Multi-objective optimization of the cathode catalyst layer micro-composition of polymer electrolyte membrane fuel cells using a multi-scale,two-phase fuel cell model and data-driven surrogates

Polymer electrolyte membrane fuel cells(PEMFCs)are considered a promising alternative to internal combustion engines in the automotive sector.Their commercialization is mainly hindered due to the cost and effectiveness of using platinum(Pt)in them.The cathode catalyst layer(CL)is considered a core component in PEMFCs,and its composition often considerably affects the cell performance(V_(cell))also PEMFC fabrication and production(C_(stack))costs.In this study,a data-driven multi-objective optimization analysis is conducted to effectively evaluate the effects of various cathode CL compositions on Vcelland Cstack.Four essential cathode CL parameters,i.e.,platinum loading(L_(Pt)),weight ratio of ionomer to carbon(wt_(I/C)),weight ratio of Pt to carbon(wt_(Pt/c)),and porosity of cathode CL(ε_(cCL)),are considered as the design variables.The simulation results of a three-dimensional,multi-scale,two-phase comprehensive PEMFC model are used to train and test two famous surrogates:multi-layer perceptron(MLP)and response surface analysis(RSA).Their accuracies are verified using root mean square error and adjusted R^(2).MLP which outperforms RSA in terms of prediction capability is then linked to a multi-objective non-dominated sorting genetic algorithmⅡ.Compared to a typical PEMFC stack,the results of the optimal study show that the single-cell voltage,Vcellis improved by 28 m V for the same stack price and the stack cost evaluated through the U.S department of energy cost model is reduced by$5.86/k W for the same stack performance.

Recent developments in electrocatalysts and future prospects for oxygen reduction reaction in polymer electrolyte membrane fuel cells

The main difficulty in the extensive commercial use of polymer electrolyte membrane fuel cells （PEMFCs） is the use of noble metals such as Pt-based electrocatalyst at the cathode, which is essential to ease the oxygen reduction reaction （ORR） in fuel cells （FCs）. To eliminate the high loading of Pt-based electrocatalysts to minimize the cost, extensive study has been carried out over the previous decades on the non-noble metal catalysts. Development in enhancing the ORR performance of FCs is mainly due to the doped carbon materials, Fe and Co-based electrocatalysts, these materials could be considered as probable substitutes for Pt-based catalysts. But the stability of these non-noble metal electrocatalysts is low and the durability of these metals remains unclear. The three basic reasons of instability are： （i） oxidative occurrence by H2O2, （ii） leakage of the metal site and （iii） protonation by probable anion adsorption of the active site. Whereas leakage of the metal site has been almost solved, more work is required to understand and avoid losses from oxidative attack and protonation. The ORR performance such as stability tests are usually run at low current densities and the lifetime is much shorter than desired need. Therefore, improvement in the ORR activity and stability afe the key issues of the non-noble metal electrocatalyst. Based on the consequences obtained in this area, numerous future research directions are projected and discussed in this paper. Hence, this review is focused on improvement of stability and durability of the non-noble metal electrocatalyst.

Phosphorus induced activity-enhancement of Fe-N-C catalysts for high temperature polymer electrolyte membrane fuel cells

Fe-N-C materials with atomically dispersed Fe–N_(4) sites could tolerate the poisoning of phosphate,is regarded as the most promising alternative to costly Pt-based catalysts for the oxygen reduction in high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs).However,they still face the critical issue of insufficient activity in phosphoric acid.Herein,we demonstrate a P-doping strategy to increase the activity of Fe-N-C catalyst via a feasible one-pot method.X-ray absorption spectroscopy and electron microscopy with atomic resolution indicated that the P atom is bonded with the N in Fe–N_(4) site through C atoms.The as prepared Fe-NCP catalyst shows a half-wave potential of 0.75 V(vs.reversible hydrogen electrode(RHE),0.1 M H_(3)PO_(4)),which is 60 and 40 mV higher than that of Fe-NC and commercial Pt/C catalysts,respectively.More importantly,the Fe-NCP catalyst could deliver a peak power density of 357 mW·cm^(−2)in a high temperature fuel cell(160℃),exceeding the non-noble-metal catalysts ever reported.The enhancement of activity is attributed to the increasing charge density and poisoning tolerance of Fe–N_(4) caused by neighboring P.This work not only promotes the practical application of Fe-N-C materials in HT-PEMFCs,but also provides a feasible P-doping method for regulating the structure of single atom site.

