Loose-fit graphitic encapsulation of silicon nanowire for one-dimensional Si anode design

doi:10.1016/j.jmst.2017.07.003

Abstract

Abstract:

Silicon nanowires (SiNWs) encapsulated with graphene-like carbon sheath (GS) having a void space in between (SiNW@V@GS) are demonstrated for the improved electrochemical performance of Si anode in lithium ion battery. The SiNW@V@GS structure was synthesized by a scalable fabrication method including four successive reactions: metal-catalyzed CVD growth of SiNWs, controlled thermal oxidation, and deposition of the graphitic layer, to form SiNW@SiO₂@GS and additional chemical etching of sacrificial SiO₂ layer between SiNWs and carbon sheath. During the synthetic process, the thickness of the void spacing was controlled by adjusting the oxidation-dependent process. The well-controlled void space and crystalline graphitic carbon sheath of the SiNW@V@GS structure enable good reversible capacity of 1444 mAh g^-1 and cycling stability of 85% over 150 cycles.

Key words: Lithium ion battery, Silicon nanowire, Graphene, Void spacing, Anode

Lim Seh-Yoon, Chae Sudong, Jung Su-Ho, Hyeon Yuhwan, Jang Wonseok, Yoon Won-Sub, Choi Jae-Young, Whang Dongmok. Loose-fit graphitic encapsulation of silicon nanowire for one-dimensional Si anode design[J]. J. Mater. Sci. Technol., 2017, 33(10): 1120-1127.

Figures/Tables 8

Fig. 1. Schematic illustration of electron transport in (a) nanoparticle electrode and (b) nanowire electrode.

Fig. 2. Schematic of the fabrication process for preparing SiNW@V@GS; Silicon nanowires were first preapred by a CVD process. The Si nanowires were coated after the oxidation process. By heat-treating the sample in methane gas, graphene-like carbon sheath was formed on the surface of SiO2 layer. The inner SiO2 templates were then selectively removed by HF etching, leaving carbon sheath encapsulated silicon nanowire with a void between them.

Fig. 3. SEM images of (a) SiNW@GS and (b) SiNW@V@GS-2h. (c) TEM images of SiNW@V@GS and inset shows electron diffraction pattern of SiNWs observed through [1-10] zone axis. (d) High-magnification TEM image of graphitic carbon sheath in SiNW@V@GS. During fabrication of SiNW@V@GS, the sacrificial SiO2 layer was grown for 2 h during the oxidation process.

Fig. 4. (a) Raman spectra and (b) TGA profile of SiNW@V@GS structure.

Fig. 5. (a) Cycling performance and (b) Coulombic efficiency of SiNW@V@GS anode samples at 0.5C. (c) Initial discharge-charge profile between 0.001 V-1.5 V and (d) rate performance of SiNW@V@GS-2h at various rates from 0.1C to 2C.

Fig. 6. Cyclic voltammograms (CV) from the first 8 cycles for (a) SiNW and (b) SiNW@V@GS-2h from 0.001 V to 1.5 V at a scan rate of 0.1 mV s-1. (c) Electrochemical impedance spectra (EIS) of the SiNW@GS, SiNW@V@GS-1h, and SiNW@V@GS-2h sample after the 30th cycles. (d) Cycling performance and Coulombic efficiency of SiNW@V@GS-2h at a current rate of 1C during 150 cycles.

Fig. 7. SEM images of (a and c) SiNW@V@GS-1h and (b and d) SiNW@V@GS-2h electrode (a and b) before cycling and (c and d) after 30 cycling, respectively. Inset in (d) is the HRTEM image of SiNW@V@GS-2h after 30 cycling; the scale bars are 200 nm.

Table 1 Comparison of electrochemical properties of Silicon anodes with different structures.

Sample	Discharge capacity (mAh g^-1)/Cycle numbers	Cycle retention	Potential range (V)	Rate/current density (mA g^-1)
Si@C nanofibers[38]	590 mAh g^-1/100 cycles	92%	0.01-1.5 V	50 mA^-1
G/Si composite[40]	800 mAh g^-1/30 cycles	83%	0-1.2 V	300 mA^-1
Hollow core-shell Si-C[41]	650 mAh g^-1/100cycles	86%	0.05-1.5 V	1 Ag^-1
Si@SiO₂@C composite[42]	800 mAh g^-1/30 cycles	96%	0-1.5 V	50 mA^-1
Si@C hollow hetero[43]	625 mAh g^-1/40 cycles	76%	0.02-1.2 V	50 mA^-1
Si@N-CNT[44]	838.2 mAh g^-1/50 cycles	74%	0.01-1.2 V	0.2C
Si Pomegranate[45]	1160 mAh g^-1/1000 cycles	97%	0.01-1V	0.5C
Si/GNs hybrid[46]	942 mAh g^-1/100 cycles	88%	0.01-1.5 V	0.2 Ag^-1
SiC@Si core-shell NW[47]	1809 mAh g^-1/50 cycles	38%	0.01-2 V	0.5C
HC-Nano Si/G[48]	864 mAh g-1/150 cycles	84%	0.005-1.5 V	0.2C
Si-rGo-C composite[49]	840 mAh g^-1/300 cycles	79%	0.005-1.5 V	1C
Si core-SiO_x shell NPs[50]	1274 mAh g^-1/50 cycles	94%	0.01-2.0 V	210 mA^-1
Si/CNFs@rGO[51]	1055 mA g^-1/130 cycles	29%	0.01-3.0 V	100 mA^-1
Si@C/RGO composite[52]	1800 mAh g^-1/100 cycles	-	0.01-1.0 V	0.2C
Our sample (for 2 h)	1444 mAh g^-1/150 cycles	85%	0.001-1.5 V	1C

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