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

超蓬松掺杂石墨烯气凝胶复合材料的制备及其吸波性能

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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- 被引次数: 0
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: 2024-03-04

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15 wt%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(RLmin)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10 wt%。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 15 wt%, the composite aerogel exhibits optimal absorption performance. At a matching thickness of 2.9 mm, it achieves a minimum reflection loss (RLmin) 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 10 wt%. 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，(b)GO、(c)GA、(d)GA-300℃、(e)GA-400℃、(f)GA-500℃的C1 s图谱

Figure 2. (a) XPS full spectrum, XPS survey curves of C 1 s of (b) GO, (c) GA,(d)GA-300℃,(e)GA-400℃,and (f)GA-500℃.

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图 3 GO、GA、GA-300℃、GA-400℃和GA-500℃的(a)红外光谱和(b)拉曼光谱

Figure 3. (a) IR spectra and (b) Raman spectra of GO, GA, GA-300℃, GA-400℃ and GA-500℃

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图 4 GO、GA、GA-300℃、GA-400℃、GA-500℃和GA-600℃的最优反射损耗

Figure 4. Optimal reflection loss at GO, GA, GA-300℃, GA-400℃,GA-500℃ and GA-600℃

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

Figure 5. SEM diagram of NiZnFe2 O4/GA composite aerogel (a-b) NiZnFe₂O₄/ Ga-15 wt %; (c-d) NiZnFe₂O₄ /GA-25 wt%; (e) NiZnFe₂O₄ /GA-35 wt%; (f) NiZnFe₂O₄ /GA-45 wt%

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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，(b)磁损耗因子tanδ，(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, (b) magnetic loss Factor tanδ (c) impedance matching coefficient Z_in/Z₀, (d) reflection loss

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

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

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图 8 (a、b)NiZnFe₂O₄@MnO₂微球的SEM图片；(c、d)NiZnFe₂O₄@MnO₂微球的TEM图片；(e)NiZnFe₂O₄@MnO₂微球的EDS mapping分析，其中绿色对应Fe元素，黄色对应Ni元素，青色对应Zn元素，红色对应Mn元素。

Figure 8. (a, b) SEM images of NiZnFe₂O₄@MnO₂ microspheres; (c, d) TEM images of NiZnFe2 O4@MnO₂ microspheres; (e) EDS mapping analysis of NiZnFe₂O₄@MnO₂ microspheres, where green corresponds to Fe element, yellow corresponds to Ni element, cyan corresponds to Zn element.Red corresponds to Mn.

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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)磁导率虚部和(f)磁损耗角正切

Figure 9. NiZnFe₂O₄@MnO₂/GA composite electromagnetic parameters (a) real part of the dielectric constant, (b) imaginary part of the dielectric constant, (c) tangent of the dielectric loss Angle,(d) the real part of the permeability, (e) the virtual part of the permeability and (f) the 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、b、c) NiZnFe₂O₄@MnO₂/GA-200℃；(d、e、f) NiZnFe₂O₄@MnO₂/GA-300℃；(g、h、i)NiZnFe₂O₄@MnO₂/GA-400℃；(j、k、l) NiZnFe₂O₄@MnO₂/GA-500℃；

Figure 10. Reflection loss curve, 3 D reflection loss plot and corresponding contour plot (a、b、c) NiZnFe₂O₄@MnO₂/GA-200℃；(d、e、f) NiZnFe2 O4@MnO2/GA-300℃； (g、h、i)NiZnFe₂O₄@MnO₂/GA-400℃；(j、k、l) NiZnFe2 O4@MnO2/GA-500℃；

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图 11 NiZnFe₂O₄@MnO₂/GA-300℃(a)RL值与四分之一波长(b)RL值与Z值的关系

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

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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	RLmin /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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