An extensive study has been conducted on the proton exchange membrane fuel cells （PEMFCs） with reducing Pt loading. This is commonly achieved by developing methods to increase the utilization of the platinum in the ...An extensive study has been conducted on the proton exchange membrane fuel cells （PEMFCs） with reducing Pt loading. This is commonly achieved by developing methods to increase the utilization of the platinum in the catalyst layer of the electrodes. In this paper, a novel process of the catalyst layers was introduced and investigated. A mixture of carbon powder and Nafion solution was sprayed on the glassy carbon electrode （GCE） to form a thin carbon layer. Then Pt particles were deposited on the surface by reducing hexachloroplatinic （IV） acid hexahydrate with methanoic acid. SEM images showed a continuous Pt gradient profile among the thickness direction of the catalytic layer by the novel method. The Pt nanowires grown are in the size of 3 nm （diameter） x l0 nm （length） by high solution TEM image. The novel catalyst layer was characterized by cyclic voltammetry （CV） and scanning electron microscope （SEM） as compared with commercial Pt/C black and Pt catalyst layer obtained from sputtering. The results showed that the platinum nanoparticles deposited on the carbon powder were highly utilized as they directly faced the gas diffusion layer and offered easy access to reactants （oxygen or hydrogen）.展开更多
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 ...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.展开更多
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 car...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.展开更多
The ultrafine platinum nanoparticles deposited on the surfaces of carbonnanotubes (Pt/CNTs) were prepared by a chemical precipitation method and used as the catalyst ofproton exchange membrane fuel cell. The depositin...The ultrafine platinum nanoparticles deposited on the surfaces of carbonnanotubes (Pt/CNTs) were prepared by a chemical precipitation method and used as the catalyst ofproton exchange membrane fuel cell. The depositing process parameters such as the solution pH value,Pt content and treatment temperature were analyzed. The experimental results show that the optimumprocess parameters to prepare Pt/CNTs are the solution pH value of 7.0, the theoretical Pt contentof 25 percent (mass fraction) and the heating temperature of 500 deg C, under the conditions thebest performance of the proton exchange membrane fuel cell can be obtained and its voltage can reach580 mV at a current density of 500 mA/cm^2.展开更多
Nanoshell-containing carbon (NSCC) is one of the Pt-surrogate catalysts for proton exchange membrane fuel cell (PEMFC) invented by us to promote oxygen reduction reaction (ORR), the cathode reaction of the cell. In th...Nanoshell-containing carbon (NSCC) is one of the Pt-surrogate catalysts for proton exchange membrane fuel cell (PEMFC) invented by us to promote oxygen reduction reaction (ORR), the cathode reaction of the cell. In the present study, we selected one of renewable resources, lignin from herbaceous plants as the carbon precursor for NSCC. The lignin was admixed with cobalt phthalocyanine (CoPc), the nanoshell (NS) forming catalyst, and then carbonized at 1000℃. Transmission electron microscopy and X-ray diffraction studies confirmed the formation of NS structure. The ORR activity of the prepared NSCC increased with the amount of CoPc, and the activity of lignin-based NSCC was higher than that of phenol-formaldehyde resin-based NSCC with the same amount of CoPc added. Surface analysis by X-ray photoelectron spectroscopy revealed no metal species on the NSCC but higher N/C ratio for the lignin-based NSCC by two folds. This study shows the possibility of lignin as a precursor of NSCC cathode catalyst for PEMFC.展开更多
Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membr...Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.展开更多
Carbon nanotube-supported-platinum (Pt/CNTs) and carbon-supported-platinum (Pt/C) catalysts were prepared by in situ chemical reduction method and analyzed by TEM and XRD. Then the experiments were carried out to test...Carbon nanotube-supported-platinum (Pt/CNTs) and carbon-supported-platinum (Pt/C) catalysts were prepared by in situ chemical reduction method and analyzed by TEM and XRD. Then the experiments were carried out to test the performance of PEMFCs with the Pt electrodes. The results showed that in both catalyst, Pt was of small particle size (about 4 nm) and Pt/CNTs exhibited higher catalytic activity than Pt/C.展开更多
Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped p...Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped porous carbon(FeNS‐PC)was synthesized using melamine formaldehyderesin as C and N precursors,Fe(SCN)3as Fe and S precursors,and CaCl2as a template via a two‐stepheat treatment without a harsh template removal step.The results show that the catalyst treated at900℃(FeNS‐PC‐900)had a high surface area of775m2/g,a high mass activity of10.2A/g in anacidic medium,and excellent durability;the half‐wave potential decreased by only20mV after10000potential cycles.The FeNS‐PC‐900catalyst was used as the cathode in a proton exchangemembrane fuel cell and delivered a peak power density of0.49W/cm2.FeNS‐PC‐900therefore hasgood potential for use in practical applications.展开更多
Ni–Cr enrichment on stainless steel SS316 L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thi...Ni–Cr enrichment on stainless steel SS316 L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thin continuous Ag-doped carbon film on a porous carbon-coated SS316 L substrate. The corrosion resistance of this film in 0.5 mol·L^（-1） H_2SO_4 solution containing 5 ppm F- at 80°C was investigated using polarization tests. The results showed that the surface treatment of the SS316 L strongly affected the adhesion of the carbon coating to the stainless steel. Compared to the bare SS316 L, the Ag-doped carbon-coated SS316 L bipolar plate was remarkably more stable in both the anode and cathode environments of proton exchange membrane fuel cell（PEMFC） and the interface contact resistance between the specimen and Toray 060 carbon paper was reduced from 333.0 m？·cm^2 to 21.6 m？·cm^2 at a compaction pressure of 1.2 MPa.展开更多
基金supported by the Royal Academy of Engineering,United Kingdom
文摘An extensive study has been conducted on the proton exchange membrane fuel cells （PEMFCs） with reducing Pt loading. This is commonly achieved by developing methods to increase the utilization of the platinum in the catalyst layer of the electrodes. In this paper, a novel process of the catalyst layers was introduced and investigated. A mixture of carbon powder and Nafion solution was sprayed on the glassy carbon electrode （GCE） to form a thin carbon layer. Then Pt particles were deposited on the surface by reducing hexachloroplatinic （IV） acid hexahydrate with methanoic acid. SEM images showed a continuous Pt gradient profile among the thickness direction of the catalytic layer by the novel method. The Pt nanowires grown are in the size of 3 nm （diameter） x l0 nm （length） by high solution TEM image. The novel catalyst layer was characterized by cyclic voltammetry （CV） and scanning electron microscope （SEM） as compared with commercial Pt/C black and Pt catalyst layer obtained from sputtering. The results showed that the platinum nanoparticles deposited on the carbon powder were highly utilized as they directly faced the gas diffusion layer and offered easy access to reactants （oxygen or hydrogen）.
