纤维素导电气凝胶及其复合材料在超级电容器中应用的研究进展

doi:10.3969/j.issn.0253-2417.2018.01.001

摘要/Abstract

摘要： 概述了纤维素气凝胶通过炭化和复合导电物质实现导电功能的技术手段，及其在超级电容器中的应用研究现状。重点介绍了纤维素导电气凝胶孔结构及其复合结构对超级电容器电化学性能的影响，包括：依据电解液离子大小调控电极材料的孔结构和孔径分布，优化双电层电容行为；借助石墨烯等高导电性物质提高复合材料的导电性和比表面积，实现复合电极材料性能的增强及其在柔性能源储存装置中的应用；结合纤维素炭气凝胶优良的导电性与结构稳定性以及金属化合物高的赝电容和大的能量密度特性，实现复合电极材料中双电层电容和赝电容的协同增效作用。最后针对纤维素导电气凝胶及其复合材料在制备和超级电容器应用中面临的机遇与挑战，指出未来发展方向。

关键词: 纤维素导电气凝胶, 炭化, 复合, 电化学性能

Abstract: The technical means that the cellulose aerogels achieving electrically conductive function by carbonization and combining conductive materials and their application in supercapacitors were summarized.The effects of pore structure and hybrid structure of cellulose conductive aerogels on the electrochemical properties were also introduced.This review also detailed the latest researches on improving electrical double-layer capacitor properties by controlling the pore structure according to the electrolyte ionic size;on compositing high conductive material (graphene);on taking advantages of excellent electrical conductivity and high structural stability in carbon aerogel together with the large capacitance and high energy density in metal compounds to achieve the synergistic effect of electric double layer capacitance and pseudocapacitance.Additionally,the prospects of the opportunities and challenges in the fabrication and energy-storage application of cellulose conductive materials were elucidated.

Key words: cellulose conductive aerogel, carbonization, composite, electrochemical properties

中图分类号:

TQ352
Q636

杨喜, 孔令宇, 刘杏娥, 马建锋, 江泽慧. 纤维素导电气凝胶及其复合材料在超级电容器中应用的研究进展[J]. 林产化学与工业, 2018, 38(1): 1-8.

YANG Xi, KONG Lingyu, LIU Xing'e, MA Jianfeng, JIANG Zehui. Research Progress of Cellulose Conductive Aerogels and Composites in Supercapacitors[J]. Chemistry and Industry of Forest Products, 2018, 38(1): 1-8.

