柔性自支撑PDDA-Si/G纳米复合薄膜的制备及储锂性能

doi:10.11949/j.issn.0438-1157.20181287

化工学报 ›› 2019, Vol. 70 ›› Issue (3): 1144-1151.DOI: 10.11949/j.issn.0438-1157.20181287

• 材料化学工程与纳米技术 • 上一篇下一篇

柔性自支撑PDDA-Si/G纳米复合薄膜的制备及储锂性能

张亚婷^1,²(),张凯博¹,贾凯丽¹,贺新福^1,²,刘国阳^1,²,王伟¹,张永玲¹,邱介山^3,⁴

1. 西安科技大学化学与化工学院，陕西西安 710054
2. 国土资源部煤炭资源勘查与综合利用重点实验室，陕西西安 710021
3. 大连理工大学化工学院，辽宁大连 116024
4. 北京化工大学化学工程学院，北京 100029

收稿日期:2018-11-02 修回日期:2018-12-24 出版日期:2019-03-05 发布日期:2019-03-05
通讯作者: 张亚婷
作者简介:张亚婷（1972—），女，博士，教授，<email>isyating@163.com</email>
基金资助:
国家自然科学基金项目(U1703251);陕西省重点研发计划项目(2017ZDCXL-GY-10-01-02);国土资源部煤炭资源勘查与综合利用重点实验室开放研究课题项目(KF2016-4)

Preparation and lithium storage properties of flexible self-standing PDDA-Si/G nanocomposite film

Yating ZHANG^1,²(),Kaibo ZHANG¹,Kaili JIA¹,Xinfu HE^1,²,Guoyang LIU^1,²,Wei WANG¹,Yongling ZHANG¹,Jieshan QIU^3,⁴

1. College of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, Shaanxi, China
2. Key Laboratory of Coal Resources Exploration and Comprehensive Utilization, Ministry of Land and Resources, Xi’an 710021, Shaanxi, China
3. School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
4. College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2018-11-02 Revised:2018-12-24 Online:2019-03-05 Published:2019-03-05
Contact: Yating ZHANG

摘要/Abstract

摘要：

通过静电自组装技术成功制备得到柔性自支撑聚二烯二甲基氯化铵-Si/石墨烯(PDDA-Si/G)纳米复合薄膜。该复合薄膜无添加黏结剂及导电炭黑且仍能保持电极结构的完整性，其中石墨烯提供完整的导电网络和机械韧性。电化学测试结果表明，当电流密度为0.2 A/g，复合材料的比容量可达1439.9 (mA·h)/g，库仑效率保持98%以上。且在高电流密度(2 A/g)下，复合材料的比容量仍可维持在499.9 (mA·h)/g，远高于商品化纯Si电极的电化学性能。

关键词: 复合材料, 纳米结构, 硅, 石墨烯薄膜, 电化学

Abstract:

Silicon is an active electrode material for future commercial lithium-ion batteries with extremely high theoretical specific capacity (4200 (mA·h)/g). However, the large volume change of silicon over charge-discharge cycles weakens its competitiveness in the capacity and cycle life. A flexible self-supporting polydiene dimethylammonium chloride-Si/graphene (PDDA-Si/G) nanocomposite film was successfully prepared by electrostatic self-assembly technique. The composite film can maintain the integrity of electrode structure without adding binder and conductive carbon black. Graphene provides complete conductive network and mechanical toughness. The electrochemical test results show that when the current density was 0.2 A/g, the specific capacity of PDDA-Si/G composite could reach 1439.9 (mA·h)/g and the Coulombic efficiency was above 98%. The specific capacity was 1209.3 (mA·h)/g after 80 cycles. The specific capacity still maintained 499.9 (mA·h)/g at a high current density (2 A/g).

Key words: composites, nanostructure, silicon, graphene film, electrochemistry

中图分类号:

TM 912.9

张亚婷, 张凯博, 贾凯丽, 贺新福, 刘国阳, 王伟, 张永玲, 邱介山. 柔性自支撑PDDA-Si/G纳米复合薄膜的制备及储锂性能[J]. 化工学报, 2019, 70(3): 1144-1151.

Yating ZHANG, Kaibo ZHANG, Kaili JIA, Xinfu HE, Guoyang LIU, Wei WANG, Yongling ZHANG, Jieshan QIU. Preparation and lithium storage properties of flexible self-standing PDDA-Si/G nanocomposite film[J]. CIESC Journal, 2019, 70(3): 1144-1151.

图/表 8

图1 基于GO制备PDDA-Si/G复合薄膜的工艺流程

Fig.1 Schematic diagram of preparation of PDDA-Si/G composite film based on GO

图2 PDDA-Si/G和GO在不同酸碱度下的Zeta电位

Fig.2 Zeta potential of PDDA-Si/G and GO at different pH

图3 柔性自支撑PDDA-Si/G薄膜的SEM图(a)、(b)；复合材料横截面的SEM图(c)以及PDDA-Si/G的C、O、Si元素mapping图(d)

Fig.3 SEM photograph of flexible self-standing PDDA-Si/G film(a),(b); cross-sectional SEM image of composite material(c) and mapping images of C, O and Si elements of PDDA-Si/G(d)

图4 Si、GO、G、PDDA-Si/G薄膜X射线衍射图(a)和拉曼光谱图(b)

Fig.4 X-Ray diffraction patterns(a) and Raman spectra (b) for Si, GO, G and PDDA-Si/G film

图5 Si、G、PDDA-Si/G薄膜在空气下的TGA曲线

Fig.5 TGA curves of Si, G and PDDA-Si/G film under air atmosphere

图6 PDDA-Si/G在0.2 mV/s下的循环伏安曲线(a)；在0.2 A/g下复合材料的恒电流充放电曲线(b)；PDDA-Si、Si、G的循环性能曲线和库仑效率(c)；复合材料的倍率性能曲线(d)

Fig.6 Cyclic voltammogram of PDDA-Si/G at 0.2 mV/s(a); constant current charge-discharge curves of composite at 0.2 A/g(b); cycle performance curves of PDDA-Si, Si, G and Coulombic efficiency(c); rate performance curve of composite film(d)

图7 Si和PDDA-Si/G的交流阻抗谱图(a)和等效电路图(b)

Fig.7 AC impedance spectroscopy of Si, PDDA-Si/G electrodes (a) and equivalent circuits diagram (b)

表1 Si和PDDA-Si/G充放电循环的交流阻抗拟合参数

Table 1 Impedance parameters of Si and PDDA-Si/G electrodes for charge-discharge cycle

Sample	Cycle	R _s/Ω	R _SEI/Ω	R _ct/Ω
pure Si	0	4.16	—	297.63
PDDA-Si/G	0	3.12	—	165.68
PDDA-Si/G	80	3.02	11.3	58.68

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柔性自支撑PDDA-Si/G纳米复合薄膜的制备及储锂性能

Preparation and lithium storage properties of flexible self-standing PDDA-Si/G nanocomposite film

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