Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electr...Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electronic conductivity.Firstly,this feature article reviews the recent studies on the development of new nonfluorinated ICMs with low cost and their macro/micro-structure control.In general,these new nonfluorinated ICMs have lower conductivity than commercial perfluorinated ones,due to their poor ion transport channels.Increasing ion exchange capacity(IEC)would create more continuous hydrophilic channels,thus enhancing the conductivity.However,high IEC also expands the overall hydrophilic domains,weakens the interaction between polymer chains,enhances the mobility of polymer chains,and eventually induces larger swelling.The micro-scale expansion and macro-scale swelling of the ICMs with high IEC could be controlled by limiting the mobility of polymer chains.Based on this strategy,some ef ficient techniques have been developed,including covalent crosslinking,semi-interpenatrating polymer network,and blending.Secondly,this review introduces the optimization of macro/microstructure of both perfluorinated and nonfluorinated ICMs to improve the performance.Macro-scale multilayer composite is an ef ficient way to enhance the mechanical strength and the dimensional stability of the ICMs,and could also decrease the content of per fluorosulfonic acid resin in the membrane,thereby reducing the cost of the perfluorinated ICMs.Long side chain,multiple functionalization,small molecule inducing micro-phase separation,electrospun nano fiber,and organic–inorganic hybrid could construct more ef ficient ion transport channels,improving the ion conductivity of ICMs.展开更多
Using a microcircuit fabricated on a diamond anvil cell, we have measured in-situ conductivity of HgSe under high pressures, and investigated the temperature dependence of conductivity under several different pressure...Using a microcircuit fabricated on a diamond anvil cell, we have measured in-situ conductivity of HgSe under high pressures, and investigated the temperature dependence of conductivity under several different pressures. The result shows that HgSe has a pressure-induced transition sequence from a semimetal to a semiconductor to a metal, similar to that in HgTe. Several discontinuous changes in conductivity are observed at around 1.5, 17, 29 and 49GPa, corresponding to the phase transitions from zinc-blende to cinnabar to rocksalt to orthorhombic to an unknown structure, respectively. In comparison with HgTe, it is speculated that the unknown structure may be a distorted CsCl structure. For the cinnabar-HgSe, the energy gap as a function of pressure is obtained according to the temperature dependence of conductivity. The plot of the temperature dependence of conductivity indicates that the unknown structure of HgSe has an electrical property of a conductor.展开更多
A perturbation method is used to study effective response of nonlinear Kerr composites, which are subject to the constitutive relation of electric displacement and electric field, Dα=εαE+xα|E|^2E. Under the ext...A perturbation method is used to study effective response of nonlinear Kerr composites, which are subject to the constitutive relation of electric displacement and electric field, Dα=εαE+xα|E|^2E. Under the external AG and DC electric field Eapp = Eα(1 + sinωt), the effective nonlinear responses and local potentials are induced by the cubic nonlinearity of Kerr materials at all harmonics. As an example in three dimensions, we have investigated this kind of nonlinear composites with spherical inclusions embedded in a host. At all harmonic frequencies, the potentials in inclusion and host regions are derived. Furthermore, the formulae of the effective linear and nonlinear responses are given in the dilute Iimit.展开更多
Synchronization is an essential technology in the radio navigation system. The technique for improving the “Beidou” positioning ability is presented through constituting the terrestrial improvement system, and the b...Synchronization is an essential technology in the radio navigation system. The technique for improving the “Beidou” positioning ability is presented through constituting the terrestrial improvement system, and the beacon synchronization of the improvement system with the “Beidou” one-way time transfer model is realized.The direct digital synthesis (DDS) is adopted to generate the pseudo-random code clock having high precision and stability. Meanwhile, the CPLD device is used to design the synchronization pulse picking-up module, the spread spectrum PN code generator and the spread spectrum modulator. Measurement results indicate that the beacon synchronization has the high precision and the stability.展开更多
