Polyaniline growing on polylactic acid substrate towards flexible and biodegradable supercapacitors
-
摘要: 随着全球经济的快速发展、化石燃料的枯竭及环境污染等问题的加剧，社会对新型的电化学储能技术的需求日趋迫切。近年来，超级电容器由于其高的功率密度、长的循环寿命、宽的工作温度、优异的稳定性等优势引起了广泛关注。但由于传统的电容器器件大而重、制造过程繁复、且大多数不能够降解，已经不能满足社会的可持续发展需要，因此制备一种新型柔性、环保的超级电容器迫在眉睫。本工作报道了以聚乳酸(PLA)薄膜为基底，在PLA表面原位化学聚合生长聚苯胺(PANI) 制备聚苯胺-聚乳酸(PANI-PLA)可降解柔性超级电容器电极。采用SEM、FTIR、UV-Vis对电极进行形貌及结构的表征；继而对其电化学性能进行测试。测试结果显示，在三电极体系下，PANI-PLA的最大面积比电容可达到5.00 mF·cm −2(@0.10 mA·cm −2)。在二电极体系下以聚乙烯醇/硫酸(PVA/H 2SO 4)作为凝胶电解质时，PANI-PLA//PANI-PLA对称固态超级电容器面积比电容为0.20 mF·cm −2，功率密度为3.60 μW·cm −2，对应的能量密度为0.02 μW·h·cm −2(@0.004 mA·cm −2)；聚苯胺-不锈钢(PANI-SS)//PANI-PLA不对称固态超级电容器面积比电容为23.33 mF·cm −2，功率密度为30.09 μW·cm −2，对应的能量密度为1.17 μW·h·cm −2(@0.05 mA·cm −2)。Abstract: With the rapid development of global economy, the depletion of fossil fuels, and the severe environmental pollution, new electrochemical energy storage technologies are in urgent need. In recent years, supercapacitors have attracted extensive attention due to their advantages of high power density, long cycle life, wide working temperature window, and excellent cycling stability. Unfortunately, traditional supercapacitor devices are big and heavy, complicated to manufacture, and most of the time undegradable, and therefore cannot achieve sustainable development goals of the society. In this content, it is imperative to develop an innovative type of flexible and environmental friendly supercapacitor. Polyaniline-polylactic acid (PANI-PLA) biodegradable flexible supercapacitor electrode was prepared by in situ chemical polymerization method utilizing polylactic acid (PLA) film as the substrate. SEM, FTIR, and UV-Vis were performed to characterize the morphology and chemical structure of the electrode. The electrochemical tests show that under the three-electrode system, the areal specific capacitance of PANI-PLA can reach 5.00 mF·cm −2 (@0.10 mA·cm −2). Under the two-electrode system employing polyvinyl alcohol/sulfuric acid (PVA/H 2SO 4) as the gel electrolyte, the symmetric PANI-PLA//PANI-PLA solid supercapacitor delivers an areal capacitance of 0.20 mF·cm −2, a power density of 3.60 μW·cm −2, and a corresponding energy density of 0.02 μW·h·cm −2 (@0.004 mA·cm −2). The asymmetric solid supercapacitor consisting of polyaniline grown on stainless steel (PANI-SS) and PANI-PLA delivers an areal capacitance of 23.33 mF·cm −2, a power density of 30.09 μW·cm −2, and a corresponding energy density of 1.17 μW·h·cm −2 (@0.05 mA·cm −2).
