Application of coal-based graphene quantum dots in supercapacitors

doi:10.16085/j.issn.1000-6613.2022-1791

Abstract

Abstract:

In order to solve the problems of excessive use of potassium hydroxide (KOH) and unreasonable pore structure distribution in the preparation of coal-based activated carbon, Taxi anthracite was used as carbon source to oxidize graphene quantum dots by potassium ferrate and hydrogen peroxide, and then mixed with KOH to prepare coal-based graphene quantum dots activated carbon. The results showed that this method could reduce the amount of KOH (making the alkali-carbon ratio less than 1), and the activation mechanism of the alkali-carbon ratio to graphene quantum dots was similar to that of coal. When the amount of KOH was small (alkali-carbon ratio with 0.25), only pore-forming effect was observed. After increasing the dosage (alkali-carbon ratio with 0.5), KOH had not only the pore-forming effect, but also the pore-expanding effect. The excess KOH (alkali carbon ratio with 0.75) was mainly focus on pore-expanding effect. With the increase of alkali-carbon ratio, the specific surface area and total pore volume of activated carbon also increased, and the micropore rate gradually decreased, while the mesoporous rate and the average pore size increased. When the alkali-carbon ratio was 0.75, the activation effect was the best. The specific surface area of GQDAC-0.75 was 1207.3m²/g, the micropore rate was 39.5%, and the mesoporous rate was 51.8%. Thanks to its unique hierarchical pore structure of "macropore-mesopore-micropore", GQDAC-0.75 showed the optimal electrochemical performance with specific capacitance of 243.6F/g at 0.5A/g current density. When the current density increased to 10A/g, the specific capacitance of GQDAC-0.75 was maintained at 202.2F/g. Even the current density continued to increase to 100A/g, the specific capacitance was still 179.5F/g, and the specific capacitance could remain 191.6F/g at the current density of 20A/g after 10000 cycles with a 98.1% retention rate, which indicated the excellent rate performance and cycle performance.

Key words: coal, graphene quantum dots, activation, microstructure, activated carbon, supercapacitor

摘要：

针对目前制备煤基活性炭氢氧化钾（KOH）使用比例过高及孔结构分布不合理问题，以太西无烟煤为碳源，先采用高铁酸钾与过氧化氢分步氧化将其氧化为石墨烯量子点，再与KOH混合活化制备煤基石墨烯量子点活性炭。结果表明，这种方法可降低KOH使用量（使碱炭比小于1），且碱炭比对煤基石墨烯量子点的活化机制与对煤的活化机制类似：KOH用量较少时（碱炭比0.25）只有造孔作用；增加用量后（碱炭比0.5），KOH不但有造孔作用，还有扩孔作用；过量的KOH（碱炭比0.75）则以扩孔为主。随着碱炭比的增加，活性炭的比表面积与总孔容也随之增加，微孔率逐渐下降，中孔率和平均孔径都在增长。在碱炭比为0.75时，活化效果最好，GQDAC-0.75比表面积为1207.3m²/g，微孔率为39.5%，中孔率为51.8%；得益于其独特的“大孔-中孔-微孔”的层次孔结构，GQDAC-0.75表现出最优的电化学性能，在0.5A/g电流密度下比电容达243.6F/g，当电流密度增大到10A/g时，GQDAC-0.75的比电容保持在202.2F/g，继续增大电流密度到100A/g，比电容仍有179.5F/g，且在20A/g电流密度下循环10000次后比电容仍有191.6F/g，保持率为98.1%，具有优异的倍率性能和循环稳定性。

关键词: 煤, 石墨烯量子点, 活化, 微观结构, 活性炭, 超级电容器

CLC Number:

TM242

ZHANG Yaojie, ZHANG Chuanxiang, SUN Yue, ZENG Huihui, JIA Jianbo, JIANG Zhendong. Application of coal-based graphene quantum dots in supercapacitors[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4340-4350.

张耀杰, 张传祥, 孙悦, 曾会会, 贾建波, 蒋振东. 煤基石墨烯量子点在超级电容器中的应用[J]. 化工进展, 2023, 42(8): 4340-4350.

