High temperature polymer electrolyte membrane fuel cell

One of the majorissuesli mitingtheintroduction of polymer electrolyte membranefuel cells(PEMFCs) is thelowtemperature ofoperation which makes platinum-based anode catalysts susceptible to poisoning by the trace amount of CO,inevitably present in reformedfuel.In order to alleviate the problemof COpoisoning andi mprove the power density of the cell,operating at temperature above 100 ℃ispreferred.Nafion-type perfluorosulfonated polymers have been typically used for PEMFC.However,the conductivity of Nafion-typepolymers is not high enoughto be usedfor fuel cell operations at higher temperature(>90 ℃) and atmospheric pressure because they dehy-drate under these condition.An additional problem which faces the introduction of PEMFCtechnology is that of supplying or storing hydrogen for cell operation,especially for vehicular applications.Consequently the use of alternative fuels such as methanol and ethanol is of interest,especially if thiscan be used directlyinthe fuel cell,without reformationto hydrogen.Ali mitation of the direct use of alcohol is thelower activity of oxida-tionin comparison to hydrogen,which means that power densities are considerably lower.Hence to i mprove activity and power outputhigher temperatures of operation are preferable.To achieve this goal,requires a newpolymer electrolyte membrane which exhibits stabilityand high conductivityin the absence of liquid water.Experi mental data on a polybenzi midazole based PEMFC were presented.Asi mple steady-stateisothermal model of the fuel cell is alsoused to aidin fuel cell performance opti misation.The governing equations involve the coupling of kinetic,ohmic and mass transport.Thispaper also considers the advances madeinthe performance of direct methanol and solid polymer electrolyte fuel cells and considers theirli mi-tations in relation to the source and type of fuels to be used.

Water-induced electrode poisoning and the mitigation strategy for high temperature polymer electrolyte membrane fuel cells

Engineering failure of membrane electrode assembly caused by increasingly fuel poisoning in the high temperature polymer electrolyte membrane fuel cells fed with humidified reformate gases is firstly demonstrated herein this work. Based on the results of the in-situ environmental scanning electron microscope, electrochemical analyses, and limiting current method, a water-induced phosphoric acid invasion model is constructed in the porous electrode to elucidate the failure causations of the hindered hydrogen mass transport and the enhanced carbon monoxide poisoning. To optimize the phosphoric acid distribution under the inevitably humidified circumstance, a facile and effective strategy of constructing acid-proofed electrode is proposed and demonstrates outstanding stability with highly humidified reformate gases as anode fuel. This work discusses a potential defect that was rarely studied previously under practical working circumstance for high temperature polymer electrolyte membrane fuel cells, providing an alternative opinion of electrode design based on the fundamental aspects towards the engineering problems.

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.

High-performance and robust high-temperature polymer electrolyte membranes with moderate microphase separation by implementation of terphenyl-based polymers

Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.

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.

Sulfonated polybenzimidazole/amine functionalized titanium dioxide(s PBI/AFT) composite electrolyte membranes for high temperature proton exchange membrane fuel cells usage

The novel sulfonated polybenzimidazole(sPBI)/amine functionalized titanium dioxide(AFT) composite membrane is devised and studied for its capability of the application of high temperature proton exchange membrane fuel cells(HT-PEMFCs),unlike the prior low temperature AFT endeavors.The high temperature compatibility was actualized because of the filling of free volumes in the rigid aromatic matrix of the composite with AFT nanoparticles which inhibited segmental motions of the chains and improved its thermal stability.Besides,amine functionalization of TiO2 enhanced their dispersion character in the sPBI matrix and shortened the interparticle separation gap which finally improved the proton transfer after establishing interconnected pathways and breeding more phosphoric acid(PA) doping.In addition,the appeared assembled clusters of AFT flourished a superior mechanical stability.Thus,the optimized sPBI/AFT(10 wt%) showed 65.3 MPa tensile strength;0.084 S·cm^-1 proton conductivity(at 160℃;in anhydrous conditions),28.6% water uptake and PA doping level of 23 mol per sPBI repeat unit.The maximum power density peak for sPBI/AFT-10 met the figure of0.42 W·cm^-2 at 160℃(in dry conditions) under atmospheric pressure with 1.5 and 2.5 stoichiometric flow rates of H2/air.These results affirmed the probable fitting of sPBI/AFT composite for HT-PEMFC applications.

