Enhanced cycling stability of antimony anode by downsizing particle and combining carbon nanotube for high-performance sodium-ion batteries

doi:10.1016/j.jmst.2019.05.031

Abstract

Abstract:

Antimony (Sb) nanoparticles (SbNP) encapsulated in multiwalled carbon nanotubes (MWCNTs) matrix has been fabricated by a facile two-step ball milling strategy, including a sand milling process to prepare Sb nanoparticles and following high-energy ball milling to synthesize SbNP-MWCNT composite. As an anode material for sodium-ion batteries (SIBs), the SbNP-MWCNT composite with high Sb content (80%) can deliver a reversible capacity of 471.1 mA h g^-1 at 50 mA g^-1 with an initial coulombic efficiency of 73.5%, excellent cycling stability (94.1% capacity retention at 800 mA g^-1) and high rate capability (210.7 mA h g^-1 at 3200 mA g^-1). The excellent electrochemical performance of the SbNP-MWCNT composite results from the synergistic effect of downsizing Sb particles and combining MWCNTs.

Key words: Antimony, Nanoparticles, Carbon nanotubes, Anode, Sodium ion battery, Mechanical ball milling

Chuang Liu, Fanxin Zeng, Li Xu, Shuangyu Liu, Jincheng Liu, Xinping Ai, Hanxi Yang, Yuliang Cao. Enhanced cycling stability of antimony anode by downsizing particle and combining carbon nanotube for high-performance sodium-ion batteries[J]. J. Mater. Sci. Technol., 2020, 55: 81-88.

Figures/Tables 9

Fig. 1. Schematic illustration of the fabrication procedure of SbNP-MWCNT composite.

Fig. 2. SEM images of (a) SbMP, (b) SbNP and (c) SbNP-MWCNT. Inset: the magnifed SEM image of SbNP-MWCNT (d) TEM image, (e) HRTEM image and (f) SAED pattern of SbNP-MWCNT. (g) SEM image, and corresponding (h) C, (i) Sb and (j) O elemental mapping images of SbNP-MWCNT.

Fig. 3. (a) XRD pattern of SbMP, SbNP and SbNP-MWCNT. (b) Raman spectra of SbNP-MWCNT and MWCNTs. (c) XPS spectrum of SbNP-MWCNT. (d) Nitrogen adsorption-desorption isotherm curves of SbMP and SbNP.

Fig. 4. Cyclic voltammogram of (a) SbMP electrode, (b) SbNP electrode and (c) SbNP-MWCNT electrodes at a scan rate of 0.1 mV s-1 between 0.01 and 2.0 V (vs. Na+/Na). The galvanostatic charge/discharge voltage profiles of (d) SbMP electrode, (e) SbNP electrode and (f) SbNP-MWCNT electrode.

Fig. 5. (a) Cycling performance of SbMP, SbNP, SbNP-MWCNT and MWCNT electrodes at 400 mA g-1. (b) Long-term cycling performance of SbMP-MWCNT and SbNP-MWCNT electrodes at 800 mA g-1. (c) The galvanostatic charge/discharge voltage profiles of SbNP-MWCNT electrode in different cycles. (d) Rate performance of SbNP-MWCNT electrode. (e) CV curves at different scan rates, and (f) the corresponding relationship between peak currents (Ip) and the square root of the scan rate (V1/2) for SbNP-MWCNT.

Table 1 Comparison of the results in this work with those of some previously reported performance of Sb-based anodes for SIBs.

Material	Capacity/ mAhg-1	Cycling stability	Initial CE	Ref.
Spherical nano-Sb@C	435 (0.1 A/g)	88.5% after 500 cycles	63.4%	[25]
Sb/C	610 (0.1 A/g)	94% after 100 cycles	85.0%	[26]
Sb/MWCNT nanocomposite	502 (0.1 A/g)	76.1% after 120 cycles,	69.7%	[28]
Sb-CNC	475 (0.1 A/g)	92.4% after 150 cycles	?62%	[29]
antimony/multilayer graphene hybrid	452 (0.1 A/g)	90% after 200 cycles	76.2%	[40]
Electrospun Sb/C Fibers	422 (0.1 A/g)	82.9% after 300 cycles	55.0%	[41]
Sb porous hollow microspheres	635 (0.1 A/g)	97.2% after 100 cycles	64.6%	[52]
Sb@C microspheres	640 (0.06 A/g)	92.3% after 300 cycles	46.0%	[53]
Sb₂Te₃/C	437 (0.02 A/g)	93% after 400 cycles	?66%	[54]
Yolk-Shell Sb@C	554 (0.05 A/g)	92% after 200 cycles	?69%	[55]
Sb/C composite	423 (0.1 A/g)	90.3% after 200 cycles	78.4%	[56]
nanoporous Sb/C	480 (0.1 A/g)	283 mA h/g after 3000 cycles	NA	[57]
SbNP-MWCNT	471.1 (0.05 A/g)	94.3% after 300 cycles	73.5%	This work

Fig. 6. SEM images of (a-b) SbMP electrode before cycling and after 10 cycles, (c-d) SbNP electrode before cycling and after 50 cycles and (e-f) SbNP-MWCNT electrode before cycling and after 50 cycles.

Table 2 Fitting results of the Nyquist plots using the equivalent circuit.

Sample	SbMP		SbNP		SbNP-MWCNT
	1 st	10th	1 st	10th	1 st	10th
Rs	6.78	8.24	7.658	9.18	5.74	5.23
R_SEI	15.56	193.4	8.88	26.32	5.24	8.72
R_CT	70.74	141	20.58	40.44	23.37	30.6

Fig. 7. EIS plots and the fitting curves of SbMP, SbNP and SbNP-MWCNT electrodes after (a) 1 cycle and (b) 10 cycles. (c) Equivalent circuit for SbNP-MWCNT electrodes.

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