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.

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.

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 components of PEMFC-membrane-electrode assembly (MEA) and seek feasible measures to avoid degradation. The effect of freeze/thaw 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 freeze/thaw 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 performance under subzero temperature and gas purging is proved to be the effective operation.

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

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.

Numerical Analysis of Temperature Distributions in Single Cell of Polymer Electrolyte Fuel Cell when Operated in Elevated Temperature Range

Abstract： The purpose of this study is to analyze the temperature distribution on the interface between the polymer electrolyte membrane and catalyst layer at the cathode in single cell of polymer electrolyte fuel cell when operated in elevated temperature range than usual. In this study, the interface between the polymer electrolyte membrane and catalyst layer at the cathode is named as reaction surface. This study has considered the 1D multi-plate heat transfer model estimating the temperature distribution on the reaction surface and verified with the 3D numerical simulation model solving many governing equations on the coupling phenomena of the polymer electrolyte fuel cell. The 3D numerical simulation model coverers a half size of actual cell including three straight parts and two turn-back corners, which can display the essential phenomena of single cell. The results from both models/simulations agreed well. The effects of initial operation temperature, flow rate, and relative humidity of supply gas on temperature distribution on the reaction surface have been investigated. Though the effect of flow rate of supply gas on temperature distribution on reaction surface has been small, low relative humidity of supply gas has caused higher temperature on the reaction surface compared to high relative humidity of the supply gas. The temperature rise of reaction surface from initial operation temperature has increased with the increasing in initial operation temperature of cell.

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.

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.

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.

Atomic layer deposition of ultrathin layered TiO_2 on Pt/C cathode catalyst for extended durability in polymer electrolyte fuel cells

This study shows the preparation of a TiO2 coated Pt/C（TiO2/Pt/C） by atomic layer deposition（ALD）,and the examination of the possibility for TiO2/Pt/C to be used as a durable cathode catalyst in polymer electrolyte fuel cells（PEFCs）. Cyclic voltammetry results revealed that TiO2/Pt/C catalyst which has 2 nm protective layer showed similar activity for the oxygen reduction reaction compared to Pt/C catalysts and they also had good durability. TiO2/Pt/C prepared by 10 ALD cycles degraded 70% after 2000 Accelerated degradation test, while Pt/C corroded 92% in the same conditions. TiO2 ultrathin layer by ALD is able to achieve a good balance between the durability and activity, leading to TiO2/Pt/C as a promising cathode catalyst for PEFCs. The mechanism of the TiO2 protective layer used to prevent the degradation of Pt/C is discussed.

Temperature Distributions in Single Cell of Polymer Electrolyte Fuel Cell Simulated by an 1D Multi-plate Heat-Transfer Model and a 3D Numerical Simulation Model

The purpose of this study is to verify an 1D multi-plate heat-transfer model estimating the temperature distribution on the interface between polymer electrolyte membrane and catalyst layer at cathode in single cell of polymer electrolyte fuel cell, which is named as reaction surface in this study, with a 3D numerical simulation model solving many governing equations on the coupling phenomena in the cell. The results from both models/simulations agreed well. The effects of initial operation temperature, flow rate, and relative humidity of supply gas on temperature distribution on the reaction surface were also investigated. It was found in both 1D and 3D simulations that, the temperature rise （i.e., Treact-Tini） of the reaction surface from initial operation temperature at 70℃ was higher than that at 80℃ irrespective of flow rate of supply gas. The effect of relative humidity of supply gas on Treact- Tini near the inlet of the cell was small. Compared to the previous studies conducted under the similar operation conditions, the Treact - Tini calculated by 1D multi-plate heat-transfer model in this study as well as numerical simulation using 3D model was reasonable.

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.

Fuel cell performance assessment for closed-loop renewable energy systems

Fuel cells and electrolysis are promising candidates for future energy production from renewable energy sources. Usually, polymer electrolyte fuel cell systems run on hydrogen and air, while the most of electrolysis systems vent out oxygen as unused by-product. Replacing air with pure oxygen, fuel cell electrochemical performance, durability and system efficiency can be significantly increased with a further overall system simplification and increased reliability. This work, which represents the initial step for pure H;/O;polymer electrolyte fuel cell operation in closed-loop systems, focuses on performance validation of a single cell operating with pure H;/O;under different relative humidity（RH） levels, reactants stoichiometry conditions and temperature. As a result of this study, the most convenient and appropriate operative conditions for a polymer electrolyte fuel cell stack integrated in a closed loop system were selected.

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.

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.

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.

