The strategy of combining highly conductive frameworks with abundant active sites is desirable in the preparation of alternative catalysts to commercial Pt/C for the oxygen reduction reaction （ORR）. In this study, N...The strategy of combining highly conductive frameworks with abundant active sites is desirable in the preparation of alternative catalysts to commercial Pt/C for the oxygen reduction reaction （ORR）. In this study, N-doped graphene （NG） and carbon nanotubes （CNT） were grown in-situ on Co-containing carbon nanofibers （CNF） to form three-dimensional （3D） interconnected networks. The NG and CNT bound the interlaced CNF together, facilitating electron transfer and providing additional active sites. The 3D interconnected fiber networks exhibited excellent ORR catalytic behavior with an onset potential of 0.924 V （vs. reversible hydrogen electrode） and a higher current density than Pt/C beyond 0.720 V. In addition, the hybrid system exhibited superior stability and methanol tolerance to Pt/C in alkaline media. This method can be extended to the design of other 3D interconnected network architectures for energy storage and conversion applications.展开更多
Three-dimensional(3D)functional graphenebased architecture with superior electrical conductivity and good mechanical strength has promising applications in energy storage and electrics.Viscoelasticity-adjustable inks ...Three-dimensional(3D)functional graphenebased architecture with superior electrical conductivity and good mechanical strength has promising applications in energy storage and electrics.Viscoelasticity-adjustable inks make it possible to achieve desired 3D architectures with interconnected and continuous interior networks by microextrusion printing.In this work,ultra-low-concentration graphene oxide(GO)inks of~15 mg·ml-1 have been obtained and demonstrated in direct 3D printing with a facile cross-linking(direct ink writing).The rheological behavior of the GO strategy by cations,which is the lowest concentration to achieve direct ink writing inks,could be adjusted from 1×10^(4) to 1×10^(5) Pa·s^(-1) with different concentrations of cations due to strong cross-linking networks between GO sheets and cations.Meanwhile,the specific strength and electrical conductivity of 3D-printed graphene architecture are notably enhanced,reaching up to 51.7×10^(3) N·m·kg^(-1)and 119 S·m^(-1),which are superior to conventional graphene aerogels.Furthermore,3D printing graphene-based architecture assembled in micro-superc apacitor exhibits excellent electrochemical performance,which can be ascribed to the effective ion transportation through the interconnected networks.The strategy demonstrated is useful in the design of complex-shaped,graphene-based architectures for scalable manufacturing of practical energy storage applications.展开更多
Organic electrochemical transistors(OECTs)have garnered significant interest due to their ability to facilitate both ionic and electronic transport.A large proportion of research efforts thus far have focused on inves...Organic electrochemical transistors(OECTs)have garnered significant interest due to their ability to facilitate both ionic and electronic transport.A large proportion of research efforts thus far have focused on investigating high-performance materials that can serve as mixed ion doping and charge transport layers.However,relatively less attention has been given to the gateelectrode materials,which play a critical role in controlling operational voltage,redox processes,and stability,especially in the context of semiconductor-based OECTs working in accumulation mode.Moreover,the demand for planarity and flexibility in modern bioelectronic devices presents significant challenges for the commonly used Ag/AgCl electrodes in OECTs.Herein,we report the construction of high-performance accumulation-mode OECTs by utilizing a gate electrode made of three-dimensional(3D)-printed graphene oxide.The 3D-printed graphene oxide electrode incorporating one-dimensional(1D)carbon nanotubes,is directly printed using an aqueous-based ink and showcases exceptional mechanical flexibility and porosity properties,enabling high-throughput preparation for both top gates and integrated planar architecture,as well as fast ion/charge transport.OECTs with high performance comparable to that of Ag/AgCl-gated OECTs are thus achieved and present promising feasibility for electrocardiograph(ECG)signal recording.This provides a promising choice for the application of flexible bioelectronics in medical care and neurological recording.展开更多
