超蓬松掺杂石墨烯气凝胶复合材料的制备及其吸波性能

任培永; 陈淼; 赵科; 高晓平

doi:10.13801/j.cnki.fhclxb.20240024.003

超蓬松掺杂石墨烯气凝胶复合材料的制备及其吸波性能

doi: 10.13801/j.cnki.fhclxb.20240024.003

内蒙古工业大学　轻工与纺织学院，呼和浩特 010080

基金项目: 国家自然科学基金(12362012；51765051)；内蒙古自然科学基金(2017MS0102)；内蒙古科技计划项目(2020GG0282)；内蒙古高等学校支持科技领军人才和创新团队建设(JY20230103)

详细信息

通讯作者:
高晓平，博士，教授，博士生导师，研究方向为功能纺织品与风电叶片用复合材料　E-mail: gaoxp@imut.edu.cn

中图分类号: TB333
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出版历程
- 收稿日期: 2023-12-04
- 修回日期: 2024-01-02
- 录用日期: 2024-01-12
- 网络出版日期: 2024-01-25
- 刊出日期: 2024-10-15

Preparation and microwave absorption properties of ultra-fluffy doped graphene aerogel composites

College of Light Industry and Textiles, Inner Mongolia University of Technology, Hohhot 010080, China

Funds: National Natural Science Foundation of China (12362012; 51765051); Natural Science Foundation of Inner Mongolia (2017MS0102); Inner Mongolia Science and Technology Program Fund (2020GG0282); Institutions of Higher Education of Inner Mongolia (JY20230103)

摘要

摘要: 伴随着智能通信的迅猛发展，信息传输带来的电磁辐射问题愈发严峻，传统吸波材料存在衰减能力差、阻抗匹配难以调节等缺点，已不能满足实际应用。本文基于电磁损耗理论、多组分协同损耗和三维多孔气凝胶构筑的设计策略，应用水热合成法制备石墨烯气凝胶(GA)，在溶剂热反应中添加由MnO₂包覆的镍锌铁氧体(NiZnFe₂O₄@MnO₂)微球，与石墨烯介电材料复合，制备超蓬松磁掺杂石墨烯基复合气凝胶(NiZnFe₂O₄@MnO₂/GA)粉体。实验测试了复合气凝胶的吸波特性，分析了热处理温度和磁掺杂量对复合气凝胶吸波性能的影响机制及规律。结果可知，热处理温度为300℃、镍锌铁氧体掺杂量为15wt%时，复合气凝胶吸波效果最优。其匹配厚度为2.9 mm时，在频率为8.72 GHz处，最小反射损耗(RL_min)达到了−47.27 dB，有效吸收带宽(EAB)为3.2 GHz，覆盖了X波段的大部分，且填料负载率仅为10wt%。本研究解决了材料阻抗匹配性差的问题，优化了吸波材料的介电损耗和磁损耗能力，满足了对吸波材料“薄、轻、宽、强”的应用要求。
- 复合材料 /
- 镍锌铁氧体 /
- 石墨烯气凝胶 /
- 核壳结构 /
- 吸波性能
Abstract: With the rapid advancement of intelligent communication, the issue of electromagnetic radiation caused by information transmission is becoming increasingly severe. However, traditional microwave absorption materials have limitations such as poor attenuation ability and difficulties in impedance matching, which no longer meet practical applications. In this paper, graphene aerogel (GA) was prepared by hydrothermal synthesis based on the theory of electromagnetic loss, the design strategy of multi-component synergistic loss and the construction of three-dimensional porous aerogel. To enhance its properties, we incorporated MnO₂-coated Ni-Zn ferrite (NiZnFe₂O₄@MnO₂) microspheres with graphene dielectric material to prepare ultra-fluffy magnetically doped graphene-based composite aerogel (NiZnFe₂O₄@MnO₂/GA) powders. The impact of heat treatment temperature and magnetic doping on the wave absorption capability of the composite aerogel was analyzed. Our results demonstrate that at a heat treatment temperature of 300℃ and a nickel-zinc ferrite doping amount of 15wt%, the composite aerogel exhibits optimal absorption performance. At a matching thickness of 2.9 mm, it achieves a minimum reflection loss (RL_min) value of −47.27 dB at a frequency of 8.72 GHz, providing an effective absorption bandwidth (EAB) spanning 3.2 GHz covering most X-band frequencies while maintaining only a packing load rate of 10wt%. The problem of poor material impedance matching is solved, the dielectric loss and magnetic loss capacity of the absorbing materials are optimized. The application requirements of the wave absorbing material for "thin, light, wide and strong" are met.
- composites /
- Ni-Zn ferrite /
- graphene aerogel /
- core-shell structure /
- absorption properties

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图 1 NiZnFe₂O₄@MnO₂/石墨烯气凝胶(GA)复合气凝胶粉体制备示意图

Figure 1. Schematic diagram of preparation of NiZnFe₂O₄@MnO₂/graphene aerogel (GA) composite aerogel powder

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图 2 (a) XPS全谱图；GO (b)、GA (c)、GA-300℃ (d)、GA-400℃ (e)、GA-500℃ (f)的C1s图谱

Figure 2. (a) XPS full spectra; XPS survey curves of C1s of GO (b), GA (c), GA-300℃ (d), GA-400℃ (e), and GA-500℃ (f)

