超级电容器用相互连接的类石墨烯纳米片

doi:10.3866/PKU.WHXB201903043

摘要/Abstract

摘要：

采用氧化镁模板耦合原位氢氧化钾活化法制备了超级电容器用煤焦油基相互连接的类石墨烯纳米片(IGNSs)。所制备的IGNS具有高达2887 m²∙g⁻¹的比表面积和大量的分级短孔。当作为超级电容器的电极材料时，在6 mol∙L⁻¹ KOH电解液中，于0.05 A∙g⁻¹的电流密度下，IGNS显示出313 F∙g⁻¹的高比容；在20 A∙g⁻¹的电流密度下，IGNS的比电容为261 F∙g⁻¹，显示了好的倍率性能；经过10000次循环测试后，其容量保持率为92.7%，展现了优异的循环稳定性。这一工作为从芳烃分子大规模生产高性能储能用类石墨烯纳米片提供了一种简单的方法。

关键词: 煤焦油, 氧化镁模板, 类石墨烯纳米片, 好的倍率性能, 超级电容器

Abstract:

The rapid economic development has necessitated increased environmental protection and tremendous efforts have been devoted to designing and preparing environmentally friendly energy storage and conversion devices, including batteries, supercapacitors (SCs), and solar cells. As useful energy storage and conversion devices, SCs have received significant attention due to their high power density, long cycle stability, and rapid charging rate. The performance of SCs largely depends on the electrode materials, which can be composed of metal oxides, conducting polymers, carbon materials, and their composites. Carbon materials, including carbon nanotubes, carbon fibers, porous carbons, template carbons, and graphene-like carbon nanosheets (GCNSs), have attracted significant attention owing to their tailorable pore size and excellent physiochemical stability. GCNSs are considered to be outstanding carbon materials for use in high-performance SC because of their large specific surface area and high electrical conductivity. To date, many carbon precursors have been used to synthesize GCNSs for SCs such as coal, biomass, and chemical by-products. In particular, cheap and abundant chemical by-products for the synthesis of carbon materials can reduce preparation costs and environmental pollution as well as achieve high value-added chemicals. Coal tar, a by-product of the coal coking process, is rich in aromatic polycyclic hydrocarbon molecules, which can be polymerized, carbonized, and activated to synthesize GCNSs for SCs. In addition, MgO particles can be used as templates due to their stable properties and low-cost compared with other metal oxide templates (e.g. Fe₂O₃, NiO, or CuO), imparting space confinement and structure guidance during the preparation of GCNSs. Herein, we report a facile method for the preparation of interconnected graphene-like nanosheets (IGNSs) from coal tar by MgO templating combined with in-situ KOH activation. The IGNSs were obtained after the impurity removal by repeated washing with dilute acid. The as-synthesized IGNSs feature high specific surface area of up to 2887 m²∙g⁻¹ and abundant hierarchical short pores, which provide abundant active sites for ion adsorption, supply plentiful channels for fast ion transport and boost electrical conductivity. As electrodes for SCs, IGNSs manifest high specific capacitance value of up to 313 F∙g⁻¹ at 0.05 A∙g⁻¹, good rate capability of 261 F∙g⁻¹ at 20 A∙g⁻¹, and excellent cycle stability with 92.7% of initial capacitance retained after 10000 cycles in 6 mol∙L⁻¹ KOH aqueous electrolyte. This study provides a facile method for large-scale production of IGNSs from aromatic hydrocarbon molecules for use in high-performance energy storage devices.

Key words: Coal tar, MgO template, Graphene-like nanosheet, Good-rate performance, Supercapacitor

魏风,毕宏晖,焦帅,何孝军. 超级电容器用相互连接的类石墨烯纳米片[J]. 物理化学学报, 2020, 36(2), 1903043. doi: 10.3866/PKU.WHXB201903043

Feng Wei,Honghui Bi,Shuai Jiao,Xiaojun He. Interconnected Graphene-like Nanosheets for Supercapacitors[J]. Acta Physico-Chimica Sinica 2020, 36(2), 1903043. doi: 10.3866/PKU.WHXB201903043

