated modes of flow are presented on a three-dimensional basis. Numerical techniques for this model are discussed in detail. Validation shows good agreement between simulating results and experimental data. Furthermore, internal transport phenomena are discussed and compared for PEM fuel cells with conventional and interdigitated flows. It is found that the dead-ended structure of an interdigitated flow does increase the oxygen mass fraction and decrease the liquid water saturation in the gas diffusion layer as compared to the conventional mode of flow. However, the cathode humidification is important for an interdigitated flow to acquire better performance than a conventional flow fuel cell.

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.

One-dimensional Dynamic Modeling and Simulation of a Planar Direct Internal Reforming Solid Oxide Fuel Cell

This article aims to investigate the transient behavior of a planar direct internal reforming solid oxide fuel cell （DIR-SOFC） comprehensively. A one-dimensional dynamic model of a planar D1R-SOFC is first developed based on mass and energy balances, and electrochemical principles. Further, a solution strategy is presented to solve the model, and the International Energy Agency （IEA） benchmark test is used to validate the model. Then, through model-based simulations, the steady-state performance of a co-flow planar DIR-SOFC under specified initial operating conditions and its dynamic response to introduced operating parameter disturbances are studied. The dynamic responses of important SOFC variables, such as cell temperature, current density, and cell voltage are all investigated when the SOFC is subjected to the step-changes in various operating parameters including both the load current and the inlet fuel and air flow rates. The results indicate that the rapid dynamics of the current density and the cell voltage are mainly influenced by the gas composition, particularly the H2 molar fraction in anode gas channels, while their slow dynamics are both dominated by the SOLID （including the PEN and interconnects） temperature. As the load current increases, the SOLID temperature and the maximum SOLID temperature gradient both increase, and thereby, the cell breakdown is apt to occur because of excessive thermal stresses. Changing the inlet fuel flow rate might lead to the change in the anode gas composition and the consequent change in the current density distribution and cell voltage. The inlet air flow rate has a great impact on the cell temperature distribution along the cell, and thus, is a suitable manipulated variable to control the cell temperature.

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.

Performance analysis and fuzzy neural networks modeling of direct methanol fuel cell

This paper introduces the effects of cell operating temperature, methanol concentration and airflow rate, respectively, on the performance of direct methanol fuel cell （DMFC）. A novel method based on fuzzy neural networks identification technique is proposed to establish the performance model of DMFC. Three dynamic performance models of DMFC under the influences of cell operating temperature, methanol concentration, and airflow rate are identified and established separately. Simulation results show that modeling using fuzzy neural networks identification is satisfactory with high accuracy. It is applicable to DMFC control systems.

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.

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.

Potential-dependent insights into the origin of high ammonia yield rate on copper surface via nitrate reduction:A computational and experimental study

Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.

New hybrid model of proton exchange membrane fuel cell

Model and simulation are good tools for design optimization of fuel cell systems. This paper proposes a new hybrid model of proton exchange membrane fuel cell (PEMFC). The hybrid model includes physical component and black-box com-ponent. The physical component represents the well-known part of PEMFC, while artificial neural network (ANN) component estimates the poorly known part of PEMFC. The ANN model can compensate the performance of the physical model. This hybrid model is implemented on Matlab/Simulink software. The hybrid model shows better accuracy than that of the physical model and ANN model. Simulation results suggest that the hybrid model can be used as a suitable and accurate model for PEMFC.

Numerical simulation of a direct internal reforming solid oxide fuel cell using computational fluid dynamics method

A detailed mathematical model of a direct internal reforming solid oxide fuel cell(DIR-SOFC) incorporating with simulation of chemical and physical processes in the fuel cell is presented. The model is developed based on the reforming and electrochemical reaction mechanisms,mass and energy conservation,and heat transfer. A computational fluid dynamics(CFD) method is used for solving the complicated multiple partial differential equations(PDEs) to obtain the numerical approximations. The resulting distributions of chemical species concentrations,temperature and current density in a cross-flow DIR-SOFC are given and analyzed in detail. Further,the influence between distributions of chemical species concentrations,temperature and current density during the simulation is illustrated and discussed. The heat and mass transfer,and the kinetics of reforming and electrochemical reactions have significant effects on the parameter distributions within the cell. The results show the particular characteristics of the DIR-SOFC among fuel cells,and can aid in stack design and control.

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.

A comprehensive review of the modeling of transport phenomenon in the flow channels of polymer electrolyte membrane fuel cells

Reactant gas and liquid water transport phenomena in the flow channels are complex and critical to the performance and durability of polymer electrolyte membrane fuel cells.The polymer membrane needs water at an optimum level for proton conductivity.Water management involves the prevention of dehydration,waterlogging,and the cell’s subsequent performance decline and degradation.This process requires the study and understanding of internal two-phase flows.Different experimental visualization techniques are used to study two-phase flows in polymer electrolyte membrane fuel cells.However,the experiments have limitations in in situ measurements;they are also expensive and time exhaustive.In contrast,numerical modeling is cheaper and faster,providing insights into the complex multiscale processes occurring across the components of the polymer electrolyte membrane fuel cells.This paper introduces the recent design of flow channels.It reviews the numerical modeling techniques adopted for the transport phenomena therein:the two-fluid,multiphase mixture,volume of fluid,lattice Boltzmann,and pressure drop models.Furthermore,this work describes,compares,and analyses the models’approaches and reviews the representative results of some selected aspects.Finally,the paper summarizes the modeling perspectives,emphasizing future directions with some recommendations.

