High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells(PEMFCs),in which Pt-based catalysts employed in the cathodic catalyst layer(CCL)account for the maj...High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells(PEMFCs),in which Pt-based catalysts employed in the cathodic catalyst layer(CCL)account for the major portion of the cost.Although nonprecious metal catalysts(NPMCs)show appreciable activity and stability in the oxygen reduction reaction(ORR),the performance of fuel cells based on NPMCs remains unsatisfactory compared to those using Pt-based CCL.Therefore,most studies on NPMC-based fuel cells focus on developing highly active catalysts rather than facilitating oxygen transport.In this work,the oxygen transport behavior in CCLs based on highly active Fe-N-C catalysts is comprehensively explored through the elaborate design of two types of membrane electrode structures,one containing low-Pt-based CCL and NPMCbased dummy catalyst layer(DCL)and the other containing only the NPMC-based CCL.Using Zn-N-C based DCLs of different thickness,the bulk oxygen transport resistance at the unit thickness in NPMC-based CCL was quantified via the limiting current method combined with linear fitting analysis.Then,the local and bulk resistances in NPMC-based CCLs were quantified via the limiting current method and scanning electron microscopy,respectively.Results show that the ratios of local and bulk oxygen transport resistances in NPMCbased CCL are 80%and 20%,respectively,and that an enhancement of local oxygen transport is critical to greatly improve the performance of NPMC-based PEMFCs.Furthermore,the activity of active sites per unit in NPMCbased CCLs was determined to be lower than that in the Pt-based CCL,thus explaining worse cell performance of NPMC-based membrane electrode assemblys(MEAs).It is believed that the development of NPMC-based PEMFCs should proceed not only through the design of catalysts with higher activity but also through the improvement of oxygen transport in the CCL.展开更多
A large-scale industrial application of proton exchange membrane fuel cells(PEMFCs)greatly depends on both substantial cost reduction and continuous durability enhancement.However,compared to effects of material degra...A large-scale industrial application of proton exchange membrane fuel cells(PEMFCs)greatly depends on both substantial cost reduction and continuous durability enhancement.However,compared to effects of material degradation on apparent activity loss,little attention has been paid to influences on the phenomena of mass transport.In this review,influences of the degradation of key materials in membrane electrode assemblies(MEAs)on oxygen transport resistance in both cathode catalyst layers(CCLs)and gas diffusion layers(GDLs)are comprehensively explored,including carbon support,electrocatalyst,ionomer in CCLs as well as carbon material and hydrophobic polytetrafluoroethylene(PTFE)in GDLs.It is analyzed that carbon corrosion in CCLs will result in pore structure destruction and impact ionomer distribution,thus affecting both the bulk and local oxygen transport behavior.Considering the catalyst degradation,an eventual decrease in electrochemical active surface area(ECSA)definitely increases the local oxygen transport resistance since a decrease in active sites will lead to a longer oxygen transport path.It is also noted that problems concerning oxygen transport caused by the degradation of ionomer chemical structure in CCLs should not be ignored.Both cation contamination and chemical decomposition will change the structure of ionomer,thus worsening the local oxygen transport.Finally,it is found that the loss of carbon and PTFE in GDLs lead to a higher hydrophilicity,which is related to an occurrence of water flooding and increase in the oxygen transport resistance.展开更多
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 ...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.展开更多
以薄层亲水电极或者厚层憎水电极作为双极燃料电池(BPFC)阴极,系统考察了薄层亲水阴极中季铵化聚砜(QAPSF)含量、厚层憎水电极中聚四氟乙烯(PTFE)含量对电池性能的影响.结果表明,采用薄层亲水阴极时,催化层中QAPSF的最佳含量是20 wt%,...以薄层亲水电极或者厚层憎水电极作为双极燃料电池(BPFC)阴极,系统考察了薄层亲水阴极中季铵化聚砜(QAPSF)含量、厚层憎水电极中聚四氟乙烯(PTFE)含量对电池性能的影响.结果表明,采用薄层亲水阴极时,催化层中QAPSF的最佳含量是20 wt%,室温下BPFC的最大输出功率达到186.1 m W/cm2.采用厚层憎水电极时,催化层中PTFE的合适含量是20 wt%,40℃时BPFC的最大输出功率达到461.5 m W/cm2.由于碱性阴极对排水的需求较高,厚层憎水电极相较于薄层亲水电极在BPFC中更有优势.展开更多
