The rapid development of the information era has led to in-creased power consumption,which generates more heat.This requires more efficient thermal management systems,with the most direct ap-proach being the developme...The rapid development of the information era has led to in-creased power consumption,which generates more heat.This requires more efficient thermal management systems,with the most direct ap-proach being the development of su-perior thermal interface materials(TIMs).Mesocarbon microbeads(MCMBs)have several desirable properties for this purpose,includ-ing high thermal conductivity and excellent thermal stability.Although their thermal conductivity(K)may not be exceptional among all carbon materials,their ease of production and low cost make them ideal filler materials for developing a new generation of carbon-based TIMs.We report the fabrication of high-performance TIMs by incorporating MCMBs in a polyimide(PI)framework,producing highly graphitized PI/MCMB(PM)foams and anisotropic polydimethylsiloxane/PM(PDMS/PM)composites with a high thermal conductivity using directional freezing and high-temperature thermal annealing.The resulting materials had a high through-plane(TP)K of 15.926 W·m^(−1)·K^(−1),4.83 times that of conventional thermally conductive silicone pads and 88.5 times higher than that of pure PDMS.The composites had excellent mechanical properties and thermal stability,meeting the de-mands of modern electronic products for integration,multi-functionality,and miniaturization.展开更多
The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion,poor conductivity,and low Coulombic efficiency.In this work...The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion,poor conductivity,and low Coulombic efficiency.In this work,a novel silica/oxidized mesocarbon microbead/amorphous carbon(SiO2/O’MCMB/C)hierarchical structure in which SiO2 is sandwiched between spherical graphite and amorphous carbon shell was succes sfully fabricated through hydrogen bonding-assisted self-assembly and post-carbon coating method.The obtained three-layer hierarchical structure effectively accommodates the volumetric expansion of SiO2 and significantly enhances the electronic conductivity of composite materials.Moreover,the outer layer of amorphous carbon effectively increases the diffusion rate of lithium ions and promotes the formation of stable SEI film.As a result,the SiO2/O’MCMB/C composite exhibits superior electrochemical performance with a reversible capacity of 459.5 mA h/g in the first cycle,and the corresponding Coulombic efficiency is 62.8%.After 300 cycles,the capacity climbs to around 600 mA h/g.This synthetic route provides an efficient method for preparing SiO2 supported on graphite with excellent electrochemical performance,which is likely to promote its commercial applications.展开更多
Dual-ion batteries(DIBs)have attracted tremendous attention owing to their high operating voltage and are considered promising candidates for low-cost clean energy storage devices.However,the decomposition of electrol...Dual-ion batteries(DIBs)have attracted tremendous attention owing to their high operating voltage and are considered promising candidates for low-cost clean energy storage devices.However,the decomposition of electrolytes and collapse of the cathode structure may lead to low Coulombic efficiency(CE)and low cycling stability of DIBs.Wide-layered electrode materials can accommodate the intercalation/deintercalation of large anions,which is believed to overcome these issues.Herein,expanded mesocarbon microbeads(200HRO-MCMB)possessing an enlarged interlayer spacing(0.405 nm)were prepared via modified Hummers and subcritical hydrothermal reduction methods.After the indispensable electrochemical activation,200HRO-MCMB(hydrothermal reduction at 200℃)exhibited a high specific capacity(120 mAh·g^(-1)at50 mA·g^(-1))when used as a cathode for a sodium-based DIB,and the CE significantly improved within the 2.0-4.5 V voltage range.Additionally,the cycling stability exceeded over 600 cycles.Remarkably,this cathode possessed enlarged interlayers that decreased the barrier of PF6^(-)transport,and the battery storage mechanism corresponded to a transitioning state between double-layer capacitance and Faradaic intercalation.Undoubtedly,this work will expand the scope of the practical application of low-cost sodium-based DIBs.展开更多
The graphene/mesocarbon microbead(MCMB)composite is assessed as an anode material with a high capacity for lithium-ion batteries.The composite electrode exhibits improved cycling stability and rate capability,deliveri...The graphene/mesocarbon microbead(MCMB)composite is assessed as an anode material with a high capacity for lithium-ion batteries.The composite electrode exhibits improved cycling stability and rate capability,delivering a high initial charge/discharge capacity of 421.4 mA·h/g/494.8 mA·h/g as well as an excellent capacity retention over 500 cycles at a current density of 40 mA/g.At a higher current density of 800 mA/g,the electrode still retains 35%of its initial capacity which exceeds the capacity retention of pure graphene or MCMB reference electrodes.Cyclic voltammetry and electrochemical impedance spectroscopy reveal that the composite electrode favors electrochemical kinetics as compared with graphene and MCMB separately.Superior electrochemical properties suggest a strong synergetic effect between highly conductive graphene and MCMB.展开更多