-
Key words:
- polylactic acid /
- polyaniline /
- in situ chemical polymerization /
- biodegradable /
- flexible /
- solid supercapacitor
-
图 1 PANI-PLA电极的制备示意图
Figure 1. Schematic preparation of PANI-PLA electrode
PLA—Polylactic acid; APS—Ammonium persulfate; PA—Phytic acid; TSA—Para-toluene sulfonate; PANI-PLA—Polyaniline-polylactic acid; AN—Aniline
图 2 PANI-PLA的SEM图像(放大倍数40000倍) (a)、PANI-PLA SEM图像(放大倍数80000倍) (b)以及PANI-PLA液氮淬断截面SEM图像(c)
Figure 2. SEM images at lower magnitude (×40000) (a) and higher magnitude (×80000) (b) and cross-sectional image (c)
图 3 PANI-PLA的UV-Vis图谱 (a)；PANI-PLA、PANI、PLA的FTIR图谱 (b)；PANI-PLA、PANI、PLA的拉曼谱图 (c)
Figure 3. UV-Vis spectrum of PANI-PLA (a)；FTIR spectra of PANI-PLA, PANI and PLA (b)；Raman spectra of PANI-PLA, PANI and PLA (c)
图 4 PLA与PANI-PLA的CV曲线 (a)、不同掺杂酸制备得到电极的CV曲线 (b)、不同浓度APS下制备得到电极的CV曲线 (c)及1 mol/L H 2SO 4、0.3 mol/L APS制备得到电极的CV曲线 (d)
Figure 4. CV curves of PLA and PANI-PLA (a), CV curves of PANI-PLA electrodes doped with different acids (b), CV curves of PANI-PLA electrodes using different concentrations of APS (c) and CV curve of PANI-PLA using 1 mol/L H 2SO 4, 0.3 mol/L APS (d)
图 5 PANI-PLA电极的CV曲线 (a)、GCD曲线 (b)、EIS曲线 (c) 及循环稳定性 (@0.3 mA·cm −2) (d)
Figure 5. CV curves (a), GCD curves (b), EIS curve (c), and cycling stability (@ 0.3 mA·cm −2) of PANI-PLA electrode (d)
图 6 PANI-PLA//PANI-PLA对称固态超级电容器的结构
Figure 6. Schematic structure of symmetric PANI-PLA//PANI-PLA solid supercapacitor
PLA—Polylactic acid; PANI—Polyaniline; PVA—Poly vinyl alcohol.
图 7 PANI-PLA//PANI-PLA对称固态超级电容器的CV曲线 (a)、GCD曲线 (b)、EIS曲线 (c) 及循环稳定性 (@0.02 mA·cm −2) (d)
Figure 7. CV curves (a), GCD curves (b), EIS curve (c), and cycling stability (@ 0.02 mA·cm −2) of symmetric PANI-PLA//PANI-PLA solid supercapacitor (d)
图 8 PANI-SS//PANI-PLA不对称固态超级电容器的CV曲线 (a)、GCD曲线 (b)、EIS曲线 (c) 及循环稳定性 (@0.3 mA·cm −2) (d)
Figure 8. CV curves (a), GCD curves (b), EIS curve (c) and cycling stability (@ 0.3 mA·cm −2) of asymmetric PANI-SS//PANI-PLA solid supercapacitor (d)
表 1 不同薄膜超级电容器的电化学性能对比
Table 1. Comparison of PANI-SS//PANI-PLA with previously reported supercapacitors
Solid supercapacitor Substrate Preparation method Areal capacitance/
(mF·cm −2)Energy density/
(μW·h·cm −2)Power density/
(μW·cm −2)Reference PANI-SS//PANI-PLA(asymmetric) PLA &SS In situ polymerization 23.33 1.17 30.09 This work Ni 3(HITP) 2//PEDOT:PSS(asymmetric) ITO coated PET Air/liquid interface method 1.06 0.12 1.35 [ 18] TI 3C 2T x //SWCNT(asymmetric) PET Spin-casting 1.60 0.05 — [ 29] PEDOT//Ti 3C 2T x (asymmetric) Glass/PET Electrochemical deposition 2.40 — — [ 30] CQDs//GO(symmetric) Paper Inkjet printing 4.20 — — [ 31] Notes: PANI-SS//PANI-PLA—Polyaniline-poly lactic acid//polyaniline-stainless steel; Ni 3 (HITP) 2//PEDOT:PSS—Ni 3(HITP) 2//poly(3,4-ethylenedioxythiophene): poly (styrenesulfonate; TI 3C 2T x //SWCNT—TI 3C 2T x //Single-walled carbon nanotubes; PEDOT//Ti 3C 2T x (Poly(3,4-ethylenedioxythiophene)//Ti 3C 2T x ; CQDs//GO—Carbon quantum dots//graphene oxide. 
