中间相沥青炭微球及其在锂离子二次电池方面的应用

中间相沥青炭微球是一种特殊形态的炭材料前驱体，在众多领域有着广泛的应用。本文介绍了中间相沥青炭微球的制备、结构及性质，在此基础上重点综述了近年来中间相沥青炭微球在高性能锂离子二次电池电极材料方面的应用进展，并指出今后的研究方向。     

中间相沥青的应用研究进展

简单介绍了中间相沥青的特性,详细综述了中间相沥青在中间相沥青基碳纤维、泡沫炭、中间相炭微球、黏结剂、C/C复合材料以及电极材料等方面的应用研究进展,并展望了其应用前景。     

煤沥青的最新研究进展

综述了最近几十年国内外对煤沥青的主要分析方法和以它为原料在制备沥青基中间相、中间相炭微球、针状焦、活性炭、泡沫炭和高性能炭/炭复合材料基体方面的研究和进展,展望了其在材料领域潜在的应用前景和未来发展的趋势.     

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。     

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.     

酚醛树脂对均相成核的中间相炭微球生成的作用

在QI含量很低的沥青中加入适量的酚醛树脂，可以改变沥青生成中间相炭微球的热缩聚反应，进而改变中间相炭微球的形貌与微观结构。酚醛树脂在沥青稠环芳烃分子热缩聚过程的初期形成共晶，在后期充当炭微球的交联剂的作用，使中间相炭微球的收率增加，尺寸变大，并影响了中间相炭微球的织构，红外光谱分析表明酚醛树脂已参与了中间相炭微球的形成；偏光显微镜、扫描电镜形象地表征出了中间相炭微球的微观织构以及酚醛树脂的作用。     

煤焦油中吡啶不溶物及聚合条件对中间相炭微球收率,球径及其分布的影响

研究了煤焦油聚合制备中间相炭微球过程中，原料中PI的含量及聚合条件对中间相炭微球的球径及球径分布的影响。发现中间相炭微球的球径，随原料中PI的含量增加而减少，球径分布变窄，随聚合时间的延长，所产生的中间相炭微球球径增大，球径分布变宽。通过控制原料中一次PI的含量及聚合条件，获得较窄粒径分布的中间相沥青炭微球。     

石墨添加对中间相炭微球电化学性能的影响

以煤焦油沥青为原料，采用聚合法制备中间相炭微球。研究了不同天然鳞片石墨添加量在相同热处理条件下得到的中间相炭微球作为锂离子电池炭负极材料的电化学性能。研究结果表明，石墨的添加使中间相炭微球内部结构变的复杂，X衍射显示石墨的添加降低了炭微球的石墨化度和晶形尺寸。随石墨添加量的增加，电池的首次充放电容量和效率有所减小，三次循环后充放电效率趋于一致。     

中间相炭微球研究进展

中间相炭微球是一种新型炭材料，它是在研究中间相的过程中发展起来的，其理论基础是中间相理论。系统地介绍了中间相炭微球的发展过程，制备原料和制备方法，此外，还对中间相炭微球的分析方法，应用领域进行了介绍，并对其发展前景作了预测，指出了几个重要的发展方向。     

低温处理中间相沥青炭微球的充放电性能研究

研究了在500-1000℃下停留不同时间低温炭化处理的中间相沥青炭微球（MCMBs)的充放电性能，并与其XRD结构相关联。研究表明：在500-1000℃停留4h炭化处理的中间相炭微球中，700℃炭化处理的MCMBs充放电性能最好，充放电容量最高，不可逆容量损失最小；在700℃炭化温度下停留时间的延长有利于MCMBs循环性能的提高。     

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。     

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。     

Multiwalled nanotube-coated mesophase carbon microbeads for use as anode material in lithium ion batteries

The recent developments in lithium ion secondary batteries (LIBs) have been achieved by using selected carbon materials as the anode. Mesophase carbon microbead (MCMB) anode materials have stable Li intercalation and de-intercalation characteristics, making them a good anode material for use in LIBs. However, batteries with pure MCMB anodes are known to have a low power density. Multiwalled carbon nanotubes (MWNTs) are one of the most promising materials for improving a range of electrochemical energy conversion and storage devices because of their unique physical properties, including high electrical conductivity and superior chemical and mechanical stability. Therefore, in this study, MWNTs were deposited on the surface of MCMB anodes to improve their electrical conductivity. The anode materials were separately functionalized using carboxylic acid and amine groups to form MWNT-COOH and MCMB-NH₂, respectively, providing them with surfaces of opposite charge. The surface morphology was assessed using scanning electron microscopy, and the electrochemical characteristics were analyzed by cyclic voltammetry and AC impedance measurements in a coin cell. The AC impedance and cyclic voltammetry measurements indicated that MCMBs with MWNTs deposited on their surfaces are promising electrode materials, providing high power density for LIBs.     

