模板剂F127对介孔SnO2的孔结构及电化学性能的影响

doi:10.15541/jim20150521

无机材料学报 ›› 2016, Vol. 31 ›› Issue (6): 588-596.DOI: 10.15541/jim20150521 CSTR: 32189.14.10.15541/jim20150521

模板剂F127对介孔SnO₂的孔结构及电化学性能的影响

翟丽丽^1,2, 张江^1,2, 李轩科^1,2, 丛野^1,2, 董志军^1,2, 袁观明^1,2

(武汉科技大学1. 耐火材料与高温陶瓷国家重点实验室培育基地; 2. 化学工程与技术学院, 湖北省煤转化与新型炭材料重点实验室, 武汉430081)

收稿日期:2015-10-26 修回日期:2015-12-22 出版日期:2016-06-20 网络出版日期:2016-05-19
作者简介:翟丽丽(1990–), 女, 硕士研究生. E-mail: happy123zhai@163.com
基金资助:
国家自然科学基金(51402221, 51472186, 51372177)

F127 Template on Pore Structure and Electrochemical Performances of Mesoporous SnO₂

ZHAI Li-Li^1,2, ZHANG Jiang^1,2, LI Xuan-Ke^1,2, CONG Ye^1,2, DONG Zhi-Jun^1,2, YUAN Guan-Ming^1,2

(1. The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China; 2. Hubei Province Key Laboratory of Coal Conversion and New Carbon Materials, School of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081, China)

Received:2015-10-26 Revised:2015-12-22 Published:2016-06-20 Online:2016-05-19
About author:ZHAI Li-Li. E-mail: happy123zhai@163.com
Supported by:
National Natural Science Foundation of China (51402221, 51472186, 51372177)

摘要/Abstract

摘要：

以SnCl₄·5H₂O和尿素为原料, 嵌段聚醚F127(EO₁₀₆-PO₇₀-EO₁₀₆)为模板剂, 通过水热法制备了介孔SnO₂材料。XRD、TEM和BET等分析结果表明, 模板剂F127添加量对介孔SnO₂的孔结构有重要影响。F127添加量增加, SnO₂比表面积增大, 孔容增大, 孔径分布变宽。电化学测试结果表明, 介孔的存在不仅能为锂离子脱嵌提供通道, 而且可以缓冲SnO₂的体积膨胀, 从而提高介孔SnO₂负极材料的电化学性能; 当F127添加量为6.0 g时, 所制备SnO₂具有124 m²/g的比表面积, 平均孔径为4.94 nm, 表现出最佳的循环性能和倍率性能, 在60 mA/g的电流密度下经30次循环后, 其可逆容量仍保持在434 mAh/g; 循环伏安测试表明部分高活性Li₂O的可逆还原提供了附加的可逆容量。

关键词: 介孔材料, 二氧化锡(SnO2), 孔结构, 锂离子电池

Abstract:

Mesoporous SnO₂ was synthesized via a hydrothermal process using tin chloride (SnCl₄·5H₂O) and urea ((NH₂)₂CO) as raw materials, with a block polyether F127(EO₁₀₆-PO₇₀-EO₁₀₆) as a template. The analysis results (XRD, TEM, BET, etc) show that the amount of F127 has significant influence on pore structure of mesoporous SnO₂. With increasing dosage of F127, specific surface area and pore volume of the mesoporous SnO₂ increase with pore size distribution relatively broad. The results of the electrochemical tests indicate that existence of mesopores not only provide the path for deinsertion and insertion of Li⁺, but also buffer the huge volume expansion of tin dioxide, which consequently improves the electrochemical performances of mesoporous SnO₂as an anode material. When the amount of F127 is 6.0 g, the as-prepared 6F-SnO₂ with a BET specific surface area of 124 m²/g and average pore size of 4.94 nm, displays optimal cycle performance and rate performance which the reversible capacity of the 6F-SnO₂ maintains 434 mAh/g at 60 mA/g after 30 cycles. In addition, the cyclic voltammetric test reveals that the reversible reduction of partial Li₂O with high activity can provide additional reversible capacity.