下载: 导出CSV
-
[1] ZHU C, YANG P, CHAO D, et al. All metal nitrides solid-state asymmetric supercapacitors[J]. Advanced Materials,2015,27(31):4566-4571. doi: 10.1002/adma.201501838 [2] ZHANG Y Z, WANG Y, CHENG T, et al. Printed supercapacitors: Materials, printing and applications[J]. Chemical Society Reviewes,2019,48(12):3229-3264. doi: 10.1039/C7CS00819H [3] ZANG X, ZHANG R, ZHEN Z, et al. Flexible, temperature-tolerant supercapacitor based on hybrid carbon film electrodes[J]. Nano Energy,2017,40:224-232. doi: 10.1016/j.nanoen.2017.08.026 [4] LEE G, KANG S K, WON S M, et al. Fully biodegradable microsupercapacitor for power storage in transient electronics[J]. Advanced Energy Materials,2017,7(18):1700157. doi: 10.1002/aenm.201700157 [5] DAI M Z, ZHAO D P, WU X. Research progress on transition metal oxide based electrode materials for asymmetric hybrid capacitors[J]. Chinese Chemical Letters,2020,31(9):2177-2188. doi: 10.1016/j.cclet.2020.02.017 [6] 王玖, 吴南石, 刘涛, 等. 用于超级电容器的锰钴氧化物/碳纤维材料(英文)[J]. 物理化学学报, 2020, 36(7):37-45.WANG Jiu, WU Nanshi, LIU Tao, et al. MnCo oxides supported on carbon fibers for high-performance supercapacitors[J]. Acta Physico-Chimica Sinica,2020,36(7):37-45(in Chinese). [7] 谢亚桥, 赵佳欣, 李杰兰, 等. 氯化钠模板诱导木质素基多孔炭的制备及其超级电容器性能[J]. 应用化学, 2019, 36(4):482-488.XIE Yaqiao, ZHAO Jiaxin, LI Jielan, et al. Synthesis of sodium chloride induced lignin-based porous carbon and their supercapacitor performances[J]. Chinese Journal of Applied Chemistry,2019,36(4):482-488(in Chinese). [8] 王宪朋, 刘阳, 王传栋, 等. 静电纺丝法制备小口径胶原-聚乳酸人工血管[J]. 复合材料学报, 2017, 34(11):2550-2555.WANG Xianpeng, LIU Yang, WANG Chuandong, et al. Preparation of small-diameter collagen-polylactic acid artificial blood vessel by electrospinning[J]. Acta Materiae Compositae Sinica,2017,34(11):2550-2555(in Chinese). [9] WANG Q, DU P, LIU J, et al. Facile strategy for mass production of polymer-supported film electrodes for high performance flexible symmetric solid-state supercapacitors[J]. Applied Surface Science,2019,487:295-303. doi: 10.1016/j.apsusc.2019.05.093 [10] WANG Q, WANG H, DU P, et al. Porous polylactic acid/carbon nanotubes/polyaniline composite film as flexible free-standing electrode for supercapacitors[J]. Electrochimica Acta,2019,294:312-24. doi: 10.1016/j.electacta.2018.10.108 [11] 王登武, 王芳. 聚苯胺复合材料研究进展[J]. 中国塑料, 2014, 28(11):7-11.WANG Dengwu, WANG Fang. Research progress of polyaniline composites[J]. China Plastics,2014,28(11):7-11(in Chinese). [12] 张悦, 汪广进, 孙爽, 等. 纳米结构聚苯胺及聚苯胺纳米复合材料的研究进展[J]. 