中空氮掺杂沥青基活性炭纤维的结构调控与电化学性能

乐丹; 杨建校; 孙兵; 石奎; 朱辉; 李轩科

中空氮掺杂沥青基活性炭纤维的结构调控与电化学性能

乐丹¹,
杨建校¹,
孙兵²,
石奎¹,
朱辉²,
李轩科^1,2,

1.
湖南大学材料科学与工程学院, 先进炭材料及应用技术湖南省重点实验室, 湖南长沙 410082;
2.
武汉科技大学化学与化工学院, 湖北武汉 430080

基金项目: 国家自然科学基金（U1864207）.

详细信息

通讯作者:
李轩科,教授.E-mail:xkli8524@sina.com

中图分类号: TM53
计量
- 文章访问数: 536
- HTML全文浏览量: 208
- PDF下载量: 102
- 被引次数: 0
出版历程
- 收稿日期: 2019-12-30
- 录用日期: 2020-04-02
- 修回日期: 2020-01-23
- 刊出日期: 2020-02-29

Preparation and electrochemical performance of the N-doped hollow pitch-based activated carbon fibers as supercapacitor electrodes

1.
College of Materials Science and Engineering, Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, Hunan University, Changsha 410082, China;
2.
School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430080, China

Funds: National Natural Science Foundation of China(U1864207).

摘要

摘要: 以聚乙烯亚胺（PEI）为氮源与乙烯焦油沥青进行复合制备了可纺沥青，通过熔融纺丝、预氧化、炭化和活化制得了具备中空结构的富氮沥青基活性炭纤维（ACF）。利用N₂吸附与脱附等温线、XPS、SEM、Mapping等分析技术对所制得的ACF的表面形貌、孔隙结构及表面化学性质进行了表征，并测试了其作为超级电容器电极材料的电化学性能。研究结果表明，PEI在纺丝沥青中的掺入可明显提升ACF的比表面积，改善其孔径分布，增加其表面含氮官能团，从而改善材料表面润湿性，同时PEI在炭化过程中的热分解促使了纤维中空结构的形成，所制得ACF具有中空结构，提高了材料的有效比表面积，进而显著提高其比电容。PEI的掺入量为20%时，合成的可纺沥青所制备的ACF的比表面积高达2 756 m²/g，孔径主要分布在0.7~2 nm，其比电容在电流密度为0.5 A/g时可达314 F/g，远高于未进行氮掺杂的ACF的比电容（194 F/g），显示出较好的电化学性能。
- 沥青 /
- 活性炭纤维 /
- 氮掺杂 /
- 超级电容器 /
- 中空结构
Abstract: Mixtures of polyethyleneimine (PEI) and ethylene tar pitch (0, 15, 20, 30 wt% of PEI) were melt-spun, stabilized, carbonized and activated to prepare nitrogen-doped (N-doped) activated carbon fibers (ACFs). The morphology, porous structure and surface chemistry of the N-doped ACFs were characterized by N₂ adsorption, XPS and SEM. Their electrochemical performance as supercapacitor electrode materials was investigated. Results indicate that the specific surface area, pore volume and number of nitrogen-containing functional groups of the N-doped ACFs are much increased compared to undoped ACFs. PEI pyrolysis during the carbonization of the fibers leads to the formation of hollow N-doped ACFs that increases the utilization% of the surface area, resulting in a significant increase of the specific capacitance. When 20 wt% PEI was added, the specific surface area of the N-doped ACF reached 2 756 m²/g, its pore sizes ranged from 0.7 to 2 nm, and its specific capacitance reached 314 F/g at 0.5 A/g, which is much higher than that (194 F/g) of the undoped ACF.
- Pitch /
- Activated carbon fiber /
- Supercapacitor /
- Nitrogen-doped /
- Hollow structure

HTML全文

下载: 全尺寸图片幻灯片

参考文献(24)

Beguin F, Presser V, Balducci A, et al. Carbons and electrolytes for advanced supercapacitors[J]. Advanced Materials, 2014, 26(14):2219-2251.

Simon P, Gogotsi Y. Materials for electrochemical capacitors[J]. Nature Materials, 2008, 7(11):845-854.

Torchala K, Kierzek K, Gryglewicz G, et al. Narrow-porous pitch-based carbon fibers of superior capacitance properties in aqueous electrolytes[J]. Electrochimica Acta, 2015,167:348-356.

