硫氮共掺杂石墨烯的制备及其电化学性能

doi:10.16085/j.issn.1000-6613.2017-1626

化工进展 ›› 2018, Vol. 37 ›› Issue (07): 2712-2719.DOI: 10.16085/j.issn.1000-6613.2017-1626

硫氮共掺杂石墨烯的制备及其电化学性能

李子庆¹, 赫文秀¹, 张永强¹, 刘斌¹, 蒋梦¹, 刘君红²

1 内蒙古科技大学化学与化工学院, 内蒙古包头 014010;
2 包头钢铁职业技术学院冶金化工系, 内蒙古包头 014010

收稿日期:2017-07-03 修回日期:2017-07-03 出版日期:2018-07-05 发布日期:2018-07-05
通讯作者: 赫文秀,研究方向为能源存储转化装置电极材料。
作者简介:李子庆(1992-),男,硕士研究生。
基金资助:
国家自然科学基金（21766024）、内蒙古自然科学基金（2015MS0208）、内蒙古自治区高等学校青年科技英才计划-青年科技领军人才A类项目（NJYT-14-A08）及包头市科技计划（2015C2004-1，2016-4）项目。

Preparation and electrochemical properties of sulfur-nitrogen co-doped graphene

LI Ziqing¹, HE Wenxiu¹, ZHANG Yongqiang¹, LIU Bin¹, JIANG Meng¹, LIU Junhong²

1 School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014010, Inner Mongolia, China;
2 Department of Metallurgy and Chemical Engineering, Baotou Iron and Steel Vocational and Technical College, Baotou 014010, Inner Mongolia, China

Received:2017-07-03 Revised:2017-07-03 Online:2018-07-05 Published:2018-07-05

摘要/Abstract

摘要： 采用改进的Hummers方法经冷冻干燥制备氧化石墨烯（GO），以硫脲作为还原剂和掺杂剂，按GO与硫脲的质量比为1∶10、1∶20、1∶30、1∶40的用量分别加入硫脲，采用一步水热法合成硫氮共掺杂石墨烯。通过X射线粉末衍射（XRD）、场发射扫描电子显微镜（FESEM）、拉曼光谱（Raman）、X射线光电子能谱（XPS）、氮气吸脱附分析等手段表征了样品的微观结构和形貌，通过循环伏安、电化学交流阻抗、恒流充放电技术对样品进行电化学性能测试。结果表明：当GO∶硫脲=1∶30（质量比）时，得到的硫氮共掺杂石墨烯（SNG）中硫掺杂量最高为1.86%（质量分数）、氮掺杂质量分数最高为7.73%，比表面积达175.8m²/g，且具有较窄的孔径分布，集中在3～5nm。在电流密度为1A/g时，SNG的比电容最高达197.2F/g，经过2000次充放电循环后，比电容为177.3F/g，电容保持率达90%。

关键词: 石墨烯, 水热, 制备, 显微结构, 电化学

Abstract: The modified Hummers method was used to prepare graphite oxide (GO) through freeze drying. The sulfur-nitrogen co-doped graphene samples were then synthesized by one-step hydrothermal method using thiourea as dopant and reductant, with mass ratios of GO to thiourea of 1:10, 1:20, 1:30, 1:40 respectively. The microstructure and morphology of the as-produced graphene were characterized by X-ray diffraction, field emission scanning electron microscope, Raman spectroscopy, X-ray photoelectron spectroscopy and nitrogen adsorption-desorption analysis. The electrochemical performances of the samples were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge (GCD) technology. The results showed that the sulfur-nitrogen co-doped graphene had the highest sulfur content of 1.86% and nitrogen content of 7.73%, with a specific surface area of 175.8m²/g and the pore sizes were narrowly distributed in between 3-5nm when the mass ratio of GO:thiourea is 1:30. At 1A/g current density, SNG had a specific capacitance of 197.2F/g, and only 10% were lost after 2000 charge and discharge cycles.

