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

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

参考文献 27

[1]	DAHN J R, ZHENG T, LIU Y, et al.Mechanisms for lithium insertion in carbonaceous materials.Science, 1995, 270(5236): 590-593.
[2]	IDOTA Y, KUBOTA T, MATSUFUJI A, et al.Tin-based amorphous oxide: a high-capacity lithium-ion-storage material.Science, 1997, 276(5317): 1395-1397.
[3]	COURTNEY I A, DAHN J R.Electrochemical and in situ X-ray diffraction studies of the reaction of lithium with tin oxide composites.Journal of the Electrochemical Society, 1997, 144(6): 2045-2052.
[4]	FAN J, WANG T, YU C Z, et al.Ordered nanostructured tin-based oxides/carbon composite as the negative-electrode material for lithium-ion batteries.Advanced Materials, 2004, 16(16): 1432-1436.
[5]	WANG J Z, DU N, ZHANG H, et al.Large-scale synthesis of SnO2 nanotube arrays as high-performance anode materials of Li-ion batteries.The Journal of Physical Chemistry, 2011, 115(22): 11302-11305.
[6]	YIN X M, LI C C, ZHANG M, et al.One-step synthesis of hierarchical SnO2 hollow nanostructures via self-assembly for high power lithium-ion batteries.The Journal of Physical Chemistry, 2010, 114(17): 8084-8088.
[7]	WANG C, ZHOU Y, GE M Y, et al.Large-scale synthesis of SnO2 nanosheets with high lithium-ion storage capacity.Journal of the American Chemical Society, 2009, 132(1): 46-47.
[8]	ZHANG X, JIANG B, GUO J X, et al.Large and stable reversible lithium-ion storages from mesoporous SnO2 nanosheets with ultralong lifespan over 1000 cycle.Journal of Power Sources, 2014, 268: 365-371.
[9]	SHIVA K, KIRAN M S R N, RAMAMURTY U, et al. A broad pore size distribution mesoporous SnO2 as anode for lithium-ion batteries.J. Solid State Electrochem., 2012, 16(11): 3643-3649.
[10]	LIU X W, ZHONG X W, YANG Z Z, et al.Gram-scale synthesis of graphene-mesoporous SnO2 composite as anode for lithium-ion batteries.Electrochimica Acta, 2015, 152(10): 178-182.
[11]	YANG Z L, ZHAO S J, JIANG W, et al.Carbon-supported SnO2 nanowire arrays with enhanced lithium storage properties.Electrochimica Acta, 2015, 158: 321-326.
[12]	WU P, DU N, ZHANG H, et al.Carbon-coated SnO2 nanotubes template-engaged synthesis and their application in lithium-ion batteries.Nanoscale, 2011, 3(2): 746-750.
[13]	YANG Q, HU W B.Amorphous SnO2-C composite fibers and their electrochemical performance.Journal of Inorganic Materials, 2015, 30(8): 861-888.
[14]	ZHANG C F, PENG X, GUO Z P, et al.Carbon-coated SnO2/graphene nanosheets as highly reversible anode materials for lithium ion batteries.Carbon, 2012, 50(5): 1897-1903.
[15]	YU Z J, WANG Y L, DENG H G, et al.Synthesis and electrochemical performance of SnO2/graphene anode material for lithium ion batteries.Journal of Inorganic Materials, 2013, 28(5): 515-520.
[16]	LI Y D, LU X, WANG H K, et al.Growth of ultrafine SnO2 nanoparticles within multiwall carbon nanotube networks: non-solution synthesis and excellent electrochemical properties as anodes for lithium ion batteries.Electrochimica Acta, 2015, 178: 778-785.
[17]	LIU Y F, HU Z H, XU K, et al.Surface modification and performance of activated carbon electrode material.Acta Phys. -Chim. Sin., 2008, 24(7): 1143-1148.
[18]	KIM H, CHO J.Hard templating synthesis of mesoporous and nanowire SnO2 lithium battery anode materials.Journal of Materials Chemistry, 2008, 18(7): 771-775.
[19]	SONG H H, YANG S B, CHEN X H.The effect on high charge/discharge rate performance of the lithium ion battery.Chinese Journal of Power Sources, 2009, 33(6): 443-448.
[20]	WANG Y, SAKAMOTO J, KOSTOV S, et al.Structural aspects of electrochemically lithiated SnO: nuclear magnetic resonance and X-ray absorption studies.Journal of Power Sources, 2000, 89(2): 232-236.
[21]	LOU X W, LI C M, ARCHER L A.Designed synthesis of coaxial SnO2@carbon hollow spheres for highly reversible lithium storage.Advanced Materials, 2009, 21(24): 2536-2539.
[22]	ZHANG Y L, LIU Y, LIU M L.Nano-structured columnar tin oxide thin film electrode for lithium ion batteries.Chemistry of Materials, 2006, 18(19): 4643-4646.
[23]	WANG J H, LI B, WU H Y, et al.Synthesis of mesoporous SnO2 and its application in lithium ion battery.Acta Phys. -Chim. Sin., 2008, 24(4): 681-685.
[24]	LIU B, CAO M H, ZHAO X Y, et al.Facile synthesis of ultraﬁne carbon-coated SnO2 nanoparticles for high-performance reversible lithium storage.Journal of Power Sources, 2013, 243: 54-59.
[25]	ZHANG Y X, ZHANG X J.The influence of the template agent on the order mesoporous carbon channel structure.Journal of Beijing University of Chemical Technology(Natural Science), 2010, 37(5): 83-87.
[26]	LI Z P, ZHAO R H, GUO F, et al.Preparation and characterization of ordered mesoporous alumina with high specific surface area with F127 as template.Chemical Journal of Chinese Universities, 2008, 29(1): 13-17.
[27]	COURTNEY I A, MCKINNON W R, Dahn J R.On the aggregation of tin in SnO composite glasses caused by the reversible reaction with lithium.Journal of the Electrochemical Society, 1999, 146(1): 59-68.

