不同氮源对掺氮石墨烯的结构和性能的影响

doi:10.11901/1005.3093.2017.331

材料研究学报

2018, Vol. 32

Issue (8): 616-624 DOI: 10.11901/1005.3093.2017.331

研究论文

本期目录 | 过刊浏览

不同氮源对掺氮石墨烯的结构和性能的影响

李子庆, 赫文秀(

), 张永强, 于慧颖, 李兴盛, 刘斌

内蒙古科技大学化学与化工学院包头 014010

Effect of Different Nitrogen Sources on Structure and Properties of Nitrogen-doped Graphene

Ziqing LI, Wenxiu HE(

), Yongqiang ZHANG, Huiying YU, Xingsheng LI, Bin LIU

School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014010, China

引用本文:

李子庆, 赫文秀, 张永强, 于慧颖, 李兴盛, 刘斌. 不同氮源对掺氮石墨烯的结构和性能的影响[J]. 材料研究学报, 2018, 32(8): 616-624.
Ziqing LI, Wenxiu HE, Yongqiang ZHANG, Huiying YU, Xingsheng LI, Bin LIU. Effect of Different Nitrogen Sources on Structure and Properties of Nitrogen-doped Graphene[J]. Chinese Journal of Materials Research, 2018, 32(8): 616-624.

全文: PDF(2822 KB) HTML

摘要:

先用改进的Hummers方法冷冻干燥制备氧化石墨(GO),再分别以水合肼、氨水、乙二胺、尿素作为掺氮剂和还原剂用一步水热法合成掺氮石墨烯。使用傅里叶变换红外光谱(FT-IR)、X射线粉末衍射 (XRD)、场发射扫描电子显微镜(FESEM)、X射线光电子能谱(XPS)、同步热重分析(TGA)、氮气吸脱附分析等手段表征了样品的微观结构和形貌,应用循环伏安、电化学交流阻抗、恒流等充放电技术测试了样品的电化学性能。结果表明：四种掺氮剂皆能有效还原GO,制备出掺氮含量(质量分数)分别为4.99%,6.35%,7.70%和9.18%的石墨烯。氮元素以“pyridinic N”、“pyrrolic N”、“graphitic N”三种形式掺杂到石墨烯的晶格中。由乙二胺和尿素还原制备的掺氮石墨烯比电容可达187.6 F·g^-1和191.6 F·g^-1,电化学性能最高。

关键词 ：无机非金属材料, 掺氮石墨烯, 水热法, 电化学性能

Abstract：

Graphite oxide (GO) was prepared via freeze-drying process of a modified Hummers method and then nitrogen-doped graphene was synthesized by one-step hydrothermal method with hydrazine hydrate, ethylenediamine, ammonia and urea as nitrogen sources and reductants respectively. The microstructure and morphology of the as-produced graphene were characterized by means of Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscope, X-ray photoelectron spectroscopy, synchronous thermogravimetric analyzer and nitrogen adsorption-desorption analyzer. The electrochemical performance of the prepared products was assessed by means of cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic charge/discharge technology. Results show that the four nitrogen-containing agents could effectively reduce GO to produce different graphenes, the corresponding nitrogen content (in mass fraction) of which is 4.99%, 7.7%, 6.35% and 9.18%, respectively. The doped-N atoms coupled into the graphene lattice in forms of "pyridinic N", "pyrrolic N" and "graphitic N". The specific capacitance of the nitrogen-doped graphene prepared with ethylenediamine and urea as reductants could reach 187.6 F·g^-1 and 191.6 F·g^-1 respectively, implying excellent electrochemical performance.

Key words： inorganic non-metalic materials nitrogen-doped graphene hydrothermal method electrochemical performance

收稿日期: 2017-05-22

ZTFLH:

TQ127

基金资助:资助项目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(NJYT-14-A08),包头市科技计划(2015C2004-1,2016-4)

作者简介:

作者简介李子庆,男,1992年生,硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2017.331 或 https://www.cjmr.org/CN/Y2018/V32/I8/616

图1 石墨、GO、RGO和NGX的FT-IR图

图2 石墨、GO、RGO和NGX的XRD图谱

图3 GO、RGO和NGX的SEM图

表1 GO、RGO和NGX的EDS定量分析数据

图4 石墨、GO、RGO和NGX的TGA曲线

表2 NGX的N1sXPS定量分析数据

图5 GO、RGO和NGX的XPS全谱图、GO的C1s XPS谱图以及NGX(c-f)的高分辨率N1s XPS谱图

图6 NGX的氮气吸附-脱附曲线

表3 石墨粉、GO、RGO和NGX的电导率(σ)

图7 NGX在10 mV s-1扫速下的循环伏安曲线以及RGO和NGX的电化学交流阻抗谱图

图8 NG4在不同电流密度下的充放电曲线和同一电流密度下NGX与RGO的循环寿命曲线

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