The influence of nitrogen-containing polycyclic aromatic hydrocarbons(NC-PAH)on the formation of carbonaceous mesophase remains enigmatic,despite extensive research on the production of carbonaceous materials from aro...The influence of nitrogen-containing polycyclic aromatic hydrocarbons(NC-PAH)on the formation of carbonaceous mesophase remains enigmatic,despite extensive research on the production of carbonaceous materials from aromatic-rich oils.Molecular dynamics simulation was used to investigate the variations in pyrolysis behavior between PAH and NC-PAH based on the composition analysis.Through adjusting the content of NC-PAH,the influence of NC-PAH on the thermal stability of slurry oils(SOs)was evaluated by thermogravimetry,viscosity,coke value,and quinoline insoluble(QI).The morphology and structure of mesocarbon microbeads(MCMBs)prepared with SOs were measured by a polarized-light microscope,SEM,XRD,and Raman.Simulation results indicate that NC-PAH possesses much higher reactivity and tends to produce highly condensed solid and coke products.It corresponds to the QI and high viscosity in thermal stability experiments.Therefore,high concentrations of NC-PAH result in nonuniform morphology and disordered structures.In a system with low viscosity and few QIs,SO,which has a low nitrogen content(475 ppm),reacts gently to produce MCMBs with a uniform particle size(10-40μm)and an excellent spherical shape.As NC-PAH content decreases,the crystalline size of graphitization elevates,as evidenced by parallel layers(10.472-11.764)and stack height(3.269-3.701 nm).The graphitization degree becomes worse and nonuniform with the increase of the content of NC-PAH,and the best is 20.58%evaluated by Raman spectra area ratio(AG/Aall).Overall,this work suggests a nitrogen content reference and a controlling technology of nitrogen for the preparation of superior MCMB.展开更多
Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morpholog...Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morphology of mesophase spheres and the structure of the MCMB carbonized at 1000℃ for lh using scanning electron microscope （SEM） and XRD, it was found that phenolic resin accelerated the formation and coalescence of mesophase spheres. Some of the obtained MCMB were hi- or tri-spheres with the distorted microtextural carbon layers. Hexamethylenetetramine in the pitch modified by phenolic resin accelerated the condensation of phenolic resin and consequently expedited the combination of mesophase spheres, which was proved by the formation of some tetra-spheres. Owing to the cross-linkage of the additives, MCMB with complex structure were obtained.展开更多
Mesoporous carbon（MC） material with high specific surface area（1432 m^2/g）, large pore volume（2.894 cm^3/g） and appropriate mesopore structure（about 6.5 nm） has been prepared. We use the magnesium citrate as t...Mesoporous carbon（MC） material with high specific surface area（1432 m^2/g）, large pore volume（2.894 cm^3/g） and appropriate mesopore structure（about 6.5 nm） has been prepared. We use the magnesium citrate as the precursor of the carbon material and the nano-sized magnesium oxide（MgO）particles as template provided by magnesium citrate. The structure characterization and the electrochemical performance of MC are investigated. Compared with commercial activated carbon（AC） cathode, the utilization of MC cathode can obviously improve the energy density of LIC device. When the MC cathode is coupled with pre-lithiated hard carbon（HC） anode, the LIC device shows the optimal electrochemical performance, high energy density up to 95.4 Wh/kg and power density as high as 7.4 kW/kg（based on active material mass of two electrodes）, excellent capacity retention of 97.3% after 2000 cycles. The present work indicates the combination of MC electrode with HC electrodes as promising candidates for the realization of LIC with high energy density, high power density and long cycle life.展开更多
Mesocarbon microbeads （MCMB） and super fine mesophase powder （SFMP） were prepared firstly from a coal tar pitch and then hot-condensed into high-density isotropic carbon （HDIC） bulks under 160 MPa and finally si...Mesocarbon microbeads （MCMB） and super fine mesophase powder （SFMP） were prepared firstly from a coal tar pitch and then hot-condensed into high-density isotropic carbon （HDIC） bulks under 160 MPa and finally sintered at 1 000 ℃. By analyzing the thermogravimetric behavior of the MCMB and SFMP powders, their volume shrinkage and weight loss during sintering and the bulk density and flexural strengths of their sintered bulks, it was found that the smaller sizes and the richer β-resin contents of SFMP ha）re facilitated formation of sintered bulks with more compact isotropic structure and higher flexural strengths than MCMB. Because of the filling and bonding effects of SFMP on MCMB bulks, addition of SFMP, albeit a little, can greatly increase the flexural strengths of sintered bulks of MCMB. However, adding MCMB, even a slight amount, into SFMP can severely impair the flexural strength of sintered bulks. This might be attributed to both the crack initiation along the boundaries between MCMB and SFMP and the formation of layered texture of MCMB sphere.展开更多
文摘The rapid development of the information era has led to in-creased power consumption,which generates more heat.This requires more efficient thermal management systems,with the most direct ap-proach being the development of su-perior thermal interface materials(TIMs).Mesocarbon microbeads(MCMBs)have several desirable properties for this purpose,includ-ing high thermal conductivity and excellent thermal stability.Although their thermal conductivity(K)may not be exceptional among all carbon materials,their ease of production and low cost make them ideal filler materials for developing a new generation of carbon-based TIMs.We report the fabrication of high-performance TIMs by incorporating MCMBs in a polyimide(PI)framework,producing highly graphitized PI/MCMB(PM)foams and anisotropic polydimethylsiloxane/PM(PDMS/PM)composites with a high thermal conductivity using directional freezing and high-temperature thermal annealing.The resulting materials had a high through-plane(TP)K of 15.926 W·m^(−1)·K^(−1),4.83 times that of conventional thermally conductive silicone pads and 88.5 times higher than that of pure PDMS.The composites had excellent mechanical properties and thermal stability,meeting the de-mands of modern electronic products for integration,multi-functionality,and miniaturization.
