高云芳,应婕,徐新,蔡良泼

• 1:浙江工业大学 化学工程学院，浙江 杭州 310014

摘要(Abstract)：

以苯胺为单体，过硫酸铵为氧化剂，草酸、柠檬酸、酒石酸、硫酸为掺杂酸，通过快速均相氧化聚合法制得微纳结构聚苯胺前驱体，在氮气保护下进行高温处理获得炭化产物。利用傅里叶变换红外光谱（FT-IR）、X射线衍射光谱（XRD）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、等温氮气吸脱附测试对材料进行物相组成及微观结构表征，通过循环伏安、恒流充放电对聚苯胺炭化产物进行电化学性能测试。结果表明，聚苯胺的炭化收率约为40%，炭化产物为无定型炭材料，含有丰富的氮氧元素，在2 mol·L^-1 H₂SO₄电解液中具有典型的双电层电容特性。其中柠檬酸掺杂聚苯胺炭化产物的比表面积最高（1 532 m²·g^-1）；酒石酸掺杂聚苯胺炭化产物的比电容最大（141 F·g^-1，5 mV·s^-1），经恒流充放电3 000次循环后的电容保持率最佳（约70%）。通过探讨掺杂酸对聚苯胺炭化产物的影响，认为掺杂酸可调控聚苯胺炭化产物的微观形貌、孔径分布、氮氧含量、电化学性能，为制备以聚苯胺为前驱体的氮氧共掺杂炭材料提供了新的研究思路。

关键词(KeyWords)： 聚苯胺;有机酸;炭化;比电容

Abstract:

Keywords:

基金项目(Foundation): 国家重点研发计划项目（2016YFC0305004）。

作者(Author): 高云芳,应婕,徐新,蔡良泼

DOI: 10.3969/j.issn.1003-9015.2019.01.026

参考文献(References)：

• [1] WANG H H, LIN J Y, SHEN Z X. Polyaniline (PANi) based electrode materials for energy storage and conversion[J]. Journal of Science Advanced Materials & Devices, 2016, 1(3):225-255.
  [2] HAN J P, XU G Y, DING B, et al. Porous nitrogen-doped hollow carbon spheres derived from polyaniline for high performance supercapacitors[J]. Journal of Materials Chemistry A, 2014, 2(15):5352-5357.
  [3] VUJKOVIC M, GAVRILOV N, PASTI I, et al. Superior capacitive and electrocatalytic properties of carbonized nanostructured polyaniline upon a low-temperature hydrothermal treatment[J]. Carbon, 2013, 64(11):472-486.
  [4] YUAN D S, ZHOU T X, ZHOU S L, et al. Nitrogen-enriched carbon nanowires from the direct carbonization of polyaniline nanowires and its electrochemical properties[J]. Electrochemistry Communications, 2011, 13(3):242-246.
  [5] YANG M M, CHENG B, SONG H H, et al. Preparation and electrochemical performance of polyaniline-based carbon nanotubes as electrode material for supercapacitor[J]. Electrochimica Acta, 2010, 55(23):7021-7027.
  [6] WANG G H, JIANG K Z, XU M L, et al. A high activity nitrogen-doped carbon catalyst for oxygen reduction reaction derived from polyaniline-iron coordination polymer[J]. Journal of Power Sources, 2014, 266(10):222-225.
  [7] LONG C L, QI D P, WEI T, et al. Nitrogen-doped carbon networks for high energy density supercapacitors derived from polyaniline coated bacterial cellulose[J]. Advanced Functional Materials, 2014, 24(25):3953-3961.
  [8] 杨小刚, 王莉, 金思毅, 等. 磷酸二次掺杂聚苯胺纳米纤维的合成及其性能的研究[J]. 高校化学工程学报, 2015, 29(3):664-670. YANG X G, WANG L, JIN S Y, et al. Synthesis and properties of polyaniline nanofibers secondary doped with phosphoric acid[J]. Journal of Chemical Engineering of Chinese Universities, 2015, 29(3):664-670.
  [9] 谢英男, 詹自力, 张红芹, 等. 有机磺酸掺杂聚苯胺的气敏性能[J]. 高校化学工程学报, 2009, 23(1):154-159. XIE Y N, ZHAN Z L, ZHANG H Q, et al. Gas-sensing properties of organic sulfonic acid doped polyaniline[J]. Journal of Chemical Engineering of Chinese Universities, 2009, 23(1):154-159.
  [10] HUANG J X, RICHARD B K. A general chemical route to polyaniline nanofibers[J]. Journal of America Chemistry Society, 2004, 126(3):851-855.
  [11] ROZLÍVKOVÁ Z, TRCHOVÁ M, EXNEROVÁ M, et al. The carbonization of granular polyaniline to produce nitrogen-containing carbon[J]. Synthetic Metals, 2011, 161(11):1122-1129.
  [12] JAYMAND M. Recent progress in chemical modification of polyaniline[J]. Progress in Polymer Science, 2013, 38(9):1287-1306.
  [13] PIELICHOWSKI K. Kinetic analysis of the thermal decomposition of polyaniline[J]. Solid State Ionics, 1997, 104(1-2):123-132.
  [14] 朱婷婷. 聚苯胺基多孔碳材料的结构设计与电容特性[D]. 淄博:山东理工大学, 2015. ZHU T T. Design of polyanilne-based hierrchical porous carbon nanomaterials for electrode materials and their electrochemical capacitve performance[D]. Zibo:Shandong University of Technology, 2015.