Lithium-air batteries have attracted significant interest for applications in high energy density mobile power supplies, yet there are considerable challenges to the development of rechargeable Li-air batteries with s...Lithium-air batteries have attracted significant interest for applications in high energy density mobile power supplies, yet there are considerable challenges to the development of rechargeable Li-air batteries with stable cycling performance under ambient conditions. Here we report a three-dimensional （3D） hydrophobic graphene membrane as a moisture-resistive cathode for high performance Li-air batteries. The 3D graphene membrane features a highly interconnected graphene network for efficient charge transport, a highly porous structure for efficient diffusion of oxygen and electrolyte ions, a large specific surface area for high capacity storage of the insulating discharge product, and a network of highly tortuous hydrophobic channels for O2/H20 selectivity. These channels facilitate 02 ingression while retarding moisture diffusion and ensure excellent charge/ discharge cycling stability under ambient conditions. The membrane can thus enable robust Li-air batteries with exceptional performance, including a maximum cathode capacity that exceeds 5,700 mAh/g and excellent recharge cycling behavior （〉2,000 cycles at 140 mAh/g, and 〉100 cycles at 1,400 mAh/g）. The graphene membrane air cathode can deliver a lifetime capacity of 100,000-300,000 mAh/g, comparable to that of a typical lithium ion battery cathode. The stable operation of Li-air batteries with significantly improved single charge capacities and lifetime capacities comparable to those of Li-ion batteries may offer an attractive high energy density storage alternative for future mobile power supplies. These batteries may provide much longer battery lives and greatly reduced recharge frequency.展开更多
With the rapid development of wearable devices, flexible pressure sensors with high sensitivity and wide workable range are highly desired. In nature, there are many well-adapted structures developed through natural s...With the rapid development of wearable devices, flexible pressure sensors with high sensitivity and wide workable range are highly desired. In nature, there are many well-adapted structures developed through natural selection, which inspired us for the design of biomimetic materials or devices. Particularl3 human fingertip skin, where many epidermal ridges amplify external stimulations, might be a good example to imitate for highly sensitive sensors. In this work, based on unique chemical vapor depositions （CVD）-grown three-dimensional （3D） graphene films that mimic the morphology of fingertip skin, we fabricated flexible pressure sensing membranes, which simultaneously showed a high sensitivity of 110 （kPa）-1 for 0-0.2 kPa and wide workable pressure range （up to 75 kPa）. Hierarchical structured polydimethylsiloxane （PDMS） films molded from natural leaves were used as the supporting elastic films for the graphene films, which also contribute to the superior performance of the pressure sensors. The pressure sensor showed a low detection limit （0.2 Pa）, fast response （〈 30 ms）, and excellent stability for more than 10,000 loading/unloading cycles. Based on these features, we demonstrated its applications in detecting tiny objects, sound, and human physiological signals, showing its potential in wearable electronics for health monitoring and human/machine interfaces.展开更多
A highly active and stable oxygen evolution reaction （OER） electrocatalyst is critical for hydrogen production from water splitting. Herein, three-dimensional Ni3Sa@graphene@Co9S8 （Ni3S2@G@Co9S8）, a sandwich- stru...A highly active and stable oxygen evolution reaction （OER） electrocatalyst is critical for hydrogen production from water splitting. Herein, three-dimensional Ni3Sa@graphene@Co9S8 （Ni3S2@G@Co9S8）, a sandwich- structured OER electro-catalyst, was grown in situ on nickel foam; it afforded an enhanced catalytic performance when highly conductive graphene is introduced as an intermediary for enhancing the electron transfer rate and stability. Serving as a free-standing electrocatalytic electrode, Ni3S2@G@Co9S8 presents excellent electrocatalytic activities for OER： A low onset overpotential （2 mA·cm^-2 at 174 mV）, large anode current density （10 mA·cm^-2 at an overpotential of 210 mV）, low Tafel slope （66 mV·dec^-1）, and predominant durability of over 96 h （releasing a current density of N 14 mA·cm^-2 with a low and constant overpotential of 215 mV） in a 1 M KOH solution. This work provides a promising, cost-efficient electrocatalyst and sheds new light on improving the electrochemical performance of composites through enhancing the electron transfer rate and stability by introducing graphene as an intermediary.展开更多
