Fast design of catalyst layer with optimal electrical-thermal-water performance for proton exchange membrane fuel cells

The catalyst layer(CL)is the core component in determining the electrical-thermal-water performance and cost of proton exchange membrane fuel cell(PEMFC).Systemic analysis and rapid prediction tools are required to improve the design efficiency of CL.In this study,a 3D multi-phase model integrated with the multi-level agglomerate model for CL is developed to describe the heat and mass transfer processes inside PEMFC.Moreover,a research framework combining the response surface method(RSM)and artificial neural network(ANN)model is proposed to conduct a quantitative analysis,and further a rapid and accurate prediction.With the help of this research framework,the effects of CL composition on the electrical-thermal-water performance of PEMFC are investigated.The results show that the mass of platinum,the mass of carbon,and the volume fraction of dry ionomer has a significant impact on the electrical-thermal-water performance.At the selected points,the sensitivity of the decision variables is ranked:volume fraction of dry ionomer>mass of platinum>mass of carbon>agglomerate radius.In particular,the sensitivity of the volume fraction of dry ionomer is over 50%at these points.Besides,the comparison results show that the ANN model could implement a more rapid and accurate prediction than the RSM model based on the same sample set.This in-depth study is beneficial to provide feasible guidance for high-performance CL design.

Development and Challenges of Electrode Ionomers Used in the Catalyst Layer of Proton-Exchange Membrane Fuel Cells:A Review

The electrode ionomer plays a crucial role in the catalyst layer(CL) of a proton-exchange membrane fuel cell(PEMFC) and is closely associated with the proton conduction and gas transport properties,structural stability,and water management capability.In this review,we discuss the CL structural characteristics and highlight the latest advancements in ionomer material research.Additionally,we comprehensively introduce the design concepts and exceptional performances of porous electrode ionomers,elaborate on their structural properties and functions within the fuel cell CL,and investigate their effect on the CL microstructure and performance.Finally,we present a prospective evaluation of the developments in the electrode ionomer for fabricating CL,offering valuable insights for designing and synthesizing more efficient electrode ionomer materials.By addressing these facets,this review contributes to a comprehensive understanding of the role and potential of electrode ionomers for enhancing PEMFC performance.

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）.

High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer

Reducing a Pt loading with improved power output and durability is essential to promote the large-scale application of proton exchange membrane fuel cells(PEMFCs).To achieve this goal,constructing optimized structure of catalyst layers with efficient mass transportation channels plays a vital role.Herein,PEMFCs with order-structured cathodic electrodes were fabricated by depositing Pt nanoparticles by Ebeam onto vertically aligned carbon nanotubes(VACNTs)growth on Al foil via plasma-enhanced chemical vapor deposition.Results demonstrate that the proportion of hydrophilic Pt-deposited region along VACNTs and residual hydrophobic region of VANCTs without Pt strongly influences the cell performance,in particular at high current densities.When Pt nanoparticles deposit on the top depth of around 600 nm on VACNTs with a length of 4.6μm,the cell shows the highest performance,compared with others with various lengths of VACNTs.It delivers a maximum power output of 1.61 W cm^(-2)(H_(2)/O_(2),150 k Pa)and 0.79 W cm^(-2)(H_(2)/Air,150 k Pa)at Pt loading of 50μg cm^(-2),exceeding most of previously reported PEMFCs with Pt loading of<100μg cm^(-2).Even though the Pt loading is down to 30μg cm^(-2)(1.36 W cm^(-2)),the performance is also better than 100μg cm^(-2)(1.24 W cm^(-2))of commercial Pt/C,and presents better stability.This excellent performance is critical attributed to the ordered hydrophobic region providing sufficient mass passages to facilitate the fast water drainage at high current densities.This work gives a new understanding for oxygen reduction reaction occurred in VACNTs-based ordered electrodes,demonstrating the most possibility to achieve a substantial reduction in Pt loading<100μg cm^(-2) without sacrificing in performance.

