聚苯胺/二氧化锰/聚吡咯复合纳米球的制备及其电化学储能性

doi:10.11949/0438-1157.20221497

摘要/Abstract

摘要：

利用化学合成法成功制备了尺寸分布均一的聚吡咯（polypyrrole，PPy）纳米球，通过酸解法将KMnO₄分解成MnO₂纳米片原位生长在PPy纳米球表面，然后采用稀溶液合成法将聚苯胺（polyaniline，PANI）生长在MnO₂表面，得到PANI@MnO₂@PPy三元复合材料。扫描电子显微镜、透射电镜、拉曼光谱、X射线粉末衍射和X射线光电子能谱证实PANI@MnO₂@PPy成功合成。通过溶液涂覆法，将PANI@MnO₂@PPy三元复合材料制备成电极并测定其电化学储能性，在1 mol·L^-1 Na₂SO₄电解质溶液中，当电流密度为0.5 A·g^-1时，PANI@MnO₂@PPy电极的比电容量约为357 F·g^-1，是MnO₂@PPy电极的1.96倍；当电流密度从0.5 A·g^-1增加到5.0 A·g^-1时，PANI@MnO₂@PPy电极的电容损失率为26.9%，说明复合体系具有良好的倍率性能；当电流密度为10.0 A·g^-1时，PPy、MnO₂@PPy和PANI@MnO₂@PPy电极经过1000次的循环恒电流充放电后电容保持率分别为45%、70%和76%，其中PANI@MnO₂@PPy电极电容保持率最高，说明PPy、PANI 和MnO₂三者的协同作用，能有效提高三元复合体系的长寿命循环稳定性。

关键词: 聚合物, 复合材料, 纳米结构, 电极材料, 超级电容器

Abstract:

Polypyrrole (PPy) nanospheres with uniform size distribution were successfully prepared by chemical synthesis, and then KMnO₄ was decomposed into MnO₂ by acid hydrolysis. Finally, the polyaniline (PANI) in-situ grew on the surface of MnO₂ by dilute solution synthesis to form PANI@MnO₂@PPy ternary composite. Scanning electron microscope, transmission electron microscope, Raman spectroscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy confirmed that the PANI@MnO₂@PPy was successfully synthesized. The PANI@MnO₂@PPy ternary composite was prepared as electrode by solution coating and its electrochemical energy storage capacity was measured in 1 mol·L^-1 Na₂SO₄ electrolyte solution. The specific capacitance of PANI@MnO₂@PPy electrode was about 357 F·g^-1 at a current density of 0.5 A·g^-1, which was 1.96 times compare to the MnO₂@PPy electrode. The capacitance loss of PANI@MnO₂@PPy electrode was 26.9% when the current density increased from 0.5 A·g^-1 to 5.0 A·g^-1, indicating it had good rate capability. When the current density was 10.0 A·g^-1, the capacitance retention rate of PPy, MnO₂@PPy and PANI@MnO₂@PPy electrodes were 45%, 70% and 76% respectively, after 1000 cycles of constant current charge and discharge, which showed that the chemical modification of PPy through PANI and MnO₂could effectively improve the long-life cycle stability of PANI@MnO₂@PPy.

Key words: polymers, composites, nanostructure, electrode materials, supercapacitor

中图分类号:

O 631

徐东, 田杜, 陈龙, 张禹, 尤庆亮, 胡成龙, 陈韶云, 陈建. 聚苯胺/二氧化锰/聚吡咯复合纳米球的制备及其电化学储能性[J]. 化工学报, 2023, 74(3): 1379-1389.

Dong XU, Du TIAN, Long CHEN, Yu ZHANG, Qingliang YOU, Chenglong HU, Shaoyun CHEN, Jian CHEN. Preparation and electrochemical energy storage of polyaniline/manganese dioxide/polypyrrole composite nanospheres[J]. CIESC Journal, 2023, 74(3): 1379-1389.

图/表 10

图1 PANI@MnO2@PPy纳米球的合成示意图

Fig.1 Schematic diagram of synthesis of PANI@MnO2@PPy nanospheres

图2 PPy、MnO2@PPy和PANI@MnO2@PPy纳米球在不同放大倍数下的SEM图

Fig.2 SEM images of PPy, MnO2@PPy and PANI@MnO2@PPy nanospheres at different magnification

图3 PPy、MnO2@PPy和PANI@MnO2@PPy纳米球的TEM图

Fig.3 TEM images of PPy, MnO2@PPy and PANI@MnO2@PPy nanospheres

图4 PPy、MnO2@PPy和PANI@MnO2@PPy纳米球的拉曼光谱图和XRD谱图

Fig.4 Raman spectra and XRD patterns of PPy, MnO2@PPy and PPy@PANI@MnO2 nanospheres

图5 PPy、MnO2@PPy和PANI@MnO2@PPy纳米球的XPS谱图

Fig.5 XPS spectra of PPy, MnO2@PPy and PPy@PANI@MnO2 nanospheres

图6 PPy、MnO2@PPy和PANI@MnO2@PPy电极在10 mV·s-1的扫描速率和1 A·g-1电流密度下的CV和GCD曲线

Fig.6 CV and GCD curves of PPy, MnO2@PPy and PANI@MnO2@PPy at a scanning rate of 10 mV·s-1 and current density of 1 A·g-1, respectively

图7 PPy、MnO2@PPy和PANI@MnO2@PPy 纳米球的BET吸附曲线和接触角测试

Fig.7 BET adsorption curves and contact angle tests of PPy, MnO2@PPy and PANI@MnO2@ PPy nanospheres

图8 MnO2@PPy 和PANI@MnO2@PPy电极在不同扫描速率和电流密度下的CV和GCD曲线

Fig.8 CV and GCD curves of MnO2@PPy and PANI@MnO2@PPy electrode at different scanning rates and current densities, respectively

图9 MnO2@PPy和PANI@MnO2@PPy电极CV曲线的峰值电流密度和扫描速率之间的关系、比电容和电流密度之间的关系

Fig.9 The relationship between peak current density of CV curves and scanning rates, specific capacitance and current densities of MnO2@PPy and PANI@MnO2@PPy electrodes

图10 PPy、MnO2@PPy和PANI@MnO2@PPy电极的循环稳定性和Nyquist阻抗谱图

Fig.10 Cyclic stability and Nyquist curves of PPy, MnO2@PPy and PANI@MnO2@PPy electrodes

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