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.

Performance Degradation Prediction of Proton Exchange Membrane Fuel Cell Based on CEEMDAN-KPCA and DA-GRU Networks

In order to improve the performance degradation prediction accuracy of proton exchange membrane fuel cell(PEMFC),a fusion prediction method(CKDG)based on adaptive noise complete ensemble empirical mode decomposition(CEEMDAN),kernel principal component analysis(KPCA)and dual attention mechanism gated recurrent unit neural network(DA-GRU)was proposed.CEEMDAN and KPCA were used to extract the input feature data sequence,reduce the influence of random factors,and capture essential feature components to reduce the model complexity.The DA-GRU network helps to learn the feature mapping relationship of data in long time series and predict the changing trend of performance degradation data more accurately.The actual aging experimental data verify the performance of the CKDG method.The results show that under the steady-state condition of 20%training data prediction,the CKDA method can reduce the root mean square error(RMSE)by 52.7%and 34.6%,respectively,compared with the traditional LSTM and GRU neural networks.Compared with the simple DA-GRU network,RMSE is reduced by 15%,and the degree of over-fitting is reduced,which has higher accuracy.It also shows excellent prediction performance under the dynamic condition data set and has good universality.

Effects of baffle position in serpentine flow channel on the performance of proton exchange membrane fuel cells

This study used a three-dimensional numerical model of a proton exchange membrane fuel cell with five types of channels:a smooth channel(Case 1);eight rectangular baffles were arranged in the upstream(Case 2),midstream(Case 3),downstream(Case 4),and the entire cathode flow channel(Case 5)to study the effects of baffle position on mass transport,power density,net power,etc.Moreover,the effects of back pressure and humidity on the voltage were investigated.Results showed that compared to smooth channels,the oxygen and water transport facilitation at the diffusion layer-channel interface were added 11.53%-20.60%and 7.81%-9.80%at 1.68 A·cm^(-2)by adding baffles.The closer the baffles were to upstream,the higher the total oxygen flux,but the lower the flux uniformity the worse the water removal.The oxygen flux of upstream baffles was 8.14%higher than that of downstream baffles,but oxygen flux uniformity decreased by 18.96%at 1.68 A·cm^(-2).The order of water removal and voltage improvement was Case 4>Case 5>Case 3>Case 2>Case 1.Net power of Case 4 was 9.87%higher than that of the smooth channel.To the Case 4,when the cell worked under low back pressure or high humidity,the voltage increments were higher.The potential increment for the back pressure of 0 atm was 0.9%higher than that of 2 atm(1 atm=101.325 kPa).The potential increment for the humidity of 100%was 7.89%higher than that of 50%.

Comparative review of corrosion-resistant coatings on metal bipolar plates of proton exchange membrane fuel cells

In the realm of proton exchange membrane fuel cells(PEMFCs),the bipolar plates(BPs)are indispensable and serve pivotal roles in distributing reactant gases,collecting current,facilitating product water removal,and cooling the stack.Metal BPs,characterized by outstanding manufacturability,cost-effectiveness,higher power density,and mechanical strength,are emerging as viable alternatives to traditional graphite BPs.The foremost challenge for metal BPs lies in enhancing their corrosion resistance and conductivity under acidic conditions,necessitating the application of various coatings on their surfaces to ensure superior performance.This review summarizes and compares recent advancements in the research of eight distinct types of coatings for BPs in PEMFCs,including noble metal,carbide,ni-tride,and amorphous carbon(a-C)/metal compound composite coatings.The various challenges encountered in the manufacturing and fu-ture application of these coatings are also delineated.

Probing the Efficiency of PPMG-Based Composite Electrolytes for Applications of Proton Exchange Membrane Fuel Cell

PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.

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.