Figures/Tables 13

样品	工业分析/%				元素分析/%
样品	水分	灰分	挥发分	固定碳	碳	氢	氧	氮	硫
太西无烟煤	1.55	2.32	6.94	93.06	94.08	3.61	1.42	0.76	0.13

样品编号	比表面积/m²·g^-1	总孔容/cm³·g^-1	微孔孔容/cm³·g^-1	微孔率/%	中孔孔容/cm³·g^-1	中孔率/%	平均孔径/nm
GQDAC-0	268.8	0.204	0.156	76.6	0.029	13.9	2.24
GQDAC-0.25	654.1	0.476	0.421	88.4	0.049	10.3	1.84
GQDAC-0.5	1166.4	0.852	0.607	71.2	0.230	26.9	2.00
GQDAC-0.75	1207.3	1.346	0.531	39.5	0.697	51.8	3.59

样品编号	C原子分数/%						氧原子分数（总含量）/%
样品编号	总含量	C—C/C $̿$ C	C—O	C—O—C	C $̿$ O	COOH	氧原子分数（总含量）/%
GQDAC-0	89.46	69.58	12.58	9.44	5.04	3.36	8.56
GQDAC-0.25	87.53	54.51	25.62	11.47	4.78	3.62	10.8
GQDAC-0.5	86.42	59.51	19.11	12.37	5.08	3.92	11.24
GQDAC-0.75	86.24	64.71	12.44	13.99	5.93	2.91	11.47

样品编号	C原子分数/%						氧原子分数（总含量）/%
样品编号	总含量	C—C/C $̿$ C	C—O	C—O—C	C $̿$ O	COOH	氧原子分数（总含量）/%
GQDAC-0	89.46	69.58	12.58	9.44	5.04	3.36	8.56
GQDAC-0.25	87.53	54.51	25.62	11.47	4.78	3.62	10.8
GQDAC-0.5	86.42	59.51	19.11	12.37	5.08	3.92	11.24
GQDAC-0.75	86.24	64.71	12.44	13.99	5.93	2.91	11.47

前体	活化剂	测试体系	电解液	比电容 /F·g^-1（A·g^-1)	参考文献
褐煤	ZnCl₂	三电极	6mol/L KOH	140.0（10）	[14]
烟煤	PAN+DMF	三电极	6mol/L KOH	200.6（10）	[40]
无烟煤	CO₂+KOH	三电极	6mol/L KOH	190.0（5)	[41]
低阶煤	FeCl₂+CO₂	三电极	6mol/L KOH	180.0（10）	[29]
煤/半焦	PAN/PVP	三电极	6mol/L KOH	152.0（4）	[42]
煤沥青	KOH	三电极	6mol/L KOH	192.0（10）	[16]
褐煤	水蒸气	三电极	6mol/L KOH	122.0（10）	[43]
煤沥青/ 氧化石墨烯	1,6-二氨基乙烷	三电极	6mol/L KOH	163.0（30）	[44]
无烟煤	KOH	三电极	6mol/L KOH	202.2（10）	本文
				179.5（100）

