无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 604-610.DOI: 10.15541/jim20250375
秦英1(
), 姚焯1(
), 郑丽君1(
), 包硕1, 李鹏2, 郭诗淇1
收稿日期:2025-09-27
修回日期:2025-11-29
出版日期:2025-12-19
网络出版日期:2025-12-19
通讯作者:
姚 焯, 讲师. E-mail: yaozhuo1986@163.com;作者简介:秦 英(2002-), 男, 硕士研究生. E-mail: qinying0570@163.com
基金资助:
QIN Ying1(
), YAO Zhuo1(
), ZHENG Lijun1(
), BAO Shuo1, LI Peng2, GUO Shiqi1
Received:2025-09-27
Revised:2025-11-29
Published:2025-12-19
Online:2025-12-19
Contact:
YAO Zhuo, lecturer. E-mail: yaozhuo1986@163.com;About author:QIN Ying (2002-), male, Master candidate. E-mail: qinying0570@163.com
Supported by:摘要:
物联网、智能医疗和可穿戴电子设备的迅猛发展, 对高性能柔性储能器件的要求日益迫切。超级电容器(SCs)因其高功率密度和长循环寿命成为理想选择, 然而, 传统电极材料在柔性条件下常面临比电容有限、机械柔韧性不足以及长期循环稳定性不佳的共性问题, 严重制约了其在实际设备中的应用。针对上述挑战, 本研究旨在开发一种兼具高电化学性能与优异机械柔性的新型电极材料。将硫掺杂石墨烯(SGO)与两种导电聚合物——聚苯胺(PANI)和聚吡咯(PPy)进行三元复合, 混合的纳米PANI/PPy导电聚合物相互交织, 形成了高导电性的分级多孔网络。SGO中引入的硫原子有效扩大了石墨烯的层间距, 显著缓解了石墨烯片层的堆叠问题, 使其暴露更多的活性表面。电化学测试结果表明, 所制备的SGO/PANI/PPy三元复合电极材料表现出卓越的性能, 其比电容高达561.8 F·g-1, 在功率密度为250.62 W·kg-1时, 器件的能量密度达到19.51 Wh·kg-1。该电极在经历10000次连续充放电循环后, 仍能保持98.12%的初始电容。本研究证实了该三元复合材料作为柔性SCs电极的应用潜力, 为通过多组分协同和结构设计解决柔性储能器件的性能瓶颈提供了新的思路。
中图分类号:
秦英, 姚焯, 郑丽君, 包硕, 李鹏, 郭诗淇. 柔性超级电容器硫掺杂石墨烯/导电聚合物复合电极材料的制备及性能研究[J]. 无机材料学报, 2026, 41(5): 604-610.
QIN Ying, YAO Zhuo, ZHENG Lijun, BAO Shuo, LI Peng, GUO Shiqi. Sulfur-doped Graphene/Conductive Polymer Composites: Preparation and Performance as Electrode of Flexible Supercapacitor[J]. Journal of Inorganic Materials, 2026, 41(5): 604-610.
图1 (a) rGO、(b) SGO、(c) PPy、(d) PANI、(e) PPG1和(f) PPG5的SEM照片; (g) PPG5的EDS元素分布图
Fig. 1 SEM images of (a) rGO, (b) SGO, (c) PPy, (d) PANI, (e) PPG1 and (f) PPG5; (g) EDS elemental distribution mappings of PPG5
图2 rGO、SGO、PPG1、PPG5、PPG10的(a)氮气吸附-解吸等温线和孔径分布曲线(插图)以及(b) XRD图谱; (c) rGO、SGO和PPG5的拉曼光谱图
Fig. 2 (a) Nitrogen adsorption-desorption isotherms and pore size distribution curves (inset), and (b) XRD patterns of rGO, SGO, PPG1, PPG5 and PPG10; (c) Raman spectra of rGO, SGO and PPG5
图3 1 mol·L-1 KOH电解液中不同三电极体系(a)在2 mV·s-1扫描速率下的CV曲线, (b)在1 A·g-1电流密度下的GCD曲线和(c)比电容
Fig. 3 (a) CV curves at a scan rate of 2 mV·s-1, (b) GCD curves at a current density of 1 A·g-1 and (c) corresponding specific capacities of different three-electrode systems with 1 mol·L-1 KOH electrolyte
图4 PPG5柔性SSD的性能
Fig. 4 Performance of PPG5 flexible SSD (a) CV curves at scan rates of 2-100 mV·s-1; (b) GCD curves at current densities of 1-7 A·g-1; (c) Specific capacity at current densities of 1-7 A·g-1; (d) Nyquist plots; (e) Ragone plots compared with literature[30-35]; (f) Capacitance retention after 10000 cycles at a current density of 1 A·g-1; (g) Pictures of bending tests (left), and CV curves of different bending angles (middle) and different bending times (right); (h) Capacitance retention and GCD curves (inset) of different bending times. Colorful figures are available on website
