The development of freestanding and binder-free electrode is an effective approach to perform the inherent capacity of active materials and promote the mechanism study by minimizing the interference from additives.Her...The development of freestanding and binder-free electrode is an effective approach to perform the inherent capacity of active materials and promote the mechanism study by minimizing the interference from additives.Herein,we construct a freestanding cathode composed of MoS_(3)/PPy nanowires(NWs)deposited on porous nickel foam(NF)(MoS_(3)/PPy/NF)through electrochemical methods,which can work efficiently as sulfur-equivalent cathode material for Li-S batteries.The structural stability of the MoS_(3)/PPy/NF cathode is greatly enhanced due to its significant tolerance to the volume expansion of MoS_(3)during the lithiation process,which we ascribe to the flexible 3D framework of PPy NWs,leading to superior cycling performance compared to the bulk-MoS_(3)/NF reference.Eliminating the interference of binder and carbon additives,the evolution of the chemical and electronic structure of Mo and S species during the discharge/charge was studied by X-ray absorption near-edge spectroscopy(XANES).The formation of lithium polysulfides was excluded as the driving cathode reaction mechanism,suggesting the great potential of MoS_(3)as a promising sulfur-equivalent cathode material to evade the shuttle effect for Li-S batteries.The present study successfully demonstrates the importance of structural design of freestanding electrode enhancing the cycling performances and revealing the corresponding mechanisms.展开更多
Metal-organic frameworks(MOFs)have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave(EMW)absorption.However,the utilization of h...Metal-organic frameworks(MOFs)have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave(EMW)absorption.However,the utilization of high-temperature treatments has introduced uncertainties regarding the compositions and microstructures of resulting derivatives.Additionally,complete carbonization has led to diminished yields of the produced carbon composites,significantly limiting their practical applications.Consequently,the exploration of pristine MOF-based EMW absorbers presents an intriguing yet challenging endeavor,primarily due to inherently low electrical conductivity.In this study,we showcase the utilization of structurally robust Zr-MOFs as scaffolds to build highly conductive Zr-MOF/PPy composites via an inner-outer dual-modification approach,which involves the production of conducting polypyrrole(PPy)both within the confined nanoporous channels and the external surface of Zr-MOFs via post-synthetic modification.The interconnection of confined PPy and surface-lined PPy together leads to a consecutive and extensive conducting network to the maximum extent.This therefore entails outstanding conductivity up to~14.3 S cm^(-1) in Zr-MOF/PPy composites,which is approximately 1-2 orders of magnitude higher than that for conductive MOF nanocomposites constructed from either inner or outer modification.Benefiting from the strong and tunable conduction loss,as well as the induced dielectric polarization originated from the porous structures and MOF-polymer interfaces,Zr-MOF/PPy exhibits excellent microwave attenuation capabilities and a tunable absorption frequency range.Specifically,with only 15 wt.%loading,the minimum reflection loss(RLmin)can reach up to-67.4 dB,accompanied by an effective absorption bandwidth(EAB)extending to 6.74 GHz.Furthermore,the microwave absorption characteristics can be tailored from the C-band to the Ku-band by adjusting the loading of PPy.This work provides valuable insights into the fabrication of conductive MOF composites by presenting a straightforward pathway to enhance and reg-ulate electrical conduction in MOF-based nanocomposites,thus paving a way to facilely fabricate pristine MOF-based microwave absorbers.展开更多
基金supported by the National Science Foundation for Young Scientists of China(21704040)the financial support of the Helmholtz AssociationOpen Access funding enabled and organized by Projekt DEAL
文摘The development of freestanding and binder-free electrode is an effective approach to perform the inherent capacity of active materials and promote the mechanism study by minimizing the interference from additives.Herein,we construct a freestanding cathode composed of MoS_(3)/PPy nanowires(NWs)deposited on porous nickel foam(NF)(MoS_(3)/PPy/NF)through electrochemical methods,which can work efficiently as sulfur-equivalent cathode material for Li-S batteries.The structural stability of the MoS_(3)/PPy/NF cathode is greatly enhanced due to its significant tolerance to the volume expansion of MoS_(3)during the lithiation process,which we ascribe to the flexible 3D framework of PPy NWs,leading to superior cycling performance compared to the bulk-MoS_(3)/NF reference.Eliminating the interference of binder and carbon additives,the evolution of the chemical and electronic structure of Mo and S species during the discharge/charge was studied by X-ray absorption near-edge spectroscopy(XANES).The formation of lithium polysulfides was excluded as the driving cathode reaction mechanism,suggesting the great potential of MoS_(3)as a promising sulfur-equivalent cathode material to evade the shuttle effect for Li-S batteries.The present study successfully demonstrates the importance of structural design of freestanding electrode enhancing the cycling performances and revealing the corresponding mechanisms.
基金supported by the Fundamental Research Funds for the Central Universities(Nos.2232023D-01 and 2232023D-07)the Shanghai Science&Technology Committee(No.22ZR1403300)the National Natural Science Foundation of China(No.52372040).
文摘Metal-organic frameworks(MOFs)have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave(EMW)absorption.However,the utilization of high-temperature treatments has introduced uncertainties regarding the compositions and microstructures of resulting derivatives.Additionally,complete carbonization has led to diminished yields of the produced carbon composites,significantly limiting their practical applications.Consequently,the exploration of pristine MOF-based EMW absorbers presents an intriguing yet challenging endeavor,primarily due to inherently low electrical conductivity.In this study,we showcase the utilization of structurally robust Zr-MOFs as scaffolds to build highly conductive Zr-MOF/PPy composites via an inner-outer dual-modification approach,which involves the production of conducting polypyrrole(PPy)both within the confined nanoporous channels and the external surface of Zr-MOFs via post-synthetic modification.The interconnection of confined PPy and surface-lined PPy together leads to a consecutive and extensive conducting network to the maximum extent.This therefore entails outstanding conductivity up to~14.3 S cm^(-1) in Zr-MOF/PPy composites,which is approximately 1-2 orders of magnitude higher than that for conductive MOF nanocomposites constructed from either inner or outer modification.Benefiting from the strong and tunable conduction loss,as well as the induced dielectric polarization originated from the porous structures and MOF-polymer interfaces,Zr-MOF/PPy exhibits excellent microwave attenuation capabilities and a tunable absorption frequency range.Specifically,with only 15 wt.%loading,the minimum reflection loss(RLmin)can reach up to-67.4 dB,accompanied by an effective absorption bandwidth(EAB)extending to 6.74 GHz.Furthermore,the microwave absorption characteristics can be tailored from the C-band to the Ku-band by adjusting the loading of PPy.This work provides valuable insights into the fabrication of conductive MOF composites by presenting a straightforward pathway to enhance and reg-ulate electrical conduction in MOF-based nanocomposites,thus paving a way to facilely fabricate pristine MOF-based microwave absorbers.
