基于PEDOT与MnO₂复合材料的电极构筑及其在超级电容器中的电化学性能

Conducting Polymer PEDOT@MnO ₂ Composite Construction and Electrochemical Behavior

摘要

超级电容器的性能受到电子材料的性质的影响,其中二氧化锰因具有本征的赝电容特性而备受关注,但其离子、电子电导率较差,限制了其实际应用。为此,开展了导电聚合物3,4-乙烯二氧噻吩(poly 3,4-ethylenedioxythiophene,PEDOT)与二氧化锰耦合效应研究。PEDOT具有高的电荷迁移率、较好的化学稳定性,但其循环稳定性较差。通过改变负载顺序和负载工艺分别在碳纤维布(Carbon cloth,CC)上制备了PEDOT/MnO₂/CC和MnO₂/PEDOT/CC这2种复合材料。结果表明:PEDOT/MnO₂/CC的电容性能要远优于MnO₂/PEDOT/CC的,其在5 mA/cm²电流密度下能达到1.26 F/cm²的面积比电容。进一步将制得的PEDOT/MnO₂/CC复合电极材料组装成对称超级电容器,该器件展现出了优异的功率密度(990 mW/cm²)和能量密度(89 mWh/cm²)。此外,该器件在1 mA/cm²的电流密度下连续充放1 500次后,电容保持率为97%,循环稳定性优良。研究发现:PEDOT/MnO₂/CC优异的电容性能和循环稳定性可归因于其独特的三维棒状和颗粒状的微观结构,这种复合结构具有较大的比表面积和更多的活性位点,且利于离子和电子扩散。该研究将为高功能能量存储和转化用电极材料的设计/构筑提供新思路。

Abstract

Supercapacitors, as a new type of green energy storage device, offer advantages such as high power density, rapid charge and discharge rates, and environmental friendliness, proposing a potential solution to the energy crisis. The electrode material is a significant factor affecting the performance of supercapacitors. Manganese dioxide has attracted considerable attention due to its intrinsic pseudocapacitive characteristics, however, its poor ionic and electronic conductivity limits its practical application. To address this, this study conducted research on the coupling of conductive poly (3,4-ethylenedioxythiophene) (PEDOT) with manganese dioxide. PEDOT possesses a high charge transfer rate and good chemical stability, however, its cycle stability is relatively poor. Two composite materials, PEDOT/MnO₂/CC and MnO₂/PEDOT/CC, were prepared by altering the loading sequence and process. Results show that the capacitive performance of PEDOT/MnO₂/CC is significantly better than that of MnO₂/PEDOT/CC, achieving an area specific capacitance of 1.26 F/cm² at a current density of 5 mA/cm², and the fabricated PEDOT/MnO₂/CC composite electrode materials were assembled into a symmetric supercapacitor, and the device exhibits excellent power density (990 mWh/cm²) and energy density (89 mWh/cm²). The superior capacitive performance and cycle stability of PEDOT/MnO₂/CC can be attributed to its unique three-dimensional rod-like and granular microstructure, which has a larger specific surface area and more active sites, facilitating the diffusion of ions and electrons. This research will provide new insights for the design and construction of electrode materials for high-performance energy storage and conversion.

关键词

二氧化锰 / 聚3,4-乙烯二氧噻吩(PEDOT) / 有机-无机复合 / 电极材料 / 超级电容器 / 耦合效应

Key words

MnO₂ / poly 3,4-ethylenedioxythiophene (PEDOT) / organic-inorganic composite / electrode material / supercapacitor / coupling

参考文献

[1] Forouzandeh P, Kumaravel V, Pillai S C . Electrode materials for supercapacitors: a review of recent advances[J]. Catalysts, 2020, 10(9): 969.

[2] Navarro G, Torres J, Blanco M, et al. Present and future of supercapacitor technology applied to powertrains, renewable generation and grid connection applications[J]. Energies, 2021, 14(11): 3060.

[3] Raghutla C, Chittedi K R . The effect of technological innovation and clean energy consumption on carbon neutrality in top clean energy—consuming countries: a panel estimation[J]. Energy Strategy Reviews, 2023, 47: 101091.

[4] Zhang H N, Shen R R, Zhang X P, et al. Implications and pathways of China's carbon neutrality: a review[J]. Advances in Climate Change Research, 2022, 18(2): 240.