Water spatial distribution in polymer electrolyte membrane fuel cell: Convolutional neural network analysis of neutron radiography

Polymer electrolyte membrane(PEM)fuel cells produce water as byproduct,which may cause electrode“flooding”and reduce cell performance.In operation,water usually builds up downstream in the gas flow channel due to the water production by the oxygen reduction reaction(ORR),leading to a water spatial dis-tribution.In this study,a convolutional neural network(CNN)is presented to analyze neutron radiography images to obtain water spatial variation under various operating conditions.5 and 10 segments of a fuel cell are analyzed for spatial variations.Image pre-processing treatments are carried out to improve the convolutional neural network accuracy to 96.6%.The results show that liquid water emerges at a position around 55%downstream for 50%relative humidity while the entire cell is subject to two-phase flow for 100%relative hu-midity under a co-flow configuration.Large water content is present in most of the segments and the near-outlet segment for the counter-flow and co-flow configurations,respectively.In addition,the quad-serpentine cell exhibits more water accumulation than the single serpentine one in most downstream segments.The convolu-tional neural network results agree well with the data obtained from a pixelation image processing method with an accuracy of 91.8%.Compared with conventional pixelation methods,the convolutional neural network method performs better in speed for high-resolution images.It also shows that the current CNN tool fails to predict local water for small spatial scales,such as 10 segments,which leads to a large error(>27%)in prediction.

Single-atom Catalysts for Polymer Electrolyte Membrane Fuel Cells

Searching for high-activity,stabilily and highly casbellective electrocalalysts for acid oxygen reaction rolutioo(ORR)has always been a urgent problem in polymer ectrolyte menbrane fuel ells(PEMFC).Nonetheless,the electrochemical poperties of various systems have their intrinsic limits and tremendous eforts have been paid oul to search for highly eficient electocatalysts by more raional control over the size,morphology,compoition,and structure.In particular,single-atom catalysts(SACs)have atrascted extensive intenest due to theirs cxcellant activity,stability,slctivity and the highest metal tiliztion In rceat yeurs,the number of papers in the field of SACs has incressed rapidly,indicating that SACs have made great progress.This review foouses on SACs electo-echemical applications in the acid ORR and introduces immovative syntheses,fiuel cell performance and long-time durabilily.

A Review of physics-based and data-driven models for real-time control of polymer electrolyte membrane fuel cells

The real-time model-based control of polymer electrolyte membrane(PEM)fuel cells requires a computationally efficient and sufficiently accurate model to predict the transient and long-term performance under various operational conditions,involving the pressure,temperature,humidity,and stoichiometry ratio.In this article,recent progress on the development of PEM fuel cell models that can be used for real-time control is reviewed.The major operational principles of PEM fuel cells and the associated mathematical description of the transport and electrochemical phenomena are described.The reduced-dimensional physics-based models(pseudo-twodimensional,one-dimensional numerical and zero dimensional analytical models)and the non-physics-based models(zero-dimensional empirical and data-driven models)have been systematically examined,and the comparison of these models has been performed.It is found that the current trends for the real-time control models are(i)to couple the single cell model with balance of plants to investigate the system performance,(ii)to incorporate aging effects to enable long-term performance prediction,(iii)to increase the computational speed(especially for one-dimensional numerical models),and(iv)to develop data-driven models with artificial intelligence/machine learning algorithms.This review will be beneficial for the development of physics or nonphysics based models with sufficient accuracy and computational speed to ensure the real-time control of PEM fuel cells.

