中间相炭微球在锂离子电池负极材料的应用进展

中间相炭微球(MCMB)具有良好锂离子扩散性、导电性和机械稳定性等优势,是目前应用广泛、综合性能优异的锂离子电池负极材料,但较低理论比容量是制约其发展的关键因素。为了获得性能优良的MCMB基锂离子电池负极材料,改性修饰和复合材料已然成为目前研发重点。笔者论述了碳结构、表界面和复合材料等微观结构设计对MCMB负极材料电化学性能的影响。从碳堆积结构类型、有序性、层间距以及球体粒径大小等方面,论述了碳结构微观设计对MCMB电化学性能的影响。发现具有乱层结构的MCMB在充放电过程中内部产生应力较小,且碳结构较稳定,具有优异循环稳定性;内部具有大量微孔或碳层间距较大的MCMB,在充放电过程中可提高锂离子在电极中的迁移速率,并提供更多的储锂空间,一般具有优良的充放电比容量和倍率性能;小粒径MCMB具有较短的锂离子迁移路径和随之增加的比表面积,通常具有较好倍率性能,伴随着可逆比容量和充放电效率的衰减。从表界面碳层改性、包覆和掺杂改性等方面,论述了表界面改性对MCMB电化学性能的影响。表面碳层修饰可增加MCMB与电解液的相容性及其比表面积,提高了与电解液的接触面积及贮锂容量,改善了锂离子电池负极材料的电化学性能;另外,MCMB表面包覆一层无定型碳,可避免其表面与电解液直接接触,减少电化学副反应的产生,提升其可逆比容量。从碳活性物质复合材料、非碳活性物质复合材料等方面,论述了复合材料微观结构设计对MCMB电化学性能的影响。碳活性物质可降低MCMB内部碳层结构的有序性,减少锂离子嵌入过程中的内部应力,提升MCMB循环稳定性。非碳活性物质诱导MCMB生成更加有序的碳层结构,提高MCMB的比表面积,从而改善MCMB表面与电解液分子的接触能力及其嵌锂性能,有利于提升MCMB负极材料可逆比容量、循环性能和倍率性能。MCMB具有高碳层间距和多缺陷位点等结构特征,有利于钠离子自由脱嵌,应用于钠离子电池时具有良好的可逆比容量、循环稳定性和倍率性能。MCMB的不规则定向层状结构经活化等处理具有较高比表面积,可应用于超级电容器电极材料。最后提出在高性能锂离子电池电极材料快速发展的需求下,从微观结构角度设计MCMB纳米复合材料将是MCMB负极材料的研究重点。     

Compact Quantum-Dot Microbeads with Sub-Nanometer Emission Linewidth

Fluorescent microbeads are widely used for applications in life sciences and medical diagnosis. The spectral contrast and sharpness of photoluminescence are critical in the utilities of microbeads for imaging and multiplexing. Here, microbeads capable of generating single-peak laser emission with a sub-nanometer linewidth are demonstrated. The microbeads are made of quantum dots that are tightly packed and crosslinked via ligand exchange for high optical gain and refractive index as well as material stability. Bright single-mode lasing with no photobleaching is achieved with particle diameters as small as 1.5 µm in the air. Sub-nm lasing emission is maintained even inside high-index surroundings, such as organic solvents and biological tissues. Feasibility of intracellular tagging and multi-color imaging in vivo is demonstrated.     

中间相炭微球制备及应用概述

中间相炭微球（MCMB）是一种新型的炭材料,拥有杰出的化学稳定性、热稳定性、优良的导电导热性能,已引起人们的广泛关注。本文概述了MCMB的结构与形成机理、各种制备方法。以及在高密度各向同性炭材料、锂离子电池负极材料的应用研究及其最新研究进展;并展望了MCMB的应用和研究前景。     

Mn2O3/carbon aerogel microbead composites synthesized by in situ coating method for supercapacitors

A series of Mn₂O₃/carbon aerogel microbead (Mn₂O₃/CAMB) composites for supercapacitor electrodes have been synthesized by in situ encapsulation method. The structure and morphology of Mn₂O₃/CAMB are characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectrum and scanning electron microscopy (SEM). Electrochemical performances of the synthesized composites are evaluated by cyclic voltammetry and galvanostatic charge/discharge measurement. All the composites with different Mn₂O₃ contents show higher specific capacitance than pure CAMB due to the pseudo-capacitance of the Mn₂O₃ particles dispersed on the surface of CAMB. The highest specific capacitance is up to 368.01 F g⁻¹ when 10 wt% Mn₂O₃ is coated on the surface of CAMB. Besides, 10%-Mn₂O₃/CAMB supercapacitor exhibits excellent cyclic stability, the specific capacitance still retains 90% of initial capacitance over 5000 cycles.     

Anode Performance of Electron Irradiated Mesocarbon Microbeads for Secondary Lithium Batteries

Mesocarbon microbeads (MCMBs) heat-treated at 1,273 and 3,073 K were irradiated with an electron beam current density ~1.34μA/cm² of 0.5–1.5 MeV for 0–600 s, and the irradiated MCMBs were examined as anode materials for secondary lithium-ion batteries. Charge capacity of both materials irradiated for short time within 100 s became larger than that before irradiation. Improvement of discharge capacity of MCMB annealed at 3,073 K was achieved by irradiation with 0.5 and 1.5 MeV electrons for 600 s. Good performance of cyclical discharge of MCMB annealed at 3,073 K was also attained by the irradiation with 0.5–1.5 MeV electrons for 600 s.     

酚醛树脂改性煤焦油沥青中制得的中间相球体的结构特征

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.     

Processing of mesocarbon microbeads to high-performance materials: Part II. Reaction bonding by in situ silicon carbide and nitride formation

The processing of carbon-ceramic composites by utilizing the unique sintering ability of mesocarbon microbeads (MCMB) is reported. The ceramic constituents (silicon nitride and silicon carbide) are formed in situ by reactions between MCMB and silicon in different atmospheres. In comparison with direct addition of ceramic (SiC, Si₃N₄) phases, in situ formation shows several appealing features. By inducing the reaction of silicon with MCMB, the sintering ability of the composite is enhanced via reaction bonding mechanisms. Similarly, it is demonstrated that composite porosity is limited owing to silicon reaction with nitrogen. The reactive formation of nanoscale ceramic reinforcements via decomposition of the silicon-containing polymer (e.g. poly-carbomethyl-silane) is also reported. This approach results in formation of uniform nanosized (>100 nm) SiC layers strongly bonded to the surface of the carbon particles. The presented results contribute to the development of carbon-ceramic materials with high-operational properties.     

沥青炭微球在锂离子电池中的应用与市场前景

介绍中间相沥青炭微球的制备方法和发展现状，分析了其在锂离子二次电池等方面的应用及国内外市场前景。     

Transport of Gellan Gum Microbeads in Soil Columns of Various Grain Size Distributions

The transport of gellan gum microbeads as potential cell carriers was investigated in horizontal columns packed with different grain size classes of gravel (2–16 mm) and sand (0.25–2 mm). A suspension of microbeads was pulsed into each column for 6 h, followed by injection of water for 42 h. In general, the total amount of microbeads travelling across a given section of the column increased with injection time but decreased towards the column outlet, varying as a direct function of grain size. The results of this study demonstrate the feasibility of the transport of gellan gum microbeads through medium sand to medium gravel across distances up to 110 cm.