基于共价键作用的四氧化三铁-还原氧化石墨烯复合材料的合成及其储锂性能

doi:10.15541/jim20170441

摘要/Abstract

摘要：

采用溶剂热法制备单分散的Fe₃O₄微球, 对其表面进行包覆SiO₂和氨基化处理, 再与氧化石墨烯复合, 化学还原后得到Fe₃O₄-W-RGO复合材料。SEM和TEM照片显示, SiO₂均匀包覆在Fe₃O₄微球(直径~440 nm)表面形成Fe₃O₄@SiO₂核壳微球, 紧密束缚于RGO纳米片表面。XRD测试结果表明Fe₃O₄微球结晶度好、纯度高。电化学性能测试结果表明: 在0.01~3.00 V电压范围和0.1C倍率下, Fe₃O₄-W-RGO复合材料的首次放电容量为1246 mAh/g, 100次循环后保持830 mAh/g; 在2C倍率下放电容量达到484 mAh/g, 具有较好的倍率性能和循环性能。

关键词: 四氧化三铁, 氧化石墨烯, 共价键作用, 锂离子电池

Abstract:

Monodispersed ferroferric oxide (Fe₃O₄) microspheres were prepared by a solvo-thermal method at first. They were coated with a thin layer of silica, and modified with amino groups. These updated microspheres were mixed with graphene oxide (GO) followed by a chemical reduction to yield Fe₃O₄-W-RGO. The sample was characterized with scanning electron microscopy (SEM) and transition electron microscopy (TEM). Fe₃O₄ microspheres (~440 nm in diameter) are proved to be surface-coated by a SiO₂ layer homogeneously to afford Fe₃O₄@SiO₂core-shell microspheres, tightly bound to reduced graphene oxide (RGO) nanosheets. From X-ray diffraction (XRD) patterns, Fe₃O₄ microspheres display good crystallinity and high purity. Results of electrochemical measurements indicate that Fe₃O₄-W-RGO sample can deliver an initial capacity of 1246 mAh/g at 0.1C rate over 0.01 V-3.00 V (vs. Li⁺/Li), and retain 830 mAh/g after 100 cycles. Even at 2C rate, it can still deliver a capacity of 484 mAh/g. All results suggest that Fe₃O₄-W-RGO composite material possesses good rate capability and cycling performance when used as anode material for lithium-ion batteries.

Key words: ferroferric oxide, graphene oxide, covalent binding interaction, lithium-ion batteries

中图分类号:

TQ174

秦士林, 李继成, 李朝晖, 胡忠良, 丁燕怀, 雷钢铁, 肖启振. 基于共价键作用的四氧化三铁-还原氧化石墨烯复合材料的合成及其储锂性能[J]. 无机材料学报, 2018, 33(7): 741-748.

QIN Shi-Lin, LI Ji-Cheng, LI Zhao-Hui, HU Zhong-Liang, DING Yan-Huai, LEI Gang-Tie, XIAO Qi-Zhen. Ferric Oxide-reduced Graphene Oxide Composite Material: Synthesis Based on Covalent Binding and Its Lithium-storage Property[J]. Journal of Inorganic Materials, 2018, 33(7): 741-748.

图/表 6

图1 样品Fe3O4的XRD图谱及其Rietveld精修图谱(a), Fe3O4、Fe3O4/RGO和Fe3O4-W-RGO样品的XRD图谱(b), Fe3O4-W-RGO样品中Fe2p(c)和C1s(d)的XPS图谱

Fig. 1 XRD patterns and the Rietveld refinement of Fe3O4 sample (a), XRD patterns of Fe3O4, Fe3O4/RGO and Fe3O4-W-RGO samples (b), Fe2p (c) and C1s (d) XPS spectra of Fe3O4-W-RGO sample

图2 样品Fe3O4(a)、Fe3O4/RGO(b)和 Fe3O4-W-RGO(c)的SEM照片; 样品Fe3O4的TEM照片(d)和Fe3O4-W-RGO的HRTEM照片(e)~(f)

Fig. 2 SEM images of Fe3O4 (a), Fe3O4/RGO (b) and Fe3O4-W-RGO (c) samples, TEM image of Fe3O4 (d) and HRTEM images (e, f) of the sample Fe3O4-W-RGO

图3 样品的N2吸附-脱附等温线(a)及其孔径分布曲线(b)

Fig. 3 N2 isothermal adsorption-desorption curves of the samples (a) and pore-size distribution curves (b)

图4 样品在不同循环次数的充放电曲线及其前3次循环伏安曲线图、0.1C倍率的循环性能和倍率性能图

Fig. 4 Galvanostatic charge/discharge profiles of the samples at various cycles and their cyclic voltammograms for the first three cycles, cycling performance and rate capability

图5 样品在充放电循环前后的形貌变化示意图

Fig. 5 Schematic illustration of the morphology change of samples before and after the repeated charging-discharging process

图6 样品循环前后的电化学阻抗谱的Nyquist图, 等效电路图及其拟合数据

Fig. 6 Electrochemical impedance spectra of the samples before and after cycling, equivalent circuit model and the stimulated data

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