| No. | Electrode | Specific capacitance/(F·g−1) | Ref. |
|---|---|---|---|
| 1 | PPy/Carbon fiber | 209 (@0.5 mA·cm-2) | [ |
| 2 | GO/PPy | 240.4 (@10 mV·s-1) | [ |
| 3 | Nanotubular graphene/PPy | 514 (@0.2 A·g-1) | [ |
| 4 | Carbon nanofibers/rGO/PPy | 405 (@0.25 mA·cm−2) | [ |
| 5 | Pt-CPPy/PANI | 325 (@0.5 A·g-1) | [ |
| 6 | 3D PPy | 168 (@2.0 mA·cm-2) | [ |
| 7 | PPy nanotubes/MoS2 | 481 (@0.5 A·g-1) | [ |
| 8 | Carbon nanotubes/PANI | 541 (@-) | [ |
| 9 | PANI-PPy/Wood | 360 (@0.2 A·g-1) | [ |
| 10 | PPy/Black phosphorus | 497.5 (@0.5 A·g-1) | [ |
| 11 | PPG5 | 561.8 (@1 A·g-1) | This work |
表1
Table 1 Comparison of PPG5 and electrode materials of reported flexible SSD[20-29]
| No. | Electrode | Specific capacitance/(F·g−1) | Ref. |
|---|---|---|---|
| 1 | PPy/Carbon fiber | 209 (@0.5 mA·cm-2) | [ |
| 2 | GO/PPy | 240.4 (@10 mV·s-1) | [ |
| 3 | Nanotubular graphene/PPy | 514 (@0.2 A·g-1) | [ |
| 4 | Carbon nanofibers/rGO/PPy | 405 (@0.25 mA·cm−2) | [ |
| 5 | Pt-CPPy/PANI | 325 (@0.5 A·g-1) | [ |
| 6 | 3D PPy | 168 (@2.0 mA·cm-2) | [ |
| 7 | PPy nanotubes/MoS2 | 481 (@0.5 A·g-1) | [ |
| 8 | Carbon nanotubes/PANI | 541 (@-) | [ |
| 9 | PANI-PPy/Wood | 360 (@0.2 A·g-1) | [ |
| 10 | PPy/Black phosphorus | 497.5 (@0.5 A·g-1) | [ |
| 11 | PPG5 | 561.8 (@1 A·g-1) | This work |
| [1] |
DING L, JIANG R, TANG Z L, et al. MXene: nanoengineering and application as electrode materials for supercapacitors. Journal of Inorganic Materials, 2023, 38(6): 619.
DOI |
| [2] |
LI Z H, TAN M J, ZHENG Y H, et al. Application of conductive metal organic frameworks in supercapacitors. Journal of Inorganic Materials, 2020, 35(7): 769.
DOI |
| [3] | 方雪, 阚侃, 马宇良, 等. 基于MXene的可印刷柔性超级电容器的研究进展. 化学与粘合, 2025, 47(4): 455. |
| [4] | 邢鑫鑫, 刘吉双, 朱岩, 等. 电极材料在柔性超级电容器中的进展. 精细化工, 2025, 42(6): 1221. |
| [5] |
AJAJ Y, AL-SALMAN H N K, HUSSEIN A M, et al. Effect and investigating of graphene nanoparticles on mechanical, physical properties of polylactic acid polymer. Case Studies in Chemical and Environmental Engineering, 2024, 9: 100612.
DOI URL |
| [6] |
LALIRE T, LONGUET C, TAGUET A. Electrical properties of graphene/multiphase polymer nanocomposites: a review. Carbon, 2024, 225: 119055.
DOI URL |
| [7] |
ZHAO Y, QIAO W, WANG H, et al. Introducing phosphoric acid to fluorinated polyimide towards high performance laser induced graphene electrodes for high energy micro-supercapacitors. Carbon, 2024, 230: 119665.
DOI URL |
| [8] |
LU J, LI Y, LI S, et al. Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells. Scientific Reports, 2016, 6: 21530.
DOI PMID |
| [9] |
ALMARZOGE M, GENCTEN M, OZSIN G. Production of sulphur-doped graphene oxide as an anode material for Na-ion batteries. ECS Journal of Solid State Science and Technology, 2024, 13(7): 071001.
DOI |
| [10] |
ZHU S, ZHANG F, LU H G, et al. Flash nitrogen-doped graphene for high-rate supercapacitors. ACS Materials Letters, 2022, 4(10): 1863.
