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

doi:10.15541/jim20180203

摘要/Abstract

摘要：

通过真空抽滤诱导自组装及热解还原处理, 制备出具有柱撑结构的聚苯胺炭/石墨烯复合材料(PGR)。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线电子能谱(XPS)和电化学测试等表征技术考察了聚苯胺单体(AN)与氧化石墨烯(GO)质量比对PGR结构和电化学性能的影响。结果表明, 聚苯胺炭均匀分布在石墨烯(GR)片层间形成三维导电网络, 有效地增大了GR的层间距, 且实现了氮掺杂, 显著提高了GR的结构稳定性和电化学性能; AN与GO质量比为1 : 1时制备的样品PGR1在100 mA/g电流密度下的首次脱锂比容量为653 mAh/g, 当电流密度增大至1 A/g时, 仍具有高达343 mAh/g的脱锂比容量, 远高于GR的脱锂比容量(101 mAh/g), 表现出优异的倍率性能。

关键词: 石墨烯, 聚苯胺, 柱撑结构, 锂离子电池, 负极材料

Abstract:

Polyaniline-carbon pillared graphene composites (PGR) were successfully prepared by vacuum extraction induced self-assembly and pyrolysis method. Effects of the mass ratio of aniline monomer (AN) and graphene oxide (GO) on structure and electrochemical properties of PGR were investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization. Results showed that the polyaniline-carbon pillars uniformly distributed between the graphene (GR) layers to form a three-dimensional conductive network with expanded interlayer space and nitrogen doping, which effectively improved the structural stability and electrochemical performance of GR. The as-prepared PGR with the mass ratio of AN and GO at 1 : 1 exhibits a high reversible capacity of 653 mAh/g at a current density of 100 mA/g and an excellent rate capability of 343 mAh/g at a current density of 1 A/g, all that is much higher than that of the GR electrode (101 mAh/g).

Key words: graphene, polyaniline, pillared structure, lithium-ion batteries, anode material

中图分类号:

TM911

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.

HU Xi, LIU Hong-Bo, XIA Xiao-Hong, GU Zhi-Qiang. Polyaniline-carbon Pillared Graphene Composite: Preparation and Electrochemical Performance[J]. Journal of Inorganic Materials, 2019, 34(2): 145-151.

图/表 9

图1 PGR复合材料的制备过程示意图

Fig. 1 Schematic illustration of the preparation of PGR composites

图2 GO、AGO1、PGO、GR和PGR复合材料的XRD图谱

Fig. 2 XRD patterns of GO, AGO1, PGOs, GR, and PGRs

图3 (a) GO, (b) PGO0.5, (c) PGO1, (d) PANI, (e) GR, (f) PGR0.5, (g) PGR1和(h) CP的SEM照片

Fig. 3 SEM images of (a) GO, (b) PGO0.5, (c) PGO1, (d) PANI, (e) GR, (f) PGR0.5, (g) PGR1 and (h) CP with insets showing magnified photos

图4 (a) GR、(b) PGR0.5、(c) PGR1和(d) CP的TEM照片

Fig. 4 TEM images of (a) GR, (b) PGR0.5, (c) PGR1, and (d) CP

图5 (a) GO、PGO和PANI的红外光谱图; (b) GR和PGR的拉曼光谱图

Fig. 5 (a) FT-IR spectra of GO, PGOs and PANI samples, and (b) Raman spectra of GR and PGRs samples

图6 (a) GR、PGR0.5、PGR1和CP的XPS图谱; (b) PGR1的N1s峰的分峰曲线; (c) GR、PGR0.5、PGR1和CP的氮气吸脱附等温线和(d)孔径分布图

Fig. 6 (a) XPS general spectra of GR, PGRs and CP, (b) curve fitting of N1s spectrum of the sample PGR1, (c) nitrogen sorption isotherms, and (d) DFT pore size distributions of GR, PGRs and CP

图7 GR、PGR0.5和PGR1的电化学性能

Fig. 7 Electrochemical performance of GR, PGR0.5, and PGR1(a) The first CV curve of the samples; (b) The first to the third CV curves of PGR1; (c) The first charge/discharge profile cycle and (d) rate capability

图8 GR、PGR0.5和PGR1的交流阻抗图谱

Fig. 8 Nyquist plots for the samples of GR, PGR0.5, and PGR1

表1 GR、PGR0.5和PGR1负极材料的交流阻抗拟合数据

Table 1 EIS fitting results of GR, PGR0.5, and PGR1 electrodes

Sample	R_s/?	R_sei/?	R_ct/?
GR	7.23	141.3	90.67
PGR0.5	6.03	47.13	82.87
PGR1	2.02	54.50	0.10

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