Pursuing all-solid-state lithium metal batteries with dual upgrading of safety and energy density is of great significance. However, searching compatible solid electrolyte and reversible conversion cathode is still a ...Pursuing all-solid-state lithium metal batteries with dual upgrading of safety and energy density is of great significance. However, searching compatible solid electrolyte and reversible conversion cathode is still a big challenge. The phase transformation at cathode and Li deformation at anode would usually deactivate the electrode-electrolyte interfaces. Herein, we propose an all-solid-state Li-FeF_(3) conversion battery reinforced by hierarchical microsphere stacked polymer electrolyte for the first time. This gC_(3)N_(4) stuffed polyethylene oxide(PEO)-based electrolyte is lightweight due to the absence of metal element doping, and it enables the spatial confinement and dissolution suppression of conversion products at soft cathode-polymer interface, as well as Li dendrite inhibition at filler-reinforced anode-polymer interface. Two-dimensional(2 D)-nanosheet-built porous g-C_(3)N_(4) as three-dimensional(3 D) textured filler can strongly cross-link with PEO matrix and Li TFSI(TFSI: bistrifluoromethanesulfonimide) anion, leading to a more conductive and salt-dissociated interface and therefore improved conductivity(2.5×10^(-4) S/cm at 60℃) and Li+transference number(0.69). The compact stacking of highly regular robust microspheres in polymer electrolyte enables a successful stabilization and smoothening of Li metal with ultra-long plating/striping cycling for at least 10,000 h. The corresponding Li/LiFePO_(4) solid cells can endure an extremely high rate of 12 C. All-solid-state Li/FeF_(3) cells show highly stabilized capacity as high as 300 m Ah/g even after 200 cycles and of 200 m Ah/g at extremely high rate of 5 C, as well as ultra-long cycling for at least 1200 cycles at 1 C. High pseudocapacitance contribution(>55%) and diffusion coefficient(as high as10^(-12) cm^(2)/s) are responsible for this high-rate fluoride conversion. This result provides a promising solution to conversion-type Li metal batteries of high energy and safety beyond Li-S batteries, which are difficult to realize true "all-solid-state" due to the indispensable step of polysulfide solid-liquid conversion.展开更多
High efficiency and flexible inverted organic solar cells have been fabricated using solution-processed silver nanowire/zinc oxide composite transparent electrodes. The transparent electrodes showed a low sheet resist...High efficiency and flexible inverted organic solar cells have been fabricated using solution-processed silver nanowire/zinc oxide composite transparent electrodes. The transparent electrodes showed a low sheet resistance of -13 ff).sq-1 and high transmittance of -93% as well as superior mechanical flexibility. Power conversion efficiencies of -7.57% and -7.21% were achieved for devices fabricated on glass and plastic substrate, respectively. Moreover, the flexible devices did not show any degradation in their performance even after being folded with a radius of-480 μm.展开更多
We report for the first time highly conductive poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS)/graphene composites fabricated by in situ polymerization and their applications in a thermo...We report for the first time highly conductive poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS)/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum (Pt)-free dye-sensitized solar cell (DSSC) as energy harvesting systems. Graphene was dispersed in a solution of poly(4-styrenesulfonate) (PSS) and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene (EDOT) monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S.cm-1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m^-1K^-2 which is 93% higher than a device based on pristine PEDOT:PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT:PSS.展开更多
The time-dependent analysis of four-wave mixing(FWM) has been performed in four-level double semiconductor quantum wells(SQWs) considering the cross-coupling of the longitude-optical phonons(LOP) relaxation. It is sho...The time-dependent analysis of four-wave mixing(FWM) has been performed in four-level double semiconductor quantum wells(SQWs) considering the cross-coupling of the longitude-optical phonons(LOP) relaxation. It is shown that both the amplitude and the conversion efficiency of the FWM field enhance greatly with the increasing strength of cross-coupling of LOP relaxation. Interestingly, a double peak value of the conversion efficiency is obtained under a relatively weak single-photon detuning considering the LOP coupling. When the detuning becomes stronger,the double peaks turn into one peak appearing at the line respect to the about equality two control fields. The results can be interpreted by the effect of electromagnetically induced transparency and the indirect transition. Such controlled high efficiency FWM based on the cross-coupling LOP may have potential applications in quantum control and communications.展开更多
Smart proton conductive metal-organic framework(MOF) membranes with dynamic remote control over proton conduction show high potential for use in advanced applications, such as sensors and bioprocesses. Here, we report...Smart proton conductive metal-organic framework(MOF) membranes with dynamic remote control over proton conduction show high potential for use in advanced applications, such as sensors and bioprocesses. Here, we report a photoswitchable proton conductive ZIF-8 membrane by coencapsulating polystyrene sulfonate and graphene quantum dots into a ZIF-8 matrix(GQDs-PSS@ZIF-8) via a solidconfined conversion process. The proton conductivity of the GQDs-PSS@ZIF-8 membrane is 6.3 times higher than that of pristine ZIF-8 and can be reversibly switched by light due to photoluminescence quenching and the photothermal conversion effect, which converts light into heat. The local increase in temperature allows water molecules to escape from the porous channels, which cuts off the proton transport pathways and results in a decrease in proton conductivity. The proton conductivity is restored when the light is off owing to regaining water molecules, which act as proton carriers, from the surroundings. The GQDs-PSS@ZIF-8 membrane responds efficiently to light and exhibits an ON/OFF ratio of 12.8. This photogated proton conduction in MOFs has potential for the development and application of MOF-based protonic solids in advanced photoelectric devices.展开更多