Patterned catalyst layer boosts the performance of proton exchange membrane fuel cells by optimizing water management

Mass transport is crucial to the performance of proton exchange membrane fuel cells,especially at high current densities.Generally,the oxygen and the generated water share same transmission medium but move towards opposite direction,which leads to serious mass transfer problems.Herein,a series of patterned catalyst layer were prepared with a simple one-step impressing method using nylon sieves as templates.With grooves 100μm in width and 8μm in depth on the surface of cathode catalyst layer,the maximum power density of fuel cell increases by 10%without any additional durability loss while maintaining a similar electrochemical surface area.The concentration contours calculated by finite element analysis reveal that the grooves built on the surface of catalyst layer serve to accumulate the water nearby while oxygen tends to transfer through relatively convex region,which results from capillary pressure difference caused by the pore structure difference between the two regions.The separation of oxidant gas and generated water avoids mass confliction thus boosts mass transport efficiency.

Revealing the concentration of hydrogen peroxide in fuel cell catalyst layers by an in‐operando approach

To evaluate the H_(2)O_(2)‐tolerance of non‐Pt oxygen reduction reaction(ORR)catalysts as well as in‐vestigate the H_(2)O_(2)‐induced decay mechanism,the selection of an appropriate H_(2)O_(2) concentration is a prerequisite.However,the concentration criterion is still unclear because of the lack of in‐operando methods to determine the actual concentration of H_(2)O_(2) in fuel cell catalyst layers.In this work,an electrochemical probe method was successfully established to in‐operando monitor the H_(2)O_(2) in non‐Pt catalyst layers for the first time.The local concentration of H_(2)O_(2) was revealed to reach 17 mmol/L,which is one order of magnitude higher than that under aqueous electrodes test conditions.Powered by the new knowledge,a concentration criterion of at least 17 mmol/L is suggested.This work fills in the large gap between aqueous electrode tests and the real fuel cell working conditions,and highlights the importance of in‐operando monitoring methods.

Progress on Platinum-Based Catalyst Layer Materials for H_(2)-PEMFC

The constant increase in energy demand and related environmental issues have made fuel cells an attractive technology as an alternative to conventional energy technologies.Like any technology,fuel cells face drawbacks that scientific society has been focused on to improve and optimize the overall technology.Thus,the cost is the main inhibitor for this technology due to the significantly high cost of the materials used in catalyst layers.The current discussion mainly focuses on the fundamental electrochemical half-cell reaction of hydrogen oxidation reaction(HOR)and oxygen reduction reaction(ORR)that are taking place in the catalyst layers consisting of Platinum-based and Platinum-non noble metals.For this purpose,studies from the literature are presented and analyzed by highlighting and comparing the variations on the catalytic activity within the experimental catalyst layers and the conventional ones.Furthermore,an economic analysis of the main platinum group metals(PGMs)such as Platinum,Palladium and Ruthenium is introduced by presenting the economic trends for the last decade.

Nanostructured ultrathin catalyst layer with ordered platinum nanotube arrays for polymer electrolyte membrane fuel cells

Fabrication of novel electrode architectures with nanostructured ultrathin catalyst layers is an effective strategy to improve catalyst utilization and enhance mass transport for polymer electrolyte membrane fuel cells (PEMFCs).Herein,we report the design and construction of a nanostructured ultrathin catalyst layer with ordered Pt nanotube arrays,which were obtained by a hard-template strategy based on ZnO,via hydrothermal synthesis and magnetron sputtering for PEMFC application.Because of the crystallographically preferential growth of Pt (111) facets,which was attributed to the structural effects of ZnO nanoarrays on the Pt nanotubes,the catalyst layers exhibit obviously higher electrochemical activity with remarkable enhancement of specific activity and mass transport compared with the state-of-the-art randomly distributed Pt/C catalyst layer.The PEMFC fabricated with the as-prepared catalyst layer composed of optimized Pt nanotubes with an average diameter of 90(±10) nm shows excellent performance with a peak power density of 6.0W/mgPt at 1 A/cm^2,which is 11.6%greater than that of the conventional Pt/C electrode.

