Ultra-thin magnetic biochar composite absorbing material derived from sycamore catkins
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摘要: 生物质衍生炭因其环保性和可持续性在微波吸收领域引起了广泛的关注。本研究主要以生物质废料梧桐絮为原料，采用绿色环保的浸渍碳化工艺，通过原位生长法来制备镍/梧桐絮衍生炭(Ni/PBDC)复合吸波材料。研究表明，在梧桐絮的碳化过程中，木质素内的官能团经历热解转化为气体释放出来，此过程同步伴随着生物炭的生成以及进一步的石墨化转变。镍颗粒生长在碳的表面和内部，这种分布增强了复合吸波材料的界面极化损耗；磁性颗粒镍的加入增加了磁损耗和界面极化损耗，但是镍含量过高会导致材料阻抗失配从而降低电磁衰减能力。性能最佳的Ni/PBDC复合吸波材料的最小反射损耗为−40 dB，有效吸收带宽为4.16 GHz，对应的匹配厚度为1.4 mm。值得注意的是，不同镍含量的Ni/PBDC复合吸波材料的最佳吸波性能的响应厚度均在1.5 mm以下。该复合吸波材料具有厚度薄、吸收性能强且带宽宽的优点，因此在吸波领域具有巨大的应用潜力。Abstract: Biomass derived carbon has attracted extensive attention in the field of microwave absorption due to its environmental protection and sustainability. In this study, Ni/phoenix tree oakum biomass derived carbon(Ni/PBDC)absorbent composite material was prepared by in-situ growth method using green impregnation carbonization process and biomass waste phoenix tree oakum as raw material. Research has shown that during the carbonization process of the phoenix tree oakum, the functional groups within the lignin undergo pyrolysis and transform into gases that are released, while this process is simultaneously accompanied by the formation of biochar and further graphitization. The growth of nickel particles on the surface and within the carbon enhances the interfacial polarization loss of the composite absorbing material. The addition of magnetic nickel particles increases both magnetic loss and interfacial polarization loss, but an excessively high nickel content can lead to impedance mismatch in the material, thereby reducing its ability to attenuate electromagnetic waves. The optimal Ni/PBDC composite absorbing material exhibits a minimum reflection loss of −40 dB, with an effective absorption bandwidth of 4.16 GHz at a corresponding matching thickness of 1.4 mm. It is worth noting that the response thickness of Ni/PBDC composite absorbing materials with the same nickel content is less than 1.5 mm. The composite absorbing material has the advantages of thin thickness, strong absorption performance and wide band, so it has great application potential in the field of wave absorption.
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图 1 镍/梧桐絮衍生炭(Ni/PBDC)的制备过程示意图
Figure 1. Schematic diagram of the preparation process of Ni/phoenix tree oakum biomass derived carbon (Ni/PBDC)
图 2 同轴环实物图(a)和光镜图(b)
Figure 2. Physical picture of coaxial ring (a) and optical picture (b)
图 3 梧桐子碳化前后的照片和CT图：(a-c) 碳化前, (d-f) 碳化后
Figure 3. Photos and CT images of phoenix tree seeds before (a-c) and after (d-f) carbonization
图 4 梧桐絮碳化过程中的TG和DTG曲线(a)和热重-红外光谱图(b)
Figure 4. The TG and DTG curves (a) and thermogravimetric infrared spectrum (b) of phoenix tree oakum during the carbonization process
