Layered-structure N-doped expanded-graphite/boron nitride composites towards high performance of microwave absorption

doi:10.1016/j.jmst.2021.10.003

Abstract

Abstract:

High-efficiency microwave absorbers with broadband absorption are strongly desired for electromagnetic protection. Herein, we successfully synthesized a hybrid microwave absorbing material with two-dimensional layered structure, which consisted of expanded graphite (EG) and boron nitride (BN). The introduction of BN is to regulate the conductivity of EG and also to improve the thermal stability of the composite material. The ultrathin BN nano-sheets were uniformly wrapped on the EG sheets via chemical vapor deposition. Attributed to the dielectric loss and conductive loss, the as-prepared hybrid material exhibited high performance for microwave absorption. The effective absorbing bandwidth (reflection loss value < -10 dB) was achieved up to 9.37 GHz with the thickness of 2.4 mm in the frequency range of 5.75-6.98 GHz and 9.86-18 GHz. And the minimum reflection loss was -51.58 dB at the thickness of 3 mm. The excellent performance of microwave absorption was attributed to the dielectric loss, interfacial polarization loss and optimized impedance matching. Moreover, compared to pure EG, the thermal decomposition temperature of EG/BN composite materials had increased by about 100 °C which was up to 714 °C. Taking the advantages of high thermal stability of BN as well as the fine microwave absorbability of EG, the EG/BN composites would be applied in high-temperature microwave absorbing fields.

Key words: Layered-structure, Expanded graphite, Boron nitride, Microwave absorption

Zhuguang Nie, Yang Feng, Qing Zhu, YingXia Li, ping Luo, Lan Ma, Jie Su, Xingman Hu, Rumin Wang, Shuhua Qi. Layered-structure N-doped expanded-graphite/boron nitride composites towards high performance of microwave absorption[J]. J. Mater. Sci. Technol., 2022, 113: 71-81.

Figures/Tables 13

Fig. 1. Schematic illustration of the fabrication of EG/BN composites.

Fig. 2. (a) Expandable graphite without any treatment, (b, c) expanded graphite treated at 900 °C for 30 s, (d-f) EG/BN-101 composites, (g-i) EG/BN-102 composites, (j-l) EG/BN-103 composites at 900 °C and (m) partial enlarged view of expandable graphite without any processing.

Fig. 3. EDS test of EG/BN-103: (a) original image of EG/BN-103, (b) EDS energy spectrum of the elements, (c) element content of the complex, (d) element mappings of the component.

Fig. 4. (A) XRD patterns of composite samples. (B) XRD patterns of BN and BN, EG mixture. XPS survey spectra of EG/BN composites: (C) full spectrum of EG/BN-103, (D-F) high-resolution XPS spectra of C 1 s, N 1 s and B 1 s of EG/BN composites.

Fig. 5. TGA curves of pure EG and EG/BN composites.

Fig. 6. Infrared thermal images of EG and EG/BN composites.

Fig. 7. Raman shift spectra of EG/BN composites.

Table 1. Conductivity of as-prepared expanded graphite and EG/BN composites.

Samples	EG/BN (wt.%)	Conductivity σ (S/cm)
Expanded graphite(EG)	-	649
EG/BN-101	10:1	34.97
EG/BN-102	10:2	20.39
EG/BN-103	10:3	17.91

Fig. 8. Microwave absorbing properties of pure EG and EG/BN composites: (a, b) belonged to pure EG, (c, e, g) three-dimensional color map of the reflection loss with absorbers frequency and thickness for the composites EG/BN-101-103 at the frequency range of 0.5-18 GHz and thickness of 1-4 mm. (d, f, h) Reflection loss plot of EG/BN-101-103 composites with different coating thicknesses.

Table 2. Partially reported carbon materials, magnetic materials, and other dielectric materials with EM microwave absorbing properties.