基金the National Key R&D Program of China(Grant No.2021YFB4001303)the National Natural Science Foundation of China(Grant No.21975157)。
文摘High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells(PEMFCs),in which Pt-based catalysts employed in the cathodic catalyst layer(CCL)account for the major portion of the cost.Although nonprecious metal catalysts(NPMCs)show appreciable activity and stability in the oxygen reduction reaction(ORR),the performance of fuel cells based on NPMCs remains unsatisfactory compared to those using Pt-based CCL.Therefore,most studies on NPMC-based fuel cells focus on developing highly active catalysts rather than facilitating oxygen transport.In this work,the oxygen transport behavior in CCLs based on highly active Fe-N-C catalysts is comprehensively explored through the elaborate design of two types of membrane electrode structures,one containing low-Pt-based CCL and NPMCbased dummy catalyst layer(DCL)and the other containing only the NPMC-based CCL.Using Zn-N-C based DCLs of different thickness,the bulk oxygen transport resistance at the unit thickness in NPMC-based CCL was quantified via the limiting current method combined with linear fitting analysis.Then,the local and bulk resistances in NPMC-based CCLs were quantified via the limiting current method and scanning electron microscopy,respectively.Results show that the ratios of local and bulk oxygen transport resistances in NPMCbased CCL are 80%and 20%,respectively,and that an enhancement of local oxygen transport is critical to greatly improve the performance of NPMC-based PEMFCs.Furthermore,the activity of active sites per unit in NPMCbased CCLs was determined to be lower than that in the Pt-based CCL,thus explaining worse cell performance of NPMC-based membrane electrode assemblys(MEAs).It is believed that the development of NPMC-based PEMFCs should proceed not only through the design of catalysts with higher activity but also through the improvement of oxygen transport in the CCL.
基金This study was supported by the National Key Research and Development Program of China(No.2021YFB4001303)the Science and Technology Commission of Shanghai Municipality(No.21DZ1208601)。
文摘A large-scale industrial application of proton exchange membrane fuel cells(PEMFCs)greatly depends on both substantial cost reduction and continuous durability enhancement.However,compared to effects of material degradation on apparent activity loss,little attention has been paid to influences on the phenomena of mass transport.In this review,influences of the degradation of key materials in membrane electrode assemblies(MEAs)on oxygen transport resistance in both cathode catalyst layers(CCLs)and gas diffusion layers(GDLs)are comprehensively explored,including carbon support,electrocatalyst,ionomer in CCLs as well as carbon material and hydrophobic polytetrafluoroethylene(PTFE)in GDLs.It is analyzed that carbon corrosion in CCLs will result in pore structure destruction and impact ionomer distribution,thus affecting both the bulk and local oxygen transport behavior.Considering the catalyst degradation,an eventual decrease in electrochemical active surface area(ECSA)definitely increases the local oxygen transport resistance since a decrease in active sites will lead to a longer oxygen transport path.It is also noted that problems concerning oxygen transport caused by the degradation of ionomer chemical structure in CCLs should not be ignored.Both cation contamination and chemical decomposition will change the structure of ionomer,thus worsening the local oxygen transport.Finally,it is found that the loss of carbon and PTFE in GDLs lead to a higher hydrophilicity,which is related to an occurrence of water flooding and increase in the oxygen transport resistance.
文摘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.
文摘以薄层亲水电极或者厚层憎水电极作为双极燃料电池(BPFC)阴极,系统考察了薄层亲水阴极中季铵化聚砜(QAPSF)含量、厚层憎水电极中聚四氟乙烯(PTFE)含量对电池性能的影响.结果表明,采用薄层亲水阴极时,催化层中QAPSF的最佳含量是20 wt%,室温下BPFC的最大输出功率达到186.1 m W/cm2.采用厚层憎水电极时,催化层中PTFE的合适含量是20 wt%,40℃时BPFC的最大输出功率达到461.5 m W/cm2.由于碱性阴极对排水的需求较高,厚层憎水电极相较于薄层亲水电极在BPFC中更有优势.