基金finically supported by the National Natural Science Foundation of China(22075055)the Guangxi Science and Technology Project(AB16380030)the Innovation Project of Guangxi Graduate Education(YCSW2020052)。
文摘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.
基金supported by the Technology Innovation Program(No.20011712)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by Advanced Facility Center for Quantum Technology in SKKUthe National R&D Program through the National Research Foundation of Koera(NRF)funded by Ministry of Science and ICT(No.2020M3F3A2A01082618)。
文摘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.
基金This work was financially supported by the State Key Project for Fundamental Research of the Ministry of Science and Technology (No. G20000264-04)
文摘The ultrafine platinum nanoparticles deposited on the surfaces of carbonnanotubes (Pt/CNTs) were prepared by a chemical precipitation method and used as the catalyst ofproton exchange membrane fuel cell. The depositing process parameters such as the solution pH value,Pt content and treatment temperature were analyzed. The experimental results show that the optimumprocess parameters to prepare Pt/CNTs are the solution pH value of 7.0, the theoretical Pt contentof 25 percent (mass fraction) and the heating temperature of 500 deg C, under the conditions thebest performance of the proton exchange membrane fuel cell can be obtained and its voltage can reach580 mV at a current density of 500 mA/cm^2.
文摘Nanoshell-containing carbon (NSCC) is one of the Pt-surrogate catalysts for proton exchange membrane fuel cell (PEMFC) invented by us to promote oxygen reduction reaction (ORR), the cathode reaction of the cell. In the present study, we selected one of renewable resources, lignin from herbaceous plants as the carbon precursor for NSCC. The lignin was admixed with cobalt phthalocyanine (CoPc), the nanoshell (NS) forming catalyst, and then carbonized at 1000℃. Transmission electron microscopy and X-ray diffraction studies confirmed the formation of NS structure. The ORR activity of the prepared NSCC increased with the amount of CoPc, and the activity of lignin-based NSCC was higher than that of phenol-formaldehyde resin-based NSCC with the same amount of CoPc added. Surface analysis by X-ray photoelectron spectroscopy revealed no metal species on the NSCC but higher N/C ratio for the lignin-based NSCC by two folds. This study shows the possibility of lignin as a precursor of NSCC cathode catalyst for PEMFC.
基金finically supported by the National Natural Science Foundation of China(22075055)the Guangxi Science and Technology Project(AB16380030)。
文摘Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.
文摘Carbon nanotube-supported-platinum (Pt/CNTs) and carbon-supported-platinum (Pt/C) catalysts were prepared by in situ chemical reduction method and analyzed by TEM and XRD. Then the experiments were carried out to test the performance of PEMFCs with the Pt electrodes. The results showed that in both catalyst, Pt was of small particle size (about 4 nm) and Pt/CNTs exhibited higher catalytic activity than Pt/C.
基金supported by the National Basic Research Program of China (973 Program,2015CB932303)the National Natural Science Founda-tion of China (21373175,21621091)~~
文摘Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped porous carbon(FeNS‐PC)was synthesized using melamine formaldehyderesin as C and N precursors,Fe(SCN)3as Fe and S precursors,and CaCl2as a template via a two‐stepheat treatment without a harsh template removal step.The results show that the catalyst treated at900℃(FeNS‐PC‐900)had a high surface area of775m2/g,a high mass activity of10.2A/g in anacidic medium,and excellent durability;the half‐wave potential decreased by only20mV after10000potential cycles.The FeNS‐PC‐900catalyst was used as the cathode in a proton exchangemembrane fuel cell and delivered a peak power density of0.49W/cm2.FeNS‐PC‐900therefore hasgood potential for use in practical applications.
基金financially supported by the National Natural Science Foundation of China(No.21106012)the Educational Department Foundation of Liaoning Province of China(NO.L2014180)
文摘Ni–Cr enrichment on stainless steel SS316 L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thin continuous Ag-doped carbon film on a porous carbon-coated SS316 L substrate. The corrosion resistance of this film in 0.5 mol·L^（-1） H_2SO_4 solution containing 5 ppm F- at 80°C was investigated using polarization tests. The results showed that the surface treatment of the SS316 L strongly affected the adhesion of the carbon coating to the stainless steel. Compared to the bare SS316 L, the Ag-doped carbon-coated SS316 L bipolar plate was remarkably more stable in both the anode and cathode environments of proton exchange membrane fuel cell（PEMFC） and the interface contact resistance between the specimen and Toray 060 carbon paper was reduced from 333.0 m？·cm^2 to 21.6 m？·cm^2 at a compaction pressure of 1.2 MPa.