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.

Polymer Electrolyte Membrane Fuel Cells (PEMFC) in Automotive Applications: Environmental Relevance of the Manufacturing Stage

This study presents a state of the art of several studies dealing with the environmental impact assessment of fuel cell (FC) vehicles and the comparison with their conventional fossil-fuelled counterparts, by means of the Life Cycle As-sessment (LCA) methodology. Results declare that, depending on the systems characteristics, there are numerous envi-ronmental advantages, but also some disadvantages can be expected. In addition, the significance of the manufac-turing process of the FC, more specifically the Polymer Electrolyte Membrane Fuel Cell (PEMFC) type, in terms of environmental impact is presented. Finally, CIEMAT’s role in HYCHAIN European project, consisting of supporting early adopters for hydrogen FCs in the transport sector, is

Effects of Freeze/Thaw Cycles and Gas Purging Method on Polymer Electrolyte Membrane Fuel Cells

At subzero temperature, the startup capability and performance of polymer electrolyte membrane fuel cell PEMFC deteriorates markedly. The object of this work is to study the degradation mechanism of key compo- nents of PEMFC—membrane-electrode assembly MEA and seek feasible measures to avoid degradation. The ef- fect of freezethaw cycles on the structure of MEA is investigated based on porosity and SEM measurement. The performance of a single cell was also tested before and after repetitious freezethaw cycles. The experimental results indicated that the performance of a PEMFC decreased along with the total operating time as well as the pore size distribution shifting and micro configuration changing. However, when the redundant water had been removed by gas purging, the performance of the PEMFC stack was almost resumed when it experienced again the same subzero temperature test. These results show that it is necessary to remove the water in PEMFCs to maintain stable per- formance under subzero temperature and gas purging is proved to be the effective operation.

Impact of Separator Thickness on Temperature Distribution in Single Polymer Electrolyte Fuel Cell Based on 1D Heat Transfer

It is known from the New Energy and Industry Technology Development Organization (NEDO) roam map Japan, 2017 that the polymer electrolyte fuel cell (PEFC) power generation system is required to operate at 100°C for application of mobility usage from 2020 to 2025. This study aims to clarify the effect of separator thickness on the distribution of the temperature of reaction surface (Treact) at the initial temperature of cell (Tini) with flow rate, relative humidity (RH) of supply gases as well as RH of air surrounding cell of PEFC. The distribution of Treact is estimated by means of the heat transfer model considering the H2O vapor transfer proposed by the authors. The relationship between the standard deviation of Treact-Tini and total voltage obtained in the experiment is also investigated. We can know the effect of the flow rate of supply gas as well as RH of air surrounding cell of PEFC on the distribution of Treact-Tini is not significant. It is observed the wider distribution of Treact-Tini provides the reduction in power generation performance irrespective of separator thickness. In the case of separator thickness of 1.0 mm, the standard deviation of Treact-Tini has smaller distribution range and the total voltage shows a larger variation compared to the other cases.

Performance Investigation of Membrane Electrode Assemblies for High Temperature Proton Exchange Membrane Fuel Cell

Different types of ABPBI (poly(2,5-benzimidazole)) membranes and polymer binders were evaluated to investigate the performance of MEAs for high temperature proton exchange membrane fuel cell (HT-PEMFC). The properties of the prepared MEAs were evaluated and analyzed by polarization curve, electrochemistry impedance spectroscopy (EIS), cyclic voltammetry (CV) and durability test. The results showed that MEA with modified ABPBI membrane (AM) has satisfactory performance and durability for fuel cell application. Compare to conventional PBI or Nafion binders, polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF) are more attractive as binders in the catalyst layer (CL) of gas diffusion electrode (GDE) for HT-PEMFC.

