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
Bimetallic Ni–Co sulfides are outstanding pseudocapacitive materials with high electrochemical activity and excellent energy storage performance as electrodes for high-performance supercapacitors.In this study,a nove...Bimetallic Ni–Co sulfides are outstanding pseudocapacitive materials with high electrochemical activity and excellent energy storage performance as electrodes for high-performance supercapacitors.In this study,a novel urchin-like NiCo2S4@mesocarbon microbead(NCS@MCMB) composite with a core–shell structure was prepared by a facile two-step hydrothermal method.The highly conductive MCMBs offered abundant adsorption sites for the growth of NCS nanoneedles,which allowed each nanoneedle to fully unfold without aggregation,resulting in improved NCS utilization and efficient electron/ion transferin the electrolyte.When applied as an electrode material for supercapacitors,the composite exhibited a maximum specific capacitance of 936 Fg-1 at 1 Ag-1 and a capacitance retention of 94% after 3000 cycles at 5 Ag-1,because of the synergistic effect of MCMB and NCS.Moreover,we fabricated an asymmetric supercapacitor based on the NCS@MCMB composite,which exhibited enlarged voltage windows and could power a light-emitting diode device for several minutes,further demonstrating the exceptional electrochemical performance of the NCS@MCMB composite.展开更多
In situ prepared mesocarbon microbead/carbon nanotube(MCMB/CNT) composites are potential precursors of high density carbon materials for various applications. Integrated MCMB/CNT composites were successfully fabricate...In situ prepared mesocarbon microbead/carbon nanotube(MCMB/CNT) composites are potential precursors of high density carbon materials for various applications. Integrated MCMB/CNT composites were successfully fabricated by hot-press sintering at 550 ℃ under 30 MPa. After further calcination at 900 ℃, the hot-press sintering fabricated MCMB block has an apparent density of 1.77 g/cm3 and the open porosity 5.1%. With the addition of 5%(mass fraction) CNTs, the density of the composite block is elevated to 1.84 g/cm3, and its open porosity is reduced to 3.5%. The flexural strength of composite block with 5% CNTs is elevated to 116 MPa. Through the hot-press sintering, pores of 10-50 nm in the calcinated bulks are remarkably eliminated. The interstice between microbeads in the composite blocks is filled up by CNTs together with β-resin and quinoline-insoluble spheres, which can further contribute to the densification.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
Mesocarbon microbeads (MCMB) with narrow size distribution, excellent sphericity and no obvious conglu-tination have been prepared with a coal tar pitch containing quinoline insolubles (QI) as the raw material. Optica...Mesocarbon microbeads (MCMB) with narrow size distribution, excellent sphericity and no obvious conglu-tination have been prepared with a coal tar pitch containing quinoline insolubles (QI) as the raw material. Optical mi-croscopy and scanning electron microscopy (SEM) are used to examine the structure of the MCMB. It has been found that SEM technique shows the structural information of MCMB clearly in the form of micrographs even when the structure of MCMB is complex, while the optical technique is useful for analysis of the regular structure of the mesophase spheres