纤维素基电极材料在柔性超级电容器中的应用研究进展

doi:10.3969/j.issn.0253-2417.2019.04.002

摘要/Abstract

摘要：

纤维素是自然界中一种轻质、生物相容性好以及柔韧性强的生物高分子材料，在柔性超级电容器、生物传感器以及电磁屏蔽等领域得到了广泛应用。在柔性超级电容器领域中，纤维素基材料的多羟基结构是电解质离子传导的良好介质，有助于提高电极材料的电容特性以及循环特性，并且易与导电活性材料（如：石墨烯、碳纳米管、导电高分子）通过涂布、共混、层层自组装以及原位聚合等方法构建导电框架以制备柔性电极材料。综述了基于纤维素材料的柔性超级电容器电极开发的相关研究，重点介绍了基于不同纤维素基原料（原生纤维素、纳米纤维素以及纤维素衍生物）制备柔性超级电容器电极的方法以及所得电极的电化学性质，分析归纳了纤维素基材料在柔性电极中的主要作用：作为骨架支撑柔性电极材料、充当柔性基底（可兼有隔膜作用）、形成多孔结构传输电解质离子。最后，对纤维素材料在柔性电极材料领域的发展趋势进行了展望。

关键词: 纤维素, 纤维素衍生物, 纳米纤维素, 柔性电极, 超级电容器

Abstract:

Cellulose has been increasingly utilized in the area of flexible supercapacitor, biosensor, and electromagnetic shielding because of its unique advantages of lightweight, biocompatibility and flexibility. The polyhydroxy structure of cellulose is beneficial for the transmission of electrolyte ions, resulting in the good performance of the electric capacity and cyclical stability for flexible electrode materials. Furthermore, flexible cellulose-based electrode can be obtained by coating, compounding, layer-by-layer self-assembling and in situ chemical polymerization with electroconductive materials(e.g., graphene, carbon nanotubes, conductive polymer and so on). Resent researches of the cellulose-based flexible electrode materials from different cellulose-based raw materials(original cellulose, nanocellulose and cellulose derivatives) were introduced in this review and the preparation methods and electrochemical properties of the obtained materials were also focused. The contributions of cellulose-based materials in the flexible electrode were categorized as:the backbone for supporting the flexible electrode material, the flexible substrates(or separator) and the ion channel for electrolyte. The future development and the challenges in the area of cellulose-based flexible electrode were also prospected.

Key words: cellulose, cellulose derivatives, nanocellulose, flexible electrode, supercapacitor

中图分类号:

TQ35

邢健雄,郑凯,韩尊强,徐伟涛,王堃. 纤维素基电极材料在柔性超级电容器中的应用研究进展[J]. 林产化学与工业, 2019, 39(4): 9-17.

Jianxiong XING,Kai ZHENG,Zunqiang HAN,Weitao XU,Kun WANG. Research Progress on Application of Cellulose-based Materials as Electrode in Flexible Supercapacitor[J]. Chemistry and Industry of Forest Products, 2019, 39(4): 9-17.