References 44

1	PERMATASARI F A, IRHAM M A, BISRI S Z, et al. Carbon-based quantum dots for supercapacitors: Recent advances and future challenges[J]. Nanomaterials, 2021, 11(1): E91.
2	YUE Xiaoming, PENG Cheng, XU Jing, et al. Preparation of carbon electrodes from alkaline extraction of lignite for double-layer capacitors[J]. Ionics, 2021, 27(8): 3605-3614.
3	杨芳, 刘晨, 杨绍斌, 等. 用于超级电容器的煤基活性炭电极材料的研究进展[J]. 硅酸盐学报, 2019, 47(10): 1499-1508.
	YANG Fang, LIU Chen, YANG Shaobin, et al. Research progress on coal-based activated carbon electrode material for supercapacitor[J]. Journal of the Chinese Ceramic Society, 2019, 47(10): 1499-1508.
4	SHI Ming, XIN Yanfei, CHEN Xinxing, et al. Coal-derived porous activated carbon with ultrahigh specific surface area and excellent electrochemical performance for supercapacitors[J]. Journal of Alloys and Compounds, 2021, 859: 157856.
5	LI Keke, LIU Guoyang, ZHENG Lisi, et al. Coal-derived carbon nanomaterials for sustainable energy storage applications[J]. New Carbon Materials, 2021, 36(1): 133-154.
6	CHEN Di, JIANG Kai, HUANG Tingting, et al. Recent advances in fiber supercapacitors: Materials, device configurations, and applications[J]. Advanced Materials (Deerfield Beach, Fla), 2020, 32(5): e1901806.
7	DONG Duo, ZHANG Yongsheng, XIAO Yi, et al. High performance aqueous supercapacitor based on nitrogen-doped coal-based activated carbon electrode materials[J]. Journal of Colloid and Interface Science, 2020, 580: 77-87.
8	解强, 张香兰, 梁鼎成, 等. 煤基活性炭定向制备: 原理·方法·应用[J]. 煤炭科学技术, 2021, 49(1): 100-127.
	XIE Qiang, ZHANG Xianglan, LIANG Dingcheng, et al. Directional preparation of coal-based activated carbon: Principles, approaches and applications[J]. Coal Science and Technology, 2021, 49(1): 100-127.
9	邢宝林. 超级电容器用低阶煤基活性炭的制备及电化学性能研究[D]. 焦作: 河南理工大学, 2011.
	XING Baolin. Preparation and electrochemical performance of low-rank coal based activated carbon for supercapacitor[D]. Jiaozuo: Henan Polytechnic University, 2011.
10	侯彩霞, 孔碧华, 樊丽华, 等. 超级电容器用煤基活性炭研究[J]. 洁净煤技术, 2017, 23(5): 56-61.
	HOU Caixia, KONG Bihua, FAN Lihua, et al. Research in coal-based activated carbon for supercapacitor[J]. Clean Coal Technology, 2017, 23(5): 56-61.
11	林国鑫, 于馨凝, 刘少俊, 等. 煤质成分对煤基活性炭活化成孔的影响机制[J]. 燃烧科学与技术, 2020, 26(1): 81-86.
	LIN Guoxin, YU Xinning, LIU Shaojun, et al. Influence mechanism of coal composition on activation pore formation of coal-based activated carbon[J]. Journal of Combustion Science and Technology, 2020, 26(1): 81-86.
12	邢宝林, 黄光许, 谌伦建, 等. 高品质低阶煤基活性炭的制备与表征[J]. 煤炭学报, 2013, 38(S1): 217-222.
	XING Baolin, HUANG Guangxu, CHEN Lunjian, et al. Preparation and characterization of high quality low-rank coal based activated carbon[J]. Journal of China Coal Society, 2013, 38(S1): 217-222.
13	ZHANG Chuanxiang, LONG Donghui, XING Baolin, et al. The superior electrochemical performance of oxygen-rich activated carbons prepared from bituminous coal[J]. Electrochemistry Communications, 2008, 10(11): 1809-1811.
14	LI Lijun, WANG Xiaoyan, WANG Shujuan, et al. Activated carbon prepared from lignite as supercapacitor electrode materials[J]. Electroanalysis, 2016, 28(1): 243-248.
15	HAN Gaoxu, JIA Jianbo, LIU Quanrun, et al. Template-activated bifunctional soluble salt ZnCl₂ assisted synthesis of coal-based hierarchical porous carbon for high-performance supercapacitors[J]. Carbon, 2022, 186: 380-390.
