Preparation and electrochemical properties of triphenyl blue doped graphene/polypyrrole composite aerogels
-
摘要: 将具有独特掺杂结构的聚吡咯(PPy)与丰富多孔结构的石墨烯(GE)气凝胶复合,可实现两种材料优势互补。通过一步水热法制备了曲利苯蓝(TB)掺杂GE/PPy复合气凝胶,采用SEM、FTIR、XRD、Raman和XPS对复合材料的形貌、化学结构、掺杂结构进行表征。结果表明,TB掺杂PPy/GE复合气凝胶呈现出三维多孔网络结构,复合气凝胶中氧化石墨烯(GO)被还原的同时,导电PPy被成功聚合,TB的引入有利于复合气凝胶掺杂水平的提高。电化学测试分析表明, TB掺杂浓度达到5 mmol·L−1时,复合气凝胶(TB-5/PPy-GO)可获得最高比电容(392 F·g−1),10000次充/放电循环后,比电容保持率可达85%;将TB-5/PPy-GO、活性炭分别作为正、负极组装为非对称超级电容器,其在功率密度为400 W·kg−1时,能量密度高达35.89 W·h·kg−1,表现出良好的超电容特性。Abstract: The combination of polypyrrole (PPy) with a unique doping structure and graphene (GE) aerogel with a rich porous structure can realize the complementary advantages of the two materials. Triphenyl blue (TB) doped GE/PPy composite aerogel was prepared by one-step hydrothermal method. The SEM, FTIR, XRD, Raman spectroscopy and XPS were used to characterize the morphological structure, chemical structure, and doping structure of the composite electrode material. The results showed that TB doped GE/PPy composite aerogel provided three porous network structure. Conductive PPy can be successfully polymerized as graphene oxide (GO) was reduced in the composite hydrogel. Due to the introduction of TB, the doping level of the composite hydrogel has been increased. The electrochemical tests demonstrated that the prepared TB-5/PPy-GO (TB concentration of 5 mmol·L−1) aerogel exhibited superior specific capacitance of 392 F·g−1 at 1 A·g−1. The capacitance retention rate can reach 85% after 10 000 cycles. The hybrid device, which was assembled with TB-5/PPy-GO and active carbon as positive and negative electrode, respectively, demonstrated maximum energy of 35.89 W·h·kg−1 at 400 W·kg−1, suggesting its good supercapacitive performances.
-
Key words:
- supercapacitor /
- polypyrrole /
- graphene /
- aerogl /
- triphenyl blue /
- electrochemical properties
-
图 7 PPy-GO、TB/PPy-GO (10 mV·s−1) (a),TB-5/PPy-GO (b)的CV曲线;(c) PPy-GO、TB/PPy-GO的GCD曲线(1 A·g−1);(d) TB-5/PPy-GO的GCD曲线;(e) PPy-GO、GBPs的EIS;(f) TB-5/PPy-GO的10 000圈循环稳定性测试(10 A·g−1)
Figure 7. CV curves of PPy-GO, TB/PPy-GO (10 mV·s−1) (a) and TB-5/PPy-GO (b); (c) GCD curves of PPy-GO, TB/PPy-GO (1 A·g−1); (d) GCD curves of TB-5/PPy-GO; (e) EIS of PPy-GO, TB/PPy-GO; (f) 10 000 cycle stability test of TB-5/PPy-GO (10 A·g−1)
t—Discharge time; −Z''—Imaginary impedance; Z'—Real impedance
图 9 TB-5/PPy-GO器件不同电压下的CV曲线(10 mV·s−1) (a),在0°、90°、135°、180°角度下弯折100次后CV (10 mV·s−1) (b)、GCD (1 A·g−1) (c)、EIS曲线 (d)
Figure 9. CV curves of TB-5/PPy-GO devices at different voltages (10 mV·s−1) (a), after bending 100 times at 0°, 90°, 135°, and 180° angles CV (10 mV·s−1) (b), GCD (1 A·g−1) (c), EIS curves(d)
表 1 聚吡咯(PPy)/TB/氧化石墨烯(GO)复合气凝胶的原材料配比
Table 1. Ratios of the raw materials used in the polypyrrole (PPy)/TB/graphene oxide (GO) composite aerogels