MoS2-rGO hybrid architecture as durable support for cathode catalyst in proton exchange membrane fuel cells

Carbon black is utilized as a conventional electrocatalyst support material for proton exchange membrane fuel cells. However, this support is prone to corrosion under oxidative and harsh environments, thus limiting the durability of the fuel cells. Meanwhile, carbon corrosion would also weaken the linkage between Pt and the support material, which causes Pt agglomeration, and consequently, deterioration of the cell performance. To overcome the drawbacks of a Pt/C electrocatalyst, a hybrid support material comprising molybdenum disulfide and reduced graphene oxide is proposed and synthesized in this study to exploit the graphitic nature of graphene and the availability of the exposed edges of MoS2. TEM results show the uniform dispersion of Pt nanoparticles over the MoS2-rGO surface. Electrochemical measurements indicate higher ECSA retention and better ORR activity after 10000 potential cycles for Pt/MoS2-rGO as compared to Pt/C, demonstrating the improved durability for this hybrid support material.

In situ grown nanoscale platinum on carbon powder as catalyst layer in proton exchange membrane fuel cells(PEMFCs)

An extensive study has been conducted on the proton exchange membrane fuel cells （PEMFCs） with reducing Pt loading. This is commonly achieved by developing methods to increase the utilization of the platinum in the catalyst layer of the electrodes. In this paper, a novel process of the catalyst layers was introduced and investigated. A mixture of carbon powder and Nafion solution was sprayed on the glassy carbon electrode （GCE） to form a thin carbon layer. Then Pt particles were deposited on the surface by reducing hexachloroplatinic （IV） acid hexahydrate with methanoic acid. SEM images showed a continuous Pt gradient profile among the thickness direction of the catalytic layer by the novel method. The Pt nanowires grown are in the size of 3 nm （diameter） x l0 nm （length） by high solution TEM image. The novel catalyst layer was characterized by cyclic voltammetry （CV） and scanning electron microscope （SEM） as compared with commercial Pt/C black and Pt catalyst layer obtained from sputtering. The results showed that the platinum nanoparticles deposited on the carbon powder were highly utilized as they directly faced the gas diffusion layer and offered easy access to reactants （oxygen or hydrogen）.

Exploration of the oxygen transport behavior in non-precious metal catalyst-based cathode catalyst layer for proton exchange membrane fuel cells

High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells(PEMFCs),in which Pt-based catalysts employed in the cathodic catalyst layer(CCL)account for the major portion of the cost.Although nonprecious metal catalysts(NPMCs)show appreciable activity and stability in the oxygen reduction reaction(ORR),the performance of fuel cells based on NPMCs remains unsatisfactory compared to those using Pt-based CCL.Therefore,most studies on NPMC-based fuel cells focus on developing highly active catalysts rather than facilitating oxygen transport.In this work,the oxygen transport behavior in CCLs based on highly active Fe-N-C catalysts is comprehensively explored through the elaborate design of two types of membrane electrode structures,one containing low-Pt-based CCL and NPMCbased dummy catalyst layer(DCL)and the other containing only the NPMC-based CCL.Using Zn-N-C based DCLs of different thickness,the bulk oxygen transport resistance at the unit thickness in NPMC-based CCL was quantified via the limiting current method combined with linear fitting analysis.Then,the local and bulk resistances in NPMC-based CCLs were quantified via the limiting current method and scanning electron microscopy,respectively.Results show that the ratios of local and bulk oxygen transport resistances in NPMCbased CCL are 80%and 20%,respectively,and that an enhancement of local oxygen transport is critical to greatly improve the performance of NPMC-based PEMFCs.Furthermore,the activity of active sites per unit in NPMCbased CCLs was determined to be lower than that in the Pt-based CCL,thus explaining worse cell performance of NPMC-based membrane electrode assemblys(MEAs).It is believed that the development of NPMC-based PEMFCs should proceed not only through the design of catalysts with higher activity but also through the improvement of oxygen transport in the CCL.

Carbon matrix effects on the micro-structure and performance of Pt nanowire cathode prepared by decal transfer method

High performance cathode for polymer electrolyte membrane fuel cell was prepared by depositing Pt nanowires in a carbon matrix coated on a substrate, and using decal transfer method to fabricate the membrane electrode assembly. The effects of carbon and ionomer contents on the electrode micro-structure and fuel cell performance are investigated by physical characterization and single cell testing. The Pt nanowires are gradient distributed across the cathode thickness, and more Pt exists near the membrane. Both the carbon and ionomer contents can affect the Pt nanowires distribution and aggregation. In addition, the carbon loading dominates the transport distance of gas and proton, and the ionomer content affects the triple phase boundaries and porosity in the cathode. The optimal structure of Pt nanowire cathode is obtained at 0.10 mg·cm^-2 carbon loading and 10 wt% ionomer.

First-principles study of catalytic activity of W-doped cobalt phosphide toward the hydrogen evolution reaction

In this study,we investigated the hydrogen evolution reaction(HER)on the(101)facet of pristine and W-doped CoP using the density functional theory.Two types of Co atoms are identified on the catalyst surface:the Co atoms that present the higher d band center are marked as valid sites,whereas the others are marked as invalid sites owing to their weaker H adsorption ability.It is further revealed that W-doping can decrease the d band center of the surface Co atoms,which is beneficial for the HER;however the exposure to W weakens the desorption of H.To address the strong adsorption effect of W,the doping sites and dopant content are analyzed,and the results indicate that 8.4 wt%W doping at the invalid surface Co sites is preferred;moreover,the optimal W content increases to 16.8 wt%when W is inserted into the subsurface.The effect of W doping is weakened when the doping site is far away from the surface.