BC/CoNi2S4@PPy柔性复合电极材料的制备及电化学性能

doi:10.13208/j.electrochem.200630

摘要/Abstract

摘要：

本文采用溶剂热、原位聚合和真空抽滤相结合的方法制备了用于超级电容器的细菌纤维素/镍钴硫化物/聚吡咯(BC/CoNi₂S₄@PPy)柔性电极材料,通过X射线衍射、场发射扫描电镜、红外光谱、氮气吸脱附、拉伸强度和接触角表征了材料的形貌结构、组成、机械性能和亲水性,并采用循环伏安法和恒电流充放电测试了复合材料的电化学性能。结果表明,表面含氧官能团丰富的BC纤维网络结构对氧化还原活性物质CoNi₂S₄的生长和导电聚合物PPy的分布具有引导作用,CoNi₂S₄均匀分布在BC网络中,且PPy均匀包覆在BC纤维和CoNi₂S₄纳米球表面构成具有丰富孔隙结构的三维导电网络,使得该复合材料具有较好的机械性(抗拉强度达28.0±0.1 MPa)、亲水性(对6 mol·L^-1 KOH的瞬间接触角为43.6°)及良好的导电性。该电极材料在1 A·g^-1下比电容高达2670 F·g^-1,充放电循环10000次后比电容的保持率为82.73%,且经1000次反复弯曲后电化学性能保持不变。此外,将其与活性炭组成的非对称超级电容器,在1 A·g^-1下比电容为1428 F·g^-1,最高能量密度和功率密度分别达49.8 Wh·kg^-1和741.8 W·kg^-1。

关键词: 柔性电极材料, 细菌纤维素, 镍钴硫化物, 聚吡咯

Abstract:

Flexible supercapacitor is one of the most promising energy storage devices for portable and wearable electronic products due to its advantages of high power density, fast charging and long cycle life. Therefore, self-supporting flexible electrode materials with high performance have attained more and more attention both in academia and in industry recently. In this work, using bacterial cellulose (BC) as a flexible substrate, the bacterial cellulose/nickel-cobalt sulfide@polypyrrole (BC/CoNi₂S₄@PPy) flexible composites with three-dimensional porous network and good conductivity were prepared by a combined solvothermal-in-situ polymerization-vacuum filtration method. The samples were characterized by X-ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectrometry, N₂ physisorption, tensile strength and contact angle measurements. Their electrochemical performances were tested by cyclic voltammetry, galvanostatic charge/discharge testing and electrochemical impedance spectroscopy. The results show that the three-dimensional porous network of BC fibers with rich oxygen-containing surface groups play a guiding role in the growth of the redox active material CoNi₂S₄ and the distribution of conductive polymer PPy, resulting in uniformly distributed CoNi₂S₄ nanospheres in the network of BC fibers, both coated evenly with a layer of conductive PPy. The resulting BC/CoNi₂S₄@PPy composites, a three-dimensional conductive network with high porosity, displayed good mechanical property (tensile strength up to 28.0±0.1 MPa), hydrophilicity (the instantaneous contact angle in 6 mol·L^-1 KOH is 43.6°), as well as excellent electrochemical performance. The specific capacitance of the flexible BC/CoNi₂S₄@PPy was 2670 F·g^-1 at 1 A·g^-1 in a three-electrode system, and retained 82.7% after 10000 charge and discharge cycles. In addition, the electrochemical performance remained unchanged after 1000 times of repeated bending. In an asymmetric supercapacitor composed of BC/CoNi₂S₄@PPy and activated carbon, the area specific capacitance was 1428 F·g^-1 at 1 A·g^-1. The asymmetric supercapacitor achieved the maximum energy density of 49.8 Wh·kg^-1 and power density of 741.8 W·kg^-1.

Key words: flexible electrode material, bacterial cellulose, nickel-cobalt sulfide, polypyrrole

彭思源, 杨实润, 周静红, 隋志军, 章涛, 石易, 周兴贵. BC/CoNi₂S₄@PPy柔性复合电极材料的制备及电化学性能[J]. 电化学（中英文）, 2021, 27(1): 14-25.

