Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated ...Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb_2S_3 hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. Even at a high currentdensity of 5000 m A g^(-1), a discharge capacity of541 m Ah g^(-1) is achieved. Sb_2S_3 hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space,which can buffer the volume expansion.展开更多
A hollow glass microsphere(HGM)/TiO2 composite hollow sphere was successfully prepared via a simple precipitation method.The TiO2 coating layers grew on the surface of the HGMs that range from 20 to 50μm in diameter ...A hollow glass microsphere(HGM)/TiO2 composite hollow sphere was successfully prepared via a simple precipitation method.The TiO2 coating layers grew on the surface of the HGMs that range from 20 to 50μm in diameter as nanoparticles with the formation of the SiO Ti bonds.The growth mechanism accounting for the formation of the TiO2 nanolayers was proposed.The morphology,composition,thermal insulation properties,and visible-near infrared(VIS-NIR)refl ectance of the HGMs/TiO2 composite hollow spheres were characterized.The VIS-NIR reflectance of the HGMs/TiO2 composite hollow spheres increased by more than 30%compared to raw HGMs.The thermal conductivity of the particles is 0.058 W/(m K).The result indicates that the VIS-NIR reflectance of the composite hollow spheres is strongly influenced by the coating of TiO2.The composite hollow spheres were used as the main functional filler to prepare the organic-inorganic composite coatings.The glass substrates coated by the organic-inorganic coatings had lower thermal conductivity and higher near infrared reflectivity.Therefore,the HGMs/TiO2 composite hollow spheres can reflect most of the solar energy and effectively keep out the heat as a thermal insulation coating for energy-saving constructions.展开更多
Deep oil and gas reservoirs are under high-temperature conditions,but traditional coring methods do not consider temperature-preserved measures and ignore the influence of temperature on rock porosity and permeability...Deep oil and gas reservoirs are under high-temperature conditions,but traditional coring methods do not consider temperature-preserved measures and ignore the influence of temperature on rock porosity and permeability,resulting in distorted resource assessments.The development of in situ temperaturepreserved coring(ITP-Coring)technology for deep reservoir rock is urgent,and thermal insulation materials are key.Therefore,hollow glass microsphere/epoxy resin thermal insulation materials(HGM/EP materials)were proposed as thermal insulation materials.The materials properties under coupled hightemperature and high-pressure(HTHP)conditions were tested.The results indicated that high pressures led to HGM destruction and that the materials water absorption significantly increased;additionally,increasing temperature accelerated the process.High temperatures directly caused the thermal conductivity of the materials to increase;additionally,the thermal conduction and convection of water caused by high pressures led to an exponential increase in the thermal conductivity.High temperatures weakened the matrix,and high pressures destroyed the HGM,which resulted in a decrease in the tensile mechanical properties of the materials.The materials entered the high elastic state at 150℃,and the mechanical properties were weakened more obviously,while the pressure led to a significant effect when the water absorption was above 10%.Meanwhile,the tensile strength/strain were 13.62 MPa/1.3%and 6.09 MPa/0.86%at 100℃ and 100 MPa,respectively,which meet the application requirements of the self-designed coring device.Finally,K46-f40 and K46-f50 HGM/EP materials were proven to be suitable for ITP-Coring under coupled conditions below 100℃ and 100 MPa.To further improve the materials properties,the interface layer and EP matrix should be optimized.The results can provide references for the optimization and engineering application of materials and thus technical support for deep oil and gas resource development.展开更多
The surface of hollow glass microspheres (HGMs) was roughened by a HCl+NH_(4)F strategy,which achieved a broken ratio as 16.10%,and then metallized by electroless plating by Co nanoparticles up to 90 wt% (abbreviated ...The surface of hollow glass microspheres (HGMs) was roughened by a HCl+NH_(4)F strategy,which achieved a broken ratio as 16.10%,and then metallized by electroless plating by Co nanoparticles up to 90 wt% (abbreviated as Co-HGMs).The average grain size of Co was measured to range from 0.4 to 0.5 μm.Then Co-HGMs were mixed with liquid silicone rubber and xylene,and cured on a perspex plate applicable for flexible electromagnetic shielding.By attentive parameter optimization,a film about 0.836 mm in thickness was obtained with a density of 0.729 g/cm^(3),showing a shielding effectiveness of 15.2 dB in the X-band (8.2-12.4 GHz) at room temperature,which was ascribed to the formation of a conductive network of Co-HGMs inside the film.Simultaneously,the tensile strength of 0.89 MPa at an elongation ratio of 194.5% was also obtained,showing good mechanical properties and tensile strength.展开更多