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201903043

https://www.whxb.pku.edu.cn/CN/Y2020/V36/I2/1903043

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参考文献 31

1	Li D. Y. ; Zhang J. T. ; Wang Z. Y. ; Jin X. B. Acta Phys. -Chim. Sin 2017, 33, 2245. doi: 10.3866/PKU.WHXB201705241
	李道琰; 张基琛; 王志勇; 金先波. 物理化学学报, 2017, 33, 2245. doi: 10.3866/PKU.WHXB201705241
2	Yao L. ; Wu Q. ; Zhang P. X. ; Zhang J. M. ; Wang D. R. ; Li Y. L. ; Ren X. Z. ; Mi H. W. ; Deng L. B. ; Zheng Z. J. Adv.Mater 2018, 30, 1706054. doi: 10.1002/adma.201706054
3	Schroeder V. ; Savagatrup S. ; He M. ; Lin S. B. ; Swager T. M. Chem. Rev 2019, 119, 599. doi: 10.1021/acs.chemrev.8b00340
4	He X. J. ; Ma H. ; Wang J. X. ; Xie Y. Y. ; Xiao N. ; Qiu J. S. J. Power Sources 2017, 357, 41. doi: 10.1016/j.jpowsour.2017.04.108
5	Dong S. A. ; He X. J. ; Zhang H. F. ; Xie X. Y. ; Yu M. X. ; Yu C. ; Xiao N. ; Qiu J. S. J. Mater. Chem. A 2018, 6, 15954. doi: 10.1039/c8ta04080j
6	Shi L. R. ; Chen K. ; Du R. ; Bachmatiuk A. ; Rümmeli M. H. ; Priydarshi M. K. ; Zhang Y. F. ; Manivannan A. ; Liu Z. F. Small 2015, 11, 6302. doi: 10.1002/smll.201502013
7	Yang Z. F. ; Tian J. R. ; Yin Z. F. ; Cui C. J. ; Qian W. Z. ; Wei F. Carbon 2019, 141, 467. doi: 10.1016/j.carbon.2018.10.010
8	Zhu Q. L. ; Pachfule P. ; Strubel P. ; Li Z. P. ; Zou R. Q. ; Liu Z. ; Kaskel S. ; Xu Q. Energy Storage Mater 2018, 13, 72. doi: 10.1016/j.ensm.2017.12.027
9	Liu M. Y. ; Niu J. ; Zhang Z. P. ; Dou M. L. ; Wang F. Nano Energy 2018, 51, 366. doi: 10.1016/j.nanoen.2018.06.037
10	Li X. Q. ; Chang L. ; Zhao S. L. ; Hao C. L. ; Lu C. G. ; Zhu Y. H. ; Tang Z. Y. Acta Phys. -Chim. Sin 2017, 33, 130. doi: 10.3866/PKU.WHXB201609012
	李雪芹; 常琳; 赵慎龙; 郝昌龙; 陆晨光; 朱以华; 唐智勇. 物理化学学报, 2017, 33, 130. doi: 10.3866/PKU.WHXB201609012
11	Zhang T. Y. ; Yang L. ; Yan X. B. ; Ding X. Small 2018, 14, 1802444. doi: 10.1002/smll.201802444
12	Zhao J. M. ; Luque R. ; Gilani M. R. H. S. ; Lai J. P. ; Nsabimana A. ; Xu G. B. J. Mater.Chem. A 2018, 6, 23780. doi: 10.1039/c8ta06574h
13	Yan R. ; Antonietti M. ; Oschatz M. Adv. Energy Mater 2018, 8, 1800026. doi: 10.1002/aenm.201800026
14	Li H. ; Tao Y. ; Zheng X. Y. ; Luo J. Y. ; Kang F. Y. ; Cheng H. M. ; Yang Q. H. Energy Environ. Sci 2016, 9, 3135. doi: 10.1039/C6ee00941g
15	Zhai T. ; Sun S. ; Liu X. J. ; Liang C. L. ; Wang G. M. ; Xia H. Adv. Mater 2018, 30, 1706640. doi: 10.1002/adma.201706640
16	Wu Z. ; Zhang X. B. Acta Phys.-Chim. Sin 2017, 33, 305. doi: 10.3866/PKU.WHXB201611012
	吴中; 张新波. 物理化学学报, 2017, 33, 305. doi: 10.3866/PKU.WHXB201611012
17	Wang D. H. ; Chen Y. ; Wang H. Q. ; Zhao P. H. ; Liu W. ; Wang Y. Z. ; Yang J. L. Appl. Surf. Sci 2018, 457, 1018. doi: 10.1016/j.apsusc.2018.07.047
18	Li X. L. ; Zhi L. J. Chem. Soc. Rev 2018, 47, 3189. doi: 10.1039/c7cs00871f
19	Cheng, C.; Jiang, G. P.; Garvey, C. J.; Wang, Y. Y.; Simon, G. P.; Liu, J. Z.; Li, D. Sci. Adv. 2016, 2, e1501272. doi: 10.1126/sciadv.1501272
20	Shi C. ; Hu L. T. ; Hou J. X. ; Guo K. ; Zhai T. Y. ; Li H. Q. Energy Storage Mater 2018, 15, 82. doi: 10.1016/j.ensm.2018.03.010
21	Liu S. B. ; Zhao Y. ; Zhang B. H. ; Xia H. ; Zhou J. F. ; Xie W. K. ; Li H. J. J. Power Sources 2018, 381, 116. doi: 10.1016/j.jpowsour.2018.02.014
22	Zhang M. ; Chen M. ; Nadimicherla R. ; Xu D. L. ; Jing Q. S. ; Zha R. H. Nanoscale 2018, 10, 6549. doi: 10.1039/c8nr00207j
23	Zhang X. Z. ; Raj D. V. ; Zhou X. F. ; Liu Z. P J. Power Sources 2018, 382, 95. doi: 10.1016/j.jpowsour.2018.02.032
24	Zhong Y. ; Shi T. L. ; Huang Y. Y. ; Cheng S. Y. ; Liao G. L. ; Tang Z. R. Electrochim. Acta 2018, 269, 676. doi: 10.1016/j.electacta.2018.03.012
25	Deng X. ; Shi W. X. ; Zhong Y. J. ; Zhou W. ; Liu M. L. ; Shao Z. P. ACS Appl. Mater. Interfaces 2018, 10, 21573. doi: 10.1021/acsami.8b04733
26	Lin G. X. ; Ma R. G. ; Zhou Y. ; Liu Q. ; Dong X. P. ; Wang J. C. Electrochim. Acta 2018, 261, 49. doi: 10.1016/j.electacta.2017.12.107
27	Xu B. ; Wang H. R. ; Zhu Q. Z. ; Sun N. ; Anasori B. ; Hu L. F. ; Wang F. ; Guan Y. B. ; Gogotsi Y. Energy Storage Mater 2018, 12, 128. doi: 10.1016/j.ensm.2017.12.006
28	Xie X. Y. ; He X. J. ; Shao X. L. ; Dong S. A. ; Xiao N. ; Qiu J. S. Electrochim. Acta 2017, 246, 634. doi: 10.1016/j.electacta.2017.06.092
29	He X. J. ; Ma H. ; Wang J. X. ; Xie Y. Y. ; Xiao N. ; Qiu J. S. J. Power Sources 2017, 357, 41. doi: 10.1016/j.jpowsour.2017.04.108
30	Liu D. Q. ; Li Q. W. ; Zhao H. Z. J. Mater. Chem. A 2018, 6, 11471. doi: 10.1039/C8TA02580K
31	Zhang M. C. ; Chen K. ; Wang C. Y. ; Jian M. Q. ; Yin Z. ; Liu Z. L. ; Hong G. ; Liu Z. F. ; Zhang Y. Y. Small 2018, 14, 1801009. doi: 10.1002/smll.201801009

