磷钼酸负载碳纳米管复合物的制备及其超级电容性能

doi:10.15541/jim20160182

无机材料学报 ›› 2017, Vol. 32 ›› Issue (2): 127-134.DOI: 10.15541/jim20160182 CSTR: 32189.14.10.15541/jim20160182

磷钼酸负载碳纳米管复合物的制备及其超级电容性能

郑譞^1,2, 龚春丽¹, 刘海¹, 汪广进^1,2, 程凡¹, 郑根稳¹, 文胜¹, 熊传溪²

(1. 湖北工程学院化学与材料科学学院, 孝感 432000; 2. 武汉理工大学材料复合新技术国家重点实验室, 武汉 430070)

收稿日期:2012-05-30 修回日期:2012-09-12 出版日期:2017-02-20 网络出版日期:2017-01-13
作者简介:郑譞(1988–), 男, 博士研究生, 实验师. E-mail:63474559@qq.com
基金资助:
国家自然科学基金青年基金(51303048, 51403058);湖北省自然科学基金(2015CFC769);中央校基本科研业务(2016-YB-011)

Preparation of Phosphomolybdic Acid Coated Carbon Nanotubes and Its Supercapacitive Properties

ZHENG Xuan^1,2, GONG Chun-Li¹, LIU Hai¹, WANG Guang-Jin^1,2, CHENG Fan¹, ZHENG Gen-Wen¹, WEN Sheng¹, XIONG Chuan-Xi²

(1. College of Chemistry and Materials Science, Hubei Engineering University, Xiaogan 432000,China; 2. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070,China)

Received:2012-05-30 Revised:2012-09-12 Published:2017-02-20 Online:2017-01-13
About author:ZHENG Xuan. E-mail:63474559@qq.com
Supported by:
National Natural Science Foundation--Youth Foundation (51303048, 51403058);Natural Science Foundation of Hubei Province (2015CFC769);Fundamental Research Funds for the Central Universities (2016-YB-011)

摘要/Abstract

摘要：

以聚多巴胺包覆碳纳米管为载体, 借助聚多巴胺超强的粘附性, 利用简单的溶液浸渍法制备了磷钼酸负载碳纳米管(PMA@CNTs)复合物。通过傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)和电化学测试等对复合物的组成、结构、形态和超级电容性能进行了表征。结果表明: 聚多巴胺可将磷钼酸均匀且牢固地负载在碳纳米管上。在0.5 mol/L的H₂SO₄电解液中, 复合物的最大比容量为511.7 F/g, 最大能量密度可达66.8 Wh/kg, 相应的功率密度为1000 W/kg。经过1000次循环, 比容量无任何衰减。以上研究结果说明PMA@CNTs复合物在电化学储能领域拥有极好的发展前景。

关键词: 聚多巴胺, 碳纳米管, 磷钼酸, 复合材料, 超级电容器

Abstract:

The phosphomolybdic acid coated carbon nanotubes (PMA@CNTs) were successfully fabricated by a facile polydopamine-assisted impregnation method, in which polydopamine can form an extraordinary adhesive interlayer to homogeneously adhere PMA on the surfaces of CNTs. The composition, structure, morphology and supercapacitive performances of the resulting PMA@CNTs hybrids were systematically characterized by a range of experimental tools including fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscope(XPS), scanning electron microscope(SEM), transmission electron microscope(TEM), cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD). The PMA can homogeneously loaded onto the surface of the CNTs with the aid of superior adhesion of polydopamine. Here, the performance of the resulting PMA@CNTs hybrids as supercapacitor electrodes was investigated in a three-electrode arrangement using an aqueous electrolyte (0.5 mol/L H₂SO₄). The supercapacitor assembled with the PMA₅₀@CNTs hybrids exhibit the highest specific capacitances (511.7 F/g at 10 mV/s) and maximum energy density of 66.8 Wh/kg at power density of 1000 W/kg, based on the total mass of active materials. In addition, the supercapacitor also has excellent cycling stability retaining>100% of its specific capacitances after 1000 cycles at current density of 5 A/g. These results demonstrate a simple and scalable application of PMA@CNTs hybrids toward electrochemical energy storage.

