无序介孔硅复合纳米结构的制备与慢活化行为

doi:10.7503/cjcu20170035

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (5): 713.doi: 10.7503/cjcu20170035

• 研究论文: 无机化学 • 上一篇下一篇

无序介孔硅复合纳米结构的制备与慢活化行为

许笑目¹, 张兴帅¹, 陈志柠¹, 王静¹, 郭玉忠¹(), 黄瑞安²(), 王剑华¹

1.昆明理工大学材料科学与工程学院, 昆明 650093
2.昆明理工大学真空冶金国家工程实验室, 昆明 650093

收稿日期:2017-01-16 出版日期:2017-05-10 发布日期:2017-04-25
作者简介:联系人简介: 郭玉忠, 男, 博士, 教授, 主要从事锂离子电池研究. E-mail:yzguocn62@sina.com; 黄瑞安, 男, 博士, 副教授, 主要从事锂离子电池研究. E-mail:rahuang2002@163.com
基金资助:
国家自然科学基金(批准号: 51464025)资助

Preparation of a Disordered Mesoporous Silicon Nanocomposite and Its Slow Activation Behavior^†

XU Xiaomu¹, ZHANG Xingshuai¹, CHEN Zhining¹, WANG Jing¹, GUO Yuzhong^1,^*(), HUANG Ruian^2,^*(), WANG Jianhua¹

1. Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China
2. National Engineering Laboratory for Vacuum Metallurgy, Kunming University of Science and Technology, Kunming 650093, China

Received:2017-01-16 Online:2017-05-10 Published:2017-04-25
Contact: GUO Yuzhong,HUANG Ruian E-mail:yzguocn62@sina.com;rahuang2002@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.51464025)

摘要/Abstract

摘要：

通过对SiO₂纳米粒子进行镁热还原及后处理, 制备了多级无序Si介孔复合纳米结构MP-Si@SiO_x@C, 此结构展现出容量非衰减缓升的电化学慢活化行为, 可抵消循环容量常规衰减趋势, 赋予负极优良的循环稳定性. 通过X射线衍射(XRD)、透射电子显微镜(TEM)、场发射扫描电子显微镜(SEM)、 N₂吸附-脱附测试和孔径分布模拟分析发现, Si介孔组织包含微-窄介孔(1~5 nm)、中介孔(5~20 nm)以及大介孔-宏孔(20~100 nm)三级孔道, 分别源于原初级粒子内部孔道、粒子团聚堆垛与粒内酸蚀、团聚体再堆垛; 此合成装配方法有效提升了Si材料的堆积密度, 电池电极能获得较高的体积比容量和储能密度.

关键词: 白炭黑, 镁热还原法, 无序介孔结构, 慢活化机制, 负极材料

Abstract:

A silicon nano composite with disordered hierarchical mesoporous architectures(MP-Si@SiO_x@C) was prepared via magnesiothermic reduction and subsequent post-processing using SiO₂ nanoparticles as a precursor. As an anode material, this MP-Si@SiO_x@C composite shows an electrochemical slow activation behavior, resulting in an abnormal slow rise in charge/discharge capacity when cycling. This unusual behavior can greatly counteract the capacity decay when cycling in pristine Si anode, endowing this MP-Si@SiO_x@C composite with the extraordinary cycling stability. Based on the characterization of X-ray diffraction(XRD), transmission electron microscopy(TEM), field emission scanning electron microscopy(FESEM), N₂-adsorption/desorption and the simulation and analysis of the pore structure, it is found that the MP-Si@SiO_x@C composite is hierarchically distributed ranging from micro-narrow mesoporous(1—5 nm), medium mesoporous(5—20 nm) to macro-mesoporous and macroporous(20—100 nm), which originating from the inner pore of the SiO₂ primary particles, particle aggregation/stacking, acid-etching of primary particles, and particle agglomeration/restacking in solution, respectively. The reconstruction of Si primary particles can greatly promote the bulk density of silicon and gives higher volume capacity and energy density to this as-assembled MP-Si@SiO_x@C composite.

Key words: White carbon black, Magnesiothermic reduction route, Disordered mesoporous architecture, Slow activation mechanism, Anode material

中图分类号:

O613
O646

TrendMD:

许笑目, 张兴帅, 陈志柠, 王静, 郭玉忠, 黄瑞安, 王剑华. 无序介孔硅复合纳米结构的制备与慢活化行为. 高等学校化学学报, 2017, 38(5): 713.

XU Xiaomu, ZHANG Xingshuai, CHEN Zhining, WANG Jing, GUO Yuzhong, HUANG Ruian, WANG Jianhua. Preparation of a Disordered Mesoporous Silicon Nanocomposite and Its Slow Activation Behavior^†. Chem. J. Chinese Universities, 2017, 38(5): 713.

图/表 7

Fig.1 XRD patterns(A) and Raman spectra(B)of samples via magnesiothermic reduction and ensuing

Fig.2 TEM images of raw WCB(A), as-reduced(B), HCl-etched(C), HCl+HF-etched(D), HCl+HF-MP-Si@SiOx(E), HCl+HF-MP-Si@SiOx@C(F) and HRTEM images of HCl+HF-etched(G) and HCl+HF-MP-Si@SiOx@C(H)

Fig.3 FESEM images of samples after different acid etching treatments(A), (B) HCl-etched; (C), (D) HCl+HF-etched.

Table 1 Tap density of samples via magnesiothermic reduction and ensuing acid etching treatments

Sample	WCB	As-reduced	HCl-etched	HCl+HF-etched
Tap density/(g·cm^-3)	0.05	0.12	0.25	0.24

Fig.4 N2 adsorption-desorption isotherms(A, B), pore size distribution curves(C, D), total specific surface area(E) and micropore surface area(F) of samples via magnesiothermic reduction and ensuing post-treatmentsa. WCB; b. as-reduced; c. HCl-etched; d. HCl+HF-etched; e. Si-HCl+HF/SiOx.

Fig. 5 Cyclic discharge capacity curves of NP-Si80@SiOx@C(a) nanoparticles and HCl-MP-Si@SiOx@C(b)

Fig.6 Cyclic capacity curves of samples under different post-treatments(A) With and without SiOx-encapsulating; (B) HCl-etched vs. HCl+HF-etched at 70 mA/g; (C) cycling of HCl+HF-MP-Si@SiOx@C at 70, 200, 500 mA/g current rates; (D) HCl+HF-MP-Si@SiOx@C at 0.1, 0.2, 0.5, 1.0, 2.0 A/g current rates.

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无序介孔硅复合纳米结构的制备与慢活化行为

Preparation of a Disordered Mesoporous Silicon Nanocomposite and Its Slow Activation Behavior^†

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无序介孔硅复合纳米结构的制备与慢活化行为

Preparation of a Disordered Mesoporous Silicon Nanocomposite and Its Slow Activation Behavior†

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Preparation of a Disordered Mesoporous Silicon Nanocomposite and Its Slow Activation Behavior^†