ZnO nanoparticles were first encapsulated in submicron PS hollow microspheres through two-step swelling process of core-shell structured PMMA/PS （PMMA： polymethyl methao- rylate） microspheres in acid-alkali solutio...ZnO nanoparticles were first encapsulated in submicron PS hollow microspheres through two-step swelling process of core-shell structured PMMA/PS （PMMA： polymethyl methao- rylate） microspheres in acid-alkali solution, and the ZnO precursors, i.e. the ethanol solu- tions of （CHaCOO）2Zn and LiOH. The transmission electron microscope, X-ray diffraction, and thermogravimetric analysis results show that the feeding order of ethanol solutions of （CH3COO）2Zn and LiOH in the second swelling step has great influence on the loading efficiency and the size of ZnO nanoparticles, but little on their crystal form. The photolumi- nescence and UV-Vis absorption behavior of ZnO/PS microspheres show that the PS shell can effectively avoid the fluorescence quenching effect.展开更多
Tin-based nanomaterials have been extensively explored as high-capacity anode materials for lithium ion batteries（LIBs）. However,the large volume changes upon repeated cycling always cause the pulverization of the e...Tin-based nanomaterials have been extensively explored as high-capacity anode materials for lithium ion batteries（LIBs）. However,the large volume changes upon repeated cycling always cause the pulverization of the electrode materials. Herein,we report the fabrication of uniform SnS_2@C hollow microspheres from hydrothermally prepared SnO_2@C hollow microspheres by a solid-state sulfurization process. The as-prepared hollow SnS_2@C microspheres with unique carbon shell,as electrodes in LIBs,exhibit high reversible capacity of 814 mA h g^（-1） at a current density of 100 mA g^（-1）,good cycling performance（783 mA h g^（-1） for 200 cycles maintained with an average degradation rate of 0.02% per cycle） and remarkable rate capability（reversible capabilities of 433 mA h g^（-1）at 2C）. The hollow space could serve as extra space for volume expansion during the charge-discharge cycling,while the carbon shell can ensure the structural integrity of the microspheres. The preeminent electrochemical performances of the SnS_2@C electrodes demonstrate their promising application as anode materials in the next-generation LIBs.展开更多
Titanium niobium oxides emerge as promising anode materials with potential for applications in lithium ion batteries with high safety and high energy density.However,the innate low electronic conductivity of such a co...Titanium niobium oxides emerge as promising anode materials with potential for applications in lithium ion batteries with high safety and high energy density.However,the innate low electronic conductivity of such a composite oxide seriously limits its practical capacity,which becomes a serious concern especially when a high rate charge/discharge capability is expected.Here,using a modified template-assisted synthesis protocol,which features an in-situ entrapment of both titanium and niobium species during the formation of polymeric microsphere followed by a pyrolysis process,we succeed in preparing hollow microspheres of titanium niobium oxide with high efficiency in structural control.When used as an anode material,the structurally-controlled hollow sample delivers high reversible capacity(103.7 m A h g^(-1)at 50 C)and extraordinary cycling capability especially at high charge/discharge currents(164.7 m A h g^(-1)after 500 cycles at 10 C).展开更多
A designed solution route was developed to fabricate size tunable SnO2 hollow microspheres based on the sol-gel theory. The hydrolysis of SnSO4 released protons to form SnO2 particulates and induced the decrease of pH...A designed solution route was developed to fabricate size tunable SnO2 hollow microspheres based on the sol-gel theory. The hydrolysis of SnSO4 released protons to form SnO2 particulates and induced the decrease of pH value. To minimize the high surface energy, the SnO2 particulates tended to assemble into large particles, the size of which was affected by the electrolyte concentration or pH value. Elevating SnSO4 content aroused the decrease of the pH value that directed to the shrinkage of the aggregated particle size of SnO2. Size tunable SnO2 hollow micro- spheres were then rationally fabricated under solvothermal conditions via Ostwald ripening by simply adjusting the SnSO4 concentration. The in situ pH decrease directed to the shrinkage of the particle size from 270 nm to 112 nm. The formation mechanism was confirmed and rationally elucidated by the time dependant morphology evolution. Charge-discharge tests revealed that the reduced particle size aroused an improved lithium ion battery performance.展开更多
基金supported financially by the National Natural Foundation of China(Grant No.51672234)the Research Foundation for Hunan Youth Outstanding People from Hunan Provincial Science and Technology Department(2015RS4030)+1 种基金Hunan 2011 Collaborative Innovation Center of Chemical Engineering&Technology with Environmental Benignity and Effective Resource UtilizationProgram for Innovative Research Cultivation Team in University of Ministry of Education of China(1337304)
文摘Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb_2S_3 hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. Even at a high currentdensity of 5000 m A g^(-1), a discharge capacity of541 m Ah g^(-1) is achieved. Sb_2S_3 hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space,which can buffer the volume expansion.
