软硬炭复合材料的制备及其储钠性能研究  

Preparation and sodium storage performance of hard-soft carbon composite materials

作　　者：徐家豪 张兆华 刘宇昊 赵玮 李秀春 贾建波 黄光许[1,2,5] 邢宝林 张传祥[1,3,5] XU Jiahao;ZHANG Zhaohua;LIU Yuhao;ZHAO Wei;LI Xiuchun;JIA Jianbo;HUANG Guangxu;XING Baolin;ZHANG Chuanxiang(Henan Key Laboratory of Coal Green Conversion,College of Chemistry and Chemical Engineering,Henan Polytechnic University,Jiaozuo 454003,China;Henan Key Laboratory of Coal Green Conversion,Henan Polytechnic University,Jiaozuo 454003,China;Henan Polytechnic University Ordos Research Institute of Clean Coal Development and Utilization,Ordos 017010,China;Hami Vocational and Technical College,Hami 839000,China;State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization,Jiaozuo 454003,China;China Coal Huali Xinjiang Carbon Technology Co.,Ltd.,Hami 839200,China)

机构地区：[1]河南理工大学化学化工学院,河南焦作454003 [2]河南理工大学河南省煤炭绿色转化重点实验室,河南焦作454003 [3]河南理工大学鄂尔多斯煤炭清洁开发利用研究院,内蒙古鄂尔多斯017010 [4]哈密职业技术学院,新疆哈密839000 [5]煤炭安全生产与清洁高效利用省部共建协同创新中心,河南焦作454003 [6]中煤华利新疆炭素科技有限公司,新疆哈密839200

出　　处：《洁净煤技术》2025年第1期95-104,共10页Clean Coal Technology

基　　金：国家自然科学基金资助项目(52074109);呼包鄂国家自主创新示范区建设科技支撑资助项目(2023XM10);中煤华利新疆炭素科技有限公司委托资助项目(TSFWCG2023-11-002)。

摘　　要：钠离子电池(SIBs)作为储能器件备受人们关注,负极材料作为钠离子电池的重要组成部分是研究的热点之一。以煤化工副产物低灰煤焦油沥青为原料,通过直接与酚醛树脂混合,加以高温炭化,成功制备出煤沥青基软硬炭复合材料,考察了不同沥青/酚醛树脂质量比对所制材料结构的影响并应用于钠离子电池。通过SEM、TEM、XRD、Raman、XPS、FTIR等测试表明,酚醛树脂可以有效地抑制沥青在高温过程的过度石墨化,沥青也可以修复酚醛树脂在炭化过程中所产生的不可逆缺陷,同时沥青与酚醛树脂二者可在炭化过程中发生交联反应,有利于复合材料中伪石墨结构的形成,从而引入更多吸附和插层位点。随着沥青与酚醛树脂质量比的逐渐增加,复合材料的伪石墨结构含量呈现先上升后下降的趋势,其中质量比为1∶4所制复合材料(LF−1∶4)的伪石墨结构含量最高,为32.88%,优于纯沥青直接炭化所制材料(LQ)的21.28%和纯酚醛树脂直接炭化所制材料(FQ)的27.08%。恒流充放电、循环伏安法等电化学测试表明,沥青与酚醛树脂制备的复合材料具有较好的储钠性能,其中LF−1∶4的首圈库伦效率和可逆容量分别为80.87%和249.10 mAh/g,对比LQ的48.39%与90.39 mAh/g和FQ的73.46%与230.48 mAh/g具有明显的优势。同时,利用LF−1∶4所制备出的全电池表现出251.37 mAh/g的可逆容量,经过计算得出该全电池的能量密度为214 Wh/Kg。Sodium-ion batteries(SIBs)have attracted significant attention as energy storage devices,while the anode material,which represents a crucial component of SIBs,has emerged as a central point of investigation in related research.The low-ash coal tar pitch,a byproduct of the coal chemical industry,as a raw material for further research.The preparation of pitch based hard-soft carbon composite material was achieved by mixing the coal tar pitch directly with phenolic resin and subjecting it to a high-temperature carbonization process.The resulting materials were successfully applied to SIBs.The results of the SEM,TEM,XRD,Raman,XPS and FTIR tests demonstrate that phenolic resin have the ability to effectively inhibit the excessive graphitization of pitch during high temperatures.Furthermore,pitch can also repair irreversible defects created by phenolic resin during the carbonization process.Meanwhile,the crosslinking can occur between pitch and phenolic resin during the carbonization process.This phenomenon is conducive to the formation of pseudo-graphite structure in the composite materials,which results in the creation of additional adsorption and intercalation sites.As the mass ratio of pitch to phenolic resin increased gradually,the pseudo-graphitic structure content of the composites displayed an upward trajectory,followed by a decline.The composite material,comprising a mass ratio of 1∶4(LF−1∶4),exhibited the highest pseudographite structure content,at 32.88%.This was superior to the 21.28%observed in the material produced by direct heating of pure pitch(LQ)and the 27.08%observed in the material produced by direct carbonization of pure phenolic resin(FQ).The electrochemical tests,including constant-current charge/discharge and cyclic voltammetry,have demonstrated that the composite material of coal tar pitch and phenolic resin exhibited superior sodium storage performance.The hard-soft carbon composite material had an initial coulombic efficiency of 80.87%and a reversible capacity of 249.10 mAh/g with a pit

关 键 词：煤沥青 酚醛树脂 负极材料 钠离子电池 电化学性能 

分 类 号：TM912[电气工程—电力电子与电力传动] TB332[一般工业技术—材料科学与工程]