多孔氧化锡团聚体的合成及其电化学性能的研究

doi:10.3724/SP.J.1077.2011.11557

摘要/Abstract

摘要：

采用十六烷基三甲基溴化铵(CTAB)为模板剂, 磷酸三甲酯(C₃H₉O₄P)为辅助模板剂, 以二水合四氯化锡(SnCl₄·2H₂O)为锡源, 在水溶液中用水热法合成了孔壁为结晶态多孔氧化锡纳米粒子团聚体. 通过扫描电子显微镜(SEM), 高分辨透射电子显微镜(HRTEM), X射线衍射(XRD), 热分析, N₂吸附-脱附等对样品的结构和形貌进行了表征分析. 结果表明: 小分子磷酸三甲酯的加入能够很好地辅助四氯化锡在CTAB胶束附近的堆积, 有利于提高材料的比表面积, 并改善体系的热稳定性. 进一步通过恒电流法研究了材料作为锂离子电池负极材料的电化学性能. 经300℃煅烧处理的多孔氧化锡团聚体表现出了高的首次可逆脱锂容量(962.4 mAh/g), 经分析原因发现, 这是由于体系内残留的不完全燃烧的碳及材料本身的多孔结构引起的. 综上可见, 加入电负性较大的大体积反离子作为共模板剂可作为一种改善多孔金属氧化物材料性能的有益尝试.

关键词: 多孔二氧化锡团聚体, 水热法, 分子共模板, 锂离子电池

Abstract:

Porous SnO₂ agglomerates with crystalline pore walls were obtained by employing CTAB and trimethyl phosphate (TMP) as molecular co-templates via hydrothermal method. Tin (IV) chloride dihydrate was used as the inorganic precursor at high molar ratio of surfactant/Sn⁴⁺. The resulting samples were characterized by SEM, (HR)TEM, XRD, thermal analysis and nitrogen adsorption-desorption to examine the structural and morphological characters. The results indicate that the addition of small co-template TMP can facilitate the assembling of tin ions near the CTAB micelles, which can increase the specific surface area and improve the thermal stability of the resulted sample. The electrochemical properties of porous SnO₂ as the anode materials of lithium-ion battery (LIB) are further investigated by using galvanostatic method. The porous SnO₂ calcined at 300℃ displays a much higher reversible capacity of 962.4 mAh/g, which can be ascribed to the incomplete combustion of the organic materials and the unique nanostructure itself. The addition of bigger counter ions with large electric negativity might give an alternative approach to improve the properties of porous metal oxides synthesized by soft template method.

Key words: porous SnO₂ agglomerates, hydrothermal method, molecular co-template, lithium ion battery

中图分类号:

TQ174

李芳, 祝迎春. 多孔氧化锡团聚体的合成及其电化学性能的研究[J]. 无机材料学报, 2012, 27(2): 219-224.

LI Fang, ZHU Ying-Chun. Synthesis and Electrochemical Properties of Porous SnO₂ Agglomerates[J]. Journal of Inorganic Materials, 2012, 27(2): 219-224.

图/表 6

Fig. 1 TG profiles of the as-synthesized sample (a) and SEM image of porous SnO2 synthesized at 300℃ (b)

Fig. 2 TEM (a) and the HRTEM (b) images of porous SnO2 synthesized at 300℃, insert is the corresponding SAED pattern

Fig. 3 TEM images of porous SnO2 synthesized at different temperatures

Fig. 4 XRD patterns (a) and nitrogen adsorption/desorption isotherms (b) of porous SnO2 synthesized at 300, 350 and 400℃

Table 1 Structural properties of the as-produced samples

Porous SnO₂	BET area /(m²∙g^-1)	Average pore size/nm	Pore volume/ (cm³∙g^-1)
300℃	146.1	6.86	0.304
350℃	67.6	4.87	0.209
400℃	59.6	2.37	0.182

Fig. 5 Comparison of (a) the first charge and discharge curves and the cycling performance of porous SnO2 synthesized at different temperatures (b) 300℃, (c) 350℃, (d) 400℃

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