基金Supported by the National Science Fund for Distinguished Young Scholars of China(Grant No.21125628)the Major National Scienti fic Instrument Development Project(Grant No.21527812)+3 种基金the National Natural Science Foundation of China(Grant Nos.21406031 and 21476044)the State Key Laboratory of Fine Chemicals(KF1507)the Fundamental Research Funds for the Central Universities(Grant Nos.DUTPJ14RC(3)003)State Key Laboratory of fine chemicals(Panjin)project(Grant No.JH2014009)
文摘Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electronic conductivity.Firstly,this feature article reviews the recent studies on the development of new nonfluorinated ICMs with low cost and their macro/micro-structure control.In general,these new nonfluorinated ICMs have lower conductivity than commercial perfluorinated ones,due to their poor ion transport channels.Increasing ion exchange capacity(IEC)would create more continuous hydrophilic channels,thus enhancing the conductivity.However,high IEC also expands the overall hydrophilic domains,weakens the interaction between polymer chains,enhances the mobility of polymer chains,and eventually induces larger swelling.The micro-scale expansion and macro-scale swelling of the ICMs with high IEC could be controlled by limiting the mobility of polymer chains.Based on this strategy,some ef ficient techniques have been developed,including covalent crosslinking,semi-interpenatrating polymer network,and blending.Secondly,this review introduces the optimization of macro/microstructure of both perfluorinated and nonfluorinated ICMs to improve the performance.Macro-scale multilayer composite is an ef ficient way to enhance the mechanical strength and the dimensional stability of the ICMs,and could also decrease the content of per fluorosulfonic acid resin in the membrane,thereby reducing the cost of the perfluorinated ICMs.Long side chain,multiple functionalization,small molecule inducing micro-phase separation,electrospun nano fiber,and organic–inorganic hybrid could construct more ef ficient ion transport channels,improving the ion conductivity of ICMs.
基金Project supported by the National Natural Science Foundation of China (Grant Nos 40473034, 40404007, 10574055 and 50532020) and by the State Key Development Program for Basic Research of China (Grant No 2005CB724404). Acknowledgment The authors would like to thank Keh-Jim Dunn for critically reviewing the manuscript
文摘Using a microcircuit fabricated on a diamond anvil cell, we have measured in-situ conductivity of HgSe under high pressures, and investigated the temperature dependence of conductivity under several different pressures. The result shows that HgSe has a pressure-induced transition sequence from a semimetal to a semiconductor to a metal, similar to that in HgTe. Several discontinuous changes in conductivity are observed at around 1.5, 17, 29 and 49GPa, corresponding to the phase transitions from zinc-blende to cinnabar to rocksalt to orthorhombic to an unknown structure, respectively. In comparison with HgTe, it is speculated that the unknown structure may be a distorted CsCl structure. For the cinnabar-HgSe, the energy gap as a function of pressure is obtained according to the temperature dependence of conductivity. The plot of the temperature dependence of conductivity indicates that the unknown structure of HgSe has an electrical property of a conductor.
文摘A perturbation method is used to study effective response of nonlinear Kerr composites, which are subject to the constitutive relation of electric displacement and electric field, Dα=εαE+xα|E|^2E. Under the external AG and DC electric field Eapp = Eα(1 + sinωt), the effective nonlinear responses and local potentials are induced by the cubic nonlinearity of Kerr materials at all harmonics. As an example in three dimensions, we have investigated this kind of nonlinear composites with spherical inclusions embedded in a host. At all harmonic frequencies, the potentials in inclusion and host regions are derived. Furthermore, the formulae of the effective linear and nonlinear responses are given in the dilute Iimit.
文摘Synchronization is an essential technology in the radio navigation system. The technique for improving the “Beidou” positioning ability is presented through constituting the terrestrial improvement system, and the beacon synchronization of the improvement system with the “Beidou” one-way time transfer model is realized.The direct digital synthesis (DDS) is adopted to generate the pseudo-random code clock having high precision and stability. Meanwhile, the CPLD device is used to design the synchronization pulse picking-up module, the spread spectrum PN code generator and the spread spectrum modulator. Measurement results indicate that the beacon synchronization has the high precision and the stability.
