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.

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.

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.

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.

Theoretical On-Board Hydrogen Redox Electric Power Generator for Infinite Cruising Range Fuel Cell Vehicles

The development of hydrogen redox electric power generators for infinite cruising range electric vehicles represents a true technological breakthrough. Such systems consist of a polymer electrolyte membrane hydrogen electrolytic cell equipped with an electrostatic-induction potential-superposed water electrolytic cell that provides a stoichiometric H2-O2 fuel mixture during operation of the vehicle. This generator functions with zero power input, zero matter input and zero emission due to the so-called ＂zero power input＂ electrostatic-to-chemical energy conversion occurring in the electrolytic cell. Here, theoretical simulations were performed to verify the target performance of such generators, assuming a pair of FC （fuel cell） and electrolytic cell stacks, both of which are commercially available.

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.

Review of characterization and modeling of polymer electrolyte fuel cell catalyst layer： The blessing and curse of ionomer

Ionomer impregnation represents a milestone in the evolution of polymer electrolyte fuel cell （PEFC） catalyst layers. Ionomer acts as the binder, facilitates proton transport, and thereby drastically improves catalyst utilization and effectiveness. However, advanced morpho- logical and functional characterizations have revealed that up to 60% of Pt nanoparticles can be trapped in the micropores of carbon support particles. Ionomer clusters and oxygen molecules can hardly enter into micropores, leading to low Pt utilization and effectiveness. Moreover, the ionomer thin-films covering Pt nanoparticles can cause significant mass transport loss especially at high current densities. Ionomer-free ultra-thin catalyst layers （UTCLs） emerge as a promising alternative to reduce Pt loading by improving catalyst utilization and effectiveness, while theoretical issues such as the proton conduction mechan- ism remain puzzling and practical issues such as the rather narrow operation window remain unsettled. At present, the development of PEFC catalyst layer has come to a crossroads： staying ionomer-impregnated or going iono- mer-free. It is always beneficial to look back into the past when coming to a crossroads. This paper addresses the characterization and modeling of both the conventional ionomer-impregnated catalyst layer and the emerging ionomer-free UTCLs, featuring advances in characterizing microscale distributions of Pt particles, ionomer, support particles and unraveling their interactions; advances in fundamental understandings of proton conduction and flooding behaviors in ionomer-free UTCLs; advances in modeling of conventional catalyst layers and especially UTCLs; and discussions on high-impact research topics in characterizing and modeling of catalyst layers.

Impact of carbon paper structural parameters on the performance of a polymer electrolyte fuel cell cathode via lattice Boltzmann method

Polymer electrolyte fuel cells(PEFCs)being employed in fuel cell electric vehicles(FCEVs)are promising power generators producing electric power from fuel stream via porous electrodes.Structure of carbon paper gas diffusion layers(GDLs)applying in the porous electrodes can greatly affect the PEFC performance,especially at the cathode side where electrochemical reaction is more sluggish.To discover the role of carbon paper GDL structure on the mass transfer properties,different cathode electrodes with dissimilar structural parameters are simulated via lattice Boltzmann method(LBM).3D contours of oxygen and water vapor concentration through the GDL as well as the 2D contours of current density on the catalyst layer are illustrated and examined.The results indicate that the carbon fiber diameter has a negligible impact on the current density while the impact of carbon paper thickness and porosity is significant.In fact,increasing of carbon paper thickness or porosity leads to lack of cell performance.

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.

Fast Numerical Simulation of Two-Phase Transport Model in the Cathode of a Polymer Electrolyte Fuel Cell

In this paper,we apply streamline-diffusion and Galerkin-least-squares fi-nite element methods for 2D steady-state two-phase model in the cathode of polymer electrolyte fuel cell(PEFC)that contains a gas channel and a gas diffusion layer(GDL).This two-phase PEFC model is typically modeled by a modified Navier-Stokes equation for the mass and momentum,with Darcy’s drag as an additional source term in momentum for flows through GDL,and a discontinuous and degenerate convectiondiffusion equation for water concentration.Based on the mixed finite element method for the modified Navier-Stokes equation and standard finite element method for water equation,we design streamline-diffusion and Galerkin-least-squares to overcome the dominant convection arising from the gas channel.Meanwhile,we employ Kirchhoff transformation to deal with the discontinuous and degenerate diffusivity in water concentration.Numerical experiments demonstrate that our finite element methods,together with these numerical techniques,are able to get accurate physical solutions with fast convergence.

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.

Alkaline polymer electrolyte fuel cells: Principle, challenges, and recent progress

Polymer electrolyte membrane fuel cells (PEMFC) have been recognized as a significant power source in future energy systems based on hydrogen. The current PEMFC technology features the employment of acidic polymer electrolytes which, albeit superior to electrolyte solutions, have intrinsically limited the catalysts to noble metals, fundamentally preventing PEMFC from widespread deployment. An effective solution to this problem is to develop fuel cells based on alkaline polymer electrolytes (APEFC), which not only enable the use of non-precious metal catalysts but also avoid the carbonate-precipitate issue which has been troubling the conventional alkaline fuel cells (AFC). This feature article introduces the principle of APEFC, the challenges, and our research progress, and focuses on strategies for developing key materials, including high-performance alkaline polyelectrolytes and stable non-precious metal catalysts. For alkaline polymer electrolytes, high ionic conductivity and satisfactory mechanical property are difficult to be balanced, therefore polymer cross-linking is an ultimate strategy. For non-precious metal catalysts, it is urgent to improve the catalytic activity and stability. New materials, such as transition-metal complexes, nitrogen-doped carbon nanotubes, and metal carbides, would become applicable in APEFC.

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.

New strategy for reversal tolerant anode for automotive polymer electrolyte fuel cell

Since the commercialization of the fuel cell electric vehicles (FCEVs), the polymer electrolyte membrane fuel cell system has been actively improved as a powertrain for ultimate environment-friendly vehicle. During the FCEV operation, various transient conditions such as start-up/shut-down and fuel starvation occur irregularly, which deteriorates the durability of the membrane electrode assembly. In particular, when fuel starvation occurs, the carbon support in the anode is oxidized within few minutes, thus the mitigation of this phenomenon is essential for securing the durability. This short review introduces the concept of reversal tolerant anode (RTA), which is a mitigation method using an oxygen evolution catalyst and reviews some previous reports. In addition, new approach for RTA suggested by authors recently, which is the replacement of Pt anode catalyst by multifunctional IrRu alloy catalyst that simultaneously exhibits the activities for the hydrogen oxidation reaction and the oxygen evolution reaction is introduced.

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.

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.

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.