SnO2 is a promising material for both Li-ion and Na-ion batteries owing to its high theoretical capacities. Unfortunately, the electrochemical performance of SnO2 is unsatisfactory because of the large volume change t...SnO2 is a promising material for both Li-ion and Na-ion batteries owing to its high theoretical capacities. Unfortunately, the electrochemical performance of SnO2 is unsatisfactory because of the large volume change that occurs during cycling, low electronic conductivity of inactive oxide matrix, and poor kinetics, which are particularly severe in Na-ion batteries. Herein, ultra-fine SnO2 nanocrystals anchored on a unique three-dimensional （3D） porous reduced graphene oxide （rGO） matrix are described as promising bifunctional electrodes for Li-ion and Na-ion batteries with excellent rate capability and long cycle life. Ultra-fine SnO2 nanocrystals of size -6 nm are well-coordinated to the graphene sheets that comprise the 3D macro-porous structure. Notably, superior rate capability was obtained up to 3 C （1In C is a measure of the rate that allows the cell to be charged/discharged in n h） for both batteries. In situ X-ray diffractometry measurements during lithiation （or sodiation） and delithiation （or desodiation） were combined with various electrochemical techniques to reveal the real-time phase evolution. This critical information was linked with the internal resistance, ion diffusivity （DLi＋ and DNa＋）, and the unique structure of the composite electrode materials to explain their excellent electrochemical performance. The improved capacity and superior rate capabilities demonstrated in this work can be ascribed to the enhanced transport kinetics of both electrons and ions within the electrode structure because of the well-interconnected, 3D macro-porous rGO matrix. The porous rGO matrix appears to play a more important role in sodium-ion batteries （SIBs）, where the larger mass/radius of Na-ions are marked concerns.展开更多
Carbon nanotube （CNT） clusters grown in situ in three-dimensional （3D） porous graphene networks （3DG-CNTs）, with integrated structure and remarkable electronic conductivity, are desirable S host materials for Li...Carbon nanotube （CNT） clusters grown in situ in three-dimensional （3D） porous graphene networks （3DG-CNTs）, with integrated structure and remarkable electronic conductivity, are desirable S host materials for Li-S batteries. 3DG-CNT exhibits a high surface area （1,645 m^2·g^-1）, superior electronic conductivity of 1,055 S·m^-1, and a 3D porous networked structure. Large clusters of CNTs anchored on the inner walls of 3D graphene networks act as capillaries, benefitting restriction of agglomeration by high contents of immersed S. Moreover, the capillary-like CNT clusters grown in situ in the pores efficiently form restricted spaces for Li polysulfides, significantly reducing the shuttling effect and promoting S utilization throughout the charge/discharge process. With an areal S mass loading of 81.6 wt.%, the 3DG-CNT/S electrode exhibits an initial specific capacity reaching 1,229 mA·h·g^-1 at 0.5 C and capacity decays of 0.044% and 0.059% per cycle at 0.5 and 1 C, respectively, over 500 cycles. The electrode material also reveals a remarkable rate performance and the large capacity of 812 mA·h·g^-1 at 3 C.展开更多
Epoxy resin(EP)composites with satisfactory thermal and tribological performance are highly required for engineering moving components.However,the simple addition of fillers leaded to the serious filler agglomeration ...Epoxy resin(EP)composites with satisfactory thermal and tribological performance are highly required for engineering moving components.However,the simple addition of fillers leaded to the serious filler agglomeration and limited promotion in tribological properties.In this work,we constructed a new kind of three-dimensional(3D)reduced graphene oxide(RGO)/Si_(3)N_(4) hybrid aerogel for EP composites,which was prepared by a facile hydrothermal self-assembly method followed by freeze-drying technique.As a result,the dispersibility of Si_(3)N_(4) whiskers was greatly improved through wrapping of polydopamine–polyethyleneimine copolymer(PDA–PEI)copolymer and physical spacing of 3D skeleton.Furthermore,benefiting from the synergistic effect of RGO and Si_(3)N_(4)@PDA–PEI in the thermal network,the thermal conductivity of RGO/Si_(3)N_(4) hybrid aerogel(GSiA)–EP increased by 45.4%compared to that of the neat EP.In addition,the friction coefficient and wear rate of GSiA–EP decreased by 83.7%and 35.8%,respectively.This work is significant for opening a tribological performance enhancement strategy though constructing 3D hybrid architecture.展开更多
基金The work was financially supported by the National Natural Science Foundation of China （Nos. 51203182 and 51173202）, Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics （No. KF201312）, Key Laboratory of High Performance Fibers ＆ Products, Ministry of Education, Donghua University, Guangxi Key Laboratory of Information Materials （Guilin University of Electronic Technology） （No. 1210908-01-K）, Research Project of NUDT （No. JC13-01-05）, Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province, and Aid Program for Innovative Group of National University of Defense Technology.
