Co/C微波吸收性能及Co/C-聚氨酯相变复合材料的微波-热转换性能

doi:10.19894/j.issn.1000-0518.210120

摘要/Abstract

摘要： 通过热解金属有机骨架ZIF-67的方法成功制备了具有优异微波吸收性能的Co/C碳基复合材料。在600 ℃热解温度下获得的吸收剂质量分数为35% 的样品,最小反射损耗可达到-54.30 dB,其厚度仅为1.75 mm。通过分析样品的损耗能力和阻抗匹配等微波吸收特性,发现复合材料中的骨架结构等对其阻抗匹配性能有非常大的影响。并通过原位复合的方法制备了分散均匀的Co/C-PU相变复合材料,初步研究了其微波-热转换性能。实验表明,微波吸收剂的添加量对其微波-热转换性能影响显著,发热效率随添加量成倍升高。本文研究的Co/C-PU相变复合材料在电磁屏蔽、雷达红外兼容隐身等方面具有很大的应用潜力。此外,固固相变材料结合微波热效应的快速高效等特点,用于储能或者其他热应用也有独特的优势。

关键词: 吸波材料, 固固相变材料, 金属有机骨架, 聚氨酯, 微波-热转换

Abstract: In this paper, a Co/C carbon-based composite material with excellent microwave absorption properties was successfully prepared by pyrolyzing metal-organic framework ZIF-67. The sample with a mass fraction of 35% of absorbent obtained at a pyrolysis temperature of 600 ℃ has a minimum reflection loss of -54.30 dB and its thickness is only 1.75 mm. By analyzing the microwave absorption characteristics of the sample′s loss capability and impedance matching, it is found that the skeleton structure in the composite material has a great influence on its impedance matching performance. And the uniformly dispersed Co/C-polyurethane (PU) phase change composite material was prepared by in-situ composite method, and its microwave-thermal conversion performance was preliminarily studied. The amount of added microwave absorbent has a significant effect on its microwave-heat conversion performance, and the heating efficiency increases exponentially with the added amount. The Co/C-PU phase change composite material studied in this paper has great application potential in electromagnetic shielding, radar and infrared compatible stealth. In addition, solid-solid phase change materials combined with the rapid and high-efficiency characteristics of microwave heating effects have unique advantages when used for energy storage or other thermal applications.

Key words: Microwave absorption materials, Phase change materials, Metal-organic frameworks, Polyurethane, Microwave-heat transportation

中图分类号:

O642

吴秋萍, 蔡昆廷, 王元康, 孙凯, 杨金波, 韩松柏, 刘蕴韬. Co/C微波吸收性能及Co/C-聚氨酯相变复合材料的微波-热转换性能[J]. 应用化学, 2021, 38(12): 1588-1598.

WU Qiu-Ping, CAI Kun-Ting, WANG Yuan-Kang, SUN Kai, YANG Jin-Bo, HAN Song-Bai, LIU Yun-Tao. Microwave Absorption Properties of Co/C and Microwave-Heat Conversion Properties of Co/C-Polyurethane Phase Change Composites[J]. Chinese Journal of Applied Chemistry, 2021, 38(12): 1588-1598.

