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...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.展开更多
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 temperat...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.展开更多
This work proposes a novel tubular structure of high-temperature proton exchange membrane fuel cell(PEMFC)integrated with a built-in packed-bed methanol steam reformer to provide hydrogen for power output.A two-dimens...This work proposes a novel tubular structure of high-temperature proton exchange membrane fuel cell(PEMFC)integrated with a built-in packed-bed methanol steam reformer to provide hydrogen for power output.A two-dimensional axisymmetric non-isothermal model was developed in COMSOL Multiphysics 5.4 to simulate the performance of a tubular high temperature proton membrane fuel cell and a packed bed methanol reformer.The model considers the coupling multi-physical processes,including methanol reforming reaction,water gas shift reaction,methanol cracking reaction as well as the heat,mass and momentum transport processes.The sub-model of the tubular packed-bed methanol reformer is validated between 433 K and 493 K with the experimental data reported in the literature.The sub-model of the high temperature proton exchange fuel cell is validated between 393 K and 433 K with the published literature.Our results show that power output and temperature distribution of the integrated unit depend on methanol flow rates and working voltages.It was suggested that stable power generation performance of 0.14 W/cm_(2)and temperature drop in methanol steam reformer of≤10 K could be achieved by controlling the methanol space-time ratio of≥250 kg·s/mol with working voltage at 0.6 V,even in the absence of an external heat source.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21776034,21476044 and 21406031)Joint Funds of the National Natural Science Foundation of China(U1663223)+1 种基金National Key Research and Development Program of China(2016YFB0101203)Changjiang Scholars Program(T2012049)。
文摘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.
基金the National Key Research and Development Program of China(No.2018YFA0702002)the Beijing Natural Science Foundation(No.Z210016)the National Natural Science Foundation of China(No.21935001)。
文摘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.
文摘This work proposes a novel tubular structure of high-temperature proton exchange membrane fuel cell(PEMFC)integrated with a built-in packed-bed methanol steam reformer to provide hydrogen for power output.A two-dimensional axisymmetric non-isothermal model was developed in COMSOL Multiphysics 5.4 to simulate the performance of a tubular high temperature proton membrane fuel cell and a packed bed methanol reformer.The model considers the coupling multi-physical processes,including methanol reforming reaction,water gas shift reaction,methanol cracking reaction as well as the heat,mass and momentum transport processes.The sub-model of the tubular packed-bed methanol reformer is validated between 433 K and 493 K with the experimental data reported in the literature.The sub-model of the high temperature proton exchange fuel cell is validated between 393 K and 433 K with the published literature.Our results show that power output and temperature distribution of the integrated unit depend on methanol flow rates and working voltages.It was suggested that stable power generation performance of 0.14 W/cm_(2)and temperature drop in methanol steam reformer of≤10 K could be achieved by controlling the methanol space-time ratio of≥250 kg·s/mol with working voltage at 0.6 V,even in the absence of an external heat source.