图/表 7

图1

图2

图3

图4

图5

图6

图7

参考文献 32

1	LI K , ZHANG J T . Recent advances in flexible supercapacitors based on carbon nanotubes and graphene[J]. Science China Materials, 2018, 61 (2): 210- 232. doi: 10.1007/s40843-017-9154-2
2	麻伍军, 陈少华, 朱美芳. 基于碳基纤维的柔性超级电容器[J]. 中国材料进展, 2016, 35 (2): 118- 127.
	MA W J , CEHN S H , ZHU M F . Carbon-based fibers for flexible supercapacitor[J]. Materials China, 2016, 35 (2): 118- 127.
3	HE Y M , CHEN W J , LI X D , et al. Freestanding three-dimensional graphene/MnO₂ composite networks as ultralight and flexible supercapacitor electrodes[J]. ACS Nano, 2013, 7 (1): 174- 182. doi: 10.1021/nn304833s
4	LU X H , YU M H , WANG G M , et al. Flexible solid-state supercapacitors:Design, fabrication and applications[J]. Energy & Environmental Science, 2014, 7 (7): 2160- 2181.
5	HASSAN S H , VOON L H , VELAYUTHAM T S , et al. Review of cellulose smart material:Biomass conversion process and progress on cellulose-based electroactive paper[J]. Journal of Renewable Materials, 2018, 6 (1): 1- 25. doi: 10.7569/JRM.2017.634173
6	DANIEL T , RONALD O . Paper electronics[J]. Advanced Materials, 2011, 23 (17): 1935- 1961. doi: 10.1002/adma.201004692
7	LÜ Y Y , LI L , ZHOU Y , et al. A cellulose-based hybrid 2D material aerogel for a flexible all-solid-state supercapacitor with high specific capacitance[J]. RSC Advances, 2017, 7 (69): 43512- 43520. doi: 10.1039/C7RA07908G
8	YANG C , LI D G . Flexible and foldable supercapacitor electrodes from the porous 3D network of cellulose nanofibers, carbon nanotubes and polyaniline[J]. Materials Letters, 2015, 155, 78- 81. doi: 10.1016/j.matlet.2015.04.096
9	XU J , ZHU L , BAI Z , et al. Conductive polypyrrole-bacterial cellulose nanocomposite membranes as flexible supercapacitor electrode[J]. Organic Electronics, 2013, 14 (12): 3331- 3338. doi: 10.1016/j.orgel.2013.09.042
10	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. doi: 10.1039/c2nr30318c
11	SU H B , ZHU P L , ZHANG L C , et al. Waste to wealth:A sustainable and flexible supercapacitor based on office waste paper electrodes[J]. Journal of Electroanalytical Chemistry, 2017, 786, 28- 34. doi: 10.1016/j.jelechem.2017.01.002
12	ZHENG G Y , HU L B , WU H , et al. Paper supercapacitors by a solvent-free drawing method[J]. Energy & Environmental Science, 2011, 4 (9): 3368- 3373.
13	WENG Z , SU Y , WANG D W , et al. Graphene-cellulose paper flexible supercapacitors[J]. Advanced Energy Materials, 2011, 1 (5): 917- 922. doi: 10.1002/aenm.201100312
14	ZHANG L C , ZHU P L , ZHOU F R , et al. Flexible asymmetrical solid-state supercapacitors based on laboratory filter paper[J]. ACS Nano, 2016, 10 (1): 1273- 1282. doi: 10.1021/acsnano.5b06648
15	QIAN J S , JIN H Y , CHEN B L , et al. Aqueous manganese dioxide ink for paper-based capacitive energy storage devices[J]. Angewandte Chemie, 2015, 54 (23): 6800- 6803. doi: 10.1002/anie.201501261
16	师少飞, 王兆梅, 郭祀远. 纤维素溶解的研究现状[J]. 纤维素科学与技术, 2007, 15 (3): 74- 78. doi: 10.3969/j.issn.1004-8405.2007.03.013
	SHI S F , WANG Z M , GUO S Y . New solvent systems of cellulose[J]. Journal of Cellulose Science and Technology, 2007, 15 (3): 74- 78. doi: 10.3969/j.issn.1004-8405.2007.03.013
17	ZHAO D W , ZHANG Q , CHEN W S , et al. Highly flexible and conductive cellulose-mediated PEDOT:PSS/MWCNT composite films for supercapacitor electrodes[J]. ACS Applied Materials and Interfaces, 2017, 9 (15): 13213- 13222. doi: 10.1021/acsami.7b01852
18	李鑫, 邓立高, 俸斌, 等. 纳米纤维素的制备工艺及其研究进展[J]. 纸和造纸, 2018, 37 (4): 11- 16.
	LI X , DENG L G , FENG B , et al. Preparation process and development of nanocellulose[J]. Paper and Paper Making, 2018, 37 (4): 11- 16.
19	LI F , MASCHERONI E , PIERGIOVANNI L . The potential of nanocellulose in the packaging field:A review[J]. Packaging Technology and Science, 2015, 28 (6): 475- 508. doi: 10.1002/pts.2121
20	ZHANG Y J , SUN T , JIANG C . Biomacromolecules as carriers in drug delivery and tissue engineering[J]. Acta Pharmaceutica Sinica B, 2018, 8 (1): 34- 50. doi: 10.1016/j.apsb.2017.11.005
21	SEABRA A B , BERMARDES J S , WAGNER J F , et al. Cellulose nanocrystals as carriers in medicine and their toxicities:A review[J]. Carbohydrate Polymers, 2018, 181, 345- 354. doi: 10.1016/j.carbpol.2017.10.085
22	GAO K , SHAO Z , WU X , et al. Paper-based transparent flexible thin film supercapacitors[J]. Nanoscale, 2013, 5 (12): 5307- 5311. doi: 10.1039/c3nr00674c
23	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.
24	WANG Z H , CARLSSON D O , TAMMELA P , et al. Surface modified nanocellulose fibers yield conducting polymer-based flexible supercapacitors with enhanced capacitances[J]. ACS Nano, 2015, 9 (7): 7563- 7571. doi: 10.1021/acsnano.5b02846
25	MA L N , LIU R , NIU H J , et al. Flexible and freestanding electrode based on polypyrrole/graphene/bacterial cellulose paper for supercapacitor[J]. Composites Science & Technology, 2016, 137, 87- 93.
26	LIU R , MA L N , HUANG S , et al. Large areal mass and high scalable and flexible cobalt oxide/graphene/bacterial cellulose electrode for supercapacitors[J]. Journal of Physical Chemistry C, 2016, 120 (50): 28480- 28488. doi: 10.1021/acs.jpcc.6b10475
27	JIANG Q , KACICA C , SOUNDAPPAN T , et al. In situ grown bacterial nanocellulose/graphene oxide composite for flexible supercapacitor[J]. Journal of Materials Chemistry A, 2017, 5 (27): 13976- 13982. doi: 10.1039/C7TA03824K
28	SU J F , ZHEN H , YUAN X Y , et al. Structure and properties of carboxymethyl cellulose/soy protein isolate blend edible films crosslinked by Maillard reactions[J]. Carbohydrate Polymers, 2010, 79 (1): 145- 153. doi: 10.1016/j.carbpol.2009.07.035
29	SMITS C H , VELDMAN A , VERSTEGEN M W , et al. Dietary carboxymethylcellulose with high instead of low viscosity reduces macronutrient digestion in broiler chickens[J]. Journal of Nutrition, 1997, 127 (3): 483- 487. doi: 10.1093/jn/127.3.483
30	闫佳欣, 张淑洁, 伏立松, 等. 醋酸纤维纺丝原液用机织过滤布的设计与性能研究[J]. 产业用纺织品, 2017, 35 (11): 22- 26. doi: 10.3969/j.issn.1004-7093.2017.11.004
	YAN J X , ZHANG S J , FU L S , et al. Study on design and performance of woven filter cloth for cellulose acetate fibers' spinning solution[J]. Technical Textiles, 2017, 35 (11): 22- 26. doi: 10.3969/j.issn.1004-7093.2017.11.004
31	尚秀丽, 伍家卫, 李薇, 等. 聚苯胺/醋酸纤维素复合膜的制备及其超级电容特性[J]. 化学通报, 2013, 76 (12): 1132- 1136.
	SHANG X L , WU J W , LI W , et al. Preparation of polyaniline/cellulose acetate composite films and their super-capacitive characteristics[J]. Chemistry, 2013, 76 (12): 1132- 1136.
32	DEVARAYAN K , LEI D , KIM H Y , et al. Flexible transparent electrode based on PANI nanowire/nylon nanofiber reinforced cellulose acetate thin film as supercapacitor[J]. Chemical Engineering Journal, 2015, 273, 603- 609. doi: 10.1016/j.cej.2015.03.115