Si-Yuan Peng, Shi-Run Yang, Jing-Hong Zhou, Zhi-Jun Sui, Tao Zhang, Yi Shi, Xing-Gui Zhou. Preparations and Electrochemical Properties of BC/CoNi₂S₄@PPy Flexible Composites for Supercapacitors[J]. Journal of Electrochemistry, 2021, 27(1): 14-25.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200630

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I1/14

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参考文献 21

[1]	Shi H M, Wen G L, Nie Y, Zhang G H, Duan H G. Flexible 3D carbon cloth as a high-performing electrode for energy storage and conversion[J]. Nanoscale, 2020,12(9):5261-5285. URL pmid: 32091524
[2]	Dai C L, Sun G Q, Hu L Y, Xiao Y K, Zhang Z P, Qu L T. Recent progress in graphene-based electrodes for flexible batteries[J]. InfoMat, 2020,2(3):509-526. doi: 10.1002/inf2.v2.3 URL
[3]	Luo Y, Wu P C, Li J W, Yang S C, Wu K L, Wu J N, Meng G H, Liu Z Y, Guo X H. Self-supported flexible supercapacitor based on carbon fibers covalently combined with monoaminophthalocyanine[J]. Chem. Eng. J., 2020,391:123535. doi: 10.1016/j.cej.2019.123535 URL
[4]	Ye J B, Guo L X, Zheng S S, Feng Y J, Zhang T T, Yang Z C, Yuan Q S, Shen G P, Zhang Z. Synjournal of bacterial cellulose based SnO₂-PPy nanocomposites as potential flexible, highly conductive material[J]. Mater. Lett., 2019,253:372-376. doi: 10.1016/j.matlet.2019.06.096 URL
[5]	Pirsa S, Shamusi T, Kia E M. Smart films based on bacterial cellulose nanofibers modified by conductive polypyrrole and zinc oxide nanoparticles[J]. J. Appl. Polym. Sci., 2018,135(33-34):46617. doi: 10.1002/app.46617 URL
[6]	Liu R, Ma L N, Huang S, Mei J, Li E Y, Yuan G H. Large areal mass and high scalable and flexible cobalt oxide/graphene/bacterial cellulose electrode for supercapacitors[J]. J. Phys. Chem. C, 2016,120(50):28480-28488. doi: 10.1021/acs.jpcc.6b10475 URL
[7]	Müller D, Rambo C R, Recouvreux D O S, Porto L M, Barra G M O. Chemical in situ polymerization of polypyrrole on bacterial cellulose nanofibers[J]. Synth. Met., 2011,161(1-2):106-111. doi: 10.1016/j.synthmet.2010.11.005 URL
[8]	Wu H, Zhang Y N, Yuan W Y, Zhao Y X, Luo S H, Yuan X W, Zheng L X, Cheng L F. Highly flexible, foldable and stretchable Ni-Co layered double hydroxide/polyaniline/bacterial cellulose electrodes for high-performance all-solid-state supercapacitors[J]. J. Mater. Chem. A, 2018,6(34):16617-16626. doi: 10.1039/C8TA05673K URL
[9]	Liu P, Sui Y W, Wei F X, Qi J Q, Meng Q K, Ren Y J, He Y Z. One-step hydrothermal synjournal of CoNi₂S₄ for hybrid supercapacitor electrodes[J]. Nano, 2019,14(7):1950088. doi: 10.1142/S1793292019500887 URL
[10]	Li L, Lou Z, Han W, Chen D, Jiang K, Shen G Z. Highly stretchable micro-supercapacitor arrays with hybrid MWCNT/PANI electrodes[J]. Adv. Mater. Technol., 2017,2(3):1600282. doi: 10.1002/admt.201600282 URL
[11]	Peng S, Fan L L, Wei C Z, Liu X H, Zhang H W, Xu W L, Xu J. Flexible polypyrrole/copper sulfide/bacterial cellulose nanofibrous composite membranes as supercapacitor electrodes[J]. Carbohydr. Polym., 2017,157:344-352. URL pmid: 27987937