文摘The strategy of combining highly conductive frameworks with abundant active sites is desirable in the preparation of alternative catalysts to commercial Pt/C for the oxygen reduction reaction （ORR）. In this study, N-doped graphene （NG） and carbon nanotubes （CNT） were grown in-situ on Co-containing carbon nanofibers （CNF） to form three-dimensional （3D） interconnected networks. The NG and CNT bound the interlaced CNF together, facilitating electron transfer and providing additional active sites. The 3D interconnected fiber networks exhibited excellent ORR catalytic behavior with an onset potential of 0.924 V （vs. reversible hydrogen electrode） and a higher current density than Pt/C beyond 0.720 V. In addition, the hybrid system exhibited superior stability and methanol tolerance to Pt/C in alkaline media. This method can be extended to the design of other 3D interconnected network architectures for energy storage and conversion applications.
基金financially supported by the National Natural Science Foundation of China(No.51802195)Chen Guang Scholar Project of Shanghai Education Commission(No.19CG53)。
文摘Three-dimensional(3D)functional graphenebased architecture with superior electrical conductivity and good mechanical strength has promising applications in energy storage and electrics.Viscoelasticity-adjustable inks make it possible to achieve desired 3D architectures with interconnected and continuous interior networks by microextrusion printing.In this work,ultra-low-concentration graphene oxide(GO)inks of~15 mg·ml-1 have been obtained and demonstrated in direct 3D printing with a facile cross-linking(direct ink writing).The rheological behavior of the GO strategy by cations,which is the lowest concentration to achieve direct ink writing inks,could be adjusted from 1×10^(4) to 1×10^(5) Pa·s^(-1) with different concentrations of cations due to strong cross-linking networks between GO sheets and cations.Meanwhile,the specific strength and electrical conductivity of 3D-printed graphene architecture are notably enhanced,reaching up to 51.7×10^(3) N·m·kg^(-1)and 119 S·m^(-1),which are superior to conventional graphene aerogels.Furthermore,3D printing graphene-based architecture assembled in micro-superc apacitor exhibits excellent electrochemical performance,which can be ascribed to the effective ion transportation through the interconnected networks.The strategy demonstrated is useful in the design of complex-shaped,graphene-based architectures for scalable manufacturing of practical energy storage applications.
基金support from the National Natural Science Foundation of China(Nos.22222205,52173176,51773143,and 51821002)the Suzhou Key Laboratory of Surface and Interface Intelligent Matter(No.SZS2022011)supported by the Collaborative Innovation Center of Suzhou Nano Science&Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD),and the 111 Project.
文摘Organic electrochemical transistors(OECTs)have garnered significant interest due to their ability to facilitate both ionic and electronic transport.A large proportion of research efforts thus far have focused on investigating high-performance materials that can serve as mixed ion doping and charge transport layers.However,relatively less attention has been given to the gateelectrode materials,which play a critical role in controlling operational voltage,redox processes,and stability,especially in the context of semiconductor-based OECTs working in accumulation mode.Moreover,the demand for planarity and flexibility in modern bioelectronic devices presents significant challenges for the commonly used Ag/AgCl electrodes in OECTs.Herein,we report the construction of high-performance accumulation-mode OECTs by utilizing a gate electrode made of three-dimensional(3D)-printed graphene oxide.The 3D-printed graphene oxide electrode incorporating one-dimensional(1D)carbon nanotubes,is directly printed using an aqueous-based ink and showcases exceptional mechanical flexibility and porosity properties,enabling high-throughput preparation for both top gates and integrated planar architecture,as well as fast ion/charge transport.OECTs with high performance comparable to that of Ag/AgCl-gated OECTs are thus achieved and present promising feasibility for electrocardiograph(ECG)signal recording.This provides a promising choice for the application of flexible bioelectronics in medical care and neurological recording.