Materials	Shapes	Thickness (mm)	Min RL(dB)	Frequency(GHz)	Bandwidh(< -10 dB) (GHz)	Refs.
Ni/graphite	Flakes	2	-42	-17.6	6.1	[32]
RGO/NiO	Nano-sheets	3.5	-55.5	10.6	6.7	[33]
FeCo/Graphite	Nano-plates	-	-53.93	-	4.3	[39]
EG	2D sheet	4.0	-26.4	-	5.2	[40]
GNPs@NixSy@MoS₂	Plates	2.2	-43.3	-	3.6	[51]
FeOx/Fe/C	Foams	2.0	-37	12	6.5	[52]
MnS₂/CNTs	Microspheres	1.4	-63.8	17.4	4.3	[53]
RGO/MWCNTs/CeO₂	Flakes	4.5	-59.3	-	3.2	[54]
CoNi/N-GCT	3D frameworks	3.5	-41.13	-	3.2	[55]
Ni/C	Foams	2	-45	13.3	4.5	[56]
SiC/C	Foams	1.5	-31.21	15.76	4.1	[57]
CNTs/Ti₃C₂	Foams	3.95	-24.4	-	4.2	[58]
N-doped graphene	Foams	3.5	-53.9	-	4.56	[59]
ZnO/C	Nanoparticles	-	-50.43	15.77	3.52	[60]
Ni@C	core-shell sphere	2.6	-60	-		[46]
EG/BN	2D Sheets	2.4	-51.58	17.3	9.37	our work

Fig. 9. Reflection loss, matching thickness and effective absorption bandwidth value of EG/BN composites compared with other peer works.

Fig. 10. Electromagnetic parameters of EG/BN: (a) real part ε′, (b) image part ε″ of complex permittivity, (c) dielectric loss tangents tanδ, (d) attenuation coefficient α.

Fig. 11. The impedance matching Z and reflection loss RL contour maps of EG/BN101 (a, d), EG/BN102 (b, e), EG/BN103 (c, f).

