钠离子电池生物质衍生硬碳负极材料的制备与研究进展

doi:10.12422/j.issn.1006-396X.2025.03.004

摘要/Abstract

摘要：

钠离子电池凭借其卓越的低温性能、显著的成本效益及高度的安全特性，在低速两轮电动车市场及大规模储能应用中正逐步成为锂离子电池的有力补充。商业化石墨负极在钠离子电池中并不兼容，取而代之的是性能表现优异的硬碳负极材料，但是其能耗大，成本高。在此背景下，研发兼具低成本、高可逆容量及卓越循环稳定性的钠离子电池负极材料成为行业亟需攻克的技术瓶颈。生物质因其可再生、低成本和环境友好的特点，成为制备硬碳材料的重要原料。生物质硬碳材料的储钠性能受碳化温度、前驱体种类及微观结构等多重因素的影响。从硬碳材料的储钠行为入手，介绍了针对储钠机制提出的相关模型；总结了硬碳负极的制备与电化学性能优化过程中热解、活化、掺杂等制备步骤的作用效果；分析了储钠机制对于解决当前硬碳负极所面临的原料选择受限、首次库仑效率低以及闭孔调控手段有限等问题的指导作用。

关键词: 钠离子电池, 生物质, 硬碳, 储钠机理, 电化学性能

Abstract:

Sodium?ion batteries are gradually becoming a powerful alternative to lithium?ion batteries in the low?speed two?wheeled electric vehicle market and large?scale energy storage applications due to their excellent low?temperature performance, significant cost?effectiveness,and high safety features.The potential of hard carbon with improved performance to substitute graphite in the sodium ion battery anode has attracted widespread attention.However,the high energy consumption and expensive cost still need to be overcome for commercialization of hard carbon anode.The key to developing anode materials for sodium?ion batteries that combine low cost,high sodium ion storage capacity,and excellent cycling stability will help to extend the application of hard carbon anodes in sodium?ion batteries.Biomass has become an attractive raw material for the preparation of hard carbon due to its renewable,low?cost,and environmentally friendly characteristics.It has been shown that the sodium storage properties of biomass?derived hard carbon are affected by multiple factors such as carbonization temperature,precursor variety,and microstructure.Hence,this review summarizes the relevant models proposed for the sodium storage mechanism in terms of the sodium storage behavior of hard carbon.The preparation of hard carbon anode materials,including the effect of electrochemical optimization procedures such as pyrolysis,activation, and doping is discussed.A further analysis of the sodium storage mechanism offers guidance for addressing the current issues such as the selection of precursors,the low initial Coulombic efficiency,and the limited means of closed pore regulation.

Key words: Sodium?ion batteries, Biomass, Hard carbon, Mechanism of Na?ion storage, Electrochemical performance

中图分类号:

TQ127.11

赵琨瑀, 王英帅, 樊博建, 黄绍雯, 高洪才. 钠离子电池生物质衍生硬碳负极材料的制备与研究进展[J]. 石油化工高等学校学报, 2025, 38(3): 32-43.

Kunyu ZHAO, Yingshuai WANG, Bojian FAN, Shaowen HUANG, Hongcai GAO. Preparation and Research Progress of Biomass⁃Derived Hard Carbon as an Anode Material for Sodium⁃Ion Batteries[J]. Journal of Petrochemical Universities, 2025, 38(3): 32-43.

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链接本文: https://journal.lnpu.edu.cn/syhg/CN/10.12422/j.issn.1006-396X.2025.03.004

https://journal.lnpu.edu.cn/syhg/CN/Y2025/V38/I3/32

图/表 6

图1 钠离子电池工作原理示意图[8]

Fig.1 The diagram of the working principle of sodium-ion battery[8]

图2 硬碳材料的微观形态结构以及化学组成[24-29]

Fig.2 Microstructure and chemical composition of hard carbon[24-29]

图3 水热炭化法制备高首次库仑效率的硬碳[38,40]

Fig.3 Preparation of hard carbon with high initial coulombic efficiency by hydrothermal carbonization[38,40]

图4 不同温度热解荞麦壳后获得硬碳的XPS光谱和氧元素分布[44-45]（a）硬碳的XPS光谱（b）硬碳的高分辨率XPS光谱 (c) 硬碳的氧元素分布占比

Fig.4 XPS spectra and oxygen distribution percentage of buckwheat hull-derived hard carbon as prepared at different pyrolysis temperatures[44-45]

图5 不同热解温度下制备的橄榄核衍生硬碳的微观结构变化[46]

Fig.5 Microstructure changes of olive shells derived hard carbon as prepared at different pyrolysis temperatures[46]

图6 酸活化前后椴木衍生硬碳的电化学动力学与孔隙度变化[54]

Fig.6 Changes in electrochemical kinetics and porosity of basswood-derived hard carbon after acid activation[54]

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