Multifunctional Ir–Ru alloy catalysts for reversal-tolerant anodes of polymer electrolyte membrane fuel cells

To address the problem of fuel starvation in fuel-cell electric vehicles,which causes cell voltage reversal and results in cell failure when repeated continuously,we developed a reversal-tolerant anode(RTA) to promote water oxidation in preference to carbon corrosion.Graphitized carbon-supported Ir-Ru alloys with different compositions are employed as RTA catalysts in an acidic polyol solution and are shown to exhibit composition-dependent average crystallite sizes of <5.33 nm.The adopted approach allows the generation of relatively well-dispersed Ir-Ru alloy nanoparticles on the carbon support without severe agglomeration.The activity of IrRu_(2)/C for the hydrogen oxidation reaction is 1.10 times that of the stateof-the-art Pt/C catalyst.Cell reversal testing by simulation of fuel starvation reveals that the durability of IrRu_(2)/C(~7 h) significantly exceeds that of the conventional Pt/C catalyst(~10 min) and is the highest value reported so far.Thus,the developed Ir-Ru alloy catalyst can be used to fabricate practical RTAs and replace Pt catalysts in the anodes of polymer electrolyte membrane fuel cells.

Anode Catalytic Dependency Behavior on Ionomer Content in Direct CO Polymer Electrolyte Membrane Fuel Cell

In this work,the effect of Nafion ionomer content on the structure and catalytic performance of direct CO polymer electrolyte membrane fuel cell(CO-PEMFC)by using Rh-N-C single-atom catalyst as the anode catalyst layers was studied.The ionic plaque and roughness of the anode catalyst layers increase with the increase of Nafion ionomer content.Furthermore,the contact angle measurement results show that the hydrophilicity of the anode catalyst layers also increases with the increase of Nafion ionomer content.However,when the Nafion ionomer content is too low,the binding between microporous layers,catalyst layers and membrane cannot meet the requirement for either electric conductivity or mass transfer.While Nafion ionomer content increased above 30%,the content of water in anode is difficult to control.Therefore,it was found that AN 30(30%Nafion ionomer content of anode)is the best level to effectively extend the three-phase boundary and improve CO-PEMFCs performance.

Towards intelligent and integrated architecture for hydrogen fuel cell system: challenges and approaches

The hydrogen fuel cell is rapidly attracting research interest for its potential in power generation and electrified transportation.The fuel cell stack(FCS)is a complex system comprising multiple coupled subsystems,and in order to maximize the utilization of an FCS,the system-level design and control can be optimized through modeling,data-based analytics and monitoring.To this end,a systematic overview of the system architecture and control of hydrogen fuel cells is provided in this review,with focus on integration and intelligence.Firstly,the fuel cell subsystems,namely the cathode,anode and cooling loops are reviewed,where their respective control methods and impact on FCS performance are discussed.DC/DC converters are another core component of FCS,and we present an overview of fuel cell DC/DC converter topologies and integrated control of DC/DC converter and air compressor.Finally,the system-level integration of fuel cells in power systems is surveyed.In the conclusions,we discuss the challenges and perspectives concerning the integrated architecture and intelligent control for FCS,including cohesive dynamic models,data-based approaches,and integrated hardware architecture.

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.

Two-step pyrolysis of ZIF-8 functionalized with ammonium ferric citrate for efficient oxygen reduction reaction

Zeolitic imidazolate frameworks（ZIFs） are widely employed in catalyst synthesis as parental materials for electrochemical energy storage and conversion. Herein, we have demonstrated a facile synthesis of highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic medium, which is derived from ZIF-8 functionalized with ammonium ferric citrate via two-step pyrolysis in Ar and NHatmosphere.The results reveal that the catalytic activity improvement after NH3 pyrolysis benefits from mesoporedominated morphology and high utilization of Fe-containing active sites. The optimum catalyst shows excellent performance in zinc-air battery and polymer electrolyte membrane fuel cell tests.

