高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (5): 1048-1057.doi: 10.7503/cjcu20190703

• 物理化学 • 上一篇    下一篇

双离子液体基多孔炭的制备与电化学性能

程时富,胡皓,陈必华,吴海虹(),高国华(),何鸣元   

  1. 上海市绿色化学与化工过程绿色化重点实验室, 华东师范大学化学与分子工程学院, 上海 200062
  • 收稿日期:2019-12-24 出版日期:2020-05-10 发布日期:2020-02-26
  • 通讯作者: 吴海虹,高国华 E-mail:hhwu@chem.ecnu.edu.cn;ghgao@chem.ecnu.edu.cn
  • 基金资助:
    国家自然科学基金(21573072);国家自然科学基金(21773068);国家自然科学基金(21811530273);国家重点研发计划项目(2017YFA0403102);上海市重点学科建设项目(B409)

Preparation and Electrochemical Performance of Porous Carbons Prepared from Binary Ionic Liquids

CHENG Shifu,HU Hao,CHEN Bihua,WU Haihong(),GAO Guohua(),HE Mingyuan   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes,School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
  • Received:2019-12-24 Online:2020-05-10 Published:2020-02-26
  • Contact: Haihong WU,Guohua GAO E-mail:hhwu@chem.ecnu.edu.cn;ghgao@chem.ecnu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(21573072);† Supported by the National Natural Science Foundation of China(21773068);† Supported by the National Natural Science Foundation of China(21811530273);the National Key Research and Development Program of China(2017YFA0403102);the Shanghai Leading Academic Discipline Project, China(B409)

摘要:

以质子型离子液体1-氢-3-乙烯基咪唑硫酸氢盐(HVImHSO4)为主炭源, 以1-丁基-3-甲基咪唑六氟磷酸盐(BMImPF6)为助剂, 在氮气气氛、 1000 ℃下一步炭化得到氮、 磷、 硫共掺杂多孔炭. 通过N2吸附-脱附、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线衍射(XRD)、 拉曼光谱(Raman)、 热重分析(TGA)和X射线光电子能谱(XPS)等技术对多孔炭进行了分析表征. 结果表明, 多孔炭的孔结构以微孔为主, 最高比表面积可达1111 m2/g, 其微晶结构中无定形碳和石墨化碳并存; 多孔炭中的氮主要以季氮(N-Q)、 吡咯氮(N-5)和吡啶氮(N-6)的形式存在, 磷以磷-氧(N—O—P)键合形式为主, 硫主要以噻吩硫(C—S—C)为主. 在6 mol/L KOH溶液、 三电极体系中, 多孔炭在0.5 A/g电流密度下的比电容为138 F/g; 在10 A/g电流密度下的比电容为100 F/g; 在2 A/g电流密度下循环充放电10000次, 其比电容保持率为95.8%, 显示出良好的电化学性能.

关键词: 离子液体, 一步炭化, 氮、 磷、 硫共掺杂, 比电容, 保持率

Abstract:

Nitrogen, phosphorus and sulfur co-doped porous carbons(PCs) were prepared with a protic ionic liquid 1-hydrogen-3-butylimidazolium hydrogen sulfate(HVImHSO4) as precursor and 1-butyl-3-methylimi-dazolium hexafurophosphate(BMImPF6) as assistant through one-step carbonization process at 1000 ℃ in nitrogen atmosphere. The PCs were characterized by nitrogen adsorption-desorption, scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), Raman spectroscopy, thermo-gravimetric analysis(TGA) and X-ray photoelectron spectroscopy(XPS). The results showed that the PCs mainly had micro pores and the specific surface area could be up to 1111 m2/g under m(BMImPF6)/m(HVImHSO4)=0.4. The amorphous and disordered graphitic layers were dominant in PCs. Nitrogen bonding state was mainly N-Q(N substituted groups of aromatic graphite structure), phosphorus was mainly in O—P type groups, and sulfur was attributed to C—S—C of thiophene-type sulfur. Meanwhile, the capacitance of PC-BMImPF6-0.5 was 138 F/g at 0.5 A/g and 100 F/g at 10 A/g, the retention ratio was 95.8% after being cycled for 10000 times at 2 A/g in the electrolyte of 6 mol/L KOH. A simple and easy method for preparation of N, P and S co-doped PCs from ionic liquids has been provided, and the PCs have a certain extent application prospect in supercapacitor electrode materials.

Key words: Ionic liquid, One-step carbonization process, N, P, S co-doping, Specific capacitance, Retention ratio

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