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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Enhanced solid-electrolyte interface efficiency for practically viable hydrogen-air fuel cell systems

Proton exchange membrane fuel cells (PEMFCs) provide an appealing sustainable energy system,with the solid-electrolyte membrane playing a crucial role in its overall performance.Currently,sulfonated poly(1,4-phenylene ether-ether sulfone)(SPEES),an aromatic hydrocarbon polymer,has garnered considerable attention as an alternative to Nafion polymers.However,the long-term durability and stability of SPEES present a significant challenge.In this context,we introduce a potential solution in the form of an additive,specifically a core–shell-based amine-functionalized iron titanate (A–Fe_(2)TiO_(5)),which holds promise for improving the lifetime,proton conductivity,and power density of SPEES in PEMFCs.The modified SPEES/A–Fe_(2)TiO_(5)composite membranes exhibited notable characteristics,including high water uptake,enhanced thermomechanical stability,and oxidative stability.Notably,the SPEES membrane loaded with 1.2 wt%of A–Fe_(2)TiO_(5)demonstrates a maximum proton conductivity of 155 mS ccm^(-1),a twofold increase compared to the SPEES membrane,at 80°C under 100%relative humidity (RH).Furthermore,the 1.2 wt%of A–Fe_(2)TiO_(5)/SPEES composite membranes exhibited a maximum power density of 397.37 mW cm^(-2)and a current density of 1148 mA cm^(-2)at 60°C under 100%RH,with an opencircuit voltage decay of 0.05 m V/h during 103 h of continuous operation.This study offers significant insights into the development and understanding of innovative SPEES nanocomposite membranes for PEMFC applications.

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.