Preparation and EMI shielding properties of three-dimensional hollow MXene-rGO-CNT composites
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摘要: 随着科学技术的不断发展，“强吸收、宽频、轻质”的电磁屏蔽材料亟需被开发。本文选用聚甲基丙烯酸甲酯(PMMA)微球和冰模板，通过牺牲模板法制备了三维空心MXene-还原氧化石墨烯(rGO)-碳纳米管(MXene-rGO-CNT)复合材料，并对复合材料的形貌结构和电磁屏蔽性能进行了表征。结果表明，丰富微孔结构的构造改善了MXene薄片团聚现象，并减轻了复合材料的密度(低于0.26 g/cm3)。同时，互连多孔结构可以引起电磁波在材料内部的多次反射和散射，增强其电磁屏蔽性能。MXene-rGO-CNT复合材料在测量的1~18 GHz的宽频率范围内表现出良好的电磁波屏蔽性能，峰值达到54 dB的高电磁屏蔽效能。这项工作为制备高效电磁屏蔽应用的纳米复合材料提供了一种便捷的方法。Abstract: With the continuous development of science and technology, "strong absorption, broadband, lightweight" electromagnetic interference shielding materials need to be developed. In this paper, three-dimensional hollow MXene-reduced graphene oxide (rGO)-carbon nanotube (MXene-rGO-CNT) composites were prepared by a sacrificial template method using polymethyl methacrylate (PMMA) microspheres and ice templates, and material morphology, structure and electromagnetic interference shielding properties of the composites were characterized. The results show that the construction of rich microporous structure reduces the agglomeration of MXene flakes and the density of the composites (below 0.26 g/cm3). Meanwhile, the interconnected porous structure can cause multiple reflections and scattering of electromagnetic waves, enhancing the electromagnetic interference shielding performance of the composite material. The MXene-rGO-CNT composites exhibit good electromagnetic interference shielding performance over a wide frequency range measured from 1~18 GHz, with a high electromagnetic interference shielding effectiveness of 54 dB at peak value. This work provides a convenient method for preparing nanocomposites for efficient electromagnetic interference shielding applications.
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图 1 三维空心MXene-还原氧化石墨烯(rGO)-碳纳米管(MXene-rGO-CNT)复合材料的制备示意图(a)和实物数码图片(b)
Figure 1. Schematic diagram (a) and physical digital image (b) of the preparation of three-dimensional hollow MXene-reduced graphene oxide (rGO)-carbon nanotube (MXene-rGO-CNT) composites
图 2 Ti3C2Tx MXene粉末(a)超声前(b)超声后的SEM图像；(c)TEM图像；(d)Ti3AlC2 MAX相前驱体和Ti3C2Tx MXene粉末的XRD图像
Figure 2. SEM images of Ti3C2Tx MXene powder (a) before sonication (b) after sonication; (c) TEM image ; (d) XRD images of Ti3AlC2 MAX phase precursor and Ti3C2Tx MXene powder
图 3 不同PMMA添加比例的PMMA@MXene-GO-CNT和MXene-rGO-CNT复合材料的SEM图像(a) PMMA@MXene-GO-CNT-10，(b) PMMA@MXene-GO-CNT-5，(e) MXene-rGO-CNT-5和(f) MXene-rGO-CNT-10；PMMA@MXene-GO-CNT-10的(c) TEM图像和(d)SEM图像及其C、O和Ti元素映射图像
Figure 3. SEM images of PMMA@MXene-GO-CNT and MXene-rGO-CNT composites with different PMMA addition ratios (a) PMMA@MXene-GO-CNT-10, (b) PMMA@MXene-GO-CNT-5, (e) MXene-rGO-CNT-5, and (f) MXene-rGO-CNT-10; (c) TEM image and (d) SEM image of PMMA@MXene-GO-CNT-10 and its C, O, and Ti elemental mapping images
图 4 (a) Ti3C2Tx MXene粉末、PMMA@MXene-GO-CNT和MXene-rGO-CNT复合材料的拉曼光谱；(b) PMMA@MXene-GO-CNT和MXene-rGO-CNT复合材料的XRD图像；(c) MXene-GO-CNT复合材料的热重曲线图谱
Figure 4. (a) Raman spectra of Ti3C2Tx MXene powder, PMMA@MXene-GO-CNT and MXene-rGO-CNT composites; (b) XRD images of PMMA@MXene-GO-CNT and MXene-rGO-CNT composites; (c) Thermogravimetric curves of MXene-GO-CNT composites graphs of MXene-GO-CNT composites
图 5 MXene、PMMA@MXene-GO-CNT和MXene-rGO-CNT复合材料的XPS测量光谱(a)；(b)(d)(g) Ti3C2Tx MXene，(c)(e)(h) PMMA@MXene-GO-CNT复合材料，(f)(i) MXene-rGO-CNT复合材料的高分辨率光谱。
Figure 5. XPS measurement spectra of MXene, PMMA@MXene-GO-CNT and MXene-rGO-CNT composites (a); (b) (d) (g) Ti3C2Tx MXene, (c) (e) (h) PMMA@MXene-GO-CNT composites, (f) (i) MXene-rGO-CNT composites with high-resolution spectra
图 6 具有不同PMMA添加量的MXene-rGO-CNT和PMMA@MXene-GO-CNT复合材料的(a)总EMI SET；(b) SEA、SER和SET平均值；以及(c) T、A和R平均比例曲线和(d)与之前报道的EMI屏蔽材料的比较
Figure 6. (a) total EMI SET; (b) average SEA, SER, and SET; and (c) T, A, and R average ratio curves for MXene-rGO-CNT and PMMA@MXene-GO-CNT composites with different PMMA additions, and (d) comparison with previously reported EMI shielding materials.
图 7 MXene-rGO-CNT复合材料电磁屏蔽机制示意图
Figure 7. Schematic diagram of electromagnetic interference shielding mechanism of MXene-rGO-CNT composites
表 1 复合材料的命名
Table 1. Nomenclature of Composites Notes：polymethyl methacrylate (PMMA); Ti3C2Tx MXene (MXene); graphene oxide (GO); carbon nanotube (CNT); reduced graphene oxide (rGO)
Sample Mass Ratio
MXene∶PMMAPMMA@MXene-GO-CNT-0 1∶0 MXene-rGO-CNT-0 1∶0 PMMA@MXene-GO-CNT-2 1∶2 MXene-rGO-CNT-2 1∶2 PMMA@MXene-GO-CNT-5 1∶5 MXene-rGO-CNT-5 1∶5 PMMA@MXene-GO-CNT-10 1∶10 MXene-rGO-CNT-10 1∶10 
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