DOI URL |
| [11] |
ELUMALAI P, CHARLES J, KENNEDY L J. Fabrication of PPy/PANI/MnO2-based electrode and its electrochemical evaluation for supercapacitor applications. Ionics, 2024, 30(11): 7397.
DOI |
| [12] |
WANG H, LIN J, SHEN Z X. Polyaniline (PANi) based electrode materials for energy storage and conversion. Journal of Science: Advanced Materials and Devices, 2016, 1(3): 225.
DOI URL |
| [13] |
TUNDWAL A, KUMAR H, BINOJ B J, et al. Developments in conducting polymer-, metal oxide-, and carbon nanotube-based composite electrode materials for supercapacitors: a review. RSC Advances, 2024, 14(14): 9406.
DOI PMID |
| [14] |
TROPP J, COLLINS C P, XIE X, et al. Conducting polymer nanoparticles with intrinsic aqueous dispersibility for conductive hydrogels. Advanced Materials, 2024, 36(1): 2306691.
DOI URL |
| [15] |
MARWAT M A, ISHFAQ S, ADAM K M, et al. Enhancing supercapacitor performance of Ni-Co-Mn metal-organic frameworks by compositing it with polyaniline and reduced graphene oxide. RSC Advances, 2024, 14(3): 2102.
DOI PMID |
| [16] |
ZHAO J, WU J, LI B, et al. Facile synthesis of polypyrrole nanowires for high-performance supercapacitor electrode materials. Progress in Natural Science: Materials International, 2016, 26(3): 237.
DOI URL |
| [17] | SUN X, GAO X, CHEN J, et al. Ultrasmall Ru nanoparticles highly dispersed on sulfur-doped graphene for HER with high electrocatalytic performance. ACS Applied Materials & Interfaces, 2020, 12(43): 48591. |
| [18] | 马茹萍, 罗剑, 吕彦, 等. 锰氧化物/聚苯胺/石墨烯三元复合电极材料的制备及电化学性能. 武汉工程大学学报, 2023, 45(6): 641. |
| [19] |
蓝瑞嵩, 刘丽华, 张倩, 等. 硫掺杂石墨烯作为MFC阴极性能和生物毒性检测. 化工进展, 2024, 43(6): 3430.
DOI |
| [20] |
DIANATDAR A, MUKHERJEE A, BOSE R K. Oxidative chemical vapor deposition of polypyrrole onto carbon fabric for flexible supercapacitive electrode material. Synthetic Metals, 2023, 298: 117444.
DOI URL |
| [21] |
KANDASAMY S K, KANDASAMY K. Structural and electrochemical analysis of microwave-assisted synthesis of graphene/polypyrrole nanocomposite for supercapacitor. International Journal of Electrochemical Science, 2019, 14(5): 4718.
DOI URL |
| [22] |
KASHANI H, CHEN L, ITO Y, et al. Bicontinuous nanotubular graphene-polypyrrole hybrid for high performance flexible supercapacitors. Nano Energy, 2016, 19: 391.
DOI URL |
| [23] | ZHANG Y, SHANG Z, SHEN M, et al. Cellulose nanofibers/ reduced graphene oxide/polypyrrole aerogel electrodes for high- capacitance flexible all-solid-state supercapacitors. ACS Sustainable Chemistry & Engineering, 2019, 7(13): 11175. |
| [24] |
OH J, KIM Y K, LEE J S, et al. Highly porous structured polyaniline nanocomposites for scalable and flexible high-performance supercapacitors. Nanoscale, 2019, 11(13): 6462.
DOI PMID |
| [25] |
GUO M, ZHOU Y, SUN H, et al. Interconnected polypyrrole nanostructure for high-performance all-solid-state flexible supercapacitor. Electrochimica Acta, 2019, 298: 918.
DOI URL |
| [26] |
YADAV R, SAINI A, CHOUDHARY J, et al. High-performance flexible supercapacitor based on morphology tuned polypyrrole/ molybdenum disulfide nanocomposites. Energy Storage, 2023, 5(8): e477.
DOI URL |
| [27] |
PANASENKO I V, BULAVSKIY M O, IURCHENKOVA A A, et al. Flexible supercapacitors based on free-standing polyaniline/ single-walled carbon nanotube films. Journal of Power Sources, 2022, 541: 231691.
DOI URL |
| [28] |
JIAO Y, LI J. Polyaniline-polypyrrole nanocomposites using a green and porous wood as support for supercapacitors. Frontiers of Agricultural Science and Engineering, 2019, 6(2): 137.