[1]	陈金伟, 王丹, 商士斌, 刘鹤, 蔡照胜. 端氨基超支化聚合物接枝双醛基纳米纤维素的制备及其对Ni²⁺的吸附[J]. 林产化学与工业, 2019, 39(4): 18-26.
[2]	熊明诚, 王梓, 鄢雨欣, 郑艳灵, 肖真真, 卢麒麟, 黄彪. 超声波辅助对甲苯磺酸催化水解纸浆制纳米纤维素晶体[J]. 林产化学与工业, 2019, 39(4): 72-76.
[3]	陈超,王傲,孙康,卢辛成,许伟,蒋剑春. 生物质原料的Ni催化石墨化研究[J]. 林产化学与工业, 2019, 39(3): 94-100.
[4]	宋豫龙,李伟,徐州,刘守新. 喷雾热解制备落叶松基炭球及其电化学性能[J]. 林产化学与工业, 2019, 39(2): 9-15.
[5]	周威,贾普友,张猛,周永红. 含氮杂环桐油基硬质聚氨酯泡沫塑料的制备及性能表征[J]. 林产化学与工业, 2019, 39(2): 53-58.
[6]	李延庆,刘志明,程小凯,曹梦楠,王佳楠. 海藻酸钠/纤维素复合微球的制备及性能表征[J]. 林产化学与工业, 2019, 39(2): 67-72.
[7]	尹文章,李建强,许正茂,张春辉. 低品质纤维制备微纤化纤维素的研究[J]. 林产化学与工业, 2019, 39(2): 89-95.
[8]	赵存异,应文俊,史正军,杨海艳,郑志锋,杨静. 羟丙基化碱木质素的制备及其对纤维素酶水解的影响[J]. 林产化学与工业, 2019, 39(2): 109-114.
[9]	李继辉,孙康,宋曜光,王傲,蒋剑春. 木质素基炭纳米片的制备及其电化学性能[J]. 林产化学与工业, 2019, 39(1): 67-74.
[10]	卢传巍,王春鹏,储富祥,王基夫. ATRP法制备纤维素-油脂-糠醛热塑性弹性体及性能表征[J]. 林产化学与工业, 2019, 39(1): 75-80.
[11]	陈金伟, 商士斌, 沈明贵, 王丹, 付飞, 蔡照胜. 端氨基纳米纤维素的制备及对Pb(Ⅱ)的吸附性能研究[J]. 林产化学与工业, 2018, 38(6): 11-19.
[12]	许升, 吕宗泽, 易雪亭, 张文, 李志国. 纸基炭电极材料的制备及其电化学性能研究[J]. 林产化学与工业, 2018, 38(6): 42-50.
[13]	宋如愿, 赵璐洋, 夏子华, 吴伟兵, 景宜, 戴红旗. 纤维素纳米晶荧光探针的制备及光学性能[J]. 林产化学与工业, 2018, 38(6): 51-58.
[14]	王傲, 孙康, 蒋剑春. Fe₃O₄@C纳米片超级电容器电极材料的制备及其电化学性能研究[J]. 林产化学与工业, 2018, 38(5): 9-16.
[15]	石纯, 李天诚, 杨静, 杨海艳, 邓佳, 史正军. 竹醋酸纤维素膜的制备及其性能研究[J]. 林产化学与工业, 2018, 38(5): 70-76.