Research progress in pore size regulation and electrochemical performance of biomass-based carbon materials

doi:10.16085/j.issn.1000-6613.2022-1056

Abstract

Abstract:

Biomass-based carbon materials have the advantages of wide source, abundant surface functional groups and diverse microstructures. However, it has the problem of unreasonable pore size distribution, limiting their applications in electrochemical energy storage. In this paper, the influence mechanism of microporous, mesoporous and macroporous structures on electrochemical performance was briefly described, and the pore size regulation methods were elaborated including alkali activation method, foaming activation method, CO₂/steam activation method and freezing treatment method for microporous, acid activation method, template method, molten salt carbonization method, catalytic activation method and cellulase hydrolysis method for mesoporous, and SiO₂-colloidal template method and soft template method for macroporous. Moreover, the influence factors, advantages and disadvantages of the above regulation methods were analyzed, and the application effects of various methods in electrode materials were summarized. The analysis showed that the foaming activation method was efficient and environmentally friendly for microporous regulation, and the acid activation method and molten salt carbonization method improved the mesoporosity significantly. In addition, according to the different sources (components) of biomass materials, the regulation methods were classified. It was found that the alkali activation method and the self-templating method were suitable for microporous and mesoporous regulation of animal-based carbon materials, while the cellulose enzymatic method provided a new green idea for mesoporous regulation of plant-based carbon materials. Finally, some suggestions were put forward on the application of pore size regulation and green preparation of biomass-based carbon materials in electrochemical energy storage.

Key words: biomass, pyrolysis, electrochemistry, electrode material, porous structure

摘要：

生物质基炭材料具有来源广泛、表面官能团丰富和微观结构多样的优点，但具有孔径分布不合理的问题，从而限制了其在电化学储能领域的应用。本文简述了微孔、介孔和大孔结构对电化学性能的影响机制，详细阐述了孔径调控方法：微孔为碱活化法、发泡活化法、CO₂/蒸汽活化法和冷冻处理法，介孔为酸活化法、模板法、熔融盐炭化法、催化活化法和纤维素酶解法，大孔为SiO₂-胶体模板法和软模板法。并将以上调控方法的影响因素和优缺点进行了分析，总结了各种方法在电极材料中的应用效果。分析表明，发泡活化法对微孔调控高效且环保，酸活化法和熔融盐炭化法对介孔率提高显著。此外，本文将调控方法按照生物质材料来源（组分）的不同进行了分类，得出碱活化法和自模板法适用于动物基炭材料微孔和介孔调控，而纤维素酶解法为植物基炭材料的介孔调控提供了绿色环保的新思路。最后，本文就生物质基炭材料孔径调控和绿色制备在电化学储能领域的应用提出了建议。

关键词: 生物质, 热解, 电化学, 电极材料, 孔结构

CLC Number:

TQ127.11

LIU Jing, LIN Lin, ZHANG Jian, ZHAO Feng. Research progress in pore size regulation and electrochemical performance of biomass-based carbon materials[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1907-1916.

刘静, 林琳, 张健, 赵峰. 生物质基炭材料孔径调控及电化学性能研究进展[J]. 化工进展, 2023, 42(4): 1907-1916.

Figures/Tables 8

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类别	原料	方法	比表面积/m²·g^-1	主要孔类型	电解液	电流密度/A·g^-1	比电容/F·g^-1	参考文献
动物基炭材料	蟹壳	自模板法	634	介孔	6mol/L KOH	0.2	220	[44]
	虾壳	CO₂活化法	431.6	微孔	6mol/L KOH	1	144.2	[31]
	鱼鳞	碱活化法	594	微孔	1mol/L NaClO₄	0.07	282	[16]
	蝉蜕	碱活化法	1676	微孔	6mol/L KOH	1	335	[23]
	壳聚糖	SiO₂-PTFE胶体模板法	1011	大孔	6mol/L KOH	0.5	250.5	[62]
	壳聚糖盐	软模板法	927	大孔	1mol/L Na₂SO₄	0.5	302	[64]
	粪便	自模板法	1000	介孔	6mol/L KOH	1	486	[46]
	骨头	自模板法	785	介孔	6mol/L KOH	0.5	230.68	[45]
植物基炭材料	椰子髓	碱活化法	2056	微孔	1mol/L H₂SO₄	0.1	232.3	[25]
	洋葱	碱活化法	1914.9	微孔	6mol/L KOH	0.5	179.5	[17]
	亚麻籽渣	碱活化法	3326	微孔	1mol/L H₂SO₄	0.5	398	[26]
	微藻	发泡活化法	856	微孔	6mol/L KOH	1	234	[27]
	稻草	发泡活化法	2786.5	微孔	6mol/L KOH	1	317	[28]
	竹笋	发泡活化法	1376.5	微孔	6mol/L KOH	0.5	178	[29]
	松子壳	CO₂活化法	956	微孔	6mol/L KOH	0.5	128	[32]
	芹菜	冷冻处理法	507.73	微孔	1mol/L H₂SO₄	1	350	[34]
	椰壳	冷冻处理法	482	微孔	—	—	—	[35]
	漆木	H₃PO₄活化法	1609.09	介孔	1mol/L H₂SO₄	0.5	354	[39]
	杨柳絮	H₃PO₄活化法	2011	介孔	6mol/L KOH	0.5	316.5	[37]
	果实绒毛	H₃PO₄活化法	1758.5	介孔	6mol/L KOH	1	247.5	[38]
	梧桐树皮	硬模板法	1587.62	介孔	6mol/L KOH	0.5	115.6	[41]
	胡萝卜	硬模板法	1265	介孔	—	1	268	[42]
	生物油	硬模板法	1409.89	介孔	6mol/L KOH	0.5	344	[43]
	稻壳	熔融盐炭化法	977	介孔	1mol/L H₂SO₄	0.5	288	[50]
	废茶叶	熔融盐炭化法	1308	介孔	6mol/L KOH	0.1	140	[52]
	柳叶	熔融盐炭化法	1065	介孔	6mol/L KOH	0.1	216	[53]
	蔗糖	催化活化法	217	介孔	—	—	—	[55]
	紫菜	催化活化法	848.4	介孔	—	—	—	[56]
	玉米淀粉	催化活化法	1775	介孔	1mol/L C₂H₅	0.1	144.8	[57]
	杨木	纤维素酶解法	1418	介孔	6mol/L KOH	1	384	[59]
	稻草	SiO₂-PTFE胶体模板法	1011	大孔	6mol/L KOH	0.5	250.5	[63]