中间相炭微球作为锂离子电池负极材料的研究现状

中间相炭微球（MCMB）由于具有独特的类石墨的片层结构,是一种极具发展潜力的锂离子电池负极材料,它除了具有一般炭负极材料的优点外,由于其球形层状结构还使其具有密度高、易脱嵌锂、边界损失小等特,董。本文主要论述了锂离子电池负极材料中间相炭微球的制备、热处理和改性等方面的研究现状及存在的问题;在当今锂离子电池高容量低成本的发展要求下,预期低温热处理的中间相炭微球将是今后的研究重点。     

Processing of mesocarbon microbeads to high-performance materials: Part III. High-temperature sintering and graphitization

The sintering and graphitization behavior of mesocarbon microbeads (MCMB) at high temperatures (1900-2800 K) is investigated. It is shown that while the low temperature sintering performance of MCMB is unique, at high temperature it appears to be similar to that of conventional materials. In contrast, the obtained activation energy for MCMB high-temperature graphitization is ∼100 kcal/mol, which is smaller than that (∼240 kcal/mol) for typical carbon systems. It is concluded that the combination of such unique properties as excellent compressibility, low temperature sinterability, and rapid graphitization makes MCMB an attractive precursor for manufacturing carbon-based materials.     

MCMB–SiC composites; new class high-temperature structural materials for aerospace applications

Graphite–silicon carbide (G–SiC), carbon/carbon–silicon carbide (C/C–SiC) and mesocarbon microbeads–silicon carbide (MCMB–SiC) composites were produced using liquid silicon infiltration (LSI) method and their physical and mechanical properties, including density, porosity, flexural strength and ablation resistance were investigated. In comparison with G–SiC and C/C–SiC composites, MCMB–SiC composites have the highest bending strength (210 MPa) and ablation resistance (9.1%). Moreover, scanning electron microscopy (SEM) and optical microscopy (OM) are used to analyze the reacted microstructure, pore morphology and pore distribution of carbon-based matrices. As a result, SiC network reinforcement was formed in situ via a reaction between liquid silicon and carbon. The unreacted carbon and solidified silicon are two phases present in the final microstructure and are characterized by X-ray diffraction (XRD). Based on the results obtained and the low-cost processing of pitch-based materials, the MCMB–SiC composite is a promising candidate for aerospace applications.     

中间相炭微球的活化与成孔过程的研究

以沥青中间相炭微球为原料，采用KOH作活化剂制备高比表面积活性炭。考察了碱炭比、活化温度和保温时间等工艺因素对活性炭结构与碘吸附性能的影响。研究表明：活性炭的比表面积、总孔容与碘吸附性能随碱炭比、活化温度和保温时间的变化均呈先增大后减小的趋势，孔径分布随碱炭比的增大、活化温度的提高和保温时间的延长向孔径增大的方向位移。由于具有独特的层状结构，中间相炭微球在KOH活化成孔过程中表现出明显的各向异性，与垂直层面方向上相比，孔隙更容易在平行层面方向上形成和生长。     

Changes in the structure and functional groups produced during the fluorination of mesophase microbeads

The mesocarbon microbead (MCMB) fluorides with different fluorine contents were obtained in the temperature range of 100–110 °C in the presence of the mixed gas containing fluorine and nitrogen. The MCMB fluorides were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and elemental analysis. The results showed that the carbon lamination of the MCMBs was severely destroyed, which was indicated by a dramatic increase in the interlayer spacing of the resultant materials from 0.345 nm of the MCMBs to the range of 0.656 to 0.722 nm. Further studies on diversity of functional groups indicated that the whole fluorination reaction process comprises two steps: include a first diffusion of fluorine gas molecules inside the voids formed due to loose packing of MCMB molecules, and then fluorination. The two steps interacted with each other and jointly determined the apparent speed of the reaction. The original lamination structure of the MCMBs was completely destroyed for volume expansion of the resultant materials and diffusion of fluorine/nitrogen mixed gases. The final MCMB fluorides are themselves a conglomeration of particles with diameters ranging from 1 to 3 μm.     

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.