Key words: graphene, hydrothermal, preparation, microstructure, electrochemistry

中图分类号:

TQ127.1⁺6

李子庆, 赫文秀, 张永强, 刘斌, 蒋梦, 刘君红. 硫氮共掺杂石墨烯的制备及其电化学性能[J]. 化工进展, 2018, 37(07): 2712-2719.

LI Ziqing, HE Wenxiu, ZHANG Yongqiang, LIU Bin, JIANG Meng, LIU Junhong. Preparation and electrochemical properties of sulfur-nitrogen co-doped graphene[J]. Chemical Industry and Engineering Progress, 2018, 37(07): 2712-2719.

参考文献

[1] SUN Z, YAN Z, YAO J, et al. Growth of graphene from solid carbon sources[J]. Nature, 2010, 468(7323):549-552.
[2] NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696):666-669.
[3] SUN Y, WU Q, SHI G. Graphene based new energy materials[J]. Energy & Environmental Science, 2011, 4(4):1113-1132.
[4] 贾进,杨晓阳,闫艳,等. 碳化物衍生碳的制备及其在气体存储与超级电容器领域的应用研究进展[J]. 化工进展, 2014, 33(10):2681-2686. JIA J, YANG X Y, YAN Y, et al. Progress of preparation of carbide-derived carbon and application in gas storage and supercapacitors[J]. Chemical Industry and Engineering Progress, 2014, 33(10):2681-2686.
[5] TOMMASO C,VALENTINA T. Multistable rippling of graphene on SiC:a density functional theory study[J]. J. Phys. Chem. C, 2016, 120(14):7670-7677.
[6] LIU Y Z, LI Y F, SU F Y. Easy one-step synthesis of N-doped graphene for supercapacitors[J]. Energy Storage Materials, 2016, 2:69-75.
[7] JIAO L Y, ZHANG L, WANG X R, et al. Narrow graphene nanoribbons from carbon nanotubes[J]. Nature, 2009, 459:877-880.
[8] QU L, LIU Y, BAEK J B, et al. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells[J]. ACS Nano, 2010, 4(3):1321-1326.
[9] NAGAIAH T C, KUNDU S, BRON M, et al. Nitrogen-doped carbon nanotubes as a cathode catalyst for the oxygen reduction reaction in alkaline medium[J]. Electrochemistry Communications, 2010, 12(3):338-341.
[10] PARK J, JANG Y, KIM Y, et al. Sulfur-doped graphene as a potential alternative metal-free electrocatalyst and Pt-catalyst supporting material for oxygen reduction reaction[J]. Physical Chemistry Chemical Physics, 2014, 16:103-109.
[11] POH H, SIMEK P, SOFER Z, et al. Sulfur-doped graphene via thermal exfoliation of graphite oxide in H₂S, SO₂, or CS₂ gas[J]. ACS Nano, 2013, 7:5262-5272.
[12] GAO H. Synthesis of S-doped graphene by liquid precursor[J]. Nanotechnology, 2012, 23:275-605.
[13] WANG R, HIGGINS D, HOQUE M. Controlled growth of platinum nanowire arrays on sulfur doped graphene as high performance electrocatalyst[J]. Scientific Reports, 2013, 3:2431.
[14] GONG K, DU F, XIA Z, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction[J]. Science, 2009, 323:760-764.
[15] QU L, LIU Y, BAEK J, et al. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells[J]. ACS Nano, 2010, 4:1321-1326.
[16] LIANG J, YAN J, MIETEK J, et al. Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance[J]. International Edition, 2012, 124:11664-11668.
[17] MIAO Q H, WANG L D, LIU Z Y, et al. Magnetic properties of N-doped graphene with high Curie temperature[J]. Scientific Reports, 2016, 6:21832.
[18] CHEN S, BI J, ZHAO Y, et al. Nitrogen-doped carbon nanocages as efficient metal-free electrocatalysts for oxygen reduction reaction[J]. Advanced Materials, 2012, 24(41):5593-5597.
[19] CHOI C H, PARK S H, WOO S I. Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity[J]. ACS Nano, 2012, 6(8):7084-7091.
[20] WEHLING T, NOVOSELOV K, MOROZOV S, et al. Molecular doping of graphene[J]. Nano Letters, 2008, 8(1):173-177.
[21] WUNSCH B, STAUBER T, SOLS F, et al. Dynamical polarization of graphene at finite doping[J]. New Journal of Physics,2006,8(12):318-323.
[22] NAGAIAH T C, KUNDU S, BRON M, et al. Nitrogen-doped carbon nanotubes as a cathode catalyst for the oxygen reduction reaction in alkaline medium[J]. Electrochemistry Communications, 2010, 12(3):338-341.
[23] XU J, DONG G, JIN C, et al. Sulfur and nitrogen co-doped, few-layered graphene oxide as a highly efficient electrocatalyst for the oxygen-reduction reaction[J]. Chem. Sus. Chem., 2013, 6(3):493-499.
[24] HUMMERS W S, OFFEMAN R E. Preparation of graphitic oxide[J]. Journal of the American Chemical Society, 1958, 80(6):1339.
[25] MOU Z G, CHEN, X Y, DU Y K, et al. Forming mechanism of nitrogen doped graphene prepared by thermal solid-state reaction of graphite oxide and urea[J]. Applied Surface Science, 2011, 258(5):1704-1710.
[26] ZHANG M Y, SUN Y Y, SHI J J, et al. Selective glycerol oxidation using platinum nanoparticles supported on multi-walled carbon nanotubes and nitrogen-doped graphene hybrid[J]. Chinese Journal of Catalysis, 2017, 38(3):537-544.
[27] NIE R F, MIAO M, DU W C, et al. Selective hydrogenation of C==C bond over N-doped reduced graphene oxides supported Pd catalyst[J]. Applied Catalysis B:Environmental, 2016, 180:607-613.