High-loading Pt-alloy catalysts for boosted oxygen reduction reaction performance

To improve performance of membrane electrode assembly(MEA)at large current density region,efficient mass transfer at the cathode is desired,for which a feasible strategy is to lower catalyst layer thickness by constructing high loading Pt-alloy catalysts on carbon.But the high loading may induce unwanted par-ticle aggregation.In this work,H-PtNi/C with 33%(mass)Pt loading on carbon and monodisperse distri-bution of 3.55 nm PtNi nanoparticles,was prepared by a bimodal-pore route.In electrocatalytic oxygen reduction reaction(ORR),H-PtNi/C displays an activity inferior to the low Pt loading catalyst L-PtNi/C(13.3%(mass))in the half-cell.While in H_(2)-0_(2) MEA,H-PtNi/C delivers the peak power density of 1.51 W·cm^(-2) and the mass transfer limiting current density of 4.4 A·cm^(-2),being 21%and 16%higher than those of L-PtNi/C(1.25 W·cm^(-2),3.8 A·cm^(-2))respectively,which can be ascribed to enhanced mass trans-fer brought by the thinner catalyst layer in the former.In addition,the same method can be used to pre-pare PtFe alloy catalyst with a high-Pt loading of 36%(mass).This work may lead to a range of catalyst materials for the large current density applications,such as fuel cell vehicles.

Accelerated life-time test of MEA durability under vehicle operating conditions in PEM fuel cell

In this paper, a novel accelerated test method was proposed to analyze the durability of MEA, considering the actual operation of the fuel cell vehicle. The proposed method includes 7 working conditions： open circuit voltage （OCV）, idling, rated output, overload, idling-rated cycle, idling-overload cycle, and OCV-idling cycle. The experimental results indicate that the proposed method can effectively destroy the MEA in a short time （165 h）. Moreover, the degradation mechanism of MEA was analyzed by measuring the polarization curve, CV, SEM and TEM. This paper may provide a new research direction for improving the durability of fuel cell.

Synthesis of dual-doped non-precious metal electrocatalysts and their electrocatalytic activity for oxygen reduction reaction

The pyrolyzed carbon supported ferrum polypyrrole （Fe-N/C） catalysts are synthesized with or without selected dopants, p-toluenesulfonic acid （TsOH）, by a facile thermal annealing approach at desired temperature for optimizing their activity for the oxygen reduction reaction （ORR） in O2-saturated 0.1 mol/L KOH solution. The electrochemical techniques such as cyclic voltammetry （CV） and rotating disk electrode （RDE） are employed with the Koutecky-Levich theory to quantitatively obtain the ORR kinetic constants and the reaction mechanisms. It is found that catalysts doped with TsOH show significantly improved ORR activity relative to the TsOH-free one. The average electron transfer numbers for the catalyzed ORR are determined to be 3.899 and 3.098, respectively, for the catalysts with and without TsOH-doping. The heat-treatment is found to be a necessary step for catalyst activity improvement, and the catalyst pyrolyzed at 600℃ gives the best ORR activity. An onset potential and the potential at the current density of -1.5 mA/cm2 for TsOH-doped catalyst after pyrolysis are 30 mV and 170 mV, which are more positive than those without pyrolized. Furthermore, the catalyst doped with TsOH shows higher tolerance to methanol compared with commercial Pt/C catalyst in 0.1 mol/L KOH. To understand this TsOH doping and pyrolyzed effect, X-ray diffraction （XRD）, scanning electron microscope （SEM） and X-ray photoelectron spectroscopy （XPS） are used to characterize these catalysts in terms of their structure and composition. XPS results indicate that the pyrrolic-N groups are the most active sites, a finding that is supported by the correspondence between changes in pyridinic-N content and ORR activity that occur with changing temperature. Sulfur species are also structurally bound to carbon in the forms of C-Sn-C, an additional beneficial factor for the ORR.

