Gel-state polybenzimidazole proton exchange membranes with flexible alkyl sulfonic acid side chains for a wider operating temperature range(25–240 ℃)

High-temperature proton exchange membrane fuel cells(HT-PEMFC) possess distinct technical advantages of high output power, simplified water/heat management, increased tolerance to fuel impurities and diverse fuel sources, within the temperature range of 120–200 ℃. However, for practical automobile applications, it was crucial to broaden their low-temperature operating window and enable cold start-up capability. Herein, gel-state phosphoric acid(PA) doped sulfonated polybenzimidazole(PBI) proton exchange membranes(PEMs) were designed and synthesized via PPA sol-gel process and in-situ sultone ring-opening reactions with various proton transport pathways based on absorbed PA, flexible alkyl chain connected sulfonic acid groups and imidazole sites. The effects of flexible alkyl sulfonic acid side chain length and content on PA doping level, proton conductivity, and membrane stability under different temperature and relative humidity(RH) were thoroughly investigated. The prepared gel-state membranes contained a self-assembled lamellar and porous structure that facilitated the absorption of a large amount of PA with rapid proton transporting mechanisms. At room temperature, the optimized membrane exhibited a proton conductivity of 0.069 S cm^(-1), which was further increased to 0.162 and 0.358 S cm^(-1)at 80 and 200 ℃, respectively, without additional humidification. The most significant contribution of this work was demonstrating the feasibility of gel-state sulfonated PBI membranes in expanding HT-PEMFC application opportunities over a wider operating range of 25 to 240 ℃.

Pore-Scale Investigation of Coupled Two-Phase and Reactive Transport in the Cathode Electrode of Proton Exchange Membrane Fuel Cells

A three-dimensional multicomponent multiphase lattice Boltzmann model(LBM)is established to model the coupled two-phase and reactive transport phenomena in the cathode electrode of proton exchange membrane fuel cells.The gas diff usion layer(GDL)and microporous layer(MPL)are stochastically reconstructed with the inside dynamic distribution of oxygen and liquid water resolved,and the catalyst layer is simplifi ed as a superthin layer to address the electrochemical reaction,which provides a clear description of the fl ooding eff ect on mass transport and performance.Diff erent kinds of electrodes are reconstructed to determine the optimum porosity and structure design of the GDL and MPL by comparing the transport resistance and per-formance under the fl ooding condition.The simulation results show that gradient porosity GDL helps to increase the reactive area and average concentration under fl ooding.The presence of the MPL ensures the oxygen transport space and reaction area because liquid water cannot transport through micropores.Moreover,the MPL helps in the uniform distribution of oxygen for an effi cient in-plane transport capacity.Crack and perforation structures can accelerate the water transport in the assembly.The systematic perforation design yields the best performance under fl ooding by separating the transport of liquid water and oxygen.

CFD Analysis of Spiral Flow Fields in Proton Exchange Membrane Fuel Cells

Proton exchange membrane fuel cells(PEMFCs)are largely used in various applications because of their pollution-free products and high energy conversion efficiency.In order to improve the related design,in the present work a new spiral flow field with a bypass is proposed.The reaction gas enters the flow field in the central path and diffuses in two directions through the flow channel and the bypass.The bypasses are arranged incrementally.The number of bypasses and the cross-section size of the bypasses are varied parametrically while a single-cell model of the PEMFC is used.The influence of the concentration of liquid water and oxygen in the cell on the performance of different flow fields is determined by means of Computational fluid dynamics(COMSOL Multiphysics software).Results show that when the bypass number is 48 and its cross-sectional area is 0.5 mm^(2),the cell exhibits the best performances.

Ti/(Ti,Cr)N/CrN multilayer coated 316L stainless steel by arc ion plating as bipolar plates for proton exchange membrane fuel cells

Arc ion plating(AIP) is applied to form Ti/(Ti,Cr)N/Cr N multilayer coating on the surface of 316 L stainless steel(SS316L) as bipolar plates for proton exchange membrane fuel cells(PEMFCs). The characterizations of the coating are analyzed by scanning electron microscopy(SEM) and X-ray diffraction(XRD). Interfacial contact resistance(ICR) between the coated sample and carbon paper is 4.9 m cm^2 under 150 N/cm^2,which is much lower than that of the SS316 L substrate. Potentiodynamic and potentiostatic tests are performed in the simulated PEMFC working conditions to investigate the corrosion behaviors of the coated sample. Superior anticorrosion performance is observed for the coated sample, whose corrosion current density is 0.12 μA/cm2. Surface morphology results after corrosion tests indicate that the substrate is well protected by the multilayer coating. Performances of the single cell with the multilayer coated SS316 L bipolar plate are improved significantly compared with that of the cell with the uncoated SS316 L bipolar plate, presenting a great potential for PEMFC application.