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图 3 GO与不同热还原温度下GA的红外图谱(a)和拉曼图谱(b)

Figure 3. IR spectra (a) and Raman spectra (b) of GO and GA at different thermal reduction temperatures

I_D/I_G—Area ratio of peak D to peak G

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图 4 GO与不同热还原温度下GA的最优反射损耗(RL)

Figure 4. Optimal reflection loss (RL) of GO and GA at different thermal reduction temperatures

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图 5 NiZnFe₂O₄/GA复合气凝胶SEM图像：((a), (b)) NiZnFe₂O₄/GA-15wt%; ((c), (d)) NiZnFe₂O₄/GA-25wt%; (e) NiZnFe₂O₄/GA-35wt%; (f) NiZnFe₂O₄/GA-45wt%

Figure 5. SEM images of NiZnFe₂O₄/GA composite aerogel: ((a), (b)) NiZnFe₂O₄/GA-15wt%; ((c), (d)) NiZnFe₂O₄/GA-25wt%; (e) NiZnFe₂O₄/GA-35wt%; (f) NiZnFe₂O₄/GA-45wt%

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图 6 GA及NiZnFe₂O₄/GA复合气凝胶的吸波性能：(a)介电损耗因子tanδ_ε；(b)磁损耗因子tanδ_μ；(c)阻抗匹配系数Z_in/Z₀ ；(d)反射损耗

Figure 6. Absorption properties of GA and NiZnFe₂O₄/GA: (a) Dielectric loss factor tanδ_ε; (b) Magnetic loss factor tanδ_μ; (c) Impedance matching coefficient Z_in/Z₀; (d) Reflection loss

EAB—Effective absorption bandwidth; RL_min—Minimum reflection loss

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图 7 不同掺杂石墨烯气凝胶热处理的XRD图谱：(a) NiZnFe₂O₄/GA；(b) NiZnFe₂O₄@MnO₂/GA

Figure 7. XRD patterns of different doped graphene aerogel heat treated: (a) NiZnFe₂O₄/GA; (b) NiZnFe₂O₄@MnO₂/GA

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图 8 ((a), (b)) NiZnFe₂O₄@MnO₂微球的SEM图像；((c), (d)) NiZnFe₂O₄@MnO₂微球的TEM图像；(e) NiZnFe₂O₄@MnO₂微球的EDS mapping图

Figure 8. ((a), (b)) SEM images of NiZnFe₂O₄@MnO₂ microspheres; ((c), (d)) TEM images of NiZnFe₂O₄@MnO₂ microspheres; (e) EDS mapping analysis of NiZnFe₂O₄@MnO₂ microspheres

d—Interplanar spacing

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图 9 NiZnFe₂O₄@MnO₂/GA复合材料电磁参数：(a)介电常数实部；(b)介电常数虚部；(c)介电损耗角正切；(d)磁导率实部；(e)磁导率虚部；(f)磁损耗角正切

Figure 9. NiZnFe₂O₄@MnO₂/GA composite electromagnetic parameters: (a) Real part of the permittivity; (b) Imaginary part of the permittivity; (c) Tangent of the dielectric loss angle; (d) Real part of the permeability; (e) Imaginary part of the permeability; (f) Tangent of the magnetic loss angle

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图 10 NiZnFe₂O₄@MnO₂/GA复合气凝胶的反射损耗曲线、三维反射损耗图和相应的等高线图：((a)~(c)) NiZnFe₂O₄@MnO₂/GA-200℃；((d)~(f)) NiZnFe₂O₄@MnO₂/GA-300℃；((g)~(i)) NiZnFe₂O₄@MnO₂/GA-400℃；((j)~(l)) NiZnFe₂O₄@MnO₂/GA-500℃

Figure 10. Reflection loss curves, 3D reflection loss plot and corresponding contour plot of NiZnFe₂O₄@MnO₂/GA: ((a)-(c)) NiZnFe₂O₄@MnO₂/GA-200℃; ((d)-(f)) NiZnFe₂O₄@MnO₂/GA-300℃; ((g)-(i)) NiZnFe₂O₄@MnO₂/GA-400℃; ((j)-(l)) NiZnFe₂O₄@MnO₂/GA-500℃

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图 11 NiZnFe₂O₄@MnO₂/GA-300℃的RL值与1/4波长λ (a)、RL值与阻抗系数Z值的关系(b)

Figure 11. Relationship between RL values versus a quarter wavelength λ (a), RL value and impedance matching coefficient Z value (b) of NiZnFe₂O₄@MnO₂/GA-300℃

t_m—Matched coating thickness

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表 1 NiZnFe₂O₄@MnO₂/GA复合气凝胶的吸波性能对比

Table 1. Comparison of wave absorption properties of NiZnFe₂O₄@MnO₂/GA composite aerogel

Sample	Thickness/mm	Frequency/GHz	RL_min/dB	EAB/GHz
NiZnFe₂O₄@MnO₂/GA-200℃	4.3	5.68	−18.53	1.2
NiZnFe₂O₄@MnO₂/GA-300℃	2.9	8.72	−47.27	3.2
NiZnFe₂O₄@MnO₂/GA-400℃	2.4	10.24	−36.70	3.44
NiZnFe₂O₄@MnO₂/GA-500℃	1.3	18.00	−17.48	2.56

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