PtAu Bimetallic Heteronanostructures Made by Post-Synthesis Modification of Pt-on-Au Nanoparticles

Bimetallic PtAu heteronanostructures have been synthesized from Pt-on-Au nanoparticles,which were made from platinum acetylacetonate and gold nanoparticles.Using the Pt-on-Au nanoparticles as precursors,Pt-surface rich PtAu bimetallic heteronanostructures can be produced through controlled thermal treatments,as confirmed by field emission high-resolution transmission electron microscopy(HR-TEM)and elemental mapping using a high-angle annular dark-field scanning transmission electron microscope(HAADF-STEM).Oxidation of formic acid was used as a model reaction to demonstrate the effects of varying composition and surface structure on the catalytic performance of PtAu bimetallic nanostructures.Cyclic voltammetry(CV)showed that these carbon-supported PtAu heteronanostructures were much more active than platinum in catalyzing the oxidation of formic acid,judging by the mass current density.The results showed that post-synthesis modification can be a very useful approach to the control of composition distributions in alloy nanostructures.

Oxygen Electroreduction on CoSe2 Nanoparticles Prepared via Hydrothermal Method in Acidic Medium

CoSe2 nanoparticles were synthesized via a facile hydrothermal method, and characterized by means of X-ray diffraction（XRD）, scanning electron microscopy（SEM） and transmission electron microscopy（TEM）. The syn- thesized CoSe2 was composed of crystalline orthorhombic phase and displayed a morphology of short and thin nano- belts. The results of the catalyst experiment demonstrate that the CoSe2 nanocrystals show high catalytic activity and methanol tolerance in oxygen reduction reaction（OR_K） with an open circuit potential（OCP） of 0.80 V（vs. NHE） in 0.5 mol/L HzSO4 at 25 ℃. The transfer process of about 3.7 electrons per oxygen molecule was determined during the reduction process and the transfer coefficient and Tafel slope were 0.50 and 118 mV, respectively, in the potential region of 0.64-0.75 V（vs. NHE）. The high catalytic activity might be related to the high crystallization of the CoSe2 powder and the modification of selenium on the cobalt element.

Balancing the corrosion resistance and through-plane electrical conductivity of Cr coating via oxygen plasma treatment

Developing an electrically conductive and corrosion-resistant coating is essential for metal bipolar plates of polymer electrolyte membrane fuel cells(PEMFCs). Although enhanced corrosion resistance was seen for Cr coated stainless steel(Cr/SS) bipolar plates, they experience a quick decrease of through-plane electrical conductivity due to the formation of a porous and low-conductive corrosion product layer at the plate surface, thus leading to an increase in interfacial contact resistance(ICR). To tackle this issue, the multilayer Cr coatings were deposited using the magnetron sputtering with a remote inductively coupled oxygen plasma(O-ICP) in the present study. After the O-ICP treatment, a Cr oxide layer(Cr O*) is formed on the specimen surface. The Cr O*/Cr/SS has a remarkably lower stable corrosion rate(iss) than that of the native Cr oxides(Cr On/Cr/SS). Compared with Cr On/Cr/SS, the excellent performance of Cr O*/Cr/SS is attributed to a denser and thicker surface layer of Cr O* with Cr being oxidized to its highest valence state,Cr(VI). More importantly, the through-plane electrical conductivity of the specimens treated by the optimized O-ICP decreases much slowly than Cr On/Cr/SS and thus, the increament of ICR of Cr O*/Cr/SS after the potentiostatic polarization test is considerably smaller than that of Cr On/Cr/SS, which is benefited from the reduced issthat mitigates the deposition of corrosion products and hinders further oxidation of Cr coating. Therefore, Cr O*/Cr/SS proves to be a well balanced trade-off between corrosion resistance and through-plane electrical conductivity. The results of this study demonstrate that O-ICP treatment on a conductive metal coating is an effective strategy to improve the corrosion resistance and suppress the increase of ICR over the long-term polarization. The technique reported herein exhibits its promising potential application in preparing corrosion resistant and electrically conductive coatings on metal bipolar plates to be used in PEMFCs.