DOI URL |
| [29] | LUO S, ZHAO J, ZOU J, et al. Self-standing polypyrrole/black phosphorus laminated film: promising electrode for flexible supercapacitor with enhanced capacitance and cycling stability. ACS Applied Materials & Interfaces, 2018, 10(4): 3538. |
| [30] |
ÇEKIÇ M G, KARACA E, PEKMEZ N Ö. A facile one-step electrosynthesis of polypyrrole/nano-SbOx composite for supercapacitors. Synthetic Metals, 2023, 293: 117262.
DOI URL |
| [31] |
ARYADEVI G, JOSEPH G, MATHEW V R, et al. Optimizing the electrochemical properties of PPy/ZnO nanocomposites for supercapacitor electrode. Journal of Materials Science: Materials in Electronics, 2024, 35(21): 1490.
DOI |
| [32] |
YUKSEL R, ALPUGAN E, UNALAN H E. Coaxial silver nanowire/polypyrrole nanocomposite supercapacitors. Organic Electronics, 2018, 52: 272.
DOI URL |
| [33] |
LI Z, YAO M, ZHANG L, et al. Preparation of flexible and free-standing polypyrrole/graphene film electrodes for supercapacitors. New Journal of Chemistry, 2022, 46(37): 17776.
DOI URL |
| [34] |
ROOHI Z, MIGHRI F, ZHANG Z. A flexible, lightweight, and high-performance supercapacitor made of nanofibrous polypyrrole electrodes. ACS Omega, 2025, 10(29): 31600.
DOI URL |
| [35] |
KWON H, HAN D J, LEE B Y. All-solid-state flexible supercapacitor based on nanotube-reinforced polypyrrole hollowed structures. RSC Advances, 2020, 10(68): 41495.
DOI PMID |
| [1] | 丁宁宁, 孙建华, 韦旭, 孙丽霞. 对氨基苯磺酸修饰MoO3/PPy复合材料室温下对氨气的监测[J]. 无机材料学报, 2024, 39(11): 1245-1253. |
| [2] | 伍凡, 赵梓俨, 黎邦鑫, 董帆, 周莹. Bi2O2CO3/PPy界面氧空位构建及其可见光下NO氧化机理研究[J]. 无机材料学报, 2020, 35(5): 541-548. |
| [3] | 张伟,高鹏,侯成义,李耀刚,张青红,王宏志. 基于ZnO复合材料的芯片式pH和温度传感器[J]. 无机材料学报, 2020, 35(4): 416-422. |
| [4] | 胡茜,刘洪波,夏笑虹,谷智强. 聚苯胺炭柱撑石墨烯复合材料的制备及其电化学性能的研究[J]. 无机材料学报, 2019, 34(2): 145-151. |
| [5] | 邓敏, 江奇, 方渊, 李欢, 邱家欣, 卢晓英. 碳纳米管/聚苯胺化学修饰电极的制备及其对抗坏血酸的检测[J]. 无机材料学报, 2018, 33(1): 53-59. |
| [6] | 柴二亚, 潘俊安, 袁国龙, 程豪, 安峰, 谢淑红. 聚苯胺包覆蛋白石页岩/硫复合材料的制备及其电化学性能[J]. 无机材料学报, 2017, 32(11): 1165-1170. |
| [7] | 张玉晖, 易清风, 刘小平, 向柏霖. 金属掺杂聚吡咯碳化物PPY-M的制备及其氧还原反应电催化活性[J]. 无机材料学报, 2014, 29(3): 269-274. |
| [8] | 肖兴中, 易清风. MnO2/SMWCNT/PANI三元复合材料的合成及其电化学电容性能[J]. 无机材料学报, 2013, 28(8): 825-830. |
| [9] | 刘建华, 张施露, 于 美, 安军伟, 李松梅. 石墨烯接枝聚吡咯复合物的原位合成及其电容特性研究[J]. 无机材料学报, 2013, 28(4): 403-408. |
| [10] | 张晓萍, 兰 章, 陈 琳, 高素雯, 吴晚霞, 阙兰芳, 张晓佩. 硫化亚锡敏化纳晶TiO2膜的制备及光电性能研究[J]. 无机材料学报, 2013, 28(10): 1093-1097. |
| [11] | 喻冬秀. 导电导磁改性短碳纤维的制备及电磁特性的研究[J]. 无机材料学报, 2010, 25(5): 463-467. |
| [12] | 赵晓锋,江 奇,郭亚楠,张 楠,单长星,赵 勇. 有机化学合成法制备碳纳米管/聚苯胺复合材料[J]. 无机材料学报, 2010, 25(1): 91-95. |
| [13] | 徐小川,王春芬,姚琴,陈立东,冯楚德. 二次电化学沉积法制备聚苯胺-碲化铋复合纳米棒[J]. 无机材料学报, 2006, 21(6): 1482-1486. |
| 阅读次数 | ||||||
|
全文 |
|
|||||
|
摘要 |
|
|||||