石墨烯装载不同含量钴锌铁氧体及其电磁行为对比

doi:10.15541/jim20180280

摘要/Abstract

摘要：

以天然鳞片石墨为原料制备氧化石墨(GO), 应用水热法制备钴锌铁氧体(Co_0.5Zn_0.5Fe₂O₄), 并将两者制备成石墨烯(rGO)/Co_0.5Zn_0.5Fe₂O₄复合材料。采用X射线衍射(XRD)、拉曼光谱(Raman)、红外光谱(FT-IR)研究rGO/Co_0.5Zn_0.5Fe₂O₄的结构; 应用透射电子显微镜(TEM)和矢量网络分析仪(VNA)研究不同复合比例对rGO/Co_0.5Zn_0.5Fe₂O₄复合材料形貌、电磁损耗特性、德拜弛豫模型及电磁响应行为的影响。结果表明: 复合反应后的GO在XRD图谱中主衍射峰由2θ=9.74°变化为2θ=24.15°, 且红外光谱图中显示含氧官能团消失, 均说明GO成功还原为rGO。透射电子显微镜图中可以看到Co_0.5Zn_0.5Fe₂O₄嵌布在rGO上。复合反应过程中, 当钴锌铁氧体的含量增大, 分散性逐渐减弱。Co_0.5Zn_0.5Fe₂O₄与GO质量比为2 : 1时制备的rGO/Co_0.5Zn_0.5Fe₂O₄复合材料的吸波性能最佳, 在15.11 GHz处反射率达到最小值-36.89 dB, 有效吸波频带宽为3.74。

关键词: 石墨烯, 复合材料, 钴锌铁氧体, 电磁行为, 氧化石墨烯

Abstract:

A kind of graphene composite (rGO/Co_0.5Zn_0.5Fe₂O₄) was synthesized with the graphene oxide (GO) prepared from natural flake graphite and cobalt-zinc ferrite (Co_0.5Zn_0.5Fe₂O₄) manufactured by the hydrothermal method. The structure of composites was characterized by X-ray diffraction (XRD), Raman spectrometer (Raman) and the Fourier-transform infrared spectroscopy (FT-IR). Morphology, electromagnetic loss properties, Debye relaxation, and microwave absorbing properties of rGO/Co_0.5Zn_0.5Fe₂O₄ were investigated by transmission electron microscope (TEM) and vector network analyser (VNA). Sharp peak of graphene oxide was changed from 2θ=9.74° to 24.15° in the XRD patterns and the oxygen functional group disappeared after the composite reaction, which demonstrated that GO was successfully reduced to rGO. The graphene was embedded with cobalt-zinc ferrite, observed by transmission electron microscope, with its dispersion worse with the loaded Co_0.5Zn_0.5Fe₂O₄ increasing. Absorbing property of rGO/Co_0.5Zn_0.5Fe₂O₄ composite prepared with w(Co_0.5Zn_0.5Fe₂O₄) : w(GO)= 2 : 1 is the best with the minimum reflectivity of -36.89 dB at 15.11 GHz and the effective absorption frequency bandwidth of 3.74.

Key words: graphene, composite materials, cobalt-zinc ferrite, electromagnetic behavior, graphene oxide

中图分类号:

TM277
TQ127

马志军, 莽昌烨, 赵海涛, 关智浩, 程亮. 石墨烯装载不同含量钴锌铁氧体及其电磁行为对比[J]. 无机材料学报, 2019, 34(4): 407-416.

Zhi-Jun MA, Chang-Ye MANG, Hai-Tao ZHAO, Zhi-Hao GUAN, Liang CHENG. Comparison of Electromagnetism Behavior of Different Content Cobalt-zinc Ferrite Loaded with Graphene[J]. Journal of Inorganic Materials, 2019, 34(4): 407-416.