Samples	D_ap/nm	S_BET/(m²·g^-1)	S_mic/(m²·g^-1)	V_t/(cm³·g^-1)	V_mic/(cm³·g^-1)	Yield/%
IGNS₁	2.27	2569	1922	1.57	0.79	36.6
IGNS₂	2.44	2887	2336	1.64	1.04	36.1
IGNS₃	2.78	2350	1560	1.63	0.66	23.4

Samples	C/%	O/%	O functionalities/%
Samples	C/%	O/%	C=O	―OH	C―O
IGNS₁	91.67	8.33	4.31	3.86	0.16
IGNS₂	90.50	9.50	6.36	3.14	0
IGNS₃	91.07	8.93	4.64	3.60	0.69

Electrode materials	KOH electrolyte	Specific capacitance/(F g^-1)		Ref.
Graphitic carbon	2 mol·L^-1	241 (1.0 A g^-1)	176 (100 A g^-1)	20
NMCSs@RSPC	6 mol·L^-1	268 (1.0 A g^-1)	215 (10 A g^-1)	21
Carbon aerogels	6 mol·L^-1	199 (0.5 A g^-1)	144 (5 A g^-1)	22
Graphene oxide	6 mol·L^-1	124 (0.1 A g^-1)	94 (100 A g^-1)	23
Porous carbon	6 mol·L^-1	272 (1.0 A g^-1)	206 (50 A g^-1)	24
HPCHG	6 mol·L^-1	248 (0.5 A g^-1)	130 (50 A g^-1)	25
ANPC	6 mol·L^-1	243 (0.5 A g^-1)	197 (10 A g^-1)	26
HPC-PTFE	6 mol·L^-1	251 (0.5 A g^-1)	146 (50 A g^-1)	27
IGNS₂	6 mol·L^-1	313 (0.05 A g^-1)	261 (20 A g^-1)	This work

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