Energy Characteristics of an Integrated Power Generation System with Photovoltaic and Fuel Cell

An integrated energy system (with photovoltaic (PV) and fuel cell (FC) for building) is proposed and assessed in term of its energy self-sufficiency rate in seven cities (Nagoya, Toyota, Tajimi, Takayama, Ogaki, Hamamatsu, Shizuoka) in Tokai region in Japan in this paper. In this work, it is considered that the electricity requirement of the building for household users is provided by a building integrated photovoltaic (BIPV) system and the gap between the energy demand and BIPV supply is fulfilled by the FC. The FC is powered by the electrolytic H2 produced when PV power was in surplus. Based on the study of applying the proposed system in seven cities, which clarifies the effectiveness of the integrated BIPV, electrolytic H2 and FC power generation system, a universal system model has been developed in this paper. It has been observed that the monthly power production from BIPV as well as FC system are higher in spring and summer, while they are both lower in autumn and winter at all considered locations. The self-sufficiency rate of the FC system is higher with decreasing households’ number and it has been observed that 16 is the most appropriate number of households in a building, whose electricity demand could be fully covered by the integrated PV and FC system. Due to its climate condition, Hamamatsu is the best city in the region for installing the proposed system. The correlation between the households’ number and self-sufficiency rate of the FC system per solar PV installation area can be expressed by the regression curve in the form of y = ax-b well.

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.

介孔碳载体缓解碱性聚电解质燃料电池阳极水淹

碱性聚电解质燃料电池(APEFCs)相较于目前研究最多的质子交换膜燃料电池(PEMFCs),其优势体现在阴/阳两极均可使用价格低廉的非贵金属催化剂,有望降低燃料电池的使用成本.APEFCs的研究在过去20年飞速发展,主要集中在高效碱性聚电解质(APE)隔膜和阴/阳极催化剂等关键材料的研发.目前,APEFCs的性能已接近于PEMFCs,针对其研究也逐渐从关键材料的研发扩展到电池的稳定性和水管理等更深层次问题.相较于PEMFCs,APEFCs的水管理问题更为复杂.每当阳极产生4个水分子,阴极会消耗2个水分子,容易导致阴极缺水和阳极水淹,进而影响电池的性能和稳定性.对APEFCs水管理的优化将是实现电池性能和稳定性突破的重要方向.本文主要研究碳载体对APEFCs水管理的影响,合成了一系列介孔碳负载的Ru催化剂(Ru/MCP-x,x为MCP的孔径,x=30,50,100 nm),并以Ru/XC72催化剂为对照.扫描电镜和N2吸附-脱附结果表明,介孔碳载体具有三维贯通的孔结构,而XC72为实心碳颗粒.溶液电化学测试结果表明,不同催化剂在0.1 mol/L的KOH溶液中的氢氧化反应(HOR)活性相当.以Ru/MCP-x和Ru/XC72为阳极催化剂进行电池装配(记为Ru/MCP-x电池和Ru/XC72电池),结果表明,当使用高进气流量(1000 mL/min)时,Ru/MCP-x电池和Ru/XC72电池性能接近;当使用更接近实际工况的低进气流量(200 mL/min)时,所有电池性能均有所下降,且降幅存在明显差距.其中,Ru/MCP-50电池和Ru/MCP-100电池的降幅分别为36%和35%,而Ru/MCP-30电池和Ru/XC72电池的降幅分别为43%和72%.通过在低进气流量下改变进气湿度,结果发现,Ru/MCP-30电池和Ru/XC72电池性能大幅下降的原因是阳极发生水淹.弛豫时间分布(DRT)方法可以将不同弛豫时间的极化过程在时域中分离开来,从而可以分辨各极化过程对电池性能的影响.利用电化学交流阻抗(EIS)技术结合DRT方法进一步分析各电池在不同电流密度下的阻抗行为,DRT结果表明,在低进气流量下Ru/XC72电池的传质极化电阻显著高于Ru/MCP-x电池,说明阳极水淹导致了Ru/XC72电池的气体传质受阻,因而电池性能大幅下降.当MCP孔径增加至50和100 nm时,传质极化电阻在不同电流密度下始终处于较低水平,电池未发生明显水淹.这说明孔径的增加有效地缓解了低进气流量下阳极的水淹问题,从而保持较高的电池性能.综上,本文利用EIS-DRT方法比较了不同阳极碳载体对APEFCs性能和气体传质极化电阻的影响,表明介孔碳载体有利于缓解APEFCs中的阳极水淹问题,具有作为阳极载体的潜力.