Key words: mesoporous materials, tin dioxide (SnO2), pore structure, lithium-ion battery

中图分类号:

O646

翟丽丽, 张江, 李轩科, 丛野, 董志军, 袁观明. 模板剂F127对介孔SnO₂的孔结构及电化学性能的影响[J]. 无机材料学报, 2016, 31(6): 588-596.

ZHAI Li-Li, ZHANG Jiang, LI Xuan-Ke, CONG Ye, DONG Zhi-Jun, YUAN Guan-Ming. F127 Template on Pore Structure and Electrochemical Performances of Mesoporous SnO₂[J]. Journal of Inorganic Materials, 2016, 31(6): 588-596.

图/表 12

图1 不同F127添加量制备的介孔SnO2的XRD图谱

Fig. 1 XRD patterns of mesoporous SnO2 samples synthesized with different F127 additive amounts

表1 不同F127添加量制备的介孔SnO2晶粒尺寸

Table 1 Crystalline sizes of mesoporous SnO2 synthesized with different F127 additive amounts

Sample	D₍₁₁₀₎/nm
SnO₂	3.98
3F-SnO₂	4.39
4.5F-SnO₂	4.06
6F-SnO₂	3.84
7.5F-SnO₂	3.66
9F-SnO₂	3.59

图2 不同F127添加量制备的介孔SnO2的SEM照片

Fig. 2 SEM images of SnO2 synthesized with different F127 additive amounts. (a) SnO2; (b) 3F-SnO2; (c) 4.5F-SnO2; (d) 6F-SnO2; (e) 7.5F-SnO2; (f) 9F-SnO2

图3 (a) SnO2和 (b) 6F-SnO2的TEM照片

Fig. 3 TEM images of (a) SnO2 and (b) 6F-SnO2

图4 不同F127添加量制备的介孔SnO2的氮气吸/脱附等温线及孔径分布图(插图)

Fig. 4 N2 adsorption/desorption isotherms and pore size distribution curves (inset) of mesoporous SnO2 synthesized with different F127 additive amounts. (a) SnO2; (b) 3F-SnO2; (c) 6F-SnO2; (d) 9F-SnO2

表2 不同F127添加量制备的介孔SnO2的孔结构参数

Table 2 Pore structural parameters of mesoporous SnO2 synthesized with different F127 additive amounts

Samples	BET/(m²·g^-1)	Pore volume/(cm³·g^-1)	Average pore size/nm
SnO₂	94	0.097	4.10
3F-SnO₂	104	0.110	4.25
4.5F-SnO₂	110	0.122	4.42
6F-SnO₂	124	0.153	4.94
7.5F-SnO₂	126	0.152	4.86
9F-SnO₂	138	0.179	5.19

图5 (a) SnO2和 (b) 6F-SnO2的恒流充放电曲线

Fig. 5 Galvanostatical charge-discharge curves of (a) SnO2 and (b) 6F-SnO2

图6 不同F127添加量制备的介孔SnO2的循环容量图和循环效率图

Fig. 6 Cycling performances and coulombic efficiency of mesoporous SnO2 synthesized with different F127 additive amounts. (a) SnO2; (b) 3F-SnO2; (c) 6F-SnO2; (d) 9F-SnO2

图7 6F-SnO2负极材料的充放电循环性能及库伦效率曲线

Fig. 7 Charge-discharge cycling performance and coulombic efficiency of 6F-SnO2 as anode material

图8 不同F127添加量制备的介孔SnO2的倍率性能曲线

Fig. 8 Rate capability of mesoporous SnO2 synthesized with different F127 additive amounts

图9 (a) SnO2和(b) 6F-SnO2前三次循环伏安曲线

Fig. 9 Cyclic voltammograms (CVs) of (a) SnO2 and (b) 6F- SnO2 for 1st, 2nd, 3rd cycle

图10 SnO2和6F-SnO2的交流阻抗图谱

Fig. 10 Nyquist plots of SnO2 and 6F-SnO2

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模板剂F127对介孔SnO₂的孔结构及电化学性能的影响

F127 Template on Pore Structure and Electrochemical Performances of Mesoporous SnO₂

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