Structure,Property,and Performance of Catalyst Layers in Proton Exchange Membrane Fuel Cells

Catalyst layer(CL)is the core component of proton exchange membrane(PEM)fuel cells,which determines the performance,durability,and cost.However,difficulties remain for a thorough understanding of the CLs’inhomogeneous structure,and its impact on the physicochemical and electrochemical properties,operating performance,and durability.The inhomogeneous structure of the CLs is formed during the manufacturing process,which is sensitive to the associated materials,composi-tion,fabrication methods,procedures,and conditions.The state-of-the-art visualization and characterization techniques are crucial to examine the CL structure.The structure-dependent physicochemical and electrochemical properties are then thoroughly scrutinized in terms of fundamental concepts,theories,and recent progress in advanced experimental techniques.The relation between the CL structure and the associated effective properties is also examined based on experimental and theoretical findings.Recent studies indicated that the CL inhomogeneous structure also strongly affects the performance and degradation of the whole fuel cell,and thus,the interconnection between the fuel cell performance,failure modes,and CL structure is comprehensively reviewed.An analytical model is established to understand the effect of the CL structure on the effective properties,performance,and durability of the PEM fuel cells.Finally,the challenges and prospects of the CL structure-associated studies are highlighted for the development of high-performing PEM fuel cells.

Functional ceramic support as an independent catalyst layer for direct liquid fuel solid oxide fuel cells

A porous ceramic support is designed as a multi-functional independent catalyst layer for solid oxide fuel cells(SOFCs)running on liquid hydrocarbon fuel.The layer consists of a highly porous Ce_(0.9)Ca_(0.1)O_(2−δ)ceramic backbone and active NiMo catalysts,which could be integrated into the conventional Ni metal containing the anode for internal reforming of the hydrocarbon fuel.Compared to conventional catalyst layers sintered on the anodes,this independent catalyst layer could be simply assembled on top of the anode without additional sintering,thereby avoiding the mismatch of the thermal expansion coefficient between the catalyst layer and the anode and improving stability of a single cell.Moreover,a current collector layer could be inserted between the catalyst and the anode to enhance current collection efficiency and electrochemical performance of the single cell.At 750℃,the independent catalyst layer displays high activity towards the catalytic decomposition of methanol,and the single cell could achieve the maximum power density of 400–500 mW·cm^(−2)in dry methanol.Furthermore,by employing the independent catalyst layer,the single cell offers additional in-situ catalyst regeneration capability under the methanol operation mode.Feeding 10 mL·min−1 air into an anode channel for 5 min is found to be effective to burn out carbon species in the catalyst layer,which reduces the degradation rate of the cell voltage by orders of magnitude from 2.6 to 0.024 mV·h−1 during the operation of 360 h in dry methanol.The results demonstrate the significance of the independent catalyst layer design for direct internal reforming methanol fuel cells.

The effect of catalyst layer design on catalyst utilization in PEMFC studied via stochastic reconstruction method

Catalyst utilization is an important determinant of proton exchange membrane fuel cell performance,and increasing the catalyst utilization is one of the most critical approaches to reducing the catalyst loading in PEMFC.4-phase stochastic reconstruction method based on the variable-resolution Quartet Structure Generation Set(QSGS)algorithm is utilized to elucidate the influence of different parameters of electrode preparation,including the porosity,the dispersion degree of carbon agglomerate,ionomer content,and carbon support size,on the catalyst utilization in the catalyst layer.It was found that there exist optimal values for the porosity,dispersion degree of carbon agglomerate,ionomer content,and carbon support sizes in CLs and any deviations from these optimal values would lead to transport issues of electron,proton and mass within CLs.Taking electron,proton and mass transport into consideration simultaneously,the optimal Pt utilization is 46.55%among 48 cases in this investigation,taken at the carbon support diameter of 40 nm,the porosity of 0.4,the agglomerate spatial density of 25μm^(−3) and I/C at 0.7.The selection of porosity,ultrasonic dispersion technique and ionomer content for conventional electrode preparation requires compromises on mass,electron and proton transport,leading to catalyst utilization in CLs hardly exceeding 50%.Therefore,the next generation of catalyst layer design and preparation technology is desired.

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.

Experimental and numerical efforts to improve oxygen mass transport in porous catalyst layer of proton exchange membrane fuel cells

The effective management of oxygen transport resistance(OTR)within the cathode catalyst layer(CCL)is crucial for achieving a high catalyst performance at low platinum(Pt)loading.Over the past two decades,significant advancements have been made in the development of various high active platinum-based catalysts,aiming at enhancing oxygen mass transport and the oxygen reduction reaction(ORR).However,experimental investigations of transport processes in porous media are often computational costs and restrained by limitations in in-situ measurement capabilities,as well as spatial and temporal resolution.Fortunately,numerical simulation provides a valuable alternative for unveiling the intricate relationship between local transport properties and overall cell performance that remain unresolved or uncoupled through experimental approach.In this review,we elucidate the primary experimental and numerical efforts undertaken to improve OTR.We consolidate the available literature on OTR values and perform a quantitative comparison of the effectiveness of different strategies in mitigating OTR.Furthermore,we analyze the intrinsic limitations and challenges associated with current experimental and numerical methods.Finally,we outline future prospect for advancements in both experimental techniques and modelling methods.