Sample Py/mg GO/mg TB/(mmol·L−1) PPy-GO 140 56 0 TB-1/PPy-GO 140 56 1 TB-3/PPy-GO 140 56 3 TB-5/PPy-GO 140 56 5 TB-8/PPy-GO 140 56 8 Note: PPy-GO, TB-1/PPy-GO, TB-3/PPy-GO, TB-5/PPy-GO and TB-8/PPy-GO—Concentration of TB in the prepared composite aerogel as 0, 1, 3, 5, 8 mmol·L−1, respectively. -
[1] SANATI S, ABAZARI R, ALBERO J, et al. Metal-organic framework derived bimetallic materials for electrochemical energy storage[J]. Angewandte Chemie International Edition,2021,60(20):11048-11067. doi: 10.1002/anie.202010093 [2] ZHANG T Q, MAO Z F, SHI X J, et al. Tissue-derived carbon microbelt paper: A high-initial-coulombic-efficiency and low-discharge-platform K+-storage anode for 4.5 V hybrid capacitors[J]. Energy & Environmental Science,2022,15(1):158-168. [3] FEI R X, WANG H W, WANG Q, et al. In situ hard-template synthesis of hollow bowl-like carbon: A potential versatile platform for sodium and zinc ion capacitors[J]. Advanced Energy Materials,2020,10(47):2002741. doi: 10.1002/aenm.202002741 [4] SUN R, QIN Z X, LIU X L, et al. Intercalation mechanism of the ammonium vanadate (NH4V4O10) 3D decussate superstructure as the cathode for high-performance aqueous zinc-ion batteries[J]. ACS Sustainable Chemistry & Engineering,2021,9(35):11769-11777. [5] FAN W, SHI Y Q, GAO W, et al. Graphene-carbon nanotube aerogel with a scroll-interconnected-sheet structure as an advanced framework for a high-performance asymmetric supercapacitor electrode[J]. ACS Applied Nano Materials,2018,1(9):4435-4441. doi: 10.1021/acsanm.8b00605 [6] SHAO Y L, EL-KADY M F, SUN J Y, et al. Design and mechanisms of asymmetric supercapacitors[J]. Chemical Reviews,2018,118(18):9233-9280. doi: 10.1021/acs.chemrev.8b00252 [7] BHOJANE P. Recent advances and fundamentals of Pseudocapacitors: Materials, mechanism, and its understanding[J]. Journal of Energy Storage,2022,45:103654. doi: 10.1016/j.est.2021.103654 [8] GONÇALVES R, PAIVA R S, LIMA T M, et al. Carbon nitride/polypyrrole composite supercapacitor: Boosting performance and stability[J]. Electrochimica Acta,2021,368:137570. doi: 10.1016/j.electacta.2020.137570 [9] ZHAN Y, HU Y, CHEN Y, et al. In-situ synthesis of flexible nanocellulose/carbon nanotube/polypyrrole hydrogels for high-performance solid-state supercapacitors[J]. Cellulose,2021,28(11):7097-7108. doi: 10.1007/s10570-021-03998-1 [10] WEI W, TANG Q L, LIU T, et al. Preparation and properties of polypyrrole/polyamide 6 nanocomposite film with core-shell architecture for the high-performance flexible supercapacitor[J]. Composites Communications,2020,22:100468. doi: 10.1016/j.coco.2020.100468 [11] 辛国祥, 王蒙蒙, 翟耀, 等. 一步法合成具有优异循环性能的聚苯胺纳米线/自支撑石墨烯复合材料[J]. 复合材料学报, 2021, 38(4): 1272-1282.XIN Guoxiang, WANG Mengmeng, ZHAI Yao, et al. One-step synthesis of polyaniline nanowire/self-supported graphene composite with excellent cycling stability[J]. Acta Materiae Compositae Sinica, 2021, 38(4):1272-1282(in Chinese). [12] DONG C, ZHANG X L, YU Y J, et al. An ionic liquid-modified RGO/polyaniline composite for high-performance flexible all-solid-state supercapacitors[J]. Chemical Communications,2020,56(80):11993-11996. doi: 10.1039/D0CC04691D [13] 杨云强, 张佳丽, 章海霞, 等. 