图 6 样品的SEM照片及局部放大图：(a-b) PBDC, (c-d) Ni/PBDC-0.1, (e-f) Ni/PBDC-0.3, (g-h) Ni/PBDC-0.5,
Figure 6. The SEM images and partial magnification of samples: (a-b) PBDC, (c-d) Ni/PBDC-0.1, (e-f) Ni/PBDC-0.3, (g-h) Ni/PBDC-0.5
图 7 Ni/PBDC样品的电磁参数: 介电常数实部$ {\varepsilon' } $ (a)、介电常数虚部$ {\varepsilon ''} $ (b)、介电损耗正切$ \text{tan}{\delta }_{\varepsilon } $ (c)、磁导率实部$ {\mu }^{\prime } $ (d)、磁导率虚部$ {\mu'' } $ (e)、磁损耗正切$ \text{tan}{\delta }_{\mu } $ (f)
Figure 7. Electromagnetic parameters of the Ni/PBDC sample: Real part of permittivity $ {\varepsilon' }$ (a), imaginary part of permittivity $ {\varepsilon'' } $ (b), tangent of dielectric loss $ \text{tan}{\delta }_{\varepsilon } $ (c), real part of permeability $ {\mu' } $ (d), imaginary part of permeability $ {\mu ''} $ (e), tangent of magnetic loss $ \text{tan}{\delta }_{\mu } $ (f)
图 8 Cole-Cole曲线: (a) PBDC, (b) Ni/PBDC-0.1, (c) Ni/PBDC-0.3, (d) Ni/PBDC-0.5
Figure 8. Cole-Cole curves: (a) PBDC, (b) Ni/PBDC-0.1, (c) Ni/PBDC-0.3, (d) Ni/PBDC-0.5
图 9 样品在不同匹配厚度(0.5-3.5 mm)下的Z值: (a) PBDC, (b) Ni/PBDC-0.1, (c) Ni/PBDC-0.3. (d) Ni/PBDC-0.5 和衰减常数(e)
Figure 9. The value of Z at different matching thicknesses (0.5-3.5 mm): (a) PBDC, (b) Ni/PBDC-0.1, (c) Ni/PBDC-0.3. (d) Ni/PBDC-0.5 and attenuation constant (e)
图 10 样品三维和二维反射损耗曲线: (a-b) PBDC, (c-d) Ni/PBDC-0.1, (e-f) Ni/PBDC-0.3、(g-h)Ni/PBDC-0.5
Figure 10. The three-dimensional and two-dimensional reflection loss curves of samples: (a-b) PBDC, (c-d) Ni/PBDC-0.1, (e-f) Ni/PBDC-0.3、(g-h)Ni/PBDC-0.5
图 11 Ni/PBDC的微波吸收机制示意图
Figure 11. Schematic diagram of Ni/PBDC microwave absorption mechanism.
表 1 Ni/PBDC-0.3 EDS结果
Table 1. Ni/PBDC-0.3 EDS results
Elemental Point A/wt% Point B/wt% Point C/wt% Ni 88.94 7.64 68.93 C 9.21 59.81 21.01 O 1.44 5.42 3.61 K 0.00 11.69 0.96 Ca 0.40 7.36 4.39 Cl 0.00 8.08 1.10 
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表 2 Ni/PBDC复合吸波材料与文献报道的其他生物质碳吸波材料的对比
Table 2. Comparison of Ni/PBDC composite absorbing materials with other biomass carbon absorbing materials reported in the literature
Absorber RLmin/dB EAB/GHz T/mm Ref. Fish skin −29.5 5.8 1.7 [19] Phragmites australis/ Fe3O4 −45.7 3.4 1.7 [20] Rice husk/NiSO4 −58.5 3.53 2.7 [38] Walnut shell −42.4 1.76 2 [39] Cotton/Co(NO3)2·6H2O −14.98 2.6 2.5 [40] Rice husk −47.46 3.4 2.8 [41] Pine pollen /NiO −52.6 4.9 3 [42] Fir wood /NiFe2O4 −17.5 2.6 2.4 [43] Walnut shell /Fe3O4 −56.61 2.72 2.46 [44] Agaric / Fe3O4 −30.41 2.45 2.06 [45] Mango leaves −22.7 5.17 1.75 [46] Juncus effusus −40.4 3.48 1.75 [47] Phoenix tree oakum/NiCl2·6H2O −40 4.16 1.4 This work Notes: RLmin, EAB, and T are minimum reflection loss, effective absorption bandwidth, and thickness of the absorber,respectively.
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