材料导报, 2014, 28(3):56-59.ZHANG Yue, WANG Guangjin, SUN Shuang, et al. Research progress of nanostructure polyaniline and polyaniline nanocomposites[J]. Materials Reports,2014,28(3):56-59(in Chinese). [13] 刘连梅, 赵健伟, 陈超. 聚苯胺-石墨烯/聚酰亚胺复合导电纱的制备及其超电容特性[J]. 复合材料学报, 2020, 37(4):786-793.LIU Lianmei, ZHAO Jianwei, CHEN Chao. Preparation and supercapacitance characteristics of polyaniline-graphene/polyimide composite conductive yarn[J]. Acta Materiae Compositae Sinica,2020,37(4):786-793(in Chinese). [14] 张政, 刘洪达, 宋朝霞, 等. 聚苯胺包覆CoFe类普鲁士蓝复合材料的超电容性能[J]. 复合材料学报, 2020, 37(3):731-739.ZHANG Zheng, LIU Hongda, SONG Zhaoxia, et al. Supercapacitive performance of polyaniline coated CoFe prussian blue analogue composite[J]. Acta Materiae Compositae Sinica,2020,37(3):731-739(in Chinese). [15] 侯朝霞, 赵蓝蔚. 三维多级孔石墨烯/聚苯胺复合材料的制备及电化学性能[J]. 复合材料学报, 2019, 36(7):1591-1600.HOU Zhaoxia, ZHAO Lanwei. Preparation and electrochemical performance of 3D hierarchical porous graphene/polyaniline composites[J]. Acta Materiae Compositae Sinica,2019,36(7):1591-1600(in Chinese). [16] 朱英, 万梅香, 江雷. 聚苯胺微/纳米结构及其应用[J]. 高分子通报, 2011(10):15-32.ZHU Ying, WAN Meixiang, JIANG Lei. Self-asseblied polyaniline micro/nanostructures and their applications[J]. Polymer Bulletin,2011(10):15-32(in Chinese). [17] 徐浩, 延卫, 冯江涛. 聚苯胺的合成与聚合机理研究进展[J]. 化工进展, 2008(10):1561-1568. doi: 10.3321/j.issn:1000-6613.2008.10.014XU Hao, YAN Wei, FENG Jiangtao. Development of synthesis and polymerization mechanism of polyaniline[J]. Chemical Industry and Engineering Progress,2008(10):1561-1568(in Chinese). doi: 10.3321/j.issn:1000-6613.2008.10.014 [18] ZHAO W, CHEN T, WANG W, et al. Conductive Ni 3(HITP) 2 MOFs thin films for flexible transparent supercapacitors with high rate capability[J]. Science Bulletin,2020,65(21):1803-1811. doi: 10.1016/j.scib.2020.06.027 [19] YU P, LI Y, YU X, et al. Polyaniline nanowire arrays aligned on nitrogen-doped carbon fabric for high-performance flexible supercapacitors[J]. Langmuir,2013,29(38):12051-12058. doi: 10.1021/la402404a [20] 罗云清, 董要, 张静怡, 等. 纳米纤维形貌聚苯胺的制备与表征[J]. 东北师大学报(自然科学版), 2014, 46(2):74-77.LUO Yunqing, DONG Yao, ZHANG Jingyi, et al. Synthesis and characterization of polyaniline nanofibers[J]. Northeast Namal University (Natural Science Edition),2014,46(2):74-77(in Chinese). [21] 黄艳仙, 叶成濠. 反相微乳法合成纳米级硫酸掺杂聚苯胺及其吸附性能的研究[J]. 化学与生物工程, 2017, 34(12):43-48. doi: 10.3969/j.issn.1672-5425.2017.12.011HUANG Yanxian, YE Chenghao. Synthesis of nanoscaled sulfuric acid doped polyaniline by reverse microemulsion Method and its adsorption propety[J]. Chemtry Bioengineering,2017,34(12):43-48(in Chinese). doi: 10.3969/j.issn.1672-5425.2017.12.011 [22] 聂凤明, 朱锐钿, 张鹏, 等. PLA/PCL共混物的红外光谱和拉曼光谱分析[J]. 