聚 3, 4-乙烯二氧噻吩/纳米多孔金复合电极的制备及其在超级电容器中的应用[J]. 复合材料学报, 2020, 37(12): 3160-3167.YANG Yunqiang, ZHANG Jiali, ZHANG Haixia, et al. Preparation of poly 3, 4-ethylenedioxythiophene/nanoporous gold composite electrode and its application in supercapacitors[J]. Acta Materiae Compositae Sinica, 2020, 37(12): 3160-3167(in Chinese). [14] ZHOU M Y, LI Y Q, GONG Q, et al. Polythiophene grafted onto single-wall carbon nanotubes through oligo(ethylene oxide) linkages for supercapacitor devices with enhanced electrochemical performance[J]. ChemElectroChem,2019,6(17):4595-4607. doi: 10.1002/celc.201901074 [15] ZHANG Q R, LI W Z, ZHU Z T, et al. Facile growth of hierarchical SnO2@PPy composites on carbon cloth as all-solid-state flexible supercapacitors[J]. Journal of Alloys and Compounds,2022,906:164275. doi: 10.1016/j.jallcom.2022.164275 [16] SHEN M, CHEN L, REN S B, et al. Construction of CuO/PPy heterojunction nanowire arrays on copper foam as integrated binder-free electrode material for high-performance supercapacitor[J]. Journal of Electroanalytical Chemistry,2021,891:115272. doi: 10.1016/j.jelechem.2021.115272 [17] LI J M, LI X, WEI W L, et al. Hollow core-shell polypyrrole@poly(1, 5-diaminoanthraquinone) compo-sites with superior electrochemical performance for supercapacitors[J]. Electrochimica Acta,2021,395:139193. doi: 10.1016/j.electacta.2021.139193 [18] 周浪, 王涛. 石墨烯/功能聚合物复合材料[J]. 复合材料学报, 2020, 37(5):997-1014.ZHOU Lang, WANG Tao. Graphene/functional polymer composites[J]. Acta Materiae Compositae Sinica,2020,37(5):997-1014(in Chinese). [19] WANG Y Y, LIU G Q, LIU Y F, et al. Heterostructural conductive polymer with multi-dimensional carbon materials for capacitive energy storage[J]. Applied Surface Science,2021,558:149910. doi: 10.1016/j.apsusc.2021.149910 [20] HAN Y Q, GAO X X, HE M S, et al. Organic sulfate modified carbon nantube/polypyrrole core-shell nanocomposites with improved electrochemical performance[J]. Synthetic Metals, 2019, 217: 288-294. [21] PARK J W, PARK S J, KWON O S, et al. In situ synthesis of graphene/polyselenophene nanohybrid materials as highly flexible energy storage electrodes[J]. Chemistry of Materials,2014,26(7):2354-2360. doi: 10.1021/cm500577v [22] YANG J J, WENG W, LIANG Y X, et al. Heterogeneous graphene/polypyrrole multilayered microtube with enhanced capacitance[J]. Electrochimica Acta,2019,304:378-385. doi: 10.1016/j.electacta.2019.03.015 [23] YE S, FENG J. Self-assembled three-dimensional hierarchical graphene/polypyrrole nanotube hybrid aerogel and its application for supercapacitors[J]. ACS Applied Materials & Interfaces 2014, 6(12): 9671-9679. [24] 喻航达. 石墨烯-导电高分子复合凝胶的制备与性能研究[D]. 