Key words: polydopamine, carbon nanotubes, phosphomolybdic acid, hybrids supercapacitors

中图分类号:

TQ174

郑譞,龚春丽, 刘海, 汪广进, 程凡, 郑根稳, 文胜, 熊传溪. 磷钼酸负载碳纳米管复合物的制备及其超级电容性能[J]. 无机材料学报, 2017, 32(2): 127-134.

ZHENG Xuan, GONG Chun-Li, LIU Hai, WANG Guang-Jin, CHENG Fan, ZHENG Gen-Wen, WEN Sheng, XIONG Chuan-Xi. Preparation of Phosphomolybdic Acid Coated Carbon Nanotubes and Its Supercapacitive Properties[J]. Journal of Inorganic Materials, 2017, 32(2): 127-134.

图/表 10

图1 多巴胺氧化自聚合机理[25-27]及PMA@CNTs复合物的制备过程示意图

Fig. 1 Illustration of oxidative self-polymerization mechanism of dopamine[25-27] and preparation procedure of PMA@CNTs hybrids

图2 CNTs、PDA-CNTs和PMA50@CNTs的FTIR谱图

Fig. 2 FTIR spectra of CNTs, PDA-CNTs and PMA50@CNTs

图3 CNTs、PDA-CNTs和PMA50@CNTs的XRD图谱

Fig. 3 XRD patterns of CNTs, PDA-CNTs and PMA50@CNTs

图4 PMA50@CNTs的(a)XPS宽谱扫描图, (b) C1s分峰图, (c)N1s分峰图, (d)Mo3d分峰图

Fig. 4 XPS spectra of PMA50@CNTs: (a) wide scan; peak deconvolution of (b) C1s, (c) N1s, and (d) Mo3d

表1 PMA50@CNTs的EDX元素组成

Table1 EDX compositions of PMA50@CNTs

Element	at/%	wt/%
C	82.99	79.93
N	3.73	5.96
O	7.05	11.37
P	1.86	0.86
M_O	2.19	1.87
Total	100.00

图5 (a)PMA50@CNTs的SEM照片, (b)PMA50@CNTs的EDX图谱, (c)、(d)PMA50@CNTs的TEM照片

Fig. 5 SEM images of PMA50@CNTs (a), EDXspectra of PMA50@CNTs (b), and TEM images of PMA50@CNTs (c), (d)

图6 CNTs、PDA-CNTs和PMA50@CNTs的TGA图谱

Fig. 6 TGA curves of CNTs, PDA-CNTs and PMA50@CNTs

图7 PDA-CNTs、PMA0.4@CNTs、PMA2@CNTs、PMA10@CNTs和PMA50@CNTs在10 mV/s扫速下的循环伏安曲线(a)和在2 A/g电流密度下的恒流充放电曲线(b)以及PMA50@CNTs在不同扫速下的循环伏安曲线(c), 不同电流密度下的恒流充放电曲线(d)

Fig. 7 (a) Cyclic voltammograms at scan rate of 10 mV/s) and (b) galvanostatic charge-dischargecyclic curves at current density of 2 A/g for PDA-CNTs, PMA0.4@CNTs, PMA2@CNTs, PMA10@CNTs andPMA50@CNTs coin cell, and (c) cyclic voltammograms at different scan rates and (d) charge/discharge curves at different current densities for PMA50@CNTs Supercapacitors in 0.5 mol/L H2SO4 electrolytes

图8 (a)PMA50@CNTs在不同电流密度和扫速下的比容量曲线和(b)PMA50@CNTs在5 A/g电流密度下的循环稳定性测试结果

Fig. 8 (a) Specific capacitance of the PMA50@CNT selectrode as a function of scan rate and current density and (b) cycling stability of the PMA50@CNTs electrode at a current density of 5 A/g

图9 PMA50@CNTs电极材料的功率密度与能量密度的关系曲线

Fig. 9 Ragone plot of PMA50@CNTs electrodes

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磷钼酸负载碳纳米管复合物的制备及其超级电容性能

Preparation of Phosphomolybdic Acid Coated Carbon Nanotubes and Its Supercapacitive Properties

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