文摘A hollow glass microsphere(HGM)/TiO2 composite hollow sphere was successfully prepared via a simple precipitation method.The TiO2 coating layers grew on the surface of the HGMs that range from 20 to 50μm in diameter as nanoparticles with the formation of the SiO Ti bonds.The growth mechanism accounting for the formation of the TiO2 nanolayers was proposed.The morphology,composition,thermal insulation properties,and visible-near infrared(VIS-NIR)refl ectance of the HGMs/TiO2 composite hollow spheres were characterized.The VIS-NIR reflectance of the HGMs/TiO2 composite hollow spheres increased by more than 30%compared to raw HGMs.The thermal conductivity of the particles is 0.058 W/(m K).The result indicates that the VIS-NIR reflectance of the composite hollow spheres is strongly influenced by the coating of TiO2.The composite hollow spheres were used as the main functional filler to prepare the organic-inorganic composite coatings.The glass substrates coated by the organic-inorganic coatings had lower thermal conductivity and higher near infrared reflectivity.Therefore,the HGMs/TiO2 composite hollow spheres can reflect most of the solar energy and effectively keep out the heat as a thermal insulation coating for energy-saving constructions.
基金supported by the Sichuan Science and Technology Program (Grant Nos.2023NSFSC0004,2023NSFSC0790)the National Natural Science Foundation of China (Grant Nos.51827901,52304033)the Sichuan University Postdoctoral Fund (Grant No.2024SCU12093)。
文摘Deep oil and gas reservoirs are under high-temperature conditions,but traditional coring methods do not consider temperature-preserved measures and ignore the influence of temperature on rock porosity and permeability,resulting in distorted resource assessments.The development of in situ temperaturepreserved coring(ITP-Coring)technology for deep reservoir rock is urgent,and thermal insulation materials are key.Therefore,hollow glass microsphere/epoxy resin thermal insulation materials(HGM/EP materials)were proposed as thermal insulation materials.The materials properties under coupled hightemperature and high-pressure(HTHP)conditions were tested.The results indicated that high pressures led to HGM destruction and that the materials water absorption significantly increased;additionally,increasing temperature accelerated the process.High temperatures directly caused the thermal conductivity of the materials to increase;additionally,the thermal conduction and convection of water caused by high pressures led to an exponential increase in the thermal conductivity.High temperatures weakened the matrix,and high pressures destroyed the HGM,which resulted in a decrease in the tensile mechanical properties of the materials.The materials entered the high elastic state at 150℃,and the mechanical properties were weakened more obviously,while the pressure led to a significant effect when the water absorption was above 10%.Meanwhile,the tensile strength/strain were 13.62 MPa/1.3%and 6.09 MPa/0.86%at 100℃ and 100 MPa,respectively,which meet the application requirements of the self-designed coring device.Finally,K46-f40 and K46-f50 HGM/EP materials were proven to be suitable for ITP-Coring under coupled conditions below 100℃ and 100 MPa.To further improve the materials properties,the interface layer and EP matrix should be optimized.The results can provide references for the optimization and engineering application of materials and thus technical support for deep oil and gas resource development.
文摘The surface of hollow glass microspheres (HGMs) was roughened by a HCl+NH_(4)F strategy,which achieved a broken ratio as 16.10%,and then metallized by electroless plating by Co nanoparticles up to 90 wt% (abbreviated as Co-HGMs).The average grain size of Co was measured to range from 0.4 to 0.5 μm.Then Co-HGMs were mixed with liquid silicone rubber and xylene,and cured on a perspex plate applicable for flexible electromagnetic shielding.By attentive parameter optimization,a film about 0.836 mm in thickness was obtained with a density of 0.729 g/cm^(3),showing a shielding effectiveness of 15.2 dB in the X-band (8.2-12.4 GHz) at room temperature,which was ascribed to the formation of a conductive network of Co-HGMs inside the film.Simultaneously,the tensile strength of 0.89 MPa at an elongation ratio of 194.5% was also obtained,showing good mechanical properties and tensile strength.