16	王凯, 高超, 李松恩, 等. 煤质沥青基超级活性炭的提质处理及其电化学性能的研究[J]. 新型炭材料, 2018, 33(6): 562-570.
	WANG Kai, GAO Chao, LI Songen, et al. Electrochemical performance of high surface area activated carbons derived from coal tar pitch[J]. New Carbon Materials, 2018, 33(6): 562-570.
17	郭秉霖, 侯彩霞, 樊丽华, 等. 萃取温度对无灰煤结构及煤基活性炭电化学性能的影响[J]. 无机化学学报, 2018, 34(9): 1615-1624.
	GUO Binglin, HOU Caixia, FAN Lihua, et al. Effect of extraction temperature on hyper-coal structure and electrochemistry of coal-based activated carbon[J]. Chinese Journal of Inorganic Chemistry, 2018, 34(9): 1615-1624.
18	裴卫兵, 邢宝林, 黄光许, 等. 预炭化时间对煤基活性炭孔结构及电化学性能的影响[J]. 洁净煤技术, 2013, 19(3): 42-45, 64.
	PEI Weibing, XING Baolin, HUANG Guangxu, et al. Influence of carbonization time on pore struture and electrochemical performance of coal-based activated carbon[J]. Clean Coal Technology, 2013, 19(3): 42-45, 64.
19	薄纯辉, 姜维佳, 王玉高, 等. 煤基碳量子点合成研究进展[J]. 应用化学, 2021, 38(7): 767-788.
	BO Chunhui, JIANG Weijia, WANG Yugao, et al. Research progress on synthesis of coal-based carbon quantum dots[J]. Chinese Journal of Applied Chemistry, 2021, 38(7): 767-788.
20	ZHANG Bo, MAIMAITI Halidan, ZHANG Dedong, et al. Preparation of coal-based C-Dots/TiO₂ and its visible-light photocatalytic characteristics for degradation of pulping black liquor[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2017, 345: 54-62.
21	CAI Tingting, LIU Bin, PANG Ernan, et al. A review on the preparation and applications of coal-based fluorescent carbon dots[J]. New Carbon Materials, 2020, 35(6): 646-666.
22	张伟, 安兴业, 刘利琴, 等. 木质素纳米颗粒/天然纤维基活性碳纤维材料的制备及其电化学性能[J]. 化工进展, 2022, 41(7): 3770-3783.
	ZHANG Wei, AN Xingye, LIU Liqin, et al. Preparation and electrochemical performance of lignin nanoparticles/natural fiber based activated carbon fiber materials[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3770-3783.
23	XING Baolin, HUANG Guangxu, CHEN Zhengfei, et al. Facile preparation of hierarchical porous carbons for supercapacitors by direct carbonization of potassium humate[J]. Journal of Solid State Electrochemistry, 2017, 21(1): 263-271.
24	张传祥, 张睿, 成果, 等. 煤基活性炭电极材料的制备及电化学性能[J]. 煤炭学报, 2009, 34(2): 252-256.
	ZHANG Chuanxiang, ZHANG Rui, CHENG Guo, et al. Preparation and electrochemical properties of coal-based activated carbons[J]. Journal of China Coal Society, 2009, 34(2): 252-256.
25	STRAUSS Volker, MARSH Kris, KOWAL Matthew D, et al. A simple route to porous graphene from carbon nanodots for supercapacitor applications[J]. Advanced Materials, 2018, 30(8): 1704449.
26	朱家瑶, 董玥, 张苏, 等. 炭-/石墨烯量子点在超级电容器中的应用[J]. 物理化学学报, 2020, 36(2): 1903052.
	ZHU Jiayao, DONG Yue, ZHANG Su, et al. Application of carbon-/graphene quantum dots for supercapacitors[J]. Acta Physico-Chimica Sinica, 2020, 36(2): 1903052.
27	马爱玲, 黄光许, 耿乾浩, 等. 硼/氮共掺杂多孔碳纳米片的制备及其电化学性能[J]. 化工进展, 2021, 40(8): 4388-4396.
	MA Ailing, HUANG Guangxu, GENG Qianhao, et al. Preparation and electrochemical properties of B/N co-doped porous carbon nanosheets[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4388-4396.
28	GAO Shasha, TANG Yakun, WANG Lei, et al. Coal-based hierarchical porous carbon synthesized with a soluble salt self-assembly-assisted method for high performance supercapacitors and Li-ion batteries[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(3): 3255-3263.
