Sodium Storage Behavior of Nanoporous Sb/MCNT Anode Material with High Cycle Stability by Dealloying Route

doi:10.15541/jim20210105

Abstract

Abstract:

To improve the cycle performance of Sb-based anode materials for sodium storage, a simple two-step method (mechanical assisted chemical alloying and acid dissolution dealloying) is proposed to prepare nano sized and porous antimony/multi-walled carbon nanotubes (De-Sb/MCNT) composite. Different methods were employed to characterize the physicochemical and electrochemical properties of De-Sb/MCNT material as anode for sodium storage. The results show that compared to the Raw-Sb/MCNT obtained by direct ball milling of commercial raw Sb and MCNT, the De-Sb/MCNT material exhibits better cycle performance of sodium storage. At a current density of 200 mA·g^-1, the De-Sb/MCNT delivers the reversible specific capacity of 408.6 mAh·g^-1 with the initial Coulombic efficiency of 69.2%. After 330 cycles at 800 mA·g^-1, the capacity retention rate can still retain 88%. The superior cycle performance of De-Sb/MCNT benefits from the “pre-pulverization” effect of mechanically-assisted chemical alloying/acid dissolution dealloying on commercial Sb, which promotes the nanocrystallization and porosity of the material. The De-Sb/MCNT relieves the volume expansion during charging and discharging, thus achieves excellent cycle stability. This dealloying process at ambient temperature is expected to provide a new approach for sodium storage of alloy anode materials with prolonged and stable cycles.

Key words: Sb, sodium ion battery, mechanical ball milling, dealloying, cycle stability

CLC Number:

O646

ZENG Fanxin, LIU Chuang, CAO Yuliang. Sodium Storage Behavior of Nanoporous Sb/MCNT Anode Material with High Cycle Stability by Dealloying Route[J]. Journal of Inorganic Materials, 2021, 36(11): 1137-1144.

Figures/Tables 10

Fig. 1 Schematic illustration for the synthetic process of De- Sb/MCNT composite

Fig. 2 SEM images of (a) Raw-Sb, (b) AlSb, (c) De-Sb, (d) MCNT, (e, f) Raw-Sb/MCNT and (g, h) De-Sb/MCNT

Fig. 3 (a) TEM image, (b) HRTEM image, (c) SAED pattern, (d) SEM image and the corresponding (e) Sb, (f) C, and (g) O elemental mapping images of De-Sb/MCNT

Fig. 4 XRD patterns of (a) AlSb, (b) Raw-Sb, De-Sb, Raw-Sb/MCNT and De-Sb/MCNT, (c) Raman spectra of MCNT, De-Sb and De-Sb/MCNT, and (d) XPS spectrum of De-Sb/MCNT Colorful figures are available on website

Fig. 5 (a) N2 adsorption-desorption isotherms of Raw-Sb, De-Sb, Raw-Sb/MCNT and De-Sb/MCNT, and (b) pore size distributions of Raw-Sb and De-Sb Colorful figures are available on website

Fig. 6 (a) Cyclic voltammogram and (b) Galvanostatic charge/discharge voltage profile at 200 mA·g-1 of De-Sb/MCNT, (c) long-term cycling performance of Raw-Sb/MCNT and De-Sb/MCNT at 800 mA·g-1, and (d) rate performance of De-Sb/MCNT Colorful figures are available on website

Fig. 7 EIS plots of Raw-Sb/MCNT and De-Sb/MCNT after 1 and 50 cycles with inset showing the corresponding equivalent circuit Colorful figures are available on website

Table 1 Fitting results of the EIS plots of Raw-Sb/MCNT and De-Sb/MCNT

Sample	Cycle number	R_S/Ω	R_SEI/Ω	R_CT/Ω
Raw-Sb/MCNT	1	2.89	37.62	23.70
Raw-Sb/MCNT	50	4.38	43.29	142.90
De-Sb/MCNT	1	1.32	21.44	44.84
De-Sb/MCNT	50	2.68	24.44	51.25

Fig. 8 SEM images of (a, c) Raw-Sb/MCNT electrode and (b, d) De-Sb/MCNT electrode (a, b) before and (c, d) after 50 cycles

Table S1 Electrochemical performance of different Sb-based materials as Na ion battery electrodes

Material	Capacity/(mAh·g^-1)	Cycling stability	Ref.
Sb/Super P	610 (0.1 A·g^-1)	94% after 100 cycles	[1]
Sb/MCNT	502 (0.1 A·g^-1)	76.1% after 120 cycles	[2]
SbO_x/RGO	427 (0.1 A·g^-1)	95% after 100 cycles	[3]
Sb-AlC_0.75-C	295 (0.1 A·g^-1)	83% after 100 cycles	[4]
Dealloyed Sb	620 (0.1 A·g^-1)	90.2 % after 100 cycles	[5]
Sb nanoparticles/RGO	476 (0.1 A·g^-1)	81% after 45 cycles	[6]
Sb₂S₃/C	598 (0.2 A·g^-1)	93.1% after 100 cycles	[7]
Nanoporous Sb/C	436 (0.05 A·g^-1)	No fading after 200 cycles	[8]
Antimony nanocrystals/C	520 (0.1 A·g^-1)	88% after 500 cycles	[9]
SiC-Sb-Cu-C	542 (0.02 A·g^-1)	No fading after 100 cycles	[10]
De-Sb/MCNT	408.6 (0.2 A·g^-1)	97% after 200 cycles, 88% after 330 cycles	This work

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