类别	原料	方法	比表面积/m²·g^-1	主要孔类型	电解液	电流密度/A·g^-1	比电容/F·g^-1	参考文献
动物基炭材料	蟹壳	自模板法	634	介孔	6mol/L KOH	0.2	220	[44]
	虾壳	CO₂活化法	431.6	微孔	6mol/L KOH	1	144.2	[31]
	鱼鳞	碱活化法	594	微孔	1mol/L NaClO₄	0.07	282	[16]
	蝉蜕	碱活化法	1676	微孔	6mol/L KOH	1	335	[23]
	壳聚糖	SiO₂-PTFE胶体模板法	1011	大孔	6mol/L KOH	0.5	250.5	[62]
	壳聚糖盐	软模板法	927	大孔	1mol/L Na₂SO₄	0.5	302	[64]
	粪便	自模板法	1000	介孔	6mol/L KOH	1	486	[46]
	骨头	自模板法	785	介孔	6mol/L KOH	0.5	230.68	[45]
植物基炭材料	椰子髓	碱活化法	2056	微孔	1mol/L H₂SO₄	0.1	232.3	[25]
	洋葱	碱活化法	1914.9	微孔	6mol/L KOH	0.5	179.5	[17]
	亚麻籽渣	碱活化法	3326	微孔	1mol/L H₂SO₄	0.5	398	[26]
	微藻	发泡活化法	856	微孔	6mol/L KOH	1	234	[27]
	稻草	发泡活化法	2786.5	微孔	6mol/L KOH	1	317	[28]
	竹笋	发泡活化法	1376.5	微孔	6mol/L KOH	0.5	178	[29]
	松子壳	CO₂活化法	956	微孔	6mol/L KOH	0.5	128	[32]
	芹菜	冷冻处理法	507.73	微孔	1mol/L H₂SO₄	1	350	[34]
	椰壳	冷冻处理法	482	微孔	—	—	—	[35]
	漆木	H₃PO₄活化法	1609.09	介孔	1mol/L H₂SO₄	0.5	354	[39]
	杨柳絮	H₃PO₄活化法	2011	介孔	6mol/L KOH	0.5	316.5	[37]
	果实绒毛	H₃PO₄活化法	1758.5	介孔	6mol/L KOH	1	247.5	[38]
	梧桐树皮	硬模板法	1587.62	介孔	6mol/L KOH	0.5	115.6	[41]
	胡萝卜	硬模板法	1265	介孔	—	1	268	[42]
	生物油	硬模板法	1409.89	介孔	6mol/L KOH	0.5	344	[43]
	稻壳	熔融盐炭化法	977	介孔	1mol/L H₂SO₄	0.5	288	[50]
	废茶叶	熔融盐炭化法	1308	介孔	6mol/L KOH	0.1	140	[52]
	柳叶	熔融盐炭化法	1065	介孔	6mol/L KOH	0.1	216	[53]
	蔗糖	催化活化法	217	介孔	—	—	—	[55]
	紫菜	催化活化法	848.4	介孔	—	—	—	[56]
	玉米淀粉	催化活化法	1775	介孔	1mol/L C₂H₅	0.1	144.8	[57]
	杨木	纤维素酶解法	1418	介孔	6mol/L KOH	1	384	[59]
	稻草	SiO₂-PTFE胶体模板法	1011	大孔	6mol/L KOH	0.5	250.5	[63]

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