[12]	Yang S R(杨实润). Preparation and electrochemical performance of the nickel cobalt sulfide as supercapacitor electrode material[D]. East China University of Science and Technology (华东理工大学), 2018.
[13]	Mao X L, Xu J H, He X, Yang W Y, Yang Y J, Xu L, Zhao Y T, Zhou Y J. All-solid-state flexible microsupercapacitors based on reduced graphene oxide/multi-walled carbon nanotube composite electrodes[J]. Appl. Surf. Sci., 2017,435:1228-1236. doi: 10.1016/j.apsusc.2017.11.248 URL
[14]	Mykhailiv O, Imierska M, Petelczyc M, Echegoyen L, Plonska-Brzezinska M E. Chemical versus electrochemical synjournal of carbon nano-onion/polypyrrole composites for supercapacitor electrodes[J]. Chem.-Eur. J., 2015,21(15):5783-5793. doi: 10.1002/chem.201406126 URL pmid: 25736714
[15]	Wu X M, Lian M. Highly flexible solid-state supercapacitor based on graphene/polypyrrole hydrogel[J]. J. Power Sources, 2017,362:184-191. doi: 10.1016/j.jpowsour.2017.07.042 URL
[16]	Wang F, Kim H J, Park S K, Kee C D, Kim S J, Oh I K. Bendable and flexible supercapacitor based on polypyrrole-coated bacterial cellulose core-shell composite network[J]. Compos. Sci. Technol., 2016,128:33-40. doi: 10.1016/j.compscitech.2016.03.012 URL
[17]	Zhang Y H, Shang Z, Shen M X, Chowdhury S P, Ignaszak A, Sun S H, Ni Y H. Cellulose nanofibers/reduced graphene oxide/polypyrrole aerogel electrodes for high-capacitance flexible all-solid-state supercapacitors[J]. ACS Sustain. Chem. Eng., 2019,7(13):11175-11185. doi: 10.1021/acssuschemeng.9b00321 URL
[18]	Luo H L, Dong J J, Zhang Y, Li G, Guo R S, Zuo G F, Ye M D, Wang Z R, Yang Z W, Wan Y Z. Constructing 3D bacterial cellulose/graphene/polyaniline nanocomposites by novel layer-by-layer, in situ, culture toward mechanically robust and highly flexible freestanding electrodes for supercapacitors[J]. Chem. Eng. J., 2018,334:1148-1158. doi: 10.1016/j.cej.2017.11.065 URL
[19]	Qian T, Yu C F, Wu S S, Shen J. A facilely prepared poly-pyrrole-reduced graphene oxide composite with a crumpled surface for high performance supercapacitor electrodes[J]. J. Mater. Chem. A, 2013,1(22):6539-6542. doi: 10.1039/c3ta11146f URL
[20]	Lv X D, Li G H, Pang Z Y, Li D W, Lei L, Lü P F, Mushtaq M, Wei Q F. Fabricate BC/Fe₃O₄@PPy 3D nanofiber film as flexible electrode for supercapacitor application[J]. J. Phys. Chem. Solids, 2018,116:153-160. doi: 10.1016/j.jpcs.2018.01.012 URL
[21]	Peng S, Xu Q, Fan L L, Wei C Z, Bao H F, Xu W L, Xu J. Flexible polypyrrole/cobalt sulfide/bacterial cellulose composite membranes for supercapacitor application[J]. Synth. Met., 2016,222:285-292. doi: 10.1016/j.synthmet.2016.11.002 URL

Sample	Tensile strength/MPa	Elastic modulus/MPa	Elongation at break/%
BC	18.0 ± 0.1	3.3 ± 0.1	8.06 ± 0.02
BC/CoNi₂S₄	23.0 ± 0.1	10.0 ± 0.2	7.92 ± 0.02
BC@PPy	20.0 ± 0.1	5.6 ± 0.1	8.01 ± 0.02
BC/CoNi₂S₄@PPy	28.0 ± 0.1	11.1 ± 0.3	6.41 ± 0.02

Sample	Specific surface area/(m²·g^-1)	Pore volume/(cm³·g^-1)
BC	82.3	0.18
PPy	19.8	0.07
BC@PPy	78.5	0.16
BC/CoNi₂S₄	109.8	0.21
BC@PPy/CoNi₂S₄	83.7	0.18
BC/CoNi₂S₄@PPy	80.2	0.20

BC/CoNi₂S₄@PPy柔性复合电极材料的制备及电化学性能

Preparations and Electrochemical Properties of BC/CoNi₂S₄@PPy Flexible Composites for Supercapacitors

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