Nano-Morphology of a Polymer Electrolyte Fuel Cell Catalyst Layer Imaging, Reconstruction and Analysis

The oxygen reduction reaction （ORR） in the cathode catalyst layer （CCL） of polymer electrolyte fuel cells （PEFC） is one of the major causes of performance loss during operation. In addition, the CCL is the most expensive component due to the use of a Pt catalyst. Apart from the ORR itself, the species transport to and from the reactive sites determines the performance of the PEFC. The effective transport properties of the species in the CCL depend on its nanostructure. Therefore a three-dimensional reconstruction of the CCL is required. A series of two-dimensional images was obtained from focused ion beam- scanning electron microscope （FIB-SEM） imaging and a segmentation method for the two-dimensional images has been developed. The pore size distribution （PSD） was calculated for the three-dimensional geometry. The influence of the alignment and the anisotropic pixel size on the PSD has been investigated. Pores were found in the range between 5 nm and 205 nm. Evaluation of the Knudsen number showed that gas transport in the CCL is governed by the transition flow regime. The liquid water transport can be described within continuum hydrodynamics by including suitable slip flow boundary conditions.

Modeling nanostructured catalyst layer in PEMFC and catalyst utilization

A lattice model of the nanoscaled catalyst layer structure in proton exchange membrane fuel cells(PEMFC)was established by Monte Carlo method.The model takes into account all the four components in a typical PEMFC catalyst layer:platinum(Pt),carbon,ionomer and pore.The elemental voxels in the lattice were setfine enough so that each average sized Pt particulate in Pt/C catalyst can be represented.Catalyst utilization in the modeled catalyst layer was calculated by counting up the number of facets of Pt voxels where“three phase contact”are met.The effects of some factors,including porosity,ionomer content,Pt/C particle size and Pt weight percentage in the Pt/C catalyst,on catalyst utilization were investigated and discussed.

Improved performance of direct methanol fuel cells with the porous catalyst layer using highly-active nanofiber catalyst

PtRu supported on TiO2-embedded carbon nanofibers(PtRu/TECNF),which was recently reported as a highly-active catalyst for methanol oxidation,was applied to a direct methanol fuel cell(DMFC),and the power generation performance was compared to that using the commercial PtRu/C.Before the comparison,the effect of the catalyst loading on the power density of the DMFC was investigated using PtRu(18 wt%)/TECNF.The DMFC power density showed a maximum at about a 1.5 mg cm
2 PtRu loading that corresponds to about an 80 mm layer thickness.A catalyst layer thicker than this value reduced the power density probably due to the concentration overvoltage.The PtRu content in the PtRu/TECNF was then increased to 30 wt%or more to reduce the layer thickness and to increase the power density.The DMFC performance was compared to that of different anode catalysts at a 1 mg cm
2 PtRu loading.The power density was maximized using the PtRu30 wt%/TECNF,which showed a 173 mW cm
2 at 353 K and had 66 mm layer thick,that was 26%higher than that of commercial PtRu/C.The current–voltage curve of the DMFC with the PtRu/TECNF suggested an improved mass transport overvoltage,but a little improvement in the activation one despite using the catalyst with about a 2 times higher activity compared to that of the commercial PtRu/C.This was attributed to the lower Pt utilization of the nanofiber catalyst layer.

Monte Carlo simulation of the PEMFC catalyst layer

The performance of the polymer electrolyte membrane fuel cell(PEMFC)is greatly controlled by the structure of the catalyst layer.Low catalyst utilization is still a significant obstacle to the commercialization of the PEMFC.In order to get a fundamental understanding of the electrode structure and to find the limiting factor in the low catalyst utilization,it is necessary to develop the mechanical model on the effect of catalyst layer structure on the catalyst utilization and the performance of the PEMFC.In this work,the structure of the catalyst layer is studied based on the lattice model with the Monte Carlo simulation.The model can predict the effects of some catalyst layer components,such as Pt/C catalyst,electrolyte and gas pores,on the utiliza-tion of the catalyst and the cell performance.The simulation result shows that the aggregation of conduction grains can greatly affect the degree of catalyst utilization.The better the dispersion of the conduction grains,the larger the total effective area of the catalyst is.To achieve higher utilization,catalyst layer components must be distributed by means of engineered design,which can prevent aggregation.