[5] Yang Z, Liu X H, He X X, et al. Rechargeable sodium—based hybrid metal—ion batteries toward advanced energy storage[J]. Advanced Functional Materials, 2021, 31(8): 2006457.

[6] Tasnin W, Saikia L C . Impact of renewables and FACT device on deregulated thermal system having sine cosine algorithm optimised fractional order cascade controller[J]. IET Renewable Power Generation, 2019, 13(9): 1420-1430.

[7] Wan L, He C, Chen D, et al. In situ grown NiFeP@NiCo₂S₄ nanosheet arrays on carbon cloth for asymmetric supercapacitors [J]. Chemical Engineering Journal, 2020, 399: 125778.

[8] Wang B, Ruan T, Chen Y, et al. Graphene—based composites for electrochemical energy storage[J]. Energy Storage Materials, 2020, 24: 22-51.

[9] Xu J, Shi Y, Cheng J, et al. Recent research of NiCo₂O₄/carbon composites for supercapacitors [J]. Surfaces, 2022, 5(3): 334-349.

[10] Gu G, Lao Y, Ji Y, et al. Development of hybrid supercapacitor and lead—acid battery power storage systems[J]. International Journal of Low—Carbon Technologies, 2023, 18: 159-166.

[11] Shafi I, Liang E, Li B . Ultrafine chromium oxide (Cr₂O₃) nanoparticles as a pseudocapacitive electrode material for supercapacitors [J]. Journal of Alloys and Compounds, 2021, 851: 156046.

[12] Ajay K, Dinesh M . Influence of various activated carbon based electrode materials in the performance of super capacitor[J]. Materials Science and Engineering, 2018, 310(1): 012083.

[13] Lakshmi K S, Vedhanarayanan B . High—performance supercapacitors: a comprehensive review on paradigm shift of conventional energy storage devices[J]. Batteries, 2023, 9(4): 202.

[14] Sharma K, Arora A, Tripathi S K . Review of supercapacitors: materials and devices[J]. Journal of Energy Storage, 2019, 21: 801-825.

[15] Sharma P, Kumar V . Current technology of supercapacitors: a review[J]. Journal of Electronic Materials, 2020, 49(6): 3520-3532.

[16] Tong L, Wu C, Hou J, et al. Construction of hollow mesoporous PPy microsphere nanostructures coated with MnO₂ nanosheet as high—performance electrodes for supercapacitors [J]. Journal of Electroanalytical Chemistry, 2023, 928: 117074.

[17] Shen X, Wei X, Wang T, et al. Solution—processable hierarchical SiNW/PEDOT/MnO_x electrodes for high—performance supercapacitors [J]. Materials Chemistry Frontiers, 2022, 6(19): 2894-904.

[18] Song K, Yang R, Chen X, et al. The structures of CoFe₂O₄/PEDOT electrodes effect on the stability and specific capacity for electrochemical energy storage [J]. Applied Surface Science, 2021, 542: 148670.

[19] Song J, Li W, Song K, et al. The interwoven porous CoCHH@PEDOT nanowire network structure improves electrochemical performance of carbon cloth for flexible supercapacitors[J]. Applied Surface Science, 2021, 562: 150198.

[20] Song K, Yang R, Chen X, et al. The structures of CoFe₂O₄/PEDOT electrodes effect on the stability and specific capacity for electrochemical energy storage [J]. Applied Surface Science, 2021, 542: 148670.

[21] Chen M, Fan H, Zhang Y, et al. Coupling PEDOT on mesoporous vanadium nitride arrays for advanced flexible all—solid—state supercapacitors[J]. Small, 2020, 16(37): 1-9, 2021, 542: 148670.

[22] 王钊 . 碳纤维基柔性电极的电化学性能研究及在超级电容器中的应用[D]. 长春: 长春工业大学, 2023.

[23] Wang Z. Study on the electrochemical performance of carbon fiber based flexible electrodes and application in supercapacitors[D]. Changchun: Changchun University of Technology, 2023. (in Chinese)

[24] Chen M, Fan H, Zhang Y, et al. Coupling PEDOT on mesoporous vanadium nitride arrays for advanced flexible all—solid—state supercapacitors[J]. Small, 2020, 16(37): 1-9.

基金资助

国家自然科学基金资助项目(22075290)