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
Synthesis of carbon nanotubes (CNTs) below 600℃ using supporting catalyst chemical vapor deposition method was reported by many research groups. However, the floating catalyst chemical vapor deposition received les...Synthesis of carbon nanotubes (CNTs) below 600℃ using supporting catalyst chemical vapor deposition method was reported by many research groups. However, the floating catalyst chemical vapor deposition received less attention due to imperfect nanotubes produced. In this work, the effects of varying the preheating temperature on the synthesis of CNT were investigated. The reaction temperature was set at 570℃. The preheating set temperature was varied from 150 to 400℃ at 50℃ interval. Three O-ring shape heating mantels were used as heating source for the preheater. In situ monitoring device was used to observe the temperature profile in the reactor. Benzene and ferrocene were used as the carbon source and catalyst precursor, respectively. Vertically aligned CNTs were synthesized when the preheating temperature was set at 400℃. When the preheating temperature was increased up to 400℃, both the length and the alignment of CNTs produced were improved.展开更多
The mechanism for the formation of double-layer vertically aligned carbon nanotube arrays(VACNTs) through single-step CVD growth is investigated. The evolution of the structures and defect concentration of the VACNTs ...The mechanism for the formation of double-layer vertically aligned carbon nanotube arrays(VACNTs) through single-step CVD growth is investigated. The evolution of the structures and defect concentration of the VACNTs are tracked by scanning electron microscopy(SEM) and Raman spectroscopy. During the growth, the catalyst particles are stayed constantly on the substrate. The precipitation of the second CNT layer happens at around 30 min as proved by SEM.During the growth of the first layer, catalyst nanoparticles are deactivated with the accumulation of amorphous carbon coatings on their surfaces, which leads to the termination of the growth of the first layer CNTs. Then, the catalyst particles are reactivated by the hydrogen in the gas flow, leading to the precipitation of the second CNT layer. The growth of the second CNT layer lifts the amorphous carbon coatings on catalyst particles and substrates. The release of mechanical energy by CNTs provides big enough energy to lift up amorphous carbon flakes on catalyst particles and substrates which finally stay at the interfaces of the two layers simulated by finite element analysis. This study sheds light on the termination mechanism of CNTs during CVD process.展开更多
Nanoscale materials are gaining massive attention in recent years due to their potential to alleviate the present electrochemical electrode constraints.Possessing high conductivity(both thermally and electrically),hig...Nanoscale materials are gaining massive attention in recent years due to their potential to alleviate the present electrochemical electrode constraints.Possessing high conductivity(both thermally and electrically),high chemical and electrochemical stability,exceptional mechanical strength and flexibility,high specific surface area,large charge storage capacity,and excellent ionadsorption,carbon nanotubes(CNTs)remain one of the most researched of other nanoscale materials for electrochemical energy storage.Rather than having them packed at random,CNTs perform better when packed/grown to order,vertically or horizontally aligned to a substrate.This study presents an overview of the impact of CNT alignment on the electrochemical performance of lithium-ion batteries(LIBs).The unique properties of vertically aligned CNTs(VACNTs)for LIB application were discussed.Furthermore,the mechanisms of charge storage and electrochemical performances in VACNT-based(pristine and composites)anodes and cathodes of LIBs were succinctly reviewed.In the end,the existing challenges and future directions in the field were also briefly discussed.展开更多
One of the critical challenges that limit broad commercialization of proton exchange membrane fuel cells(PEMFC)is to reduce the usage of Pt while maintaining high power output and sufficient durability.Herein,a novel ...One of the critical challenges that limit broad commercialization of proton exchange membrane fuel cells(PEMFC)is to reduce the usage of Pt while maintaining high power output and sufficient durability.Herein,a novel bifunctional layer consisting of vertically aligned carbon nanotubes(VACNTs)and nanoparticles of Pt-Co catalysts(Pt-Co/VACNTs)is reported for highperformance PEMFCs.Readily prepared by a two-step process,the Pt-Co/VACNTs layer with a hydrophilic catalyst-loaded side and a hydrophobic gas diffusion side enables a PTFE-free electrode structure with fully exposed catalyst active sites and superior gas–water diffusion capability.When tested in a PEMFC,the bi-functional Pt-Co/VACNTs layer with ultralow Pt loading(~65μgcathodecm-2)demonstrates a power density of 19.5 kW gPt cathode-1 at 0.6 V,more than seven times that of a cell with commercial Pt/C catalyst(2.7 kW gPt cathode-1 at 0.6 V)at a loading of 400μgcathodecm-2 tested under similar conditions.This remarkable design of VACNTs-based catalyst with dual functionalities enables much lower Pt loading,faster mass transport,and higher electrochemical performance and stability.Further,the preparation procedure can be easily scaled up for low-cost fabrication and commercialization.展开更多
