首页|期刊导航|燃料化学学报(中英文)|包覆沥青软化点对预氧化路径及其衍生硬炭储钠性能的调控研究

包覆沥青软化点对预氧化路径及其衍生硬炭储钠性能的调控研究OA

Effect of coating asphalt softening point on the pre-oxidation pathway and sodium storage performance of derived hard carbon

中文摘要英文摘要

本研究阐明了包覆沥青软化点对其氧化交联过程及衍生硬炭材料储钠性能的非线性作用机制.通过对低(80℃)、中(160 ℃)和高(260℃)三种软化点沥青的对比分析发现,80与260 ℃沥青在氧化过程中可引入较高氧含量(20%-25%),形成以酸酐/酯基为主的深度交联结构,有效抑制了炭化过程中的石墨化倾向,最终获得层间距大、无序度高且闭孔丰富的硬炭材料.该材料展现出优异的储钠性能:EPOC-80和EPOC-260的首次充电容量分别达314.7与306.6 mA·h/g,首次库伦效率分别为81.3%与79.3%,并具备良好的循环稳定性和倍率性能.相比之下,中等软化点(160℃)沥青氧化后氧含量较低(约5%),交联程度不足,导致所得硬炭结构致密、层间距较小(3.46 Å)、可用于储钠的有效空间有限,其容量显著降低至173.2 mA·h/g.本研究为通过前驱体软化点的精准调控以优化硬炭负极结构提供了新的设计思路与理论支撑.

This study clarifies the nonlinear relationship between the softening point of coating asphalt and its oxidative cross-linking behavior,as well as the sodium storage performance of the derived hard carbon.Comparative analysis of asphaltes with low(80 ℃),medium(160℃)and high(260 ℃)softening points revealed that both the 80 and 260 ℃ asphaltes incorporated a higher oxygen content(20%-25%)during oxidation,leading to the formation of a deeply cross-linked structure dominated by anhydride and ester groups.This effectively suppressed graphitization during carbonization,yielding hard carbon with large interlayer spacing,high disorder,and abundant closed pores.The derived hard carbon exhibited superior sodium storage performance,the initial charge capacities of EPOC-80 and EPOC-260 reached 314.7 and 306.6 mA·h/g,with first-cycle coulombic efficiencies of 81.3%and 79.3%,respectively,along with excellent cycling stability and rate capability.In contrast,the medium softening point asphalt(160 ℃)showed limited oxygen incorporation(~5%)and insufficient cross-linking after oxidation,resulting in a densely packed hard carbon with smaller interlayer spacing(3.46 Å)and restricted sodium storage sites,which led to a significantly reduced capacity of 173.2 mA·h/g.This work provides new design principles and theoretical support for optimizing hard carbon anode structures through precise control of the precursor softening point.

吕小军;刁晶晶;赵卿波;蔡天凤;韩冬云;杨占旭;曹祖斌

新疆天利石化股份有限公司,新疆克拉玛依 833699新疆天利石化股份有限公司,新疆克拉玛依 833699新疆天利石化股份有限公司,新疆克拉玛依 833699辽宁石油化工大学,辽宁抚顺 113001辽宁石油化工大学,辽宁抚顺 113001辽宁石油化工大学,辽宁抚顺 113001新疆天利石化股份有限公司,新疆克拉玛依 833699||辽宁石油化工大学,辽宁抚顺 113001

化学化工

包覆沥青软化点预氧化硬炭储钠性能

coating asphaltsoftening pointpre-oxidationhard carbonsodium storage performance

《燃料化学学报(中英文)》 2026 (4)

171-179,9

Supported by the Key Research and Development Program of Xinjiang Uygur Autonomous Region(2024B04008)and the Basic Scientific Research Project of the Liaoning Provincial Department of Education for Higher Education Institutions(LJ212410148007).新疆维吾尔自治区重点研发项目(2024B04008)和辽宁省教育厅高校基本科研项目(LJ212410148007)资助

10.3724/2097-213X.2025.JFCT.0032

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