Modeling of Packed Bed Methanol Steam Reformer Integrated with Tubular High Temperature Proton Exchange Membrane Fuel Cell

This work proposes a novel tubular structure of high-temperature proton exchange membrane fuel cell(PEMFC)integrated with a built-in packed-bed methanol steam reformer to provide hydrogen for power output.A two-dimensional axisymmetric non-isothermal model was developed in COMSOL Multiphysics 5.4 to simulate the performance of a tubular high temperature proton membrane fuel cell and a packed bed methanol reformer.The model considers the coupling multi-physical processes,including methanol reforming reaction,water gas shift reaction,methanol cracking reaction as well as the heat,mass and momentum transport processes.The sub-model of the tubular packed-bed methanol reformer is validated between 433 K and 493 K with the experimental data reported in the literature.The sub-model of the high temperature proton exchange fuel cell is validated between 393 K and 433 K with the published literature.Our results show that power output and temperature distribution of the integrated unit depend on methanol flow rates and working voltages.It was suggested that stable power generation performance of 0.14 W/cm_(2)and temperature drop in methanol steam reformer of≤10 K could be achieved by controlling the methanol space-time ratio of≥250 kg·s/mol with working voltage at 0.6 V,even in the absence of an external heat source.

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.

Synthesis and Characterization of Photosensitive Poly(imide sulfonates) for Fuel Cell Application

The novel sulfonated polyimide membranes were successfully synthesized by thermal imidization with monomers of 4,4＇-（hexafluoroisopropylidene）diphthalic anhydride （6FDA）, 4,4＇-diamino- diphenyl ether-2,2＇-disulfonic acid （SODA） and 3,3 ＇-diaminochalcone （3DAC）. Photosensitive chalcone moiety was introduced to the main chain of copolymers, and the photocrosslinking of resulting copolymer in aqueous electrolyte was attempted. A series of sulfonated copolyimide precursors containing chalcone functional groups in the main chain were prepared with different sulfonation degrees by controlling the molar ratio of SODA, 6FDA and 3DAC. The polymer membranes were prepared from these sulfonated aromatic precursors by solution casting and subsequent thermal imidization. The crosslinking with UV irradiation was attempted in the presence or absence of distilled water. The characterizations of the resulting membrane such as the ion-exchange capacity, water absorption and ionic conductivity were performed with respect to the copolymer compositions and the photocrosslinking conditions.

Estimation of equivalent internal-resistance of PEM fuel cell using artificial neural networks

A practical method of estimation for the internal-resistance of polymer electrolyte membrane fuel cell (PEMFC) stack was adopted based on radial basis function (RBF) neural networks. In the training process, k-means clustering algorithm was applied to select the network centers of the input training data. Furthermore, an equivalent electrical-circuit model with this internal-resistance was developed for investigation on the stack. Finally using the neural networks model of the equivalent resistance in the PEMFC stack, the simulation results of the estimation of equivalent internal-resistance of PEMFC were presented. The results show that this electrical PEMFC model is effective and is suitable for the study of control scheme, fault detection and the engineering analysis of electrical circuits.

Graphene-based bipolar plates for polymer electrolyte membrane fuel cells

Bipolar plates(BPs)are a major component of polymer electrolyte membrane fuel cells(PEMFCs).BPs play a multifunctional character within a PEMFC stack.It is one of the most costly and critical part of the fuel cell,and hence the development of efficient and cost-effective BPs is of much interest for the fabrication of next-generation PEMFCs in future.Owing to high electrical conductivity and chemical inertness,graphene is an ideal candidate to be utilized in BPs.This paper reviews recent advances in the area of graphene-based BPs for PEMFC applications.Various aspects including the momentous functions of BPs in the PEMFC,favorable features of graphene.based BPs,performance evaluation of various reported BPs with their advantages and disadvantages,challenges at commercial level products and future prospects of frontier research in this direction are extensively documented.

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.

Fabrication of Pt deposited on carbon nanotubes and performance of its polymer electrolyte membrane fuel cells

A new method of depositing nano-sized Pt particles on the surface of the carbon nano-tubes was introduced, and the performance of Pt/carbon nanotube compound on polymer electrolyte membrane fuel cells was measured. The experimental results show that the fine platinum particles (about 3 nm) were well dispersed on carbon nanotubes, which demonstrates the excellent catalytic properties of the Pt/CNTs compound in polymer electrolyte membrane fuel cells.

Water Transport Analysis in Polymer Electrolyte Membrane Fuel Cells by Magnetic Resonance Imaging

1 Results Polymer electrolyte fuel cells (PEFCs) have beenintensively developedfor future vehicle applications andon-site power generation owing to its high energy efficiency and high power density.In PEFCs ,appropriatewater management to maintain polymer electrolyte membrane (PEM) hydratedis of great i mportance ,becausethe ion conductivity of membraneislower at lower water content .Consequently,it is of great interest to watercontent and water transport process in PEMs during fuel cell operation.