半空心/实心ZnMn2O4微球: 合成及锂离子电池性能

doi:10.15541/jim20170169

摘要/Abstract

摘要：

采用模板、溶剂热法分别制备出半空心及实心ZnMn₂O₄微球。采用XRD、SEM、TEM等对制备的纳米材料的晶体结构和形貌等进行了表征。结果表明, 不同的溶剂配比对产物的形貌和结构有一定的影响。当乙二醇和水的体积比为3∶1时, 可以得到ZnMn₂O₄多孔实心微球。采用模板-溶剂热法及后续焙烧可得到ZnMn₂O₄半空心微球, 这种半空心结构包含双层的ZnMn₂O₄壳及一个小的碳核。比较研究了ZnMn₂O₄空心微球与多孔实心微球的电化学性能, 结果显示, 半空心结构的ZnMn₂O₄材料比实心的ZnMn₂O₄微球具有更高的初始放电容量、更好的倍率性能及循环性能。

关键词: ZnMn₂O₄, 空心微球, 多孔材料, 锂离子电池

Abstract:

Porous semi-hollow/solid ZnMn₂O₄ microspheres were controllably synthesized via template and solvothermal methods respectively. The as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). It is found that the solvent ratio exerts a crucial effect on the morphology and microstructure of solid ZnMn₂O₄ microspheres. The porous solid ZnMn₂O₄microspheres could be obtained when the volume ratio of ethylene glycol to deionized water was 3 : 1. The semi-hollow ZnMn₂O₄microspheres with a double-layer ZnMn₂O₄ shell and a small C core could be synthesized via a template-solvothermal method and post-calcination process. The electrochemical properties of as-prepared semi-hollow/solid ZnMn₂O₄microspheres as anode materials of lithium-ion batteries were investigated. Semi-hollow ZnMn₂O₄ microspheres exhibit higher initial discharge capacity, better rate capacity and cycling performance than solid ZnMn₂O₄ microspheres.

Key words: ZnMn₂O₄, hollow microsphere, porous materials, lithium-ion battery

中图分类号:

TQ174

李波, 郝文, 文晓刚. 半空心/实心ZnMn₂O₄微球: 合成及锂离子电池性能[J]. 无机材料学报, 2018, 33(3): 307-312.

LI Bo, HAO Wen, WEN Xiao-Gang. Semi-hollow/Solid ZnMn₂O₄ Microspheres: Synthesis and Performance in Li Ion Battery[J]. Journal of Inorganic Materials, 2018, 33(3): 307-312.

图/表 8

图1 不同样品的XRD图谱

Fig. 1 XRD patterns of different samples

图2 ZMO-1焙烧前(a)和焙烧后(b), ZMO-2焙烧前(c)和焙烧后(d)的SEM照片

Fig. 2 SEM images of uncalcined ZMO-1 (a), calcined ZMO-1 (b), uncalcined ZMO-2 (c), and calcined ZMO-2 (d)

图3 C微球(a)、未焙烧C/ZnMn2O4微球(b)、500℃焙烧C/ZnMn2O4微球(c)和600℃焙烧 C/ZnMn2O4微球(d)的SEM图片

Fig. 3 SEM images of carbon microspheres (a), uncalcined C/ZnMn2O4 core/shell microspheres (b), hollow ZnMn2O4 calcined at 500℃ (c) and 600℃ (d)

图4 600℃焙烧产物(ZMO-4)的TEM照片及元素分布图

Fig. 4 TEM images and element mappings of the samples calcined at 600℃(a) Bright-field TEM image of ZnMn2O4 hollow microsheres, (b) Dark-field TEM image of a single ZnMn2O4 hollow microshere, (c-f) elements mapping of (c) Mn, (d) Zn, (e) O and (f) C in a single ZnMn2O4 microsphere

图5 半空心结构ZnMn2O4微球的生长机理示意图

Fig. 5 Schematic diagram showing the growth process of semi-hollow ZnMn2O4 microspheres

图6 ZMO-1(a)、ZMO-2(b)和 ZMO-4(c)的充放电曲线

Fig. 6 Discharge-charge curves of ZMO-1 (a), ZMO-2 (b) and ZMO-4 (c)

图7 ZMO-1、ZMO-2(a)和ZMO-4(b)的倍率性能

Fig. 7 Rate performance of ZMO-1, ZMO-2 (a) and ZMO-4 (b)

图8 ZMO-1(a)、ZMO-2(b)及ZMO-4(c)的循环性能

Fig. 8 Cycling performances of ZMO-1 (a), ZMO-2 (b) and ZMO-4 (c)

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半空心/实心ZnMn₂O₄微球: 合成及锂离子电池性能

Semi-hollow/Solid ZnMn₂O₄ Microspheres: Synthesis and Performance in Li Ion Battery

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