文摘ZnO nanoparticles were first encapsulated in submicron PS hollow microspheres through two-step swelling process of core-shell structured PMMA/PS （PMMA： polymethyl methao- rylate） microspheres in acid-alkali solution, and the ZnO precursors, i.e. the ethanol solu- tions of （CHaCOO）2Zn and LiOH. The transmission electron microscope, X-ray diffraction, and thermogravimetric analysis results show that the feeding order of ethanol solutions of （CH3COO）2Zn and LiOH in the second swelling step has great influence on the loading efficiency and the size of ZnO nanoparticles, but little on their crystal form. The photolumi- nescence and UV-Vis absorption behavior of ZnO/PS microspheres show that the PS shell can effectively avoid the fluorescence quenching effect.
基金supported by the National Natural Science Foundation of China (51302323)the Program for New Century Excellent Talents in University (NCET-13-0594)the Innovationdriven Project of Central South University (2017CX001)
文摘Tin-based nanomaterials have been extensively explored as high-capacity anode materials for lithium ion batteries（LIBs）. However,the large volume changes upon repeated cycling always cause the pulverization of the electrode materials. Herein,we report the fabrication of uniform SnS_2@C hollow microspheres from hydrothermally prepared SnO_2@C hollow microspheres by a solid-state sulfurization process. The as-prepared hollow SnS_2@C microspheres with unique carbon shell,as electrodes in LIBs,exhibit high reversible capacity of 814 mA h g^（-1） at a current density of 100 mA g^（-1）,good cycling performance（783 mA h g^（-1） for 200 cycles maintained with an average degradation rate of 0.02% per cycle） and remarkable rate capability（reversible capabilities of 433 mA h g^（-1）at 2C）. The hollow space could serve as extra space for volume expansion during the charge-discharge cycling,while the carbon shell can ensure the structural integrity of the microspheres. The preeminent electrochemical performances of the SnS_2@C electrodes demonstrate their promising application as anode materials in the next-generation LIBs.
基金supported by the National Natural Science Foundation of China (51672282, 21373238)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA09010101)
文摘Titanium niobium oxides emerge as promising anode materials with potential for applications in lithium ion batteries with high safety and high energy density.However,the innate low electronic conductivity of such a composite oxide seriously limits its practical capacity,which becomes a serious concern especially when a high rate charge/discharge capability is expected.Here,using a modified template-assisted synthesis protocol,which features an in-situ entrapment of both titanium and niobium species during the formation of polymeric microsphere followed by a pyrolysis process,we succeed in preparing hollow microspheres of titanium niobium oxide with high efficiency in structural control.When used as an anode material,the structurally-controlled hollow sample delivers high reversible capacity(103.7 m A h g^(-1)at 50 C)and extraordinary cycling capability especially at high charge/discharge currents(164.7 m A h g^(-1)after 500 cycles at 10 C).
基金Supported by the National Natural Science Foundation of China（Nos.21271138, 21371070, 21071060）, the Natural Science Foundation of Tianjin, China（No.10JCZDJC21500） and the Open Fund of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University, China（No.2015-02）.
文摘A designed solution route was developed to fabricate size tunable SnO2 hollow microspheres based on the sol-gel theory. The hydrolysis of SnSO4 released protons to form SnO2 particulates and induced the decrease of pH value. To minimize the high surface energy, the SnO2 particulates tended to assemble into large particles, the size of which was affected by the electrolyte concentration or pH value. Elevating SnSO4 content aroused the decrease of the pH value that directed to the shrinkage of the aggregated particle size of SnO2. Size tunable SnO2 hollow micro- spheres were then rationally fabricated under solvothermal conditions via Ostwald ripening by simply adjusting the SnSO4 concentration. The in situ pH decrease directed to the shrinkage of the particle size from 270 nm to 112 nm. The formation mechanism was confirmed and rationally elucidated by the time dependant morphology evolution. Charge-discharge tests revealed that the reduced particle size aroused an improved lithium ion battery performance.
