一维有序聚苯胺纳米阵列的制备及电化学储能性能

doi:10.7503/cjcu20180590

摘要/Abstract

摘要：

以导电玻璃FTO为基底电极, 在硫酸溶液中, 分别研究了苯胺单体浓度和恒定电流大小对聚苯胺(PANI)形貌的影响; 同时恒定苯胺单体的浓度和工作电流, 探究了不同类型的质子酸对PANI阵列形貌的影响. 结果表明, 采用恒电流方法可以制备出一维有序PANI纳米线阵列, 而且当苯胺的浓度为0.1 mol/L, 恒电流法的工作电流密度为0.03 mA/cm²时, 所制备的PANI纳米线阵列形貌最佳; 当用HCl, HNO₃和对甲苯磺酸(p-TSA)作为合成PANI的支持液时, 得到树桩状的PANI 纳米结构, 不能得到均一的纳米线阵列结构. 电化学性能测试结果表明, 制备的最佳形貌PANI纳米线阵列的比电容值可达560 F/g; 循环1000周后电容损失率为11%.

关键词: 聚苯胺, 恒定电流法, 超级电容器, 电极材料, 纳米线阵列

Abstract:

One dimensional orderly polyaniline(PANI) nanowires array were prepared on conducting substrate by using a galvanostatic current method. The effects of preparation factors, including concentration of aniline(0.01—0.3 mol/L), working current density(0.01—0.13 mA/cm²) and kinds of protonic acid(1 mol/L H₂SO₄, HCl, HNO₃ and p-TSA), on the morphology of the as-prepared PANI nanowires were investigated. It was found that the best morphology of PANI nanowires array could be obtained when the concentration of aniline was 0.1 mol/L and the working current density was 0.03 mA/cm². Also, the PANI with uniform nanowires array structure could not be formed when HCl, HNO₃ and p-TSA acted as supporting liquid. The as-prepared PANI nanowire arrays had narrow diameters and were oriented perpendicularly to the FTO, which was beneficial to the ion diffusion when being used as the supercapacitor electrode. The highest specific capacitance of PANI nanowire arrays was measured as 560 F/g at a charge-discharge current density of 1 A/g, and the PANI nanowire arrays also exhibited good capability and cycling stability with capacitance retentions of 89% after 1000 cycles, which is superior or close to some individual PANI nanostructures and PANI composite materials.

Key words: Polyaniline, Galvanostatic current method, Supercapacitor, Electrode material, Nanowire array

中图分类号:

O646

TrendMD:

刘奔, 张行颖, 陈韶云, 胡成龙. 一维有序聚苯胺纳米阵列的制备及电化学储能性能. 高等学校化学学报, 2019, 40(3): 498.

LIU Ben,ZHANG Xingying,CHEN Shaoyun,HU Chenglong. Preparation and Electrochemical Energy Storage Performance of One Dimensional Orderly Polyaniline Nanowires Array^†. Chem. J. Chinese Universities, 2019, 40(3): 498.

图/表 12

Fig.1 Raman spectrum of the prepared PANI nanowire arrays

Scheme 1 Mehanism of electrochemical synthesis of PANI

Scheme 2 Growth mechanism of 1D PANI nanowire arrays

Fig.2 Optical picture of as-prepared PANI(A) and SEM images of the as-prepared PANI upon different concentration of ANI(B—F)cANI/(mol·L-1): (B) 0.02; (C) 0.05; (D) 0.10; (E) 0.20; (F) 0.30.

Fig.3 Cyclic voltammograms of the as-prepared PANI upon different concentrations of aniline by galvanostatic current method(0.03 mA/cm2)(A), cyclic voltammograms of PANI at different scan rates(cANI=0.1 mol/L)(B) and plots of specific capacitance as a function of the scan rate(C)The inset of (A) shows the relationship between specific capacitance and concentration of aniline.

Fig.4 Charge-discharging curves(A) and Nyquist polts(B) of the as-prepared PANI upon different concentration of anilinecANI/(mol·L-1): a. 0.02; b. 0.05; c. 0.10; d. 0.20; e. 0.30. The inset of (A) shows the relationship between specific capacitance and concentration of aniline.

Fig.5 SEM images of the as-prepared PANI at different galvanostatic currents(cANI=0.1 mol/L) Current density/(mA·cm-2): (A) 0.01; (B) 0.03; (C) 0.05; (D) 0.07; (E) 0.09; (F) 0.13.

Fig.6 Cyclic voltammograms of the as-prepared PANI nanostructure at different galvanostatic currents at the scan rate of 10 mV/s(A), plots of specific capacitance as a function of scan rate(B) and charge-discharge curves(C) and Nyquist polts(D) of the as-prepared PANI nanostructureThe inset of (A) shows the relationship between specific capacitance and galvanostatic current.

Fig.7 SEM images of as-prepared PANI under different protonic acid(A) 1 mol/L HCl; (B) 1 mol/L HNO3; (C) 1 mol/L p-TSA.

Fig.8 Cyclic voltammograms of the as-prepared PANI nanostructure with different protonic acid at deposition current density of 0.03 mA/cm2 and cANI of 0.1 mol/L(A), plots of specific capacitance as a function of scan rate(B), charge-discharging curves at 1 A/g(C) and Nyquist polts(D) of the as-prepared PANI nanostructures

Fig.9 Cycling stability of PANI nanostructure with different protonic acid(A), CV curves of PANI nanostructure before cycle and after 1000 cycles in H2SO4(B) and SEM image of PANI nanostructure after 1000 cycles in H2SO4(C)

Fig.10 Electrical conductivity of the PANI nanostructure prepared upon different cANI(A) and working current density(B)

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