基金supported by the National Key Research and Development Program of China (No.2016YFB0100511)
文摘The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion,poor conductivity,and low Coulombic efficiency.In this work,a novel silica/oxidized mesocarbon microbead/amorphous carbon(SiO2/O’MCMB/C)hierarchical structure in which SiO2 is sandwiched between spherical graphite and amorphous carbon shell was succes sfully fabricated through hydrogen bonding-assisted self-assembly and post-carbon coating method.The obtained three-layer hierarchical structure effectively accommodates the volumetric expansion of SiO2 and significantly enhances the electronic conductivity of composite materials.Moreover,the outer layer of amorphous carbon effectively increases the diffusion rate of lithium ions and promotes the formation of stable SEI film.As a result,the SiO2/O’MCMB/C composite exhibits superior electrochemical performance with a reversible capacity of 459.5 mA h/g in the first cycle,and the corresponding Coulombic efficiency is 62.8%.After 300 cycles,the capacity climbs to around 600 mA h/g.This synthetic route provides an efficient method for preparing SiO2 supported on graphite with excellent electrochemical performance,which is likely to promote its commercial applications.
基金financially supported by the National Natural Science Foundation(NSFC)of China(No.22179094)。
文摘Dual-ion batteries(DIBs)have attracted tremendous attention owing to their high operating voltage and are considered promising candidates for low-cost clean energy storage devices.However,the decomposition of electrolytes and collapse of the cathode structure may lead to low Coulombic efficiency(CE)and low cycling stability of DIBs.Wide-layered electrode materials can accommodate the intercalation/deintercalation of large anions,which is believed to overcome these issues.Herein,expanded mesocarbon microbeads(200HRO-MCMB)possessing an enlarged interlayer spacing(0.405 nm)were prepared via modified Hummers and subcritical hydrothermal reduction methods.After the indispensable electrochemical activation,200HRO-MCMB(hydrothermal reduction at 200℃)exhibited a high specific capacity(120 mAh·g^(-1)at50 mA·g^(-1))when used as a cathode for a sodium-based DIB,and the CE significantly improved within the 2.0-4.5 V voltage range.Additionally,the cycling stability exceeded over 600 cycles.Remarkably,this cathode possessed enlarged interlayers that decreased the barrier of PF6^(-)transport,and the battery storage mechanism corresponded to a transitioning state between double-layer capacitance and Faradaic intercalation.Undoubtedly,this work will expand the scope of the practical application of low-cost sodium-based DIBs.
基金Project supported by the National Natural Science Foundation of China(No.21573239)the Guangdong Provincial Project for Science and Technology(Nos.2014TX01N14,2015B010135008,and 2016B010114003)+1 种基金the Guangzhou Municipal Project for Science and Technology(No.201509010018)the K.C.WONG Education Foundation,China。
文摘The graphene/mesocarbon microbead(MCMB)composite is assessed as an anode material with a high capacity for lithium-ion batteries.The composite electrode exhibits improved cycling stability and rate capability,delivering a high initial charge/discharge capacity of 421.4 mA·h/g/494.8 mA·h/g as well as an excellent capacity retention over 500 cycles at a current density of 40 mA/g.At a higher current density of 800 mA/g,the electrode still retains 35%of its initial capacity which exceeds the capacity retention of pure graphene or MCMB reference electrodes.Cyclic voltammetry and electrochemical impedance spectroscopy reveal that the composite electrode favors electrochemical kinetics as compared with graphene and MCMB separately.Superior electrochemical properties suggest a strong synergetic effect between highly conductive graphene and MCMB.