武汉: 武汉工程大学, 2019.YU Hangda. Preparation and properties of graphene/conductive polymer composite gel[D]. Wuhan: Wuhan Institute of Technology, 2019(in Chinese). [25] ZHANG E H, LIU W F, LIU X G, et al. Pulse electrochemical synthesis of polypyrrole/graphene oxide@graphene aerogel for high-performance supercapacitor[J]. RSC Advances,2020,10(20):11966-11970. doi: 10.1039/D0RA01181A [26] YANG J B, JI X X, LIU L B, et al. One step fabrication of graphene/polypyrrole/Ag composite electrode towards compressible supercapacitor[J]. Journal of Alloys and Compounds,2020,820:153081. doi: 10.1016/j.jallcom.2019.153081 [27] YANG C Y, ZHANG P F, NAUTIYAL A, et al. Tunable three-dimensional nanostructured conductive polymer hydrogels for energy-storage applications[J]. ACS Applied Materials & Interfaces,2019,11(4):4258-4267. [28] ALVES A P P, KOIZUMI R, SAMANTA A, et al. One-step electrodeposited 3D-ternary composite of zirconia nanoparticles, rGO and polypyrrole with enhanced supercapacitor performance[J]. Nano Energy,2017,31:225-232. doi: 10.1016/j.nanoen.2016.11.018 [29] RAJESH M, RAJ C J, KIM B C, et al. Supercapacitive studies on electropolymerized natural organic phosphate doped polypyrrole thin films[J]. Electrochimica Acta,2016,220:373-383. doi: 10.1016/j.electacta.2016.10.118 [30] YANG J, WANG X, LI B, et al. Novel iron/cobalt-containing polypyrrole hydrogel-derived trifunctional electrocatalyst for self-powered overall water splitting[J]. Advanced Functional Materials,2017,27(17):1606497. doi: 10.1002/adfm.201606497 [31] MARCANO D C, KOSYNKIN D V, BERLIN J M, et al. Improved synthesis of graphene oxide[J]. ACS Nano,2010,4(8):4806-4814. doi: 10.1021/nn1006368 [32] WANG Q L, SONG H M, LI W Q, et al. Facile synthesis of polypyrrole/graphene composite aerogel with Alizarin Red S as reactive dopant for high-performance flexible supercapacitor[J]. Journal of Power Sources,2022,517:230737. doi: 10.1016/j.jpowsour.2021.230737 [33] SHI K Y, ZHITOMIRSKY I. Polypyrrole nanofiber-carbon nanotube electrodes for supercapacitors with high mass loading obtained using an organic dye as a co-dispersant[J]. Journal of Materials Chemistry A,2013,1(38):11614-11622. doi: 10.1039/c3ta12466e [34] 黄凯. 三维石墨烯及其复合材料的制备与性能研究[D]. 上海: 中国科学院大学, 2018.HUANG Kai. The study on preparation and properties of three dimensional graphene and graphene-based compo-sites[D]. Shanghai: Chinese Academy of Sciences, 2018(in Chinese). [35] TANG L H, WANG Y, LI Y M, et al. Preparation, structure, and electrochemical properties of reduced graphene sheet films[J]. Advanced Functional Materials,2009,19(17):2782-2789. doi: 10.1002/adfm.200900377 [36] LIM S P, PANDIKUMAR A, LIM Y S, et al. In-situ electrochemically deposited polypyrrole nanoparticles incorporated reduced graphene oxide as an efficient counter electrode for platinum-free dye-sensitized solar cells[J]. Scientific Reports,2014,4:5305. [37] CAO A P, CHEN Z X, WANG Y K, et al. Redox-active doped polypyrrole microspheres induced by phosphomolybdic acid as supercapacitor electrode materials[J]. Synthetic Metals,2019,252:135-141. doi: 10.1016/j.synthmet.2019.04.019