Closely packed Si@C and Sn@C nano-particles anchored by reduced graphene oxide sheet boosting anode performance of lithium ion batteries

doi:10.1016/j.jmst.2020.12.075

Abstract

Abstract:

Both silicon and tin are promising anodes for new generation lithium ion batteries due to high lithium storage capacities (theoretically 4200 mA h g^-1 and 992 mA h g^-1, respectively). However, their large volumetric expansions (both are above 300 %) usually lead to poor cycling stability. In this case, we synthesized closely packed Si@C and Sn@C nano-particles anchored by reduced graphene oxide (denoted as Si@C/Sn@C/rGO) by the way of solution impregnation and subsequent hydrogenation reduction. Sn particles with a diameter of 100 nm are coated by carbon and surrounded by Si@C particles around 40 nm in average diameter through the high-resolution transmission electron microscopy. Expansions of Si and Sn are alleviated by carbon shells, and reduced graphene oxide sheets accommodate their volume changes. The prepared Si@C/Sn@C/rGO electrode delivers an enhanced initial coulombic efficiency (78 %), rate capability and greatly improved cycle stability (a high reversible capacity of nearly 1000 mA h g^-1 is achieved after 300 cycles at a current density of 1000 mA g^-1). It can be believed that packing Sn@C nano-particles with Si@C relieves the volume expansion of both and releases the expansion stresses. Sn@C particles enhance anode process kinetics by reducing charge transfer resistance and increasing lithium ion diffusion coefficient. The present work provides a viable strategy for facilely synthesizing silicon-tin-carbon composite anode with long life.

Key words: Sn-Si-C nano-composites, Anode, Lithium ion batteries

Chaoye Zhu, Yao Zhang, Ziqiang Wu, Zhihong Ma, Xinli Guo, Fuyi Guo, Jiakun Zhang, Yushu Li. Closely packed Si@C and Sn@C nano-particles anchored by reduced graphene oxide sheet boosting anode performance of lithium ion batteries[J]. J. Mater. Sci. Technol., 2021, 87: 18-28.

Figures/Tables 12

Scheme 1. Schematic illustration on the synthesis of Si@C/Sn@C/rGO.

Fig. 1. XRD patterns of Si@C/(7.5)Sn@C/rGO, Si@C/(15)Sn@C/rGO, Si@C/(30)Sn@C/rGO, Si-(15)Sn, and Si@C/rGO, respectively.

Fig. 2. (a, b) TEM images of Si@C/(15)Sn@C/rGo; (c) HRTEM images of Si@C/(15)Sn@C/rGO; (d) Si and Sn particles are wrapped by carbon shell, denoted as Si@C and Sn@C; (e, f) C, O, Si and Sn mappings of Si@C/(15)Sn@C/rGO, respectively.

Fig. 3. XPS spectra of (a) Si 2p of Si@C/(15)Sn@C/rGO before charge-discharge cycle; (b) Sn 3d of Si@C/(15)Sn@C/rGO before charge-discharge cycle; (c) Si 2p of Si@C/(15)Sn@C/rGO after five charge-discharge cycles; (d) Sn 3d of Si@C/(15)Sn@C/rGO after five charge-discharge cycles.

Fig. 4. (a) Cyclic discharge capacities of Si@C/rGO, Si-Sn and Si@C/Sn@C/rGO samples within initial 60 cycles at a current density of 500 mA g-1; (b) Discharge curves at different cycle about Si@C/(15)Sn@C/rGO electrode; (c) Cyclic discharge capacities of Si@C/(15)Sn@C/rGO samples within initial 300 cycles at a current density of 1000 mA g-1; (d) Rate capability of Si@C/rGO, Si-Sn and Si@C/Sn@C/rGO electrodes at a specific current density increasing from 200 mA g-1 to 2000 mA g-1; (e) Cyclic voltammogram diagrams of Si@C/rGO electrode; (f) Si@C/(15)Sn@C/rGO electrode after initial 5 cycles.

Table 1 Coulombic efficiencies, cyclic discharge capacities, and capacity retention rates of Si-(15)Sn and Si@C/Sn@C/rGO samples.

Samples	Columbic efficiency (%) of the 1 st cycle	The discharge capacity (mAh g^-1) of the 1 st cycle	The discharge capacity (mAh g^-1) of the 60th cycle	The capacity retention rate (%)
Si@C/rGO	69	2740	1181	43
Si-(15)Sn	67.0	2789	1019	37
Si@C/(7.5)Sn@C/rGO	79	2241	1129	50
Si@C/(15)Sn@C/rGO	78	2680	1880	70
Si@C/(30)Sn@C/rGO	78	2223	1067	48

Table 2 Comparison of the present work with previously studied Sn-Si-C composite anodes in electrochemical performances.

Materials	Columbic efficiency (%) of the 1 st cycle	Current density (mA g^-1)	Cycle number	Reversible capacity (mAh g^-1)	Refs.
Macroporous Si/Sn composites	75	200	70	1660	[23]
Si-Sn-DHCNFs	75.26	100	35	1000	[25]
Si-Sn nanocomposites	61.5	400	50	1100	[27]
Si_ySn_1-_yO_x@C	75.9	100	150	823	[28]
Si@C/Sn@C/rGO	78	500	60	1880	This work

Fig. 5. (a) Nyquist diagrams of Si@C/rGO, Si-Sn and Si@C/Sn@C/rGO before charge-discharge cycle; (b) Relationship of Zreal-ω-1/2 curves in the low-frequency region of the Si@C/rGO, Si-Sn and Si@C/Sn@C/rGO samples.

Table 3 Charge transfer resistance values (Rct) and diffusion coefficient values (DLi) of Si-(15)Sn and Si@C/Sn@C/rGO samples.

Parameter	Si@C/rGO	Si-(15)Sn	Si@C/(7.5)Sn@C/rGO	Si@C/(15)Sn@C/rGO	Si@C/(30)Sn@C/rGO
R_ct (Ω)	160.9	145.9	73.3	62.5	55.1
D_Li (cm² s^-1)	1.8 × 10^-18	2.4 × 10^-18	1.2 × 10^-17	5.6 × 10^-17	1.9 × 10^-17

Fig. 6. (a-d) HRTEM images of Si-(15)Sn@C/rGO after 60 cycles; (e) Enlarged graph of selected area; (f) TEM-EDS elemental mappings of Si-(15)Sn@C/rGO after 60 cycles; (g-i) The mappings of C, Si, Sn, respectively.

Fig. 7. SEM images of these anodes after 60 cycles: (a, c) Si@C/rGO; (b, d) Si@C/(15)Sn@C/rGO; Cross-sectional SEM images of those anodes before cycles; (e) Si@C/rGO; (f) Si@C/(15)Sn@C/rGO; Cross-sectional SEM images of those anodes after 60 cycles: (g) Si@C/rGO ; (h) Si@C/(15)Sn@C/rGO.

Fig. 8. (a) FTIR patterns of Si@C/rGO and Si@C/(15)Sn@C/rGO samples before cycles and after the 5th cycle; (b) Raman spectra of Si@C/rGO and before cycles and after the 5th cycle.(c) Raman spectra of Si@C/(15)Sn@C/rGO samples before cycles and after the 5th cycle.

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