基金support of National Natural Science Foundation of P.R.China(22308104).
文摘The influence of nitrogen-containing polycyclic aromatic hydrocarbons(NC-PAH)on the formation of carbonaceous mesophase remains enigmatic,despite extensive research on the production of carbonaceous materials from aromatic-rich oils.Molecular dynamics simulation was used to investigate the variations in pyrolysis behavior between PAH and NC-PAH based on the composition analysis.Through adjusting the content of NC-PAH,the influence of NC-PAH on the thermal stability of slurry oils(SOs)was evaluated by thermogravimetry,viscosity,coke value,and quinoline insoluble(QI).The morphology and structure of mesocarbon microbeads(MCMBs)prepared with SOs were measured by a polarized-light microscope,SEM,XRD,and Raman.Simulation results indicate that NC-PAH possesses much higher reactivity and tends to produce highly condensed solid and coke products.It corresponds to the QI and high viscosity in thermal stability experiments.Therefore,high concentrations of NC-PAH result in nonuniform morphology and disordered structures.In a system with low viscosity and few QIs,SO,which has a low nitrogen content(475 ppm),reacts gently to produce MCMBs with a uniform particle size(10-40μm)and an excellent spherical shape.As NC-PAH content decreases,the crystalline size of graphitization elevates,as evidenced by parallel layers(10.472-11.764)and stack height(3.269-3.701 nm).The graphitization degree becomes worse and nonuniform with the increase of the content of NC-PAH,and the best is 20.58%evaluated by Raman spectra area ratio(AG/Aall).Overall,this work suggests a nitrogen content reference and a controlling technology of nitrogen for the preparation of superior MCMB.
基金Supported by the National Natural Science Foundation of China (No.50172034).
文摘Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morphology of mesophase spheres and the structure of the MCMB carbonized at 1000℃ for lh using scanning electron microscope （SEM） and XRD, it was found that phenolic resin accelerated the formation and coalescence of mesophase spheres. Some of the obtained MCMB were hi- or tri-spheres with the distorted microtextural carbon layers. Hexamethylenetetramine in the pitch modified by phenolic resin accelerated the condensation of phenolic resin and consequently expedited the combination of mesophase spheres, which was proved by the formation of some tetra-spheres. Owing to the cross-linkage of the additives, MCMB with complex structure were obtained.
基金financially supported by the National Natural Science Foundation of China(No.51603147)Tianjin Application Foundation and Advanced Technology Research Plan Project(Nos.15ZCZDGX00270,14RCHZGX00859)China Postdoctoral Science Foundation(No.2017M621079)
文摘Mesoporous carbon（MC） material with high specific surface area（1432 m^2/g）, large pore volume（2.894 cm^3/g） and appropriate mesopore structure（about 6.5 nm） has been prepared. We use the magnesium citrate as the precursor of the carbon material and the nano-sized magnesium oxide（MgO）particles as template provided by magnesium citrate. The structure characterization and the electrochemical performance of MC are investigated. Compared with commercial activated carbon（AC） cathode, the utilization of MC cathode can obviously improve the energy density of LIC device. When the MC cathode is coupled with pre-lithiated hard carbon（HC） anode, the LIC device shows the optimal electrochemical performance, high energy density up to 95.4 Wh/kg and power density as high as 7.4 kW/kg（based on active material mass of two electrodes）, excellent capacity retention of 97.3% after 2000 cycles. The present work indicates the combination of MC electrode with HC electrodes as promising candidates for the realization of LIC with high energy density, high power density and long cycle life.
文摘Mesocarbon microbeads （MCMB） and super fine mesophase powder （SFMP） were prepared firstly from a coal tar pitch and then hot-condensed into high-density isotropic carbon （HDIC） bulks under 160 MPa and finally sintered at 1 000 ℃. By analyzing the thermogravimetric behavior of the MCMB and SFMP powders, their volume shrinkage and weight loss during sintering and the bulk density and flexural strengths of their sintered bulks, it was found that the smaller sizes and the richer β-resin contents of SFMP ha）re facilitated formation of sintered bulks with more compact isotropic structure and higher flexural strengths than MCMB. Because of the filling and bonding effects of SFMP on MCMB bulks, addition of SFMP, albeit a little, can greatly increase the flexural strengths of sintered bulks of MCMB. However, adding MCMB, even a slight amount, into SFMP can severely impair the flexural strength of sintered bulks. This might be attributed to both the crack initiation along the boundaries between MCMB and SFMP and the formation of layered texture of MCMB sphere.
