共轭微孔聚合物管状硬炭的氮掺杂与储锂性能

兰州理工大学学报 ›› 2020, Vol. 46 ›› Issue (1): 71-76.

共轭微孔聚合物管状硬炭的氮掺杂与储锂性能

张庆堂, 白永保, 李萌

兰州理工大学石油化工学院, 甘肃兰州 730050

收稿日期:2018-09-13 出版日期:2020-02-28 发布日期:2020-06-23
作者简介:张庆堂(1976-),男,河南新野人,博士,副教授.
基金资助:
国家自然科学基金(21466020)

Nitrogen doping of tubular hard carbon as conjugate microporous polymer and its lithium storage performance

ZHANG Qing-tang, BAI Yong-bao, LI Meng

School of Petrochemical Engineering, Lanzhou Univ. of Tech. , Lanzhou 730050, China

Received:2018-09-13 Online:2020-02-28 Published:2020-06-23

摘要/Abstract

摘要： 通过选择不同单体合成了共轭微孔聚合物(CMP)和含氮共轭微孔聚合物(NCMP),并分别将其高温热解制备管状硬炭(THC)和氮掺杂管状硬炭(NTHC).通过SEM、TEM和BET对两种管状材料的形貌结构进行了表征,THC和NTHC材料具有相似的形貌和比表面积.进一步采用恒电流充放电法对THC和NTHC进行电化学性能分析,并与普通碳纳米管(CNT)的电化学性能相比较.结果表明,NTHC储锂性能最好,在0.1 A/g时,NTHC的可逆储锂容量高达541.2 mAh/g,在0.6 A/g电流密度下,其比容量在经过500次循环后仍高达458 mAh/g.

关键词: 共轭微孔聚合物, 管状硬炭, 氮掺杂, 负极, 锂离子电池

Abstract: Conjugate microporous polymer (CMP) and nitrogen-contained conjugate microporous polymer (NCMP) were synthesized with chosen different monomers and the tubular hard carbon(THC) and N-doped tubular hard carbon(NTHC) were prepared by means of pyrolysis of those two kinds of CMP. The morphology and structure of the two tubular hard carbons were characterized with SEM, TEM and BET and it is shown that the materials of THC and NTHC have similar morphology and specific surface area. Further, The electrochemical property of THC and NTHC then compared with that of common carbon nanotube(CNT) was analyzed by constant current charge and discharge method and the result showed that the lithium storage performance of NTHC would be the best and it would have a high reversible lithium storage capacity of 541.2 mAh/g at 0.1 A/g and its specific capacity would retain around 458 mAh/g at 0.6 A/g after 500 cycles.

Key words: conjugate microporous polymer, tubular hard carbon, nitrogen doping, cathode, lithium ion battery

中图分类号:

O646

张庆堂, 白永保, 李萌. 共轭微孔聚合物管状硬炭的氮掺杂与储锂性能[J]. 兰州理工大学学报, 2020, 46(1): 71-76.

ZHANG Qing-tang, BAI Yong-bao, LI Meng. Nitrogen doping of tubular hard carbon as conjugate microporous polymer and its lithium storage performance[J]. Journal of Lanzhou University of Technology, 2020, 46(1): 71-76.

参考文献

[1] SONG W,JI K,AGUADERO A,et al.Co₃O₄ hollow nanospheres doped with ZnCo₂O₄ via thermal vapor mechanism for fast lithium storage [J].Energy Storage Materials,2018,14:324-333.
[2] ZHANG Q,DAI Q,LI M,et al.Incorporation of MnO nanoparticles inside porous carbon nanotubes originated from conjugated microporous polymers for lithium storage [J].Journal of Materials Chemistry A,2016,4:19132-19139.
[3] ZHANG Q,ZHAO Y,SU C,et al.Nano/micro lithium transition metal (Fe,Mn,Co and Ni) silicate cathode materials for lithium ion batteries [J].Recent Patents on Nanotechnology,2011,5(3):225-233.
[4] 汤富领,颉小龙,王晓梅,等.碳纳米管辅助溶液燃烧法合成超细颗粒LiMn₂O₄[J].兰州理工大学学报,2016,42(4):1-5.
[5] LIU B,LI D,LIU Z,et al.Carbon-wrapped MnO nanodendrites interspersed on reduced graphene oxide sheets as anode materials for lithium-ion batteries [J].Applied Surface Science,2016,394:1-8.
[6] FUJIMOTO H,TOKUMITSU K,MABUCHI A,et al.The anode performance of the hard carbon for the lithium ion battery derived from the oxygen-containing aromatic precursors [J].Journal of Power Sources,2010,195(21):7452-7456.
[7] NI J,HUANG Y,GAO L.A high-performance hard carbon for Li-ion batteries and supercapacitors application [J].Journal of Power Sources,2013,223:306-311.
[8] ZHANG J,ZHANG L,YANG S,et al.Facile strategy to produce N-doped carbon aerogels derived from seaweed for lithium-ion battery anode [J].Journal of Alloys and Compounds,2017,701:256-261.
[9] CHEN T,PAN L,LIH T G A,et al.Porous nitrogen-doped carbon microspheres as anode materials for lithium ion batteries [J].Dalton Transactions,2014,43:14931-14935.
[10] LIU T,LUO R,YOON S H,et al.Effect of vacuum carbonization treatment on the irreversible capacity of hard carbon prepared from biomass material [J].Materials Letters,2010,64(1):74-76.
[11] LI J,ZHANG F,WANG C,et al.Self nitrogen-doped carbon nanotubes as anode materials for high capacity and cycling stability lithium-ion batteries [J].Materials and Design,2017,133:169-175.
[12] ALKARMO W,OUHIB F,AQIL A,et al.Continuous-porous N-doped carbon network as high-performance electrode for lithium-ion batteries [J].Journal of Materials Science,2018,53(8):6135-6146.
[13] 史倩,安进,王睿,等.共轭微孔聚合物材料的研究进展 [J].现代化工,2014,34(4):46-50.
[14] XIANG Z,SUN H,ZHU Z,et al.Synthesis of conjugated microporous polymer nanotubes for polymer composites [J].Rsc Advances,2015,5:24893-24898.
[15] BAO L,SUN H,ZHU Z,et al.Synthesis and properties of tubular-shape conjugated microporous polymers with high purity [J].Materials Letters,2016,178:5-9.