Process and challenges of stainless steel based bipolar plates for proton exchange membrane fuel cells

Proton exchange membrane fuel cell(PEMFC)powered automobiles have been recognized to be the ultimate solution to replace traditional fuel automobiles because of their advantages of PEMFCs such as no pollution,low temperature start-up,high energy density,and low noise.As one of the core components,the bipolar plates(BPs)play an important role in the PEMFC stack.Traditional graphite BPs and composite BPs have been criticized for their shortcomings such as low strength,high brittleness,and high processing cost.In contrast,stainless steel BPs(SSBPs)have recently attracted much attention of domestic and foreign researchers because of their excellent comprehensive performance,low cost,and diverse options for automobile applications.However,the SSBPs are prone to corrosion and passivation in the PEMFC working environment,which lead to reduced output power or premature failure.This review is aimed to summarize the corrosion and passivation mechanisms,characterizations and evaluation,and the surface modification technologies in the current SSBPs research.The non-coating and coating technical routes of SSBPs are demonstrated,such as substrate component regulation,thermal nitriding,electroplating,ion plating,chemical vapor deposition,and physical vapor deposition,etc.Alternative coating materials for SSBPs are metal coatings,metal nitride coatings,conductive polymer coatings,and polymer/carbon coatings,etc.Both the surface modification technologies can solve the corrosion resistance problem of stainless steel without affecting the contact resistance,however still facing restraints such as long-time stability,feasibility of low-cost,and mass production process.This paper is believed to enrich the knowledge of high-performance and long-life BPs applied for PEMFC automobiles.

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.

Water induced phase segregation in hydrocarbon proton exchange membranes

Proton exchange membranes(PEMs) are a key material for proton exchange membrane fuel cells(PEMFCs). Non-fluorinated hydrocarbon PEMs are low-cost alternatives to Nafion, but limited by the low proton conductivity, because of the weak phase segregation structure and narrow ion-transport channels.Various efforts have been taken to improve the performance of hydrocarbon PEMs, but mostly with complex methodologies. Here we demonstrate a simple, yet very efficient method to create phase segregation structure inside a typical hydrocarbon PEM, sulfonated poly(ether ether ketone)(SPEEK). By simply adding appropriate amounts of water into the DMF solvent, the resulting SPEEK membrane exhibits widened ion-transport channels, with the phase size of 2.7 nm, as indicated by both molecular dynamic(MD) simulations and transmission electron microscope(TEM) observations, and the proton conductivity is thus improved by 200%. These findings not only further our fundamental understanding of hydrocarbon PEMs, but are also valuable to the development of low-cost and practical fuel cell technologies.

Recent advances in phosphoric acid-based membranes for high-temperature proton exchange membrane fuel cells

High-temperature proton exchange membrane fuel cells(HT-PEMFCs)are pursued worldwide as efficient energy conversion devices.Great efforts have been made in the area of designing and developing phosphoric acid(PA)-based proton exchange membrane(PEM)of HT-PEMFCs.This review focuses on recent advances in the limitations of acid-based PEM(acid leaching,oxidative degradation,and mechanical degradation)and the approaches mitigating the membrane degradation.Preparing multilayer or polymers with continuous network,adding hygroscopic inorganic materials,and introducing PA doping sites or covalent interactions with PA can effectively reduce acid leaching.Membrane oxidative degradation can be alleviated by synthesizing crosslinked or branched polymers,and introducing antioxidative groups or highly oxidative stable materials.Crosslinking to get a compact structure,blending with stable polymers and inorganic materials,preparing polymer with high molecular weight,and fabricating the polymer with PA doping sites away from backbones,are recommended to improve the membrane mechanical strength.Also,by comparing the running hours and decay rate,three current approaches,1.crosslinking via thermally curing or polymeric crosslinker,2.incorporating hygroscopic inorganic materials,3.increasing membrane layers or introducing strong basic groups and electron-withdrawing groups,have been concluded to be promising approaches to improve the durability of HT-PEMFCs.The overall aim of this review is to explore the existing degradation challenges and opportunities to serve as a solid basis for the deployment in the fuel cell market.

