去合金化制备具有高循环稳定性的纳米多孔Sb/MCNT储钠负极材料

doi:10.15541/jim20210105

摘要/Abstract

摘要：

为提升Sb基负极材料的储钠循环性能, 通过简单的两步法(机械辅助化学合金化和酸溶解去合金化)制备纳米化和多孔化的去合金锑/多壁碳纳米管(De-Sb/MCNT)复合物, 采用不同方法表征材料的物理化学性质和储钠电化学性能。结果显示, De-Sb/MCNT材料的可逆比容量达到408.6 mAh·g^-1 (200 mA·g^-1), 首周库仑效率为69.2%; 在800 mA·g^-1循环330周后, 容量保持率仍可达88%, 展现出优异的储钠循环性能。这得益于机械辅助化学合金化/酸溶解去合金化对商品化Sb的“预粉化”作用, 促进了材料的纳米化和多孔化, 缓解了充放电过程中的体积膨胀, 实现了高的循环稳定性。这种常温合金化/去合金化的方法为制备循环稳定的储钠合金负极材料提供了新的途径。

关键词: Sb, 钠离子电池, 机械球磨, 去合金化, 循环稳定性

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

中图分类号:

O646

曾凡鑫, 刘创, 曹余良. 去合金化制备具有高循环稳定性的纳米多孔Sb/MCNT储钠负极材料[J]. 无机材料学报, 2021, 36(11): 1137-1144.

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.

图/表 10

图1 De-Sb/MCNT复合物合成示意图

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

图2 (a)Raw-Sb、(b)AlSb、(c)De-Sb、(d)MCNT、(e, f)Raw-Sb/ MCNT和(g, h)De-Sb/MCNT的SEM照片

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

图3 De-Sb/MCNT的(a)TEM照片、(b)高分辨TEM照片、(c)电子衍射图、(d)SEM照片及对应的(e)Sb、(f)C和(g)O的元素分布图

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

图4 (a)AlSb合金、(b)Raw-Sb、De-Sb、Raw-Sb/MCNT和De-Sb/MCNT的XRD图谱; (c)MCNT、De-Sb和De-Sb/MCNT的拉曼光谱图; (d)De-Sb/MCNT的XPS图谱

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

图5 (a)Raw-Sb、De-Sb、Raw-Sb/MCNT和De-Sb/MCNT的N2吸附-脱附等温线; (b)Raw-Sb和De-Sb的孔径分布

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

图6 De-Sb/MCNT的(a)循环伏安曲线和(b)在200 mA·g-1电流下的充放电曲线; (c) Raw-Sb/MCNT和De-Sb/MCNT在800 mA·g-1下的长循环性能; (d) De-Sb/MCNT的倍率性能图

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

图7 Raw-Sb/MCNT和De-Sb/MCNT循环1周和50周后的EIS图谱和对应的等效电路图(插图)

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

表1 Raw-Sb/MCNT和De-Sb/MCNT的EIS图谱的拟合结果

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

图8 (a, c)Raw-Sb/MCNT电极和(b, d)De-Sb/MCNT电极50圈循环(a, b)前(c, d)后的SEM照片

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

表S1 Sb基材料的Na离子电池电化学性能

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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