有序介孔硅/碳复合结构负极材料的制备与电化学性能研究

doi:10.15541/jim20170145

摘要/Abstract

摘要：

以SBA-15( SiO₂)有序介孔模板为前驱体, 通过镁热还原和碳包覆修饰路线, 制备出二维定向组装的束捆状有序介孔覆碳纳米组织(OMP-Si/C), 并细致研究了SBA-15的镁热还原过程, 对OMP-Si/C复合结构进行电化学性能测试。经XRD测试分析发现: 镁热还原过程中存在Mg₂Si中间相反应路径, 基于此提出反应温度-时间(T-t)相转变图; DSC/TG表明, Mg相通过反应-熔化协调联动作用, 在低于熔点(648℃)时熔化, 且发生液/固反应。从FE-SEM观察到SBA-15柱状单元被装配成类藕根链束捆状Si有序介孔组织, 并基于镁液微涡流场卷吸作用机理解释了该二维定向组装过程。所得致密纳米组织能有效抵消充放电过程中Si相的固有体积变化, 从而表现出优异的循环稳定性能和倍率性能。

关键词: 锂离子电池, Si有序介孔组织, 镁热还原反应, Mg₂Si中间相, 微流场装配

Abstract:

Using SBA-15 of SiO₂ template as precursor, a bundle-shaped ordered mesoporous nanoarchitecture Si/C composite (OMP-Si/C) was successfully assembled 2D-directionally by a magnesiothermic reduction reaction (MRR) route and the ensuing carbon-coating modification processing, and the MRR process of the SBA-15 was investigated in depth, the electrochemical performance of as-prepared OMP-Si/C composites was tested. Analysis based on XRD data reveals the presence of a reaction path of Mg₂Si intermediate phase in MRR process, on which a T-t (reaction temperature-reaction time) phase transition diagram is proposed. DSC/TG analysis shows that Mg particles may melt below its melting point (648℃) upon reaction, and in liquid-solid reaction pattern react with SiO₂ via melting-reaction teamwork. Observed from FE-SEM, SBA-15 column units are validated to assemble into a lotus-root-chain-bundle shaped nanoarchitecture of ordered mesoporous silicon, which can effectively offset the drastic volume change of Si material inherent in the charge/discharge process, and exhibit excellent cycling stability and rate capability. Based on the micro-fluid field assembling mechanism, the two-dimensional directional assembly process can be reasonably interpreted.

Key words: Li-ion battery, ordered mesoporous Si architecture, magnesiothermic reduction reaction, intermediate phase of Mg₂Si, micro fluid field assembly

中图分类号:

O646

王静, 陈志柠, 郭玉忠, 黄瑞安, 王剑华. 有序介孔硅/碳复合结构负极材料的制备与电化学性能研究[J]. 无机材料学报, 2018, 33(3): 313-319.

WANG Jing, CHENG Zhi-Ning, GUO Yu-Zhong, HUANG Rui-An, WANG Jian-Hua. Preparation and Electrochemical Performance of Ordered Mesoporous Si/C Composite for Anode Material[J]. Journal of Inorganic Materials, 2018, 33(3): 313-319.

图/表 8

图1 SBA-15镁热还原样品的XRD图谱

Fig. 1 XRD patterns of the samples prepared by magnesiothermic reduction routes(a) Reaction at 400, 500, 600 and 660℃for 5 h, OMP-Si and OMP-Si/C; (b) Reaction at 560℃for 5, 10, 15 and 20 h

图2 SBA-15镁热还原反应相变温度-时间图(T-t图)

Fig. 2 Temperature-time graph reaction transformation of SBA-15 via magnesiothermic reduction routes (T-t graph)

图3 不同条件下合成的多孔硅FESEM照片

Fig. 3 FESEM images of porous Si synthesized under different conditions(a, b) SBA-15; (c, d) Without acid etching, 400℃, 20 h; (e, f) Without acid etching, 500℃, 20 h; (g, h) Without acid etching, 600℃, 5 h; (i, j) Without acid etching, 660℃, 5 h; (k, l) Hydrochloric acid treatment OMP-Si, 660℃, 5 h

图4 SBA-15/Mg混合粉体DSC/TG分析曲线

Fig. 4 DSC/TG analyzing curves of SBA-15/Mg powdery admixture sample with weight ratio of 1∶1 at temperature rise rate of 10℃/min

图5 SBA-15镁热还原反应机理示意图

Fig. 5 Schematic illustration of the mechanism of SBA-15 magnesiothermic reduction

图6 N2吸附-解吸等温线和孔径分布图

Fig. 6 N2 adsorption and desorption isotherms with inset showing the pore size distribution curve for synthesized samples

图7 OMP-Si/C样品的充放电曲线(a), 比容量和库仑效率(b)

Fig. 7 (a) Charge/discharge curves of OMP-Si/C sample and (b) the specific capacity and columbic efficiency versus cycle number for as-prepared samples

图8 (a) OMP-Si样品的倍率性能和(b) OMP-Si/C样品的倍率性能

Fig. 8 Rate performance of (a) OMP-Si and (b) OMP-Si/C

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