图/表 9

图1 天然鳞片石墨(a)、GO(b)、Co0.5Zn0.5Fe2O4(c)和rGO/Co0.5Zn0.5Fe2O4复合材料(d)的XRD图谱

Fig. 1 XRD patterns of natural flake graphite (a), GO (b), Co0.5Zn0.5Fe2O4 (c), and rGO/Co0.5Zn0.5Fe2O4 composite (d)

表1 铁氧体的组分和结构参数

Table 1 Composition and structure parameters of ferrite

Structural formula	2θ/(°)	a/nm	(311) Priority crystallization diffraction peak
Structural formula	2θ/(°)	a/nm	FWHM/rad	Intensity/(a.u.)	Size/nm
Co_0.5Zn_0.5Fe₂O₄	35.597	0.8391	0.618	86	13.8
rGO/Co_0.5Zn_0.5Fe₂O₄	35.595	0.8358	0.466	94	17.7

图2 天然鳞片石墨、GO(a)和Co0.5Zn0.5Fe2O4、rGO/Co0.5Zn0.5Fe2O4复合材料(b)的拉曼光谱

Fig. 2 Raman spectra of natural flake graphite, GO (a) and Co0.5Zn0.5Fe2O4, rGO/Co0.5Zn0.5Fe2O4 composite (b)

表2 天然鳞片石墨、GO和rGO/Co0.5Zn0.5Fe2O4复合材料的ID值与IG值的比率

Table 2 ID/IG ratios of natural flake graphite, GO and rGO/Co0.5Zn0.5Fe2O4 composite

Samples	Graphite	GO	rGO/Co_0.5Zn_0.5Fe₂O₄
I_D/I_G	0.21	0.95	1.02

图3 天然鳞片石墨、GO (a)、Co0.5Zn0.5Fe2O4 (b)和rGO/Co0.5Zn0.5Fe2O4 (c)的FT-IR谱图

Fig. 3 FT-IR spectra of natural flake graphite, GO (a), Co0.5Zn0.5Fe2O4 (b) and rGO/Co0.5Zn0.5Fe2O4 (c)

图4 rGO/Co0.5Zn0.5Fe2O4-1(a)、rGO/Co0.5Zn0.5Fe2O4-2(b)、rGO/Co0.5Zn0.5Fe2O4-3(c)和rGO/Co0.5Zn0.5Fe2O4-4(d)的TEM照片

Fig. 4 TEM images of rGO/Co0.5Zn0.5Fe2O4-1(a), rGO/ Co0.5Zn0.5Fe2O4-2 (b), rGO/Co0.5Zn0.5Fe2O4-3 (c), and rGO/ Co0.5Zn0.5Fe2O4-4 (d)

图5 GO、Co0.5Zn0.5Fe2O4和不同比例的rGO/Co0.5Zn0.5Fe2O4复合材料的复介电常数实部(a)、复介电常数虚部(b)、磁导率实部(c)、磁导率虚部(d)、介电损耗(e)和磁滞损耗(f)

Fig. 5 Real part of complex permittivity (a), imaginary part of complex permittivity (b), real part of complex permeability (c), imaginary part of complex permeability (d), dielectric loss tangent (e) and magnetic loss tangent (f) of GO、Co0.5Zn0.5Fe2O4 and rGO/Co0.5Zn0.5Fe2O4 composite with different ratios

图6 GO和不同复合比例rGO/Co0.5Zn0.5Fe2O4复合材料的复介电常数(ε°)-复介电常数虚部(ε?)曲线

Fig. 6 Real part of complex permittivity (ε°)-imaginary part of complex permittivity (ε?) curves of GO and rGO/Co0.5Zn0.5Fe2O4 composites with different ratios

图7 GO和不同复合比例rGO/Co0.5Zn0.5Fe2O4复合材料的反射率与曲线频率的关系曲线

Fig. 7 Curves of reflectivity and frequency of GO and rGO/Co0.5Zn0.5Fe2O4 composites with different ratios

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