High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer

Reducing a Pt loading with improved power output and durability is essential to promote the large-scale application of proton exchange membrane fuel cells(PEMFCs).To achieve this goal,constructing optimized structure of catalyst layers with efficient mass transportation channels plays a vital role.Herein,PEMFCs with order-structured cathodic electrodes were fabricated by depositing Pt nanoparticles by Ebeam onto vertically aligned carbon nanotubes(VACNTs)growth on Al foil via plasma-enhanced chemical vapor deposition.Results demonstrate that the proportion of hydrophilic Pt-deposited region along VACNTs and residual hydrophobic region of VANCTs without Pt strongly influences the cell performance,in particular at high current densities.When Pt nanoparticles deposit on the top depth of around 600 nm on VACNTs with a length of 4.6μm,the cell shows the highest performance,compared with others with various lengths of VACNTs.It delivers a maximum power output of 1.61 W cm^(-2)(H_(2)/O_(2),150 k Pa)and 0.79 W cm^(-2)(H_(2)/Air,150 k Pa)at Pt loading of 50μg cm^(-2),exceeding most of previously reported PEMFCs with Pt loading of<100μg cm^(-2).Even though the Pt loading is down to 30μg cm^(-2)(1.36 W cm^(-2)),the performance is also better than 100μg cm^(-2)(1.24 W cm^(-2))of commercial Pt/C,and presents better stability.This excellent performance is critical attributed to the ordered hydrophobic region providing sufficient mass passages to facilitate the fast water drainage at high current densities.This work gives a new understanding for oxygen reduction reaction occurred in VACNTs-based ordered electrodes,demonstrating the most possibility to achieve a substantial reduction in Pt loading<100μg cm^(-2) without sacrificing in performance.

Recent Advances in Electrode Design Based on One-Dimensional Nanostructure Arrays for Proton Exchange Membrane Fuel Cell Applications

One-dimensional(1D)Pt-based electrocatalysts demonstrate outstanding catalytic activities and stability toward the oxygen reduction reaction(ORR).Advances in three-dimensional(3D)ordered electrodes based on 1D Pt-based nanostructure arrays have revealed great potential for developing highperformance proton exchange membrane fuel cells(PEMFCs),in particular for addressing the mass transfer and durability challenges of Pt/C nanoparticle electrodes.This paper reviews recent progress in the field,with a focus on the 3D ordered electrodes based on self-standing Pt nanowire arrays.Nanostructured thin-film(NSTF)catalysts are discussed along with electrodes made from Pt-based nanoparticles deposited on arrays of polymer nanowires,and carbon and TiO2 nanotubes.Achievements on electrodes from Pt-based nanotube arrays are also reviewed.The importance of size,surface properties,and the distribution control of 1D catalyst nanostructures is indicated.Finally,challenges and future development opportunities are addressed regarding increasing electrochemical surface area(ECSA)and quantifying oxygen mass transport resistance for 1D nanostructure array electrodes.

Preparation and evaluation of crosslinked sulfonated polyphosphazene with poly(aryloxy cyclotriphosphazene) for proton exchange membrane

Several crosslinked proton exchange membranes with high proton conductivities and low methanol permeability coefficients were prepared, based on the sulfonated poly[(4-fluorophenoxy)(phenoxy)] phosphazene(SPFPP) and newly synthesized water soluble sulfonated poly(cyclophosphazene)(SPCP) containing clustered flexible pendant sulfonic acids. The structure of SPCP was characterized by fourier transform infrared spectroscopy(FTIR) and ~1H NMR spectra. The membranes showed moderate proton conductivities and much lower methanol permeability coefficients when compared to Nafion 117. Transmission electron microscopy(TEM) results indicated the well-defined phase separation between the locally and densely sulfonated units and hydrophobic units, which induced efficient proton conduction. In comparison with SPFPP membrane, the proton conductivities, oxidative stabilities and mechanical properties of crosslinked membranes remarkably were improved. The selectivity values of all the crosslinked membranes were also much higher than that of Nafion 117(0.74×10~5S· s/cm^3). These results suggested that the c SPFPP/SPCP membranes were promising candidate materials for proton exchange membrane in direct methanol fuel cells.

High-performance polymer electrolyte membranes incorporated with 2D silica nanosheets in high-temperature proton exchange membrane fuel cells