硫氮共掺杂石墨烯的制备及其电化学性能

Preparation and electrochemical properties of sulfur-nitrogen co-doped graphene

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	胡喜, 王明珊, 李恩智, 黄思鸣, 陈俊臣, 郭秉淑, 于博, 马志远, 李星. 二硫化钨复合材料制备与储钠性能研究进展[J]. 化工进展, 2023, 42(S1): 344-355.
[3]	张杰, 白忠波, 冯宝鑫, 彭肖林, 任伟伟, 张菁丽, 刘二勇. PEG及其复合添加剂对电解铜箔后处理的影响[J]. 化工进展, 2023, 42(S1): 374-381.
[4]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[5]	高彦静. 单原子催化技术国际研究态势分析[J]. 化工进展, 2023, 42(9): 4667-4676.
[6]	雷伟, 姜维佳, 王玉高, 和明豪, 申峻. N、S共掺杂煤基碳量子点的电化学氧化法制备及用于Fe³⁺检测[J]. 化工进展, 2023, 42(9): 4799-4807.
[7]	王雪婷, 顾霞, 徐先宝, 赵磊, 薛罡, 李响. 水热预处理对餐厨垃圾厌氧发酵产戊酸的影响[J]. 化工进展, 2023, 42(9): 4994-5002.
[8]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[9]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[10]	刘毅, 房强, 钟达忠, 赵强, 李晋平. Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原[J]. 化工进展, 2023, 42(8): 4136-4142.
[11]	李润蕾, 王子彦, 王志苗, 李芳, 薛伟, 赵新强, 王延吉. CuO-CeO₂/TiO ₂ 高效催化CO低温氧化反应性能[J]. 化工进展, 2023, 42(8): 4264-4274.
[12]	张亚娟, 徐惠, 胡贝, 史星伟. 化学镀法制备NiCoP/rGO/NF高效电解水析氢催化剂[J]. 化工进展, 2023, 42(8): 4275-4282.
[13]	王帅晴, 杨思文, 李娜, 孙占英, 安浩然. 元素掺杂生物质炭材料在电化学储能中的研究进展[J]. 化工进展, 2023, 42(8): 4296-4306.
[14]	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.
[15]	赵健, 卓泽文, 董航, 高文健. 含蜡原油及其乳状液体系微观结构观测的新方法[J]. 化工进展, 2023, 42(8): 4372-4384.