References 68

[1]	H. Wei, X.M. Ma, C.Y. Du, Y.N. Wu, K. Liu, H.S.L. Wen, J. Mater. Sci. Mater. Elec-tron. 31 (2020) 6418-6434.
[2]	J. Yu, R. Su, J. Yu, X. Liu, X. Zhang, X. Dong, Ceram. Int. 46 (2020) 18339-18346. DOI URL
[3]	Y. Zheng, W. Zhang, X. Zhang, Q. Zhu, W. Zhu, R. Wang, J. Phys. D 52 (2019) 485003. DOI URL
[4]	W. Zhang, Y. Zheng, X. Zhang, Q. Zhu, H. Yan, L.F. Liotta, J. Alloy. Compd. 792 (2019) 945-952. DOI URL
[5]	H. Wang, F. Meng, J. Li, T. Li, Z. Chen, H. Luo, ACS Sustain. Chem. Eng. 6 (2018) 11801-11810. DOI URL
[6]	Q. Hu, R. Yang, Z. Mo, D. Lu, L. Yang, Z. He, Carbon 153 (2019) 737-744.
[7]	X. Zhao, L. Xu, Q. Chen, Q. Peng, M. Yang, W. Zhao, Adv. Mater. Technol 4 (2019) 1900443. DOI URL
[8]	J. Zhang, H. Li, T. Xu, J. Wu, S. Zhou, Z.H. Hang, Carbon 165 (2020) 404-411.
[9]	X. Zhou, Z. Jia, A. Feng, X. Wang, J. Liu, M. Zhang, Carbon 152 (2019) 827-836.
[10]	Z. Mo, R. Yang, D. Lu, L. Yang, Q. Hu, H. Li, Carbon 144 (2019) 433-439.
[11]	X. Ye, Z. Chen, M. Li, T. Wang, J. Zhang, C. Wu, Compos. B Eng. 178 (2019) 107479. DOI URL
[12]	R. Wang, E. Yang, X. Qi, R. Xie, S. Qin, C. Deng, Appl. Surf. Sci. 516 (2020) 146159. DOI URL
[13]	J. Chai, J. Cheng, D. Zhang, Y. Xiong, X. Yang, X. Ba, J. Alloy. Compd. 829 (2020) 154531. DOI URL
[14]	H. Liu, J. Wu, Q. Zhuang, A. Dang, T. Li, T. Zhao, J. Eur. Ceram. Soc. 36 (2016) 3939-3946. DOI URL
[15]	B.H.K. Lopes, R.C. Portes, M.A.D. Amaral, D.E. Florez-Vergara, A.M. Gama, V. A. Silva, J. Mater. Res. Technol. 9 (2020) 2369-2375. DOI URL
[16]	P. Yin, L. Zhang, X. Feng, J. Wang, J. Dai, Y. Tang, Integr. Ferroelectr. 211 (2020) 82-103. DOI URL
[17]	J. Ju, T. Kuang, X. Ke, M. Zeng, Z. Chen, S. Zhang, Compos. Sci. Technol. 193 (2020) 108116. DOI URL
[18]	X. Chen, X. Jia, Z. Wu, Z. Tang, Y. Zeng, X. Wang, IEEE Antennas Wirel. Propag. Lett. 18 (2019) 1016-1020. DOI URL
[19]	X. Su, J. Wang, X. Zhang, S. Huo, W. Chen, W. Dai, Ceram. Int. 46 (2020) 12353-12363. DOI URL
[20]	J. Qiu, T. Qiu, Carbon 81 (2015) 20-28.
[21]	D. Min, W. Zhou, Y. Qing, F. Luo, D. Zhu, J. Alloy. Compd. 744 (2018) 629-636. DOI URL
[22]	J. Zeng, H.Q. Fan, S.Q. Wang, J. Zhang, X.Y. Xue, Thin Solid Films 520 (2012) 5053-5059. DOI URL
[23]	C. Liu, Y. Duan, J. Cai, X. Li, D. Zhang, J. Gao, Mater. Res. Express 6 (2019) 106114. DOI URL
[24]	Y. Zhao, Z. Zhou, G.X. Chen, Q. Li, Mater. Lett. 233 (2018) 203-206. DOI URL
[25]	H. Wei, W. Zheng, Z. Jiang, Y. Huang, J. Mater. Chem. C 7 (2019) 14375-14383. DOI URL
[26]	F. Sultanov, C. Daulbayev, B. Bakbolat, O. Daulbayev, Adv. Colloid Interface Sci. 285 (2020) 102281. DOI URL
[27]	H. Lv, Y. Li, Z. Jia, L. Wang, X. Guo, B. Zhao, Compos. B Eng. 196 (2020) 108122. DOI URL
[28]	Y. Kang, Z. Jiang, T. Ma, Z. Chu, G. Li, ACS Appl. Mater. Interfaces 8 (2016) 32468-32476. DOI URL
[29]	C. Chen, J. Xi, E. Zhou, L. Peng, Z. Chen, C. Gao, Nanomicro Lett. 10 (2018) 26-37.
[30]	K. Raagulan, B.M. Kim, K.Y. Chai, Nanomaterials 10 (2020) 702-724. DOI URL
[31]	H. Jia, Q.Q. Kong, Z. Liu, X.X. Wei, X.M. Li, J.P. Chen, Compos. A Appl. Sci. Manuf. 129 (2020) 105712. DOI URL
[32]	Z. Zhu, X. Sun, G. Li, H. Xue, H. Guo, X. Fan, J. Magn. Magn. Mater. 377 (2015) 95-103. DOI URL
[33]	H. Zhang, X. Tian, C. Wang, H. Luo, J. Hu, Y. Shen, Appl. Surf. Sci. 314 (2014) 228-232. DOI URL
[34]	C. Wang, X. Han, P. Xu, J. Wang, Y. Du, X. Wang, J. Phys. Chem. C 114 (2010) 3196-3203. DOI URL