Silica nanosheets(SN)derived from natural vermiculite(Verm)were successfully incorporated into polyethersulfone-polyvinylpyrrolidone(PES-PVP)polymer to fabricate high-temperature proton exchange membranes(HT-PEMs).The content of SN filler was varied(0.1-0.75 wt%)to study its influence on proton conductivity,power density and durability.Benefiting from the hydroxyl groups of SN that enable the formation of additional proton-transferring pathways,the inorganic-organic membrane displayed enhanced proton conductivity of 48.2 mS/cm and power density of 495 mW/cm^(2) at 150℃ without humidification when the content of SN is 0.25 wt%.Furthermore,exfoliated SN(E-SN)and sulfonated SN(S-SN),which were fabricated by a liquid-phase exfoliation method and silane condensation,respectively,were embedded in PES-PVP polymer matrix by a simple blending method.Due to the significant contribution from sulfonic groups in S-SN,the membrane with 0.25 wt%S-SN reached the highest proton conductivity of51.5 mS/cm and peak power density of 546 mW/cm^(2) at150℃,48%higher than the pristine PES-PVP membranes.Compared to unaltered PES-PVP membrane,SN added hybrid composite membrane demonstrated excellent durability for the fuel cell at 150℃.Using a facile method to prepare 2D SN from natural clay minerals,the strategy of exfoliation and functionalization of SN can be potentially used in the production of HT-PEMs.

Influence of solvent on ion conductivity of polybenzimidazole proton exchange membranes for vanadium redox flow batteries

Polybenzimidazole(PBI)is a kind of proton transport membrane material,and its ion conductivity is a key factor affecting its application in vanadium redox flow batteries(VRFBs).The casting solvent of PBI has a significant influence on the acid doping level of PBI membranes which is closely related to ionic conductivity.In this paper,3,3′-diaminobenzidine(DABz)and 4,4′-Dicarboxydiphenylether(DCDPE)were used as raw materials by solution condensation to prepare the PBI with ether bond groups.The chemical structure of PBI was determined by1H NMR and FT-IR,and the prepared PBI had good solubility which can be dissolved in a variety of solvents.The PBI proton exchange membranes were prepared by solution coating with 5 different solvents of N,N-dimethylformamide(DMF),N,N-dimethylacetamide(DMAc),dimethyl sulfoxide(DMSO),1-methyl-2-pyrrolidone(NMP),methane sulfonic acid(MSA).The effects of different solvents on the ion conductivity and physicochemical properties were discussed in detail.The results showed that the PBI membrane prepared by using MSA as solvent(the PBI+MSA membrane)exhibits high water uptake,acid doping level and low vanadium ion permeability.The VRFB assembled with the PBI+MSA membrane exhibited higher coulombic efficiency(CE)99.87%and voltage efficiency(VE)84.50%than that of the commercial Nafion115 membrane at100 m A·cm-2,and after 480 cycles,the EE value can still be maintained at 83.73%.The self-discharge time of a single battery was recorded to be as long as 1000 h.All experimental data indicated that MSA is the best solvent for casting PBI membrane.

Novel phosphonated polymer without anhydride formation for proton exchange membrane fuel cells

Proton exchange membrane fuel cells(PEMFCs)are regarded as one of the most promising clean energy technology because of their high energy density,silent emission-free operation,and wide applications[1].Recently,anion exchange membrane fuel cells(AEMFCs)has emerged as an alternative to PEMFCs.

Segmented tomographic evaluation of structural degradation of carbon support in proton exchange membrane fuel cells

The variation of the three-dimensional(3D)structure of the membrane electrode of a fuel cell during proton exchange cycling involves the corrosion/compaction of the carbon support.The increasing degradation of the carbon structure continuously reduces the electrocatalytic performance of proton exchange membrane fuel cells(PEM-FCs).This phenomenon can be explained by performing 3D tomographic analysis at the nanoscale.However,conventional tomographic approaches which present limited experimental feasibility,cannot perform such evaluation and have not provided sufficient structural information with statistical significance thus far.Therefore,a reliable methodology is required for the 3D geometrical evaluation of the carbon structure.Here,we propose a segmented tomographic approach which employs pore network analysis that enables the visualization of the geometrical parameters corresponding to the porous carbon structure at a high resolution.This approach can be utilized to evaluate the 3D structural degradation of the porous carbon structure after cycling in terms of local surface area,pore size distribution,and their 3D networking.These geometrical parameters of the carbon body were demonstrated to be substantially reduced owing to the cycling-induced degradation.This information enables a deeper understanding of the degradation phenomenon of carbon supports and can contribute to the development of stable PEM-FC electrodes.

