磷酸-硫酸协同制备木屑基碳材料及其电化学性能研究

doi:10.19964/j.issn.1006-4990.2024-0191

摘要/Abstract

摘要：

以生物质废弃物木屑为原料，采用磷酸法、磷酸-硫酸协同活化法制备用于超级电容器电极材料的碳材料。通过BET、FT-IR、XPS、XRD和Raman等手段对生物炭的微观结构、化学组成及石墨化程度进行表征分析。结果表明：最佳制备工艺条件为磷酸木屑质量比（浸渍比）为2.0∶1、升温速率为10 ℃/min、活化温度为550 ℃、活化时间为60 min时，磷酸法木屑基碳材料的比表面积为1 717 m²/g、总孔容为1.00 cm³/g、微孔孔容为0.83 m³/g、中孔孔容为0.17 m³/g；磷酸-硫酸协同活化法木屑基碳材料（MSC-4-98）的比表面积为1 951 m²/g、总孔容为1.66 cm³/g、微孔孔容为0.60 m³/g、中孔孔容为1.06 m³/g；XPS等测试结果表明碳材料具有较高的石墨化程度。电化学性能测试结果表明，MSC-4-98在电流密度为0.5 A/g时比电容为250.38 F/g，当电流密度进一步增加到2.0 A/g时比电容依旧达到204.56 F/g，仍保持为最高比电容的81.7%，具有较高的比电容和较好的电容保持率。磷酸法制备的木屑碳材料，尽管具有高比表面积、高微孔率，但中孔不发达不满足电极材料要求；磷酸-硫酸协同制备的木屑基碳材料，具有高比表面积且中微双孔孔容均衡，电化学性能较为优异，在超级电容器应用中有巨大潜力。

关键词: 生物质, 碳材料, 磷酸, 协同活化, 电化学性能

Abstract:

Carbon materials for supercapacitor electrode materials were prepared using biomass waste wood chips as raw materials by phosphoric acid method and phosphoric acid-sulfuric acid synergistic activation method.Characterization and analysis of the microstructure，chemical composition，and degree of graphitization of biochar were carried out using techniques such as BET，FT-IR，XPS，XRD，and Raman.The results showed that the optimal preparation process conditions were impregnation ratio of 2.0∶1，heating rate of 10 ℃/min，activation temperature of 550 ℃，and activation time of 60 min.The specific surface area of phosphoric acid based wood chip carbon material was 1 717 m²/g，total pore volume was 1.00 cm³/g，microporous pore volume was 0.83 m³/g，and mesoporous pore volume was 0.17 m³/g.The specific surface area of wood chip based carbon material（MSC-4-98） using phosphoric acid-sulfuric acid synergistic activation method was 1 951 m²/g，with a total pore volume of 1.66 cm³/g，a microporous pore volume of 0.60 m³/g，and a mesoporous pore volume of 1.06 m³/g.The results of XPS tests indicated that carbon materials had a high degree of graphitization.According to electrochemical performance tests，the specific capacitance of MSC-4-98 was 250.38 F/g at a current density of 0.5 A/g.When the current density was further increased to 2.0 A/g，the specific capacitance still reached 204.56 F/g，remaining at 81.7% of the highest specific capacitance，with high specific capacitance and good capacitance retention.Although the wood chip carbon material prepared by the phosphoric acid method had a high specific surface area and high porosity，the underdeveloped mesopores did not meet the requirements of electrode materials.The wood chip based carbon materials prepared with phosphoric acid and sulfuric acid had high specific surface area，well-developed and balanced mesopores，and excellent electrochemical performance，which had great potential in the application of supercapacitors.

Key words: biomass, carbon materials, phosphoric acid, synergistic activation, electrochemical performance

中图分类号:

TM53

于盼盼, 吴宗金, 吴浪, 杨毅, 林倩, 潘红艳. 磷酸-硫酸协同制备木屑基碳材料及其电化学性能研究[J]. 无机盐工业, 2025, 57(4): 79-88.

YU Panpan, WU Zongjin, WU Lang, YANG Yi, LIN Qian, PAN Hongyan. Study on synergistic preparation of wood chip based carbon materials with phosphoric acid-sulfuric acid and their electrochemical properties[J]. Inorganic Chemicals Industry, 2025, 57(4): 79-88.

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活化时间/min	S_BET/（m²·g^-1）	S_mic/（m²·g^-1）	S_mes/（m²·g^-1）	V_total/（cm³·g^-1）	V_mic/（cm³·g^-1）	V_mes/（cm³·g^-1）	D_average/nm
60	1 717	1 531	186	1.00	0.83	0.17	1.9
70	1 558	1 368	190	0.91	0.74	0.17	1.7
80	1 214	1 153	61	0.58	0.46	0.12	1.5
90	1 105	1 041	64	0.50	0.43	0.07	1.7

碳材料	S_BET/（m²·g^-1）	S_mic/（m²·g^-1）	S_mes/（m²·g^-1）	V_total/（cm³·g^-1）	V_mic/（cm³·g^-1）	V_mes/（cm³·g^-1）	D_average/nm
MSC-0-0	1 717	1 531	186	1.00	0.83	0.17	1.9
MSC-1-98	1 689	896	793	1.78	0.49	1.29	4.4
MSC-4-98	1 951	1 191	760	1.66	0.60	1.06	3.6
MSC-8-20	1 846	815	1 031	1.67	0.38	1.29	3.6
MSC-8-45	2 044	1 261	783	1.58	0.59	0.99	3.1
MSC-8-68	2 147	1 321	826	1.94	0.62	1.32	3.6
MSC-8-98	2 123	1 208	914	1.60	0.57	1.03	3.0

样品名称	w（C）	w（N）	w（O）	w（P）
MSC-4-98	94.05	0.78	4.69	0.48
MSC-8-68	92.69	1.01	5.73	0.57
MSC-8-45	91.97	1.04	6.28	0.71

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