[35]	C. Wang, X. Han, P. Xu, X. Zhang, Y. Du, S. Hu, Appl. Phys. Lett. 98 (2011) 072906. DOI URL
[36]	X. Zhang, H. Wang, R. Hu, C. Huang, W. Zhong, L. Pan, Appl. Surf. Sci. 484 (2019) 383-391. DOI URL
[37]	C. Basavaraja, W.J. Kim, Y.D. Kim, D.S. Huh, Mater. Lett. 65 (2011) 3120-3123. DOI URL
[38]	H. Wang, P. Shi, M. Rui, A. Zhu, R. Liu, C. Zhang, Prog. Org. Coat. 139 (2020) 105476.
[39]	X. Su, J. Wang, X. Zhang, S. Huo, W. Dai, B. Zhang, J. Alloy. Compd. 829 (2020) 154426. DOI URL
[40]	V. Pratap, A.K. Soni, A.M. Siddiqui, S.M. Abbas, R. Katiyar, N.E. Prasad, J. Elec- tron. Mater. 49 (2020) 3972-3981.
[41]	F. Wang, C. Bai, L. Chen, Y. Yu, Mater. Today Nano 13 (2021) 100108.
[42]	Y. Yu, M. Wang, Y. Bai, B. Zhang, L. An, J. Zhang, Chem. Eng. J. 375 (2019) 121914. DOI URL
[43]	B. Zhong, W. Liu, Y. Yu, L. Xia, J. Zhang, Z. Chai, Appl. Surf. Sci. 420 (2017) 858-867. DOI URL
[44]	Y. Bai, B. Zhong, Y. Yu, M. Wang, J. Zhang, B. Zhang, NPJ 2D Mater. Appl. 3 (2019) 32. DOI URL
[45]	B. Zhong, Y. Cheng, M. Wang, Y. Bai, X. Huang, Y. Yu, Compos. A Appl. Sci. Manuf. 112 (2018) 515-524. DOI URL
[46]	S. Gao, G. Zhang, Y. Wang, X. Han, Y. Huang, P. Liu, J. Mater. Sci. Technol. 88 (2021) 56-65. DOI URL
[47]	P. Liu, S. Gao, G. Zhang, Y. Huang, W. You, R. Che, Adv. Funct. Mater. 31 (2021) 2102812. DOI URL
[48]	S. Zhang, L. Sui, H. Kang, H. Dong, L. Dong, L. Yu, Small 14 (2018) 1702570. DOI URL
[49]	H. Wang, T. Maiyalagan, X. Wang, ACS Catal. 2 (2012) 781-794. DOI URL
[50]	H. Xu, X. Yin, M. Li, F. Ye, M. Han, Z. Hou, Carbon 132 (2018) 343-351.
[51]	W. Zhu, L. Zhang, W. Zhang, F. Zhang, Z. Li, Q. Zhu, Nanomaterials 9 (2019) 1403-1420. DOI URL
[52]	W. Chen, H. Zhao, B. Xu, Q. Jiang, S. Bao, Z. Jiang, J. Alloy. Compd. 829 (2020) 154519. DOI URL
[53]	C. Liu, B. Wang, C. Mu, K. Zhai, F. Wen, J. Xiang, J. Magn. Magn. Mater. 502 (2020) 166432. DOI URL
[54]	Y. Wu, R. Shu, J. Zhang, Z. Wan, J. Shi, Y. Liu, J. Alloy. Compd. 819 (2020) 152944. DOI URL
[55]	X. Zhang, X. Zhang, H. Yuan, K. Li, Q. Ouyang, C. Zhu, Chem. Eng. J. 383 (2020) 123208. DOI URL
[56]	H.B. Zhao, Z.B. Fu, H.B. Chen, M.L. Zhong, C.Y. Wang, ACS Appl. Mater. Interfaces 8 (2016) 1468-1477. DOI URL
[57]	B. Li, B. Mao, X. Wang, T. He, H. Huang, J. Alloy. Compd. 829 (2020) 154609. DOI URL
[58]	X. Liu, N. Chai, Z. Yu, H. Xu, X. Li, J. Liu, J. Mater. Sci. Technol. 35 (2019) 2859-2867. DOI URL
[59]	P. Liu, Y. Zhang, J. Yan, Y. Huang, L. Xia, Z. Guang, Chem. Eng. J. 368 (2019) 285-298. DOI URL
[60]	D. Wei, Y. Qi, S. Lv, G. Shi, Y. Dai, Y. Qi, Ceram. Int. 45 (2019) 4448-4454. DOI URL
[61]	W. Zhu, L. Zhang, W. Zhang, F. Zhang, Z. Li, Q. Zhu, Nanomaterials 9 (2019) 1403-1420. DOI URL
[62]	H. Xu, L. Ma, Z. Jin, J. Energy Chem. 27 (2018) 146-160. DOI URL
[63]	W.Q. Cao, X.X. Wang, J. Yuan, W.Z. Wang, M.S. Cao, J. Mater. Chem. C 3 (2015) 10017-10022. DOI URL
[64]	Q. Hu, R. Yang, Z. Mo, D. Lu, L. Yang, Z. He, Carbon 153 (2019) 737-744.
[65]	Y. Bi, M. Ma, Z. Liao, Z. Tong, Y. Chen, R. Wang, J. Colloid Interface Sci. 605 (2022) 483-492. DOI URL
[66]	Z. Tong, Z. Liao, Y. Liu, M. Ma, Y. Bi, W. Huang, Carbon 179 (2021) 646-654.
[67]	M. Ma, W. Li, Z. Tong, Y. Ma, Y. Bi, Z. Liao, J. Colloid Interface Sci. 578 (2022) 58-68. DOI URL
[68]	Z. Liao, M. Ma, Y. Bi, Z. Tong, K.L. Chung, Z. Li, J. Colloid Interface Sci. 606 (2022) 709-718. DOI URL