参考文献

[1] PÉREZMADRIGAL M M,EDO M G,ALEMÁN C. Powering the future:Application of cellulose-based materials for supercapacitors[J]. Green Chemistry,2016,18:5930-5956.
[2] MOHAMMADINEJAD R,KARIMI S,IRAVANI S,et al. Plant-derived nanostructures:Types and applications[J]. Green Chemistry,2016,18:20-52.
[3] PEKALA R W,KONG F M. Resoreional-formaldehyde aerogels and their carbonized derivatives[J]. Polymer Preprint,1989,30(1):221-223.
[4] TAN C B,FUNG B M,NEWMAN J K,et al. Organic aerogels with very high impact strength[J]. Advanced Materials,2001,13(9):644-646.
[5] MI Q Y,MA S R,YU J,et al. Flexible and transparent cellulose aerogels with uniform nanoporous structure by a controlled regeneration process[J]. ACS Sustainable Chemistry & Engineering,2016,4(3):656-660.
[6] 郝品. 可再生资源制备的炭气凝胶及其复合电极材料的电化学性能研究[D]. 济南:山东大学博士学位论文,2015. HAO P. Biopolymer derived porous carbon aerogels and their hybrid nanostructures for elecyrochemical energy storage application[D]. Jinan:Doctoral Dissertation of Shandong University,2015.
[7] 杨喜,刘杏娥,马建锋,等. 生物质基炭气凝胶制备及应用研究[J]. 材料导报,2017,31(7):45-53. YANG X,LIU X E,MA J F,et al. Fabrication and application of carbon aerogel derived from biomass materials[J]. Materials Review,2017,31(7):45-53.
[8] 林东瀚,陈港,方志强. 纳米纤维素复合气凝胶超级电容器的制备与性能[J]. 造纸科学与技术,2017,36(1):28-35. LIN D H,CHEN G,FAMG Z Q. Preparation and properties of NFC composite aerogel supercapacitors[J]. Paper Science & Technology,2017,36(1):28-35.
[9] 郭新,张建明,段咏欣. 纤维素基碳气凝胶研究进展[J]. 纤维素科学与技术,2017,25(1):65-74,82. GUO X,ZHANG J M,DUAN Y X. Progress of carbon aerogels based on cellulose[J]. Fiber Science and Technology,2017,25(1):65-74,82.
[10] ZHENG Q F,CAI Z Y,MA Z Q,et al. Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors[J]. ACS Applied Materials Interfaces,2015,7(5):3263-3271.
[11] QI H S,MÄDER E,LIU J W. Electrically conductive aerogels composed of cellulose and carbon nanotubes[J]. Journal of Materials Chemistry A,2013,1(34):9714-9720.
[12] NIU Q Y,GUO Y Q,GAO K Z,et al. Polypyrrole/cellulose nanofiber aerogel as a supercapacitor electrode material[J]. RSC Advances,2016,6(110):109143-109149.
[13] HAO P,ZHAO Z H,TIAN J,et al. Hierarchical porous carbon aerogel derived from bagasse for high performance supercapacitor electrode[J]. Nanoscale,2014,6(20):12120-12129.
[14] HU Y J,TONG X,ZHUO H,et al. 3D Hierarchical porous N-doped carbon aerogel from renewable cellulose:An attractive carbon for high-performance supercapacitor electrodes and CO₂ absorption[J]. RSC Advances,2016,6(19):15788-15795.
[15] CHENG P,LI T,YU H,et al. Biomass-derived carbon fiber aerogel as a binder-free electrode for high-rate supercapacitors[J]. The Journal of Physical Chemistry C,2016,120(4):2079-2086.
[16] YANG X,FEI B H,MA J F,et al. Porous nanoplatelets wrapped carbon aerogel by pyrolysis of regenerated bamboo cellulose aerogels as supercapacitor electrodes[J]. Carbohydrate Polymers,2018,108:385-392.
[17] BUDINOVA T,EKINCI E,YARDIM F,et al. Characterization and application of activated carbon produced by H₃PO₄,and water vapor activation[J]. Fuel Processing Technology,2006,87(10):899-905.
[18] ZHUO H,HU Y,TONG X,et al. Sustainable hierarchical porous carbon aerogel from cellulose for high-performance supercapacitor and CO₂ capture[J]. Industrial Crops and Products,2016,87:229-235.
[19] ZU G,SHEN J,ZOU L,et al. Nanocellulose-derived highly porous carbon aerogels for supercapacitors[J]. Carbon,2016,99:203-211.
[20] WANG T,TAN S,LIANG C. Preparation and characterization of activated carbon from wood via microwave-induced ZnCl₂ activation[J]. Carbon,2009,47(7):1880-1883.
[21] ELMOUWAHIDI A,BAILÓN-GARCÍA E,PÉREZ-CADENAS A F,et al. Activated carbons from KOH and H₃PO₄-activation of olive residues and its application as supercapacitor electrodes[J]. Electrochimica Acta,2017,229:219-228.
[22] ZHANG Y F,ZUO L Z,LU H Y,et al. Immobilization of NiS nanoparticles on N-doped carbon fiber aerogels as advanced electrode materials for supercapacitors[J]. Nano Research,2016,9(9):2747-2759.
[23] HAO P,ZHAO Z H,LI L Y,et al. The hybrid nanostructure of MnCo₂O_4.5 nanoneedle/carbon aerogel for symmetric supercapacitors with high energy density[J]. Nanoscale,2015,7(34):14401-14412.
[24] HAO P,ZHAO Z,LENG Y,et al. Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high performance supercapacitors[J]. Nano Energy,2015,15:9-23.
[25] WANG C H,LI Y B,HE X D,et al. Cotton-derived bulk and fiber aerogels grafted with nitrogen-doped graphene[J]. Nanoscale,2015,7(17):7550-7558.
[26] NIU Z,ZHANG L,LIU L,et al. All-solid-state flexible ultrathin micro-supercapacitors based on graphene[J]. Advanced Materials,2013,25(29):4035-4042.
[27] IAMPRASERTKUN P,KRITTAYAVATHANANON A,SAWANGPHRUK M. N-doped reduced graphene oxide aerogel coated on carboxyl-modified carbon fiber paper for high-performance ionic-liquid supercapacitors[J]. Carbon,2016,102:455-461.
[28] CHOI B G,YANG M,HONG W H,et al. 3D Macroporous graphene frameworks for supercapacitors with high energy and power densities[J]. ACS Nano,2012,6(5):4020-4028.
