双离子液体基多孔炭的制备与电化学性能  

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

作　　者：程时富 胡皓 陈必华 吴海虹 高国华 何鸣元 CHENG Shifu;HU Hao;CHEN Bihua;WU Haihong;GAO Guohua;HE Mingyuan(Shanghai Key Laboratory of Green Chemistry and Chemical Processes,School of Chemistry and Molecular Engineering,East China Normal University,Shanghai 200062,China)

机构地区：[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

出　　处：《高等学校化学学报》2020年第5期1048-1057,共10页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21573072,21773068,21811530273);国家重点研发计划项目(批准号:2017YFA0403102);上海市重点学科建设项目(批准号:B409)资助.

摘　　要：以质子型离子液体1-氢-3-乙烯基咪唑硫酸氢盐(HVImHSO 4)为主炭源,以1-丁基-3-甲基咪唑六氟磷酸盐(BMImPF 6)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N 2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 m 2/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.Nitrogen,phosphorus and sulfur co-doped porous carbons(PCs)were prepared with a protic ionic liquid 1-hydrogen-3-butylimidazolium hydrogen sulfate(HVImHSO 4)as precursor and 1-butyl-3-methylimi-dazolium hexafurophosphate(BMImPF 6)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 m 2/g under m(BMImPF 6)/m(HVImHSO 4)=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-BMImPF 6-0.5 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.

关 键 词：离子液体 一步炭化 氮、磷、硫共掺杂 比电容 保持率 

分 类 号：O646[理学—物理化学]