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 27

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨卓, 卢勇, 赵庆, 陈军. X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用[J]. 无机材料学报, 2023, 38(6): 589-605.
[2]	宿拿拿, 韩静茹, 郭印毫, 王晨宇, 石文华, 吴亮, 胡执一, 刘婧, 李昱, 苏宝连. 基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究[J]. 无机材料学报, 2022, 37(9): 1016-1022.
[3]	王洋, 范广新, 刘培, 尹金佩, 刘宝忠, 朱林剑, 罗成果. 钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制[J]. 无机材料学报, 2022, 37(9): 1023-1029.
[4]	朱河圳, 王选朋, 韩康, 杨晨, 万睿哲, 吴黎明, 麦立强. 超高镍LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂正极材料的储锂稳定性的提升机制[J]. 无机材料学报, 2022, 37(9): 1030-1036.
[5]	冯锟, 朱勇, 张凯强, 陈长, 刘宇, 高彦峰. 勃姆石纳米片增强锂离子电池隔膜性能研究[J]. 无机材料学报, 2022, 37(9): 1009-1015.
[6]	陈莹, 栾伟玲, 陈浩峰, 朱轩辰. 基于应力场的锂离子电池正极多尺度失效研究[J]. 无机材料学报, 2022, 37(8): 918-924.
[7]	苏东良, 崔锦, 翟朋博, 郭向欣. 石榴石型Li_6.4La₃Zr_1.4Ta_0.6O₁₂对Si/C负极表面固体电解质中间相的调控机制研究[J]. 无机材料学报, 2022, 37(7): 802-808.
[8]	江依义, 沈旻, 宋半夏, 李南, 丁祥欢, 郭乐毅, 马国强. 双功能电解液添加剂对锂离子电池高温高电压性能的影响[J]. 无机材料学报, 2022, 37(7): 710-716.
[9]	肖美霞, 李苗苗, 宋二红, 宋海洋, 李钊, 毕佳颖. 表面端基卤化Ti₃C₂ MXene应用于锂离子电池高容量电极材料的研究[J]. 无机材料学报, 2022, 37(6): 660-668.
[10]	王禹桐, 张非凡, 许乃才, 王春霞, 崔立山, 黄国勇. 水系锂离子电池负极材料LiTi₂(PO₄)₃的研究进展[J]. 无机材料学报, 2022, 37(5): 481-492.
[11]	李昆儒, 胡省辉, 张正富, 郭玉忠, 黄瑞安. 源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料[J]. 无机材料学报, 2021, 36(9): 929-935.
[12]	王影, 张文龙, 邢彦锋, 曹苏群, 戴新义, 李晶泽. 非晶态磷酸锂包覆钛酸锂电极在0.01~3.00 V电压范围的性能研究[J]. 无机材料学报, 2021, 36(9): 999-1005.
[13]	刘勇, 白海军, 赵奇志, 杨金戈, 李宇杰, 郑春满, 谢凯. LiNi_0.8Co_0.15Al_0.05O₂/石墨锂离子电池高荷电存储老化机理研究[J]. 无机材料学报, 2021, 36(2): 175-180.
[14]	湛菁,徐昌藩,龙怡宇,李启厚. 聚丙烯酰胺凝胶法制备Bi₂Mn₄O₁₀及其电化学性能[J]. 无机材料学报, 2020, 35(7): 827-833.
[15]	黄谢意,王鹏,尹国恒,张绍宁,赵伟,王东,毕庆员,黄富强. 掺磷非晶氧化钛负载铂用于高效催化氧化挥发性有机化合物[J]. 无机材料学报, 2020, 35(4): 482-490.