Binary ligand strategy toward interweaved encapsulation-nanotubes structured electrocatalyst for proton exchange membrane fuel cell

Hierarchically porous architecture of ir on-nitroge n-carb on(Fe-N-C)for oxyge n reducti on reaction(ORR)is highly desired towards efficient mass transfer in the fuel cell device manner.Herein,we reported a binary ligand strategy to prepare zeolitic imidazolate frameworks(ZIFs)-derived precursors,wherein the addition of secondary ligand endows precursors with the capabilities to transform into porously interweaved encapsulation-nanotubes structured composites after calcination.The optimal catalyst,i.e.,termed as Fe_(6)-M/C-3,exhibits excellent durability with 88.8%current retention after 50,000 seconds in 0.1 M HClO_(4)solution by virtue of nanoparticles-encapsulation features,which is more positive than the benchmark commercial 20 wt%Pt/C catalyst.Moreover,a promising maximum power density of Fe_(6)-M/C-3 as cathode catalyst was also dem on strated in proton exchange membrane fuel cells(PEMFCs)measurements.Therefore,this binary ligand approach to the fabrication of hierarchically porous structures would also have significant implications for various other electrochemical reactions.

Patterned catalyst layer boosts the performance of proton exchange membrane fuel cells by optimizing water management

Mass transport is crucial to the performance of proton exchange membrane fuel cells,especially at high current densities.Generally,the oxygen and the generated water share same transmission medium but move towards opposite direction,which leads to serious mass transfer problems.Herein,a series of patterned catalyst layer were prepared with a simple one-step impressing method using nylon sieves as templates.With grooves 100μm in width and 8μm in depth on the surface of cathode catalyst layer,the maximum power density of fuel cell increases by 10%without any additional durability loss while maintaining a similar electrochemical surface area.The concentration contours calculated by finite element analysis reveal that the grooves built on the surface of catalyst layer serve to accumulate the water nearby while oxygen tends to transfer through relatively convex region,which results from capillary pressure difference caused by the pore structure difference between the two regions.The separation of oxidant gas and generated water avoids mass confliction thus boosts mass transport efficiency.

Multiscale structural engineering of atomically dispersed FeN4 electrocatalyst for proton exchange membrane fuel cells

Atomically dispersed iron-nitrogen-carbon(Fe-N-C) catalysts have emerged as the most promising alternative to the expensive Pt-based catalysts for the oxygen reduction reaction(ORR) in proton exchange membrane fuel cells(PEMFCs),however suffer from low site density of active Fe-N4 moiety and limited mass transport during the catalytic reaction.To address these challenges,we report a three-dimensional(3D) metal-organic frameworks(MOF)-derived Fe-N-C single-atom catalyst.In this well-designed Fe-N-C catalyst,the micro-scale interconnected skeleton,the nano-scale ordered pores and the atomic-scale abundant carbon edge defects inside the skeleton significantly enhance the site density of active Fe-N4 moiety,thus improving the Fe utilization in the final catalyst.Moreover,the combination of the above mentioned micro-and nano-scale structures greatly facilitates the mass transport in the 3D Fe-N-C catalyst.Therefore,the multiscale engineered Fe-N-C single-atom catalyst achieves excellent ORR performance under acidic condition and affords a significantly enhanced current density and power density in PEMFC.Our findings may open new opportunities for the rational design of FeN-C catalysts through multiscale structural engineering.

Recent insights on iron based nanostructured electrocatalyst and current status of proton exchange membrane fuel cell for sustainable transport

Bridging the performance gap of the electrocatalyst between the rotating disk electrode(RDE) and membrane electrode assembly(MEA) level testing is the key to reducing the total cost of proton exchange membrane fuel cell(PEMFC) vehicles. Presently, platinum metal accounts for ~42% of the total cost of the PEMFC vehicles for usage in the cathode catalyst layer, where the sluggish oxygen reduction reaction(ORR) occurs. An alternative to the platinum catalyst, the Fe-N-C catalyst has attracted considerable interest for PEMFC due to its cost-effectiveness and high catalytic activity towards ORR. However, the excellent ORR activity of Fe-N-C obtained from RDE studies rarely translates the same performance into MEA operating conditions. Such a performance gap is mainly attributed to the lack of atomic-level understanding of Fe-N-C active sites and their ORR mechanism. Besides, unless the cost of expensive electrocatalyst is reduced, the total operation cost of the PEMFC vehicles remains constant. Therefore,developing highly efficient Fe-N-C catalysts from academic and industrial perspectives is critical for commercializing PEMFC vehicles. Here, the scope of the review is three-fold. First, we discussed the atomiclevel insights of Fe-N-C active sites and ORR mechanism, followed by unraveling the different iron-based nanostructured ORR electrocatalysts, including oxide, carbide, nitride, phosphide, sulfide, and singleatom catalysts. And then we bridged their ORR catalytic performance gap between the RDE and MEA tests for real operating conditions of PEMFC vehicles. Second, we focused on bridging the cost barriers of PEMFC vehicles between capital, operation, and end-user. Finally, we provided the path to achieve sustainable development goals by commercializing PEMFC vehicles for a better world.