全木质素衍生硬碳电极的制备及储钠性能研究  

Study on Preparation of All Lignin Derived Hard Carbon Electrode and Its Sodium Storage Performance

作　　者：华梓锋 李庚辰 吴瑶 林嫦妹 黄海[1] 马晓娟[1] 曹石林[1] HUA Zifeng;LI Gengchen;WU Yao;LIN Changmei;HUANG Hai;MA Xiaojuan;CAO Shilin(College of Materials Engineering,Fujian Agriculture and Forestry University,Fuzhou,Fujian Province,350002)

机构地区：[1]福建农林大学材料工程学院,福建福州350002

出　　处：《中国造纸学报》2024年第2期104-114,共11页Transactions of China Pulp and Paper

基　　金：国家自然科学基金(31770632)。

摘　　要：钠离子电容器结合了电池型负极的高能量密度和电容型正极的高功率密度,成为新一代储能器件,硬碳材料作为电池型负极,是当前的研究热点。本研究以制浆黑液为原料,通过提纯、预碳化和高温热解碳化制备木质素衍生硬碳材料,分析其石墨层间距、微晶结构等性质随碳化温度变化的规律,研究了木质素衍生硬碳电极的电化学性能及储钠机理。研究结果表明,随着碳化温度从800℃升高至1600℃,木质素衍生硬碳材料的石墨层间距从0.406 nm减小至0.378 nm,赝石墨层比例从52.69%升高至77.60%。此外,在木质素衍生硬碳电极充放电过程中,更多的Na^(+)在石墨层间嵌入和脱嵌,电极的平台容量从56.8 mAh/g提高至236.0 mAh/g;在斜坡容量变化不大的情况下,平台容量的大幅增加使木质素衍生硬碳电极的可逆容量高达333.7 mAh/g。根据恒电流间歇滴定技术(GITT)分析可知,Na+在木质素衍生硬碳电极中的存储机制符合“吸附-嵌入/填充”模型。Sodium-ion capacitors have become a new generation of energy storage devices by combining the high energy density of batterytype anode and the high power density of capacitive cathode.Hard carbon materials as battery-type anodes are currently a research hotspot.In this study,lignin-derived hard carbon materials were prepared by lignin purification,pre-carbonization and high-temperature pyrolysis carbonization using black liquor from pulping process as raw material.The variation of graphite layer spacing and crystallite structure with carbonization temperature was analyzed.The electrochemical properties and sodium storage mechanism of lignin-derived hard carbon electrodes were studied.The results showed that with the increase of pyrolysis temperature from 800℃to 1600℃,the graphite layer spacing of hard carbon materials decreased from 0.406 nm to 0.378 nm,and the proportion of pseudo-graphite area increased from 52.69%to 77.60%.Therefore,more Na+is intercalated and deintercalated between the graphite layers during the charge and discharge process of the hard carbon electrode.The plateau capacity of the electrode increased from 56.8 mAh/g to 236.0 mAh/g and reversible capacity up to 333.7 mAh/g because of the significant increase in platform capacity.According to the Galvanostatic Intermittent Titration Technique(GITT)analysis,the storage mechanism of sodium ions in the lignin-derived hard carbon electrode conformed to the“Adsorption-Intercalation/Filling”hybrid model.

关 键 词：木质素 硬碳 石墨化程度 平台容量 钠离子电容器 

分 类 号：TS79[轻工技术与工程—制浆造纸工程]