基金supported by the National Key R&D Program of China (2016YFB0901600),NSAF (U1830113)the National Natural Science Foundation of China (51772313 and 21975276)Shanghai Science and Technology Committee (20520710800)。
文摘Pursuing all-solid-state lithium metal batteries with dual upgrading of safety and energy density is of great significance. However, searching compatible solid electrolyte and reversible conversion cathode is still a big challenge. The phase transformation at cathode and Li deformation at anode would usually deactivate the electrode-electrolyte interfaces. Herein, we propose an all-solid-state Li-FeF_(3) conversion battery reinforced by hierarchical microsphere stacked polymer electrolyte for the first time. This gC_(3)N_(4) stuffed polyethylene oxide(PEO)-based electrolyte is lightweight due to the absence of metal element doping, and it enables the spatial confinement and dissolution suppression of conversion products at soft cathode-polymer interface, as well as Li dendrite inhibition at filler-reinforced anode-polymer interface. Two-dimensional(2 D)-nanosheet-built porous g-C_(3)N_(4) as three-dimensional(3 D) textured filler can strongly cross-link with PEO matrix and Li TFSI(TFSI: bistrifluoromethanesulfonimide) anion, leading to a more conductive and salt-dissociated interface and therefore improved conductivity(2.5×10^(-4) S/cm at 60℃) and Li+transference number(0.69). The compact stacking of highly regular robust microspheres in polymer electrolyte enables a successful stabilization and smoothening of Li metal with ultra-long plating/striping cycling for at least 10,000 h. The corresponding Li/LiFePO_(4) solid cells can endure an extremely high rate of 12 C. All-solid-state Li/FeF_(3) cells show highly stabilized capacity as high as 300 m Ah/g even after 200 cycles and of 200 m Ah/g at extremely high rate of 5 C, as well as ultra-long cycling for at least 1200 cycles at 1 C. High pseudocapacitance contribution(>55%) and diffusion coefficient(as high as10^(-12) cm^(2)/s) are responsible for this high-rate fluoride conversion. This result provides a promising solution to conversion-type Li metal batteries of high energy and safety beyond Li-S batteries, which are difficult to realize true "all-solid-state" due to the indispensable step of polysulfide solid-liquid conversion.
文摘High efficiency and flexible inverted organic solar cells have been fabricated using solution-processed silver nanowire/zinc oxide composite transparent electrodes. The transparent electrodes showed a low sheet resistance of -13 ff).sq-1 and high transmittance of -93% as well as superior mechanical flexibility. Power conversion efficiencies of -7.57% and -7.21% were achieved for devices fabricated on glass and plastic substrate, respectively. Moreover, the flexible devices did not show any degradation in their performance even after being folded with a radius of-480 μm.
文摘We report for the first time highly conductive poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS)/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum (Pt)-free dye-sensitized solar cell (DSSC) as energy harvesting systems. Graphene was dispersed in a solution of poly(4-styrenesulfonate) (PSS) and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene (EDOT) monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S.cm-1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m^-1K^-2 which is 93% higher than a device based on pristine PEDOT:PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT:PSS.
基金Supported by Program for Changjiang Scholars and Innovative Research Team in University under Grant(IRT1080)National Natural Science Foundation of China under Grant Nos.51272158,11374252,and 51372214+2 种基金Changjiang Scholar Incentive Program under Grant No.[2009]17Scientific Research Fund of Hunan Provincial Education Department of China under Grant No.12A140the Science and Technology Foundation of Guizhou Province of China under Grant No.J20122314
文摘The time-dependent analysis of four-wave mixing(FWM) has been performed in four-level double semiconductor quantum wells(SQWs) considering the cross-coupling of the longitude-optical phonons(LOP) relaxation. It is shown that both the amplitude and the conversion efficiency of the FWM field enhance greatly with the increasing strength of cross-coupling of LOP relaxation. Interestingly, a double peak value of the conversion efficiency is obtained under a relatively weak single-photon detuning considering the LOP coupling. When the detuning becomes stronger,the double peaks turn into one peak appearing at the line respect to the about equality two control fields. The results can be interpreted by the effect of electromagnetically induced transparency and the indirect transition. Such controlled high efficiency FWM based on the cross-coupling LOP may have potential applications in quantum control and communications.
基金supported by the National Natural Science Foundation of China (21875212)the Key Program of National Natural Science Foundation (51632008)+2 种基金the Major R&D Plan of Zhejiang Natural Science Foundation (LD18E020001)the National Key Research and Development Program (2016YFA0200204)the Fundamental Research Funds for the Central Universities。
文摘Smart proton conductive metal-organic framework(MOF) membranes with dynamic remote control over proton conduction show high potential for use in advanced applications, such as sensors and bioprocesses. Here, we report a photoswitchable proton conductive ZIF-8 membrane by coencapsulating polystyrene sulfonate and graphene quantum dots into a ZIF-8 matrix(GQDs-PSS@ZIF-8) via a solidconfined conversion process. The proton conductivity of the GQDs-PSS@ZIF-8 membrane is 6.3 times higher than that of pristine ZIF-8 and can be reversibly switched by light due to photoluminescence quenching and the photothermal conversion effect, which converts light into heat. The local increase in temperature allows water molecules to escape from the porous channels, which cuts off the proton transport pathways and results in a decrease in proton conductivity. The proton conductivity is restored when the light is off owing to regaining water molecules, which act as proton carriers, from the surroundings. The GQDs-PSS@ZIF-8 membrane responds efficiently to light and exhibits an ON/OFF ratio of 12.8. This photogated proton conduction in MOFs has potential for the development and application of MOF-based protonic solids in advanced photoelectric devices.