文摘Lithium-air batteries have attracted significant interest for applications in high energy density mobile power supplies, yet there are considerable challenges to the development of rechargeable Li-air batteries with stable cycling performance under ambient conditions. Here we report a three-dimensional （3D） hydrophobic graphene membrane as a moisture-resistive cathode for high performance Li-air batteries. The 3D graphene membrane features a highly interconnected graphene network for efficient charge transport, a highly porous structure for efficient diffusion of oxygen and electrolyte ions, a large specific surface area for high capacity storage of the insulating discharge product, and a network of highly tortuous hydrophobic channels for O2/H20 selectivity. These channels facilitate 02 ingression while retarding moisture diffusion and ensure excellent charge/ discharge cycling stability under ambient conditions. The membrane can thus enable robust Li-air batteries with exceptional performance, including a maximum cathode capacity that exceeds 5,700 mAh/g and excellent recharge cycling behavior （〉2,000 cycles at 140 mAh/g, and 〉100 cycles at 1,400 mAh/g）. The graphene membrane air cathode can deliver a lifetime capacity of 100,000-300,000 mAh/g, comparable to that of a typical lithium ion battery cathode. The stable operation of Li-air batteries with significantly improved single charge capacities and lifetime capacities comparable to those of Li-ion batteries may offer an attractive high energy density storage alternative for future mobile power supplies. These batteries may provide much longer battery lives and greatly reduced recharge frequency.
文摘With the rapid development of wearable devices, flexible pressure sensors with high sensitivity and wide workable range are highly desired. In nature, there are many well-adapted structures developed through natural selection, which inspired us for the design of biomimetic materials or devices. Particularl3 human fingertip skin, where many epidermal ridges amplify external stimulations, might be a good example to imitate for highly sensitive sensors. In this work, based on unique chemical vapor depositions （CVD）-grown three-dimensional （3D） graphene films that mimic the morphology of fingertip skin, we fabricated flexible pressure sensing membranes, which simultaneously showed a high sensitivity of 110 （kPa）-1 for 0-0.2 kPa and wide workable pressure range （up to 75 kPa）. Hierarchical structured polydimethylsiloxane （PDMS） films molded from natural leaves were used as the supporting elastic films for the graphene films, which also contribute to the superior performance of the pressure sensors. The pressure sensor showed a low detection limit （0.2 Pa）, fast response （〈 30 ms）, and excellent stability for more than 10,000 loading/unloading cycles. Based on these features, we demonstrated its applications in detecting tiny objects, sound, and human physiological signals, showing its potential in wearable electronics for health monitoring and human/machine interfaces.
基金The work was supported by the National Natural Science Foundation of China （NSFC） （Nos. 61525402 and 5161101159）, Key University Science Research Project of Jiangsu Province （No. 15KJA430006）, QingLan Project, National Postdoctoral Program for Innovative Talents （No. BX201600072）, China Postdoctoral Science Foundation （No. 2016M601792）.
文摘A highly active and stable oxygen evolution reaction （OER） electrocatalyst is critical for hydrogen production from water splitting. Herein, three-dimensional Ni3Sa@graphene@Co9S8 （Ni3S2@G@Co9S8）, a sandwich- structured OER electro-catalyst, was grown in situ on nickel foam; it afforded an enhanced catalytic performance when highly conductive graphene is introduced as an intermediary for enhancing the electron transfer rate and stability. Serving as a free-standing electrocatalytic electrode, Ni3S2@G@Co9S8 presents excellent electrocatalytic activities for OER： A low onset overpotential （2 mA·cm^-2 at 174 mV）, large anode current density （10 mA·cm^-2 at an overpotential of 210 mV）, low Tafel slope （66 mV·dec^-1）, and predominant durability of over 96 h （releasing a current density of N 14 mA·cm^-2 with a low and constant overpotential of 215 mV） in a 1 M KOH solution. This work provides a promising, cost-efficient electrocatalyst and sheds new light on improving the electrochemical performance of composites through enhancing the electron transfer rate and stability by introducing graphene as an intermediary.