Using an ILU/Deflation Preconditioner for Simulation of a PEMFuel Cell Cathode Catalyst Layer

Numerical aspects of a pore scale model are investigated for the simulation of catalyst layers of polymer electrolyte membrane fuel cells.Coupled heat,mass and charged species transport together with reaction kinetics are taken into account using parallelized finite volume simulations for a range of nanostructured,computationally reconstructed catalyst layer samples.The effectiveness of implementing deflation as a second stage preconditioner generally improves convergence and results in better convergence behavior than more sophisticated first stage pre-conditioners.This behavior is attributed to the fact that the two stage preconditioner updates the preconditioning matrix at every GMRES restart,reducing the stalling effects that are commonly observed in restarted GMRES when a single stage preconditioner is used.In addition,the effectiveness of the deflation preconditioner is independent of the number of processors,whereas the localized block ILU preconditioner deteriorates in quality as the number of processors is increased.The total number of GMRES search directions required for convergence varies considerably depending on the preconditioner,but also depends on the catalyst layer microstructure,with low porosity microstructures requiring a smaller number of iterations.The improved model and numerical solution strategy should allow simulations for larger computational domains and improve the reliability of the predicted transport parameters.The preconditioning strategies presented in the paper are scalable and should prove effective for massively parallel simulations of other problems involving nonlinear equations.

MgFe hydrotalcites-derived layered structure iron molybdenum sulfide catalysts for eugenol hydrodeoxygenation to produce phenolic chemicals

Hydrodeoxygenation（HDO） is an effective alternative to produce value-added chemicals and liquid fuels by removing oxygen from lignin-derived compounds. Sulfide catalysts have been proved to have good activity for the HDO and particularly high selectivity to phenolic products. Herein, we presented a novel way to prepare the layered structure sulfide catalysts（MgFeMo-S） derived from MgFe hydrotalcites via the intercalation of Mo in consideration of the memory effect of the calcined hydrotalcite. By varying the Mg/Fe mole ratio, a series of MgFeMo-S catalysts were successfully prepared and characterized by nitrogen adsorption/desorption isotherms, X-ray diffraction（XRD）, transmission electron microscopy（TEM）,and inductively coupled plasma optical emission spectrometer（ICP-OES）. The characterization results indicated that the MgFeMo-S catalyst has retained the unique layered structure, which can facilitate uniform dispersion of the MoS2 species on both the surface and interlayer of the catalysts. For the HDO of eugenol, the Mg1Fe2Mo-S catalysts exhibited the best HDO activity among all the catalysts due to its higher active metal contents and larger pore size. The HDO conversion was 99.6% and the yield of phenolics was 63.7%, under 5 MPa initial H2 pressure（measured at RT） at 300 ℃ for 3 h. More importantly,MoS2 species deposited on the interlayer galleries in the MgFeMo-S catalysts resulted in dramatically superior HDO activity to MoS2/Mg1Fe2-S catalyst. Based on the mechanism investigation for eugenol, the HDO reaction route of eugenol under sulfide catalytic system has been proposed for the first time. Further applicability of the catalyst on HDO of more lignin-derived compounds was operated, which showed good HDO activity and selectivity to produce aromatic products.

双极膜水解离性能改进研究进展

双极膜因其独特的水解离性能、易与其他电化学技术集成等优势,在碳捕获、节能减排和资源综合利用等领域具有重要的应用。现有双极膜存在水解离效率低、选择渗透性和稳定性差等问题,严重制约其广泛应用,因此近年来,大量研究工作致力于提升双极膜水解离性能。本文从离子交换层性能优化、中间层催化剂及几何结构调控三方面,梳理了国内外双极膜水解离性能改进及优化策略,重点评述了水解离催化剂、膜结构调控规律等方面的研究进展,并对该领域面临的主要挑战和未来发展方向进行展望,以期为高水解离性能双极膜的开发提供借鉴,从而促进其在能源转化和资源再利用等领域的应用。