合成树脂及塑料, 2015, 32(1):59-62. doi: 10.3969/j.issn.1002-1396.2015.01.017NIE Fengming, ZHU Ruitian, ZHANG Peng, et al. Infrared and Raman spectra analysis of PLA/PCL blend[J]. China Synthetic Resin and Plastics,2015,32(1):59-62(in Chinese). doi: 10.3969/j.issn.1002-1396.2015.01.017 [23] 曹慧, 庞智, 高肖汉, 等. 有机酸掺杂聚苯胺的研究进展[J]. 化工进展, 2016, 35(10):3226-3235.CAO Hui, PANG Zhi, GAO Xiaohan, et al. Research progress of organic acids doped polyaniline[J]. Chemical Industry and Engineering Progress,2016,35(10):3226-3235(in Chinese). [24] 高云芳, 应婕, 徐新, 等. 不同酸掺杂聚苯胺炭化产物的制备及其电化学性能[J]. 高校化学工程学报, 2019, 33(1):193-198. doi: 10.3969/j.issn.1003-9015.2019.01.026GAO Yunfang, YING Jie, XU Xin, et al. Preparation of carbonized products of acid doped polyaniline and their electrochemical properties[J]. Journal of Chemical Engineering of Chinese Universities,2019,33(1):193-198(in Chinese). doi: 10.3969/j.issn.1003-9015.2019.01.026 [25] WEI H, WANG H, LI A, et al. Advanced porous hierarchical activated carbon derived from agricultural wastes toward high performance supercapacitors[J]. Journal of Alloys and Compounds,2020,820:153111. doi: 10.1016/j.jallcom.2019.153111 [26] WEI H, YAN X, LI Y, et al. Hybrid electrochromic fluorescent poly(DNTD)/CdSe@ZnS composite films[J]. The Journal of Physical Chemistry C,2012,116(7):4500-4510. doi: 10.1021/jp2117906 [27] LIU F, LUO S, LIU D, et al. Facile processing of free-standing polyaniline/SWCNT film as an integrated electrode for flexible supercapacitor application[J]. ACS Applied Materials Interfaces,2017,9(39):33791-33801. doi: 10.1021/acsami.7b08382 [28] ZHAO D, GUO X, GAO Y, et al. An electrochemical capacitor electrode based on porous carbon spheres hybrided with polyaniline and nanoscale ruthenium oxide[J]. ACS Applied Materials Interfaces,2012,4(10):5583-5589. doi: 10.1021/am301484s [29] ZHANG C J, ANASORI B, SERAL-ASCASO A, et al. Transparent, flexible, and conductive 2D titanium carbide (MXene) films with high volumetric capacitance[J]. Advanced Materials,2017,29(36):1702678. doi: 10.1002/adma.201702678 [30] LI J, LEVITT A, KURRA N, et al. MXene-conducting polymer electrochromic microsupercapacitors[J]. Energy Storage Materials,2019,20:455-461. doi: 10.1016/j.ensm.2019.04.028 [31] LIU J, YE J, PAN F, et al. Solid-state yet flexible supercapacitors made by inkjet-printing hybrid ink of carbon quantum dots/graphene oxide platelets on paper[J]. Science China Materials,2018,62(4):545-554. -
下载:
点击查看大图
计量
- 文章访问数: 1047
- HTML全文浏览量: 467
- PDF下载量: 105
- 被引次数: 0