Intermolecular Acid-Base-Pairs Containing Poly(p-Terphenyl-co-lsatin Piperidinium)for High Temperature Proton Exchange Membrane Fuel Cells

How to optimize and regulate the distribution of phosphoric acid in matrix,and pursuing the improved electrochemical performance and service lifetime of high temperature proton exchange membrane(HT-PEMs)fuel cell are significant challenges.Herein,bifunctional poly(p-terphenyl-co-isatin piperidinium)copolymer with tethered phosphonic acid(t-PA)and intrinsic tertiary amine base groups are firstly prepared and investigated as HT-PEMs.The distinctive architecture of the copolymer provides a well-designed platform for rapid proton transport.Protons not only transports through the hydrogen bond network formed by the adsorbed free phosphoric acid(f-PA)anchored by the tertiary amine base groups,but also rely upon the proton channel constructed by the ionic cluster formed by the t-PA aggregation.Thorough the design of the structure,the bifunctional copolymers with lower PA uptake level(<100%)display prominent proton conductivities and peak power densities(99 mS cm^(-1),812 mW cm^(-2)at 160℃),along with lower PA leaching and higher voltage stability,which is a top leading result in disclosed literature.The results demonstrate that the design of intermolecular acid-base-pairs can improve the proton conductivity without sacrificing the intrinsic chemical stability or mechanical property of the thin membrane,realizing win-win demands between the mechanical robustness and electrochemical properties of HT-PEMs.

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.

Water induced phase segregation in hydrocarbon proton exchange membranes

Proton exchange membranes （PEMs） are a key material for proton exchange membrane fuel cells （PEM-FCs）, Non-fluorinated hydrocarbon PEMs are low-cost alternatives to Nation, but limited by the low pro-ton 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 com-plex methodologies. Here we demonstrate a simple, yet very efficient method to create phase segrega-tion structure inside a typical hydrocarbon PEM, sulfonated poly（ether ether ketone） （SPEEK）. By sim-ply adding appropriate amounts of water into the DMF solvent, the resulting SPEEK membrane exhibitswidened 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 conductivityis thus improved by 200%. These findings not only further our fundamental understanding of hydrocarbonPEMs, but are also valuable to the development of low-cost and practical fuel cell technologies.

Synthesis and Water Uptake of Sulfonated Poly (phthalazinone ether sulfone ketone)/Polyacrylic Acid Proton Exchange Membranes

Novel SPPESK/PAA composite proton exchange membranes with semi-interpenetrating polymer network （sIPN） structure have been synthesized through the in-situ polymerization of acrylic acid （AA） in the presence of sulfonated poly （phthalazinone ether sulfone ketone） （SPPESK）. The composite membranes were identified by FT-IR analysis. Water uptake of the composite membranes was as high as 89.7% at 90℃, nearly one time higher than that of the corresponding SPPESK membrane.

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 ℃.

Sulfonic Acid Modified Hollow Silica Spheres and Its Application in Proton Exchange Membranes

In order to improve the proton conductivity of hollow silica spheres （HSS）/perfluorosulfonic acid ion-exchange （PFSA） composite membranes as proton exchange membrane,sulfonic acid groups were grafted onto the surfaces of HSS via post grafting methods.TEM images and FT-IR spectra of the obtained sulfonic acid groups modified hollow silica spheres （SAMHSS） illustrated that the sulfonic acid groups were successfully grafted onto the surfaces of HSS.Water uptake and swelling degree of SAMHSS/PFSA composite membranes were found much higher than those of HSS/PFSA membranes due to the introduction of hydrophilic sulfonic acid groups.In a range from 50 ℃ to 130 ℃,the highest conductivity of composite membranes was obtained when 5 wt% SAMHSS was loaded.The maximum conductivity reached 7.5×10-2 S·cm-1 at 100 ℃ and 100% relative humidity,even the temperature increased to 130 ℃,the conductivity of composite membranes with 5 wt% SAMHSS could reach 3.7×10-2 S·cm-1 at 100 % relative humidity,while the conductivity of the recast PFSA was only 2.2×10-3 S·cm-1.