but cannot be effectively used to analyze either the complex structure of the green MCMB or the structures of the further heat-treated ones at different temperatures. Ac-cording to the characteristics of the carbon layers, the struc-tures of the as-prepared MCMB in the present experiment could be classified as (1) Parallel Layer type structure and (2) Bent Layer type structure with the carbon layers gathering at one or two points in the MCMB. In the experiments, SEM is also utilized to investigate the structures of MCMB that are heat-treated at different temperatures. It has been found that the MCMB without any further heat-treatment show no layered-carbons, while the ones heat-treated at temperature higher than 1000℃ exhibit obvious layered carbons across their sections. When increasing the heat-treatment tempera-ture, the carbon layers become thinner and flatter.展开更多
石墨具有成本低、放电稳定等优点,是钾离子电池极具发展前景的负极材料之一,但其倍率性能仍需改进。本文以中间相炭微球(MCMB)为原料,经KOH处理,设计了一种新型的石墨化负极。通过有限的氧化和轻微的嵌入,在MCMB表面形成了层间距增大的...石墨具有成本低、放电稳定等优点,是钾离子电池极具发展前景的负极材料之一,但其倍率性能仍需改进。本文以中间相炭微球(MCMB)为原料,经KOH处理,设计了一种新型的石墨化负极。通过有限的氧化和轻微的嵌入,在MCMB表面形成了层间距增大的膨胀层,K+的扩散系数明显提高。作为负极时,改性MCMB在低于0.25 V下展现出高平台容量(271 mAh g^(-1)),优越的倍率性能(在1.0 A g^(-1)下,容量可达160 mAh g^(-1)),良好的循环稳定性(在0.1 A g^(-1)下循环100圈后,容量维持为184 mAh g^(-1));当采用羧甲基纤维素作为黏结剂时,KOH处理的MCMB具有高的首次库仑效率(79.2%)。本工作为设计具有优良储钾性能的石墨化材料提供了一种简便的策略。展开更多
基于沥青在熔融纺丝过程中的滴落行为和流变学理论,提出了一种新型高效的中间相炭微球(MCMB)制备方法—毛细管破裂法(DCB法)。本实验以中间相沥青为原料,采用DCB法考察了不同接收相(水或THF)对MCMB制备的影响规律,并系统研究了相应MCMB...基于沥青在熔融纺丝过程中的滴落行为和流变学理论,提出了一种新型高效的中间相炭微球(MCMB)制备方法—毛细管破裂法(DCB法)。本实验以中间相沥青为原料,采用DCB法考察了不同接收相(水或THF)对MCMB制备的影响规律,并系统研究了相应MCMB微观结构的演变规律。在此基础上,所制MCMB经750℃的KOH活化制备了A-MCMB,以及经2800℃的石墨化制备了G-MCMB,并分别探究了它们作为超级电容器(EDLC)和锂离子电池(LIB)电极材料的电化学性能。结果表明:采用DCB方法所制备的水接收相的MCMB-W和THF接收相的MCMBT均呈现尺寸约1~2μm的球形结构特征。此外,A-MCMB-T具有高比表面积1391 m^(2)g^(-1)、微孔体积0.55 cm^(3)g^(-1)和中孔体积0.24 cm^(3)g^(-1),作为EDLC的电极材料时,其比电容比MP衍生的炭材料提高了30%,且电容保持率也显著提升。同时,G-MCMB-T具有较高的石墨化度0.895和有序的层状结构,作为LIB的负极材料时,在100 mA g^(-1)下进行100次循环后,具有353.5 m Ah g^(-1)的高比容量。因此,本文提出并验证了一种新的MCMB制备方法,有望为储能材料的设计和开发提供了一种思路和途径。展开更多
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jointly supported by the National Natural Science Foundations of China(No.51572246)the Fundamental Research Funds for the Central Universities(Nos.2652017401 and 2652015425)
文摘Bimetallic Ni–Co sulfides are outstanding pseudocapacitive materials with high electrochemical activity and excellent energy storage performance as electrodes for high-performance supercapacitors.In this study,a novel urchin-like NiCo2S4@mesocarbon microbead(NCS@MCMB) composite with a core–shell structure was prepared by a facile two-step hydrothermal method.The highly conductive MCMBs offered abundant adsorption sites for the growth of NCS nanoneedles,which allowed each nanoneedle to fully unfold without aggregation,resulting in improved NCS utilization and efficient electron/ion transferin the electrolyte.When applied as an electrode material for supercapacitors,the composite exhibited a maximum specific capacitance of 936 Fg-1 at 1 Ag-1 and a capacitance retention of 94% after 3000 cycles at 5 Ag-1,because of the synergistic effect of MCMB and NCS.Moreover,we fabricated an asymmetric supercapacitor based on the NCS@MCMB composite,which exhibited enlarged voltage windows and could power a light-emitting diode device for several minutes,further demonstrating the exceptional electrochemical performance of the NCS@MCMB composite.