[29] XIONG R,HU K,GRANT A M,et al. Ultrarobust transparent cellulose nanocrystal-graphene membranes with high electrical conductivity[J]. Advanced Materials,2016,28(7):1501-1509.
[30] SEVILLA M,FERRERO G A,FUERTES A B. Graphene-cellulose tissue composites for high power supercapacitors[J]. Energy Storage Materials,2016,5:33-42.
[31] WENG Z,SU Y,WANG D W,et al. Graphene-cellulose paper flexible supercapacitors[J]. Advanced Energy Materials,2011,1(5):917-922.
[32] KANG Y R,LI Y L,HOU F,et al. Fabrication of electric papers of graphene nanosheet shelled cellulose fibres by dispersion and infiltration as flexible electrodes for energy storage[J]. Nanoscale,2012,4(10):3248-3253.
[33] GAO K Z,SHAO Z Q,LI J,et al. Cellulose nanofiber-graphene all solid-state flexible supercapacitors[J]. Journal of Materials Chemistry A,2013,1(1):63-67.
[34] ZHANG J,CAO Y W,FENG J C,et al. Graphene oxide sheet induced gelation of cellulose and promoted mechanical properties of composite aerogels[J]. The Journal of Physical Chemistry C,2012,116(14):8063-8068.
[35] RAGHUNATHAN S P,NARAYANANC S,POULOSE A C,et al. Flexible regenerated cellulose/polypyrrole composite films with enhanced dielectric properties[J]. Carbohydrate Polymers,2017,157:1024-1032.
[36] WANG H,BIAN L Y,ZHOU P P,et al. Core-sheath structured bacterial cellulose/polypyrrole nanocomposites with excellent conductivity as supercapacitors[J]. Journal of Materials Chemistry A,2013,1(3):578-584.
[37] SIMON P,GOGOTSI Y. Materials for electrochemical capacitors[J]. Nature Materials,2008,7(11):845-854.
[38] HUANG J H,SUMPTER B G,MEUNIER V. A universal model for nanoporous carbon supercapacitors applicable to diverse pore regimes,carbon materials,and electrolytes[J]. Chemistry (Weinheim an der Bergstrasse,Germany),2008,14(22):6614-6626.
[39] OSCHATZ M,BOUKHALFA S,NICKEL W,et al. Carbide-derived carbon aerogels with tunable pore structure as versatile electrode material in high power supercapacitors[J]. Carbon,2017,113:283-291.
[40] BARROSO-BOGEAT A,ALEXANDRE-FRANCO M,FERNÁNDEZ-GONZÁLEZ C,et al. Temperature dependence of the electrical conductivity of activated carbons prepared from vine shoots by physical and chemical activation methods[J]. Microporous & Mesoporous Materials,2015,209:90-98.
[41] HU C C,CHANG K H,LIN M C,et al. Design and tailoring of the nanotubular arrayed architecture of hydrous RuO₂ for next generation supercapacitors[J]. Nano Letters,2006,6(12):2690-2695.
[42] YUAN L,LU X H,XIAO X,et al. Flexible solid-state supercapacitors based on carbon nanoparticles/MnO₂ nanorods hybrid structure[J]. ACS Nano,2012,6(1):656-661.
[43] NOH J,YOON C M,YUN K K,et al. High performance asymmetric supercapacitor twisted from carbon fiber/MnO₂ and carbon fiber/MoO₃[J]. Carbon,2017,116:470-478.
[44] YU N,YIN H,ZHANG W,et al. High-performance fiber-shaped all-solid-state asymmetric supercapacitors based on ultrathin MnO₂ nanosheet/carbon fiber cathodes for wearable electronics[J]. Advanced Energy Materials,2016,6(2):1501458-1501466.
[45] SUN G,MA L Y,RAN J B,et al. Incorporation of homogeneous Co₃O₄ into a nitrogen-doped carbon aerogel via a facile in situ synthesis method:Implications for high performance asymmetric supercapacitors[J]. Journal of Materials Chemistry A,2016,4(24):9542-9554.
[46] HAO P,TIAN J,SANG Y,et al. 1D Ni-Co oxide and sulfide nanoarray/carbon aerogel hybrid nanostructures for asymmetric supercapacitors with high energy density and excellent cycling stability[J]. Nanoscale,2016,8(36):16292-16301.
[47] CAI F,SUN R,KANG Y R,et al. One-step strategy to a three-dimensional NiS-reduced graphene oxide hybrid nanostructure for high performance supercapacitors[J]. RSC Advances,2015,5(29):23073-23079.
[48] YU W D,LIN W R,SHAO X F,et al. High performance supercapacitor based on Ni₃S₂/carbon nanofibers and carbon nanofibers electrodes derived from bacterial cellulose[J]. Journal of Power Sources,2014,272:137-143.
[49] YANG J Q,GUO W,LI D,et al. Synthesis and electrochemical performances of novel hierarchical flower-like nickel sulfide with tunable number of composed nanoplates[J]. Journal of Power Sources,2014,268:113-120.
[50] XU C,LI B,DU H,et al. Supercapacitive studies on amorphous MnO₂ in mild solutions[J]. Journal of Power Sources,2008,184(2):691-694.
[51] AND S D,MUNICHANDRAIAH N. Effect of crystallographic structure of MnO₂ on its electrochemical capacitance properties[J]. Journal of Physical Chemistry C,2008,112(11):4406-4417.
[52] LYU S,CHANG H J,FU F,et al. Cellulose-coupled graphene/polypyrrole composite electrodes containing conducting networks built by carbon fibers as wearable supercapacitors with excellent foldability and tailorability[J]. Journal of Power Sources,2016,327:438-446.
[53] LIU R,MA L,HUANG S,et al. Large areal mass and high scalable and flexible cobalt oxide/graphene/bacterial cellulose electrode for supercapacitors[J]. The Journal of Physical Chemistry C,2016,120(50):28480-2848.