Nanocomposite Membranes based on Perfl uorosulfonic Acid/Ceramic for Proton Exchange Membrane Fuel Cells

Perfl uorosulfonic acid/ceramic nanocomposite membranes were investigated as electrolytes for polymer electrolyte membrane fuel cell applications under low relative humidity. Different nanosized ceramics（SiO2, ZrO2, TiO2） with diameters in the range of 2-6 nm were synthesized in situ in Nafion solution through a sol-gel process and the formed nanosized ceramics were well-dispersed in the solution.The nanocomposite membranes were formed through a casting process. The nanocomposite membrane showes enhanced water retention ability and improved proton conductivity compared to those of pure Nafi on membrane. The mechanical strength of the formed nanocomposite membranes is slightly less than that of pure Nafi on membrane. The experimental results demonstrate that the polymer ceramic nanocompsite membranes are potential electrolyte for fuel cells operating at elevated temperature.

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.

Studies on Preparation and Properties of Proton Exchange Membranes Based on Phosphotungstic Acid/Silica and Polysulfonamide

Membranes formed by polysulfonamide(PSA)and phosphotungstic acid(PWA)supported on nano-silica have been prepared.Fourier transform infrared spectra(FTIR)and thermogravimetric analysis(TGA)were used to characterize the structure and thermal properties of obtained membranes.The analyses of water uptake,proton conductivity and mechanical properties of the membranes revealed that PWA and silica produced a beneficial effect on proton conduction of the membranes.The membranes with 50 wt% of PWA-SiO2 /PSA were mechanically stable and gave proton conductivity of 2.57×10-2 S·cm-1 at 90℃ and 100% relative humidity.According to the obtained results,PWA and SiO2 doped PSA is a promising material for proton exchange membrane.

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/CrN multilayer coating on the surface of 316L 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 Omega cm(2) under 150 N/cm(2), which is much lower than that of the SS316L 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 mu A/cm(2). 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 SS316L bipolar plate are improved significantly compared with that of the cell with the uncoated SS316L bipolar plate, presenting a great potential for PEMFC application. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

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.

Carbon-supported ultrafine Pt nanoparticles modified with trace amounts of cobalt as enhanced oxygen reduction reaction catalysts for proton exchange membrane fuel cells

To accelerate the kinetics of the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells,ultrafine Pt nanoparticles modified with trace amounts of cobalt were fabricated and decorated on carbon black through a strategy involving modified glycol reduction and chemical etching.The obtained Pt36Co/C catalyst exhibits a much larger electrochemical surface area(ECSA)and an improved ORR electrocatalytic activity compared to commercial Pt/C.Moreover,an electrode prepared with Pt36Co/C was further evaluated under H2-air single cell test conditions,and exhibited a maximum specific power density of 10.27 W mgPt^-1,which is 1.61 times higher than that of a conventional Pt/C electrode and also competitive with most state-of-the-art Pt-based architectures.In addition,the changes in ECSA,power density,and reacting resistance during the accelerated degradation process further demonstrate the enhanced durability of the Pt36Co/C electrode.The superior performance observed in this work can be attributed to the synergy between the ultrasmall size and homogeneous distribution of catalyst nanoparticles,bimetallic ligand and electronic effects,and the dissolution of unstable Co with the rearrangement of surface structure brought about by acid etching.Furthermore,the accessible raw materials and simplified operating procedures involved in the fabrication process would result in great cost-effectiveness for practical applications of PEMFCs.

Graphite-polypyrrole coated 316L stainless steel as bipolar plates for proton exchange membrane fuel cells

316L stainless steel（SS 316L） is quite attractive as bipolar plates in proton exchange membrane fuel cells（PEMFC）.In this study,graphite-polypyrrole was coated on SS 316L by the method of cyclic voltammetry.The surface morphology and chemical composition of the graphite-polypyrrole composite coating were investigated by scanning electron microscopy（SEM） and X-ray photoelectron spectroscopy（XPS）.A simulated working environment of PEMFC was applied for testing the corrosion properties of graphite-polypyrrole coated SS 316L.The current densities in the simulated PEMFC anode and cathode conditions are around 3×10-9 and 9×10-5 A·cm-2,respectively.In addition,the interfacial contact resistance（ICR） was also investigated.The ICR value of graphite-polypyrrole coated SS 316L is much lower than that of bare SS 316L.Therefore,graphite-polypyrrole coated SS 316L indicates a great potential for the application in PEMFC.