文摘SnO2 is a promising material for both Li-ion and Na-ion batteries owing to its high theoretical capacities. Unfortunately, the electrochemical performance of SnO2 is unsatisfactory because of the large volume change that occurs during cycling, low electronic conductivity of inactive oxide matrix, and poor kinetics, which are particularly severe in Na-ion batteries. Herein, ultra-fine SnO2 nanocrystals anchored on a unique three-dimensional （3D） porous reduced graphene oxide （rGO） matrix are described as promising bifunctional electrodes for Li-ion and Na-ion batteries with excellent rate capability and long cycle life. Ultra-fine SnO2 nanocrystals of size -6 nm are well-coordinated to the graphene sheets that comprise the 3D macro-porous structure. Notably, superior rate capability was obtained up to 3 C （1In C is a measure of the rate that allows the cell to be charged/discharged in n h） for both batteries. In situ X-ray diffractometry measurements during lithiation （or sodiation） and delithiation （or desodiation） were combined with various electrochemical techniques to reveal the real-time phase evolution. This critical information was linked with the internal resistance, ion diffusivity （DLi＋ and DNa＋）, and the unique structure of the composite electrode materials to explain their excellent electrochemical performance. The improved capacity and superior rate capabilities demonstrated in this work can be ascribed to the enhanced transport kinetics of both electrons and ions within the electrode structure because of the well-interconnected, 3D macro-porous rGO matrix. The porous rGO matrix appears to play a more important role in sodium-ion batteries （SIBs）, where the larger mass/radius of Na-ions are marked concerns.
基金This work was supported by the Innovation Project of Guangxi Graduate Education （No. P3090098101）, the China Postdoctoral Science Foundation （No. 2017M612864）, the Major International （Regional） Joint Research Project （No. 51210002）, the National Basic Research Program of China （No. 2015CB932304） and the Natural Science Foundation of Guangdong province （No. 2015A030312007）.
文摘Carbon nanotube （CNT） clusters grown in situ in three-dimensional （3D） porous graphene networks （3DG-CNTs）, with integrated structure and remarkable electronic conductivity, are desirable S host materials for Li-S batteries. 3DG-CNT exhibits a high surface area （1,645 m^2·g^-1）, superior electronic conductivity of 1,055 S·m^-1, and a 3D porous networked structure. Large clusters of CNTs anchored on the inner walls of 3D graphene networks act as capillaries, benefitting restriction of agglomeration by high contents of immersed S. Moreover, the capillary-like CNT clusters grown in situ in the pores efficiently form restricted spaces for Li polysulfides, significantly reducing the shuttling effect and promoting S utilization throughout the charge/discharge process. With an areal S mass loading of 81.6 wt.%, the 3DG-CNT/S electrode exhibits an initial specific capacity reaching 1,229 mA·h·g^-1 at 0.5 C and capacity decays of 0.044% and 0.059% per cycle at 0.5 and 1 C, respectively, over 500 cycles. The electrode material also reveals a remarkable rate performance and the large capacity of 812 mA·h·g^-1 at 3 C.
基金The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China(Grant No.52005487)Natural Science Foundation of Gansu Province(Grant No.20JR10RA057).
文摘Epoxy resin(EP)composites with satisfactory thermal and tribological performance are highly required for engineering moving components.However,the simple addition of fillers leaded to the serious filler agglomeration and limited promotion in tribological properties.In this work,we constructed a new kind of three-dimensional(3D)reduced graphene oxide(RGO)/Si_(3)N_(4) hybrid aerogel for EP composites,which was prepared by a facile hydrothermal self-assembly method followed by freeze-drying technique.As a result,the dispersibility of Si_(3)N_(4) whiskers was greatly improved through wrapping of polydopamine–polyethyleneimine copolymer(PDA–PEI)copolymer and physical spacing of 3D skeleton.Furthermore,benefiting from the synergistic effect of RGO and Si_(3)N_(4)@PDA–PEI in the thermal network,the thermal conductivity of RGO/Si_(3)N_(4) hybrid aerogel(GSiA)–EP increased by 45.4%compared to that of the neat EP.In addition,the friction coefficient and wear rate of GSiA–EP decreased by 83.7%and 35.8%,respectively.This work is significant for opening a tribological performance enhancement strategy though constructing 3D hybrid architecture.
