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

doi:10.7503/cjcu20170035

Abstract

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

CLC Number:

O613
O646

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2017, 38(5): 713.

Figures/Tables 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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