生物油分级多孔碳超级电容器电极材料的制备及性能

doi:10.16085/j.issn.1000-6613.2022-1517

摘要/Abstract

摘要：

以稻壳生物油为碳源，氯化镁（MgCl₂）为模板剂，采用草酸钾（K₂C₂O₄）活化制备分级多孔碳（BOCs），研究了工艺参数对多孔碳物理化学特性的影响，并测试其电化学性能。结果表明，K₂C₂O₄作为活化剂可对碳骨架产生蚀刻效果，大幅增加碳的孔隙结构；MgCl₂作为模板可以改善活化效果并提高介孔率。最佳工艺参数下制得的BOC-3具备高比表面积（1961.1m²/g）、高介孔率（47.25%）、高含氧量（15.0%，原子分数）的特点和三维泡沫结构。得益于这些特性的多重协同效应，BOC-3的质量比电容可达280F/g，5000次循环充放电后比电容保持率仍达到94.8%，具有优异的倍率性能和循环稳定性。本研究表明以MgCl₂为模板结合K₂C₂O₄进行活化的工艺，可作为从生物油制备高性能超级电容器用分级多孔碳的有效途径，有利于实现生物油的高价值利用。

关键词: 生物油, 超级电容器, 分级多孔碳, 稻壳

Abstract:

The hierarchical porous carbons were prepared from rice husk bio-oil as carbon precursor by using magnesium chloride (MgCl₂) as a template agent and potassium oxalate (K₂C₂O₄) as activator. The effect of process parameters on the physicochemical properties and electrochemical properties of porous carbon was investigated. It was shown that K₂C₂O₄ as an activator could etch the carbon skeleton and greatly increase the pore structure of carbon. MgCl₂ template could improve the activation effect and increase the mesopore ratio. The BOC-3 prepared under the optimal activation conditions had a three-dimensional foam structure, high specific surface area (1961.1m²/g), high mesoporosity (47.25%) and high oxygen content (15.0%). Benefiting from the multiple synergistic effects of these properties, BOC-3 has a mass specific capacitance of 280F/g, and a specific capacitance retention rate of 94.8% after 5000 cycles of charging and discharging. BOC-3 had excellent rate performance and cycle stability. This study revealed that the combination of K₂C₂O₄ activator and MgCl₂ template could be used as an efficient route to fabricate hierarchical porous carbons for high-performance supercapacitors from bio-oil, which was conducive to the high value utilization of bio oil.

Key words: bio-oil, supercapacitor, hierarchical porous carbon, rice husk

中图分类号:

朱薇, 齐鹏刚, 苏银海, 张书平, 熊源泉. 生物油分级多孔碳超级电容器电极材料的制备及性能[J]. 化工进展, 2023, 42(6): 3077-3086.

ZHU Wei, QI Penggang, SU Yinhai, ZHANG Shuping, XIONG Yuanquan. Preparation and properties of bio-oil hierarchical porous carbon electrode materials for supercapacitor[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3077-3086.

图/表 11

参考文献 26

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样品	比表面积/m²·g^-1	平均孔径/nm	总孔容/cm³·g^-1	微孔孔容/cm³·g^-1	介孔孔容/cm³·g^-1	介孔率/%
BOC-1	1656.3	2.399	1.041	0.656	0.385	36.94
BOC-2	1807	3.133	1.501	0.730	0.772	51.41
BOC-3	1961.1	2.881	1.476	0.779	0.697	47.25
BOC-4	2042.5	2.467	1.359	0.816	0.543	39.95
BOC-K	1275.1	1.884	0.633	0.489	0.144	22.80
BOC-M	62.2	7.904	0.140	0.025	0.115	82.20

样品	比表面积/m²·g^-1	平均孔径/nm	总孔容/cm³·g^-1	微孔孔容/cm³·g^-1	介孔孔容/cm³·g^-1	介孔率/%
BOC-1	1656.3	2.399	1.041	0.656	0.385	36.94
BOC-2	1807	3.133	1.501	0.730	0.772	51.41
BOC-3	1961.1	2.881	1.476	0.779	0.697	47.25
BOC-4	2042.5	2.467	1.359	0.816	0.543	39.95
BOC-K	1275.1	1.884	0.633	0.489	0.144	22.80
BOC-M	62.2	7.904	0.140	0.025	0.115	82.20

生物质原料	电解液	电极类型	电流密度 /A·g^-1	比电容 /F·g^-1
板栗壳^[22]	6mol/L KOH	双电极	1	118
马铃薯皮^[23]	6mol/L KOH	双电极	1	143
石榴皮^[24]	6mol/L KOH	双电极	1	84
铜绿微囊藻^[25]	2mol/L KOH	双电极	1	40
玉米秸秆^[26]	3mol/L KOH	三电极	1	113.4
稻壳生物油（本研究）	6mol/L KOH	双电极	1	148

生物质原料	电解液	电极类型	电流密度 /A·g^-1	比电容 /F·g^-1
板栗壳^[22]	6mol/L KOH	双电极	1	118
马铃薯皮^[23]	6mol/L KOH	双电极	1	143
石榴皮^[24]	6mol/L KOH	双电极	1	84
铜绿微囊藻^[25]	2mol/L KOH	双电极	1	40
玉米秸秆^[26]	3mol/L KOH	三电极	1	113.4
稻壳生物油（本研究）	6mol/L KOH	双电极	1	148

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