29	WANG Lijie, SUN Fei, GAO Jihui, et al. A novel melt infiltration method promoting porosity development of low-rank coal derived activated carbon as supercapacitor electrode materials[J]. Journal of the Taiwan Institute of Chemical Engineers, 2018, 91: 588-596.
30	YAO Youheng, HUANG Guangxu, LIU Yingbin, et al. Facile synthesis of B/N co-doped porous carbon nanosheets with high heteroatom content and electrical conductivity for excellent-performance supercapacitors[J]. Applied Surface Science, 2022, 580: 152236.
31	王博阳, 夏吉利, 董晓玲, 等. 不同变质程度煤衍生硬炭的储钠行为研究[J]. 化工学报, 2021, 72(11): 5738-5750.
	WANG Boyang, XIA Jili, DONG Xiaoling, et al. Study on sodium storage behavior of hard carbons derived from coal with different grades of metamorphism[J]. CIESC Journal, 2021, 72(11): 5738-5750.
32	DENG Jun, BAI Zujin, XIAO Yang, et al. Effects of imidazole ionic liquid on macroparameters and microstructure of bituminous coal during low-temperature oxidation[J]. Fuel, 2019, 246: 160-168.
33	ZHANG Su, ZHU Jiayao, QING Yan, et al. Ultramicroporous carbons puzzled by graphene quantum dots: Integrated high gravimetric, volumetric, and areal capacitances for supercapacitors[J]. Advanced Functional Materials, 2018, 28(52): 1805898.
34	YAGLIKCI Savas, GOKCE Yavuz, YAGMUR Emine, et al. Does high sulphur coal have the potential to produce high performance-low cost supercapacitors?[J]. Surfaces and Interfaces, 2021, 22: 100899.
35	DONG Xiaoxi, WANG Jingyue, YAN Meifang, et al. Hierarchically Fe-doped porous carbon derived from phenolic resin for high performance supercapacitor[J]. Ceramics International, 2021, 47(5): 5998-6009.
36	ZHANG Hongyue, WANG Bolun, YU Xiaowei, et al. Carbon dots in porous materials: Host-guest synergy for enhanced performance[J]. Angewandte Chemie International Edition, 2020, 59(44): 19390-19402.
37	WANG Dawei, LI Feng, LIU Min, et al. 3D aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storage[J]. Angewandte Chemie International Edition, 2009, 48(9): 1525.
38	XING Baolin, HUANG Guangxu, CHEN Lunjian, et al. Microwave synthesis of hierarchically porous activated carbon from lignite for high performance supercapacitors[J]. Journal of Porous Materials, 2016, 23(1): 67-73.
39	DONG Duo, ZHANG Yongsheng, XIAO Yi, et al. Oxygen-enriched coal-based porous carbon under plasma-assisted MgCO₃ activation as supercapacitor electrodes[J]. Fuel, 2022, 309: 122168.
40	HE Yitao, WANG Luxiang, JIA Dianzeng. Coal/PAN interconnected carbon nanofibers with excellent energy storage performance and electrical conductivity[J]. Electrochimica Acta, 2016, 194: 239-245.
41	YUE Xiaoming, AN Zhaoyang, YE Mei, et al. Preparation of porous activated carbons for high performance supercapacitors from Taixi anthracite by multi-stage activation[J]. Molecules, 2019, 24(19): 3588.
42	TAN Shuai, KRAUS Theodore John, LI-OAKEY Katie Dongmei. Understanding the supercapacitor properties of electrospun carbon nanofibers from Powder River Basin coal[J]. Fuel, 2019, 245: 148-159.
43	徐园园, 陆倩, 木沙江, 等. 煤基多孔炭的制备及其在超级电容器中的应用[J]. 煤炭转化, 2016, 39(1): 76-81.
	XU Yuanyuan, LU Qian, MU Shajiang, et al. Preparation of coal-based porous carbon and utilization in supercapacitor[J]. Coal Conversion, 2016, 39(1): 76-81.
44	QU Wenhui, GUO Yubo, SHEN Wenzhong, et al. Using asphaltene supermolecules derived from coal for the preparation of efficient carbon electrodes for supercapacitors[J]. The Journal of Physical Chemistry C, 2016, 120(28): 15105-15113.

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