基金Project(10332020) supported by the National Natural Science Foundation of China
文摘In situ prepared mesocarbon microbead/carbon nanotube(MCMB/CNT) composites are potential precursors of high density carbon materials for various applications. Integrated MCMB/CNT composites were successfully fabricated by hot-press sintering at 550 ℃ under 30 MPa. After further calcination at 900 ℃, the hot-press sintering fabricated MCMB block has an apparent density of 1.77 g/cm3 and the open porosity 5.1%. With the addition of 5%(mass fraction) CNTs, the density of the composite block is elevated to 1.84 g/cm3, and its open porosity is reduced to 3.5%. The flexural strength of composite block with 5% CNTs is elevated to 116 MPa. Through the hot-press sintering, pores of 10-50 nm in the calcinated bulks are remarkably eliminated. The interstice between microbeads in the composite blocks is filled up by CNTs together with β-resin and quinoline-insoluble spheres, which can further contribute to the densification.
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.
文摘Mesocarbon microbeads (MCMB) with narrow size distribution, excellent sphericity and no obvious conglu-tination have been prepared with a coal tar pitch containing quinoline insolubles (QI) as the raw material. Optical mi-croscopy and scanning electron microscopy (SEM) are used to examine the structure of the MCMB. It has been found that SEM technique shows the structural information of MCMB clearly in the form of micrographs even when the structure of MCMB is complex, while the optical technique is useful for analysis of the regular structure of the mesophase spheres but cannot be effectively used to analyze either the complex structure of the green MCMB or the structures of the further heat-treated ones at different temperatures. Ac-cording to the characteristics of the carbon layers, the struc-tures of the as-prepared MCMB in the present experiment could be classified as (1) Parallel Layer type structure and (2) Bent Layer type structure with the carbon layers gathering at one or two points in the MCMB. In the experiments, SEM is also utilized to investigate the structures of MCMB that are heat-treated at different temperatures. It has been found that the MCMB without any further heat-treatment show no layered-carbons, while the ones heat-treated at temperature higher than 1000℃ exhibit obvious layered carbons across their sections. When increasing the heat-treatment tempera-ture, the carbon layers become thinner and flatter.
文摘石墨具有成本低、放电稳定等优点,是钾离子电池极具发展前景的负极材料之一,但其倍率性能仍需改进。本文以中间相炭微球(MCMB)为原料,经KOH处理,设计了一种新型的石墨化负极。通过有限的氧化和轻微的嵌入,在MCMB表面形成了层间距增大的膨胀层,K+的扩散系数明显提高。作为负极时,改性MCMB在低于0.25 V下展现出高平台容量(271 mAh g^(-1)),优越的倍率性能(在1.0 A g^(-1)下,容量可达160 mAh g^(-1)),良好的循环稳定性(在0.1 A g^(-1)下循环100圈后,容量维持为184 mAh g^(-1));当采用羧甲基纤维素作为黏结剂时,KOH处理的MCMB具有高的首次库仑效率(79.2%)。本工作为设计具有优良储钾性能的石墨化材料提供了一种简便的策略。
文摘基于沥青在熔融纺丝过程中的滴落行为和流变学理论,提出了一种新型高效的中间相炭微球(MCMB)制备方法—毛细管破裂法(DCB法)。本实验以中间相沥青为原料,采用DCB法考察了不同接收相(水或THF)对MCMB制备的影响规律,并系统研究了相应MCMB微观结构的演变规律。在此基础上,所制MCMB经750℃的KOH活化制备了A-MCMB,以及经2800℃的石墨化制备了G-MCMB,并分别探究了它们作为超级电容器(EDLC)和锂离子电池(LIB)电极材料的电化学性能。结果表明:采用DCB方法所制备的水接收相的MCMB-W和THF接收相的MCMBT均呈现尺寸约1~2μm的球形结构特征。此外,A-MCMB-T具有高比表面积1391 m^(2)g^(-1)、微孔体积0.55 cm^(3)g^(-1)和中孔体积0.24 cm^(3)g^(-1),作为EDLC的电极材料时,其比电容比MP衍生的炭材料提高了30%,且电容保持率也显著提升。同时,G-MCMB-T具有较高的石墨化度0.895和有序的层状结构,作为LIB的负极材料时,在100 mA g^(-1)下进行100次循环后,具有353.5 m Ah g^(-1)的高比容量。因此,本文提出并验证了一种新的MCMB制备方法,有望为储能材料的设计和开发提供了一种思路和途径。