Vertically aligned carbon nanotubes arrays(VACNTs)are a promising candidate for the thermal interface material(TIM)of next-generation electronic devices due to their attractive thermal and mechanical properties.Howeve...Vertically aligned carbon nanotubes arrays(VACNTs)are a promising candidate for the thermal interface material(TIM)of next-generation electronic devices due to their attractive thermal and mechanical properties.However,the environment required for synthesizing VACNTs is harsh and severely incompatible with standard device packaging processes.VACNTs’extremely low in-plane thermal conductivity also limits its performance for cooling hot spots.Here,using a transfer-and-encapsulate strategy,a two-step soldering method is developed to cap both ends of the VACNTs with copper microfoils,forming a standalone Cu-VACNTs-Cu sandwich TIM and avoiding the need to directly grow VACNTs on chip die.This new TIM is fully compatible with standard packaging,with excellent flexibility and high thermal conductivities in both in-plane and through-plane directions.The mechanical compliance behavior and mechanism,which are critical for TIM applications,are investigated in depth using in situ nanoindentation.The thermal performance is further verified in an actual light emitting diode(LED)cooling experiment,demonstrating low thermal resistance,good reliability,and achieving a 17℃ temperature reduction compared with state-of-the-art commercial TIMs.This study provides a viable solution to VACNTs’longstanding problem in device integration and free-end contact resistance,bringing it much closer to application and solving the critical thermal bottleneck in next-generation electronics.展开更多
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 Research Universiti Grant,Universiti Putra Malaysia (Project No. RU01154)
文摘Synthesis of carbon nanotubes (CNTs) below 600℃ using supporting catalyst chemical vapor deposition method was reported by many research groups. However, the floating catalyst chemical vapor deposition received less attention due to imperfect nanotubes produced. In this work, the effects of varying the preheating temperature on the synthesis of CNT were investigated. The reaction temperature was set at 570℃. The preheating set temperature was varied from 150 to 400℃ at 50℃ interval. Three O-ring shape heating mantels were used as heating source for the preheater. In situ monitoring device was used to observe the temperature profile in the reactor. Benzene and ferrocene were used as the carbon source and catalyst precursor, respectively. Vertically aligned CNTs were synthesized when the preheating temperature was set at 400℃. When the preheating temperature was increased up to 400℃, both the length and the alignment of CNTs produced were improved.
基金supported by NSFC(51422204,51372132)National Basic Research Program of China(2013CB934200)+2 种基金SRFDP(20120002120038)TNLIST Cross-discipline FoundationBNLMS Cross-discipline Foundation
文摘The mechanism for the formation of double-layer vertically aligned carbon nanotube arrays(VACNTs) through single-step CVD growth is investigated. The evolution of the structures and defect concentration of the VACNTs are tracked by scanning electron microscopy(SEM) and Raman spectroscopy. During the growth, the catalyst particles are stayed constantly on the substrate. The precipitation of the second CNT layer happens at around 30 min as proved by SEM.During the growth of the first layer, catalyst nanoparticles are deactivated with the accumulation of amorphous carbon coatings on their surfaces, which leads to the termination of the growth of the first layer CNTs. Then, the catalyst particles are reactivated by the hydrogen in the gas flow, leading to the precipitation of the second CNT layer. The growth of the second CNT layer lifts the amorphous carbon coatings on catalyst particles and substrates. The release of mechanical energy by CNTs provides big enough energy to lift up amorphous carbon flakes on catalyst particles and substrates which finally stay at the interfaces of the two layers simulated by finite element analysis. This study sheds light on the termination mechanism of CNTs during CVD process.