Wang K, Song Y, Yan R, et al. High capacitive performance of hollow activated carbon fibers derived from willow catkins[J]. Applied Surface Science, 2017,394(1):569-577.

Lee H M, Kwac L K, An K H, et al. Electrochemical behavior of pitch-based activated carbon fibers for electrochemical capacitors[J]. Energy Conversion and Management, 2016,125(1):347-352.

Qu D, Shi H, Studies of activated carbons used in double-layer capacitors[J]. Journal of Power Sources, 1998, 74(1):99-107.

Xu Q, Yu X L, Huang Z H, et al. Nitrogen-doped hollow activated carbon nanofibers as high performance supercapacitor electrodes[J]. Journal of Electroanalytical Chemistry, 2015, 739:84-88

Park S H, Kim B K, Lee W J. Electrospun activated carbon nanofibers with hollow core/highly mesoporous shell structure as counter electrodes for dye-sensitized solar cells[J]. Journal of Power Sources, 2013, 239:122-127,

Lee B S, Son S B, Park K M, et al. Effect of pores in hollow carbon nanofibers on their negative electrode properties for alithium rechargeable battery[J]. ACS Applied Materials Interfaces, 2012, 12(4):6702-6710.

Park S H, Jung H R, Lee W J. Hollow activated carbon nanofibers prepared by electrospinning as counter electrodes for dye-sensitized solar cells[J]. Electrochimica Acta, 2013, 102:423-428,

Lee, B S, Park K M, Yu W R, et al. An effective method for manufacturing hollow carbon nanofibers and microstructural analysis[J]. Macromolecular Research, 2012, 20(6):605-613.

Kim N D, Kim W, Joo J B, et al. Electrochemical capacitor performance of N-doped mesoporous carbons prepared by ammoxidation[J]. Journal of Power Sources, 2008, 180(1):671-675.

Guo H, Gao Q, Boron and nitrogen co-doped porous carbon and its enhanced properties as supercapacitor[J]. Journal of Power Sources, 2009, 186(2):551-556.

Hulicova-Jurcakova D, Puziy A M, Poddubnaya O I, et al. Highly stable performance of supercapacitors from phosphorus-enriched carbons[J]. Journal of the American Chemical Society, 2009, 131(14):5026-5027.

Hulicova-Jurcakova D, Seredych M, Lu G Q, et al. Combined effect of nitrogen- and oxygen-containing functional groups of microporous activated carbon on its electrochemical performance in supercapacitors[J]. Advanced Functional Materials, 2009, 19(3):438-447.

Hu Z X, Li S S, Cheng P P, et al. N, P-co-doped carbon nanowires prepared from bacterial cellulose[J]. Materials Science, 2016, 51:2627-2633.

Candelaria S L, Garcia B B, Liu D, et al. Nitrogen modification of highly porous carbon for improved supercapacitor performance[J]. Journal of Materials Chemistry, 2012, 22(19):9884-9889.

Chen L F, Zhang X D, Liang H W. Synthesis of nitrogen-doped porous carbon nanofibers as an efficient electrode material for supercapacitors[J]. ACS Nano, 2012, 6(8):7092-7102.

Ismagiloy Z R, Shalagina A E, Podyacheya O Y, et al. Structure and electrical conductivity of nitrogen-doped carbon nanofibers[J]. Carbon, 2009, 47(8):1922-1929.

Cheng Y L, Huang L, Xiao X, et al. Flexible and cross-linked N-doped carbon nanofiber network for high performance free-standing supercapacitor electrode[J]. Nano Energy, 2015, 15:66-74.

Zhang S, Kang P, Ubnoske S, et al. Polyethylenimine enhanced electrocatalytic reduction of CO₂ to formate at nitrogen-doped carbon nanomaterials[J]. Journal of the American Chemical Society, 2014, 136(22):7845-7848.

Liu B, Liu Y, Chen H, et al. Oxygen and nitrogen co-doped porous carbon nanosheets derived from perilla frutescens for high volumetric performance supercapacitors[J]. Journal of Power Sources, 2017, 341:309-317.

Chmiola J, Yushin G, Gogotsi Y, et al. Effect of pore size and surface area of carbide derived carbons on specific capacitance[J]. Journal of Power Sources, 2006,158(1):765-772

Wei X, Jiang X, Wei J, et al. Functional groups and pore size distribution do matter to hierarchically porous carbons as high-rate-performance supercapacitors[J]. Chemistry of Materials,2016,28(2):445-458.

施引文献

资源附件(0)

访问统计