基金supported by the National Science Foundation of the United States(Nos.1506640,2134375,and 2213923).
文摘Nanoscale materials are gaining massive attention in recent years due to their potential to alleviate the present electrochemical electrode constraints.Possessing high conductivity(both thermally and electrically),high chemical and electrochemical stability,exceptional mechanical strength and flexibility,high specific surface area,large charge storage capacity,and excellent ionadsorption,carbon nanotubes(CNTs)remain one of the most researched of other nanoscale materials for electrochemical energy storage.Rather than having them packed at random,CNTs perform better when packed/grown to order,vertically or horizontally aligned to a substrate.This study presents an overview of the impact of CNT alignment on the electrochemical performance of lithium-ion batteries(LIBs).The unique properties of vertically aligned CNTs(VACNTs)for LIB application were discussed.Furthermore,the mechanisms of charge storage and electrochemical performances in VACNT-based(pristine and composites)anodes and cathodes of LIBs were succinctly reviewed.In the end,the existing challenges and future directions in the field were also briefly discussed.
基金supported by the National Natural Science Foundation of China under(No.21878158,2182880,51678291)Jiangsu Natural Science Foundation for Distinguished Young Scholars(No.BK20170043)+3 种基金the National Key R&D Program of China(2018YFB1502903)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)China Postdoctoral Science Foundation(2019M660112)the Jiangsu Postdoctoral Science Funding Project
文摘One of the critical challenges that limit broad commercialization of proton exchange membrane fuel cells(PEMFC)is to reduce the usage of Pt while maintaining high power output and sufficient durability.Herein,a novel bifunctional layer consisting of vertically aligned carbon nanotubes(VACNTs)and nanoparticles of Pt-Co catalysts(Pt-Co/VACNTs)is reported for highperformance PEMFCs.Readily prepared by a two-step process,the Pt-Co/VACNTs layer with a hydrophilic catalyst-loaded side and a hydrophobic gas diffusion side enables a PTFE-free electrode structure with fully exposed catalyst active sites and superior gas–water diffusion capability.When tested in a PEMFC,the bi-functional Pt-Co/VACNTs layer with ultralow Pt loading(~65μgcathodecm-2)demonstrates a power density of 19.5 kW gPt cathode-1 at 0.6 V,more than seven times that of a cell with commercial Pt/C catalyst(2.7 kW gPt cathode-1 at 0.6 V)at a loading of 400μgcathodecm-2 tested under similar conditions.This remarkable design of VACNTs-based catalyst with dual functionalities enables much lower Pt loading,faster mass transport,and higher electrochemical performance and stability.Further,the preparation procedure can be easily scaled up for low-cost fabrication and commercialization.
基金supported by the National Natural Science Foundation of China(No.52076041)the Natural Science Foundation of Jiangsu Province(No.BK20200371)the Nanjing Carbon Peak and Carbon Neutrality Science and Technology Innovation Project(No.202211009)。
文摘Vertically aligned carbon nanotubes arrays(VACNTs)are a promising candidate for the thermal interface material(TIM)of next-generation electronic devices due to their attractive thermal and mechanical properties.However,the environment required for synthesizing VACNTs is harsh and severely incompatible with standard device packaging processes.VACNTs’extremely low in-plane thermal conductivity also limits its performance for cooling hot spots.Here,using a transfer-and-encapsulate strategy,a two-step soldering method is developed to cap both ends of the VACNTs with copper microfoils,forming a standalone Cu-VACNTs-Cu sandwich TIM and avoiding the need to directly grow VACNTs on chip die.This new TIM is fully compatible with standard packaging,with excellent flexibility and high thermal conductivities in both in-plane and through-plane directions.The mechanical compliance behavior and mechanism,which are critical for TIM applications,are investigated in depth using in situ nanoindentation.The thermal performance is further verified in an actual light emitting diode(LED)cooling experiment,demonstrating low thermal resistance,good reliability,and achieving a 17℃ temperature reduction compared with state-of-the-art commercial TIMs.This study provides a viable solution to VACNTs’longstanding problem in device integration and free-end contact resistance,bringing it much closer to application and solving the critical thermal bottleneck in next-generation electronics.