参考文献

[1] LIU W, SHAO Q, JI G, et al. Metal organic-frameworks derived porous carbon-wrapped Ni composites with optimized impedance matching as excellent lightweight electromagnetic wave absorber[J]. Chem Eng J, 2017, 313: 734-744.
[2] LIU T, PANG Y, XIE X B, et al. Co/C nanoparticles with low graphitization degree: a high performance microwave-absorbing material[J]. J Mater Chem C , 2016, 4(8): 1727-1735.
[3] CHEN D, WANG G S, HE S, et al. Controllable fabrication of mono-dispersed RGO-hematite nanocomposites and their enhanced wave absorption properties[J]. J Mater Chem A, 2013, 1(19): 5996-6003.
[4] ZHAO H B, CHENG J B, ZHU J Y, et al. Ultralight CoNi/rGO aerogels toward excellent microwave absorption at ultrathin thickness[J]. J Mater Chem C, 2019, 7(2): 441-448.
[5] KIM T, LEE J, LEE K, et al. Magnetic and dispersible FeCoNi-graphene film produced without heat treatment for electromagnetic wave absorption[J]. Chem Eng J, 2019, 361: 1182-1189.
[6] WEN B, CAO M S, HOU Z L, et al. Temperature dependent microwave attenuation behavior for carbon-nanotube/silica composites[J]. Carbon, 2013, 65: 124-139.
[7] WANGL, BAI X Y, WEN B, et al. Honeycomb-like Co/C composites derived from hierarchically nanoporous ZIF-67 as a lightweight and highly efficient microwave absorber[J]. Compos B Eng, 2019, 166: 464-471.
[8] LI H, LIANG X, CHENG Y, et al. Coin-like α-Fe₂O₃@CoFe₂O₄ core-shell composites with excellent electromagnetic absorption performance[J]. ACS Appl Mater Interfaces, 2015, 7(8): 4744-4750.
[9] LI Z, HAN X, MA Y, et al. MOFs-derived hollow Co/C microspheres with enhanced microwave absorption performance[J]. ACS Sustainable Chem Eng, 2018, 6(7): 8904-8913.
[10] LIANG X H, QUAN B, CHEN J, et al. Nano bimetallic@carbon layer on porous carbon nanofibers with multiple interfaces for microwave absorption applications[J]. ACS Appl Nano Mater, 2018, 1(10): 5712-5721.
[11] LIU Q, ZHANG D, FAN T. Electromagnetic wave absorption properties of porous carbon/Co nanocomposites[J]. Appl Phys Lett, 2008, 93(1): 401.
[12] MA J N, ZHANG X M, LIU W, et al. Direct synthesis of MOF-derived nanoporous CuO/carbon composites for high impedance matching and advanced microwave absorption[J]. J Mater Chem C, 2016, 4(48): 11419-11426.
[13] SHARMA A, TYAGI V V, CHEN C R, et al. Review on thermal energy storage with phase change materials and applications[J]. Renew Sustainable Energy Rev, 2009, 13(2): 318-345.
[14] LIU C, LI F, MA L P, et al. Advanced materials for energy storage[J]. Adv Mater, 2010, 22(8): E28-E62.
[15] SAN, AHME T. Thermal energy storage characteristics of bentonite-based composite PCMs with enhanced thermal conductivity as novel thermal storage building materials[J]. Energy Convers Manage, 2016, 117: 132-141.
[16] CHEN R, YAO R, XIA W, et al. Electro/photo to heat conversion system based on polyurethane embedded graphite foam[J]. Appl Energy, 2015, 152: 183-188.
[17] BHATTACHARYA P, DHIBAR S, HATUI G, et al. Graphene decorated with hexagonal shaped M-type ferrite and polyaniline wrapper: a potential candidate for electromagnetic wave absorbing and energy storage device applications[J]. RSC Adv, 2014, 4(33): 17039-17053.
[18] WANG Y, DU Y C, GUO D, et al. Precursor-directed synthesis of porous cobalt assemblies with tunable close-packed hexagonal and face-centered cubic phases for the effective enhancement in microwave absorption[J]. J Mater Sci, 2017, 52(8): 4399-4411.
[19] DINEGA D P, BAWENDI M G. A solution-phase chemical approach to a new crystal structure of cobalt[J]. Angew Chem Int Ed, 1999, 38(12): 1788-1791.
[20] KIM S S, JO S B, GUEON K I, et al. Complex permeability and permittivity and microwave absorption of ferrite-rubber composite at X-band frequencies[J]. IEEE Trans Magn, 1991, 27(6): 5462-5464.
[21] ZHANG X M, GUANG B J, LIU W, et al. Thermal conversion of an Fe₃O₄@metal-organic framework: a new method for an efficient Fe-Co/nanoporous carbon microwave absorbing material[J]. Nanoscale, 2015, 7(30): 12932-12942.
[22] ZHOU X, WANG B, JIA Z, et al. Dielectric behavior of Fe₃N@C composites with green synthesis and their remarkable electromagnetic wave absorption performance[J]. J Colloid Interface Sci, 2020, 582: 515-525.
[23] XIONG Y, XU L, YANG C, et al. Implanting FeCo/C nanocages with tunable electromagnetic parameters in anisotropic wood carbon aerogels for efficient microwave absorption[J]. J Mater Chem A. 2020, 8(36): 18863-18871.
[24] ZHANG Y, YAO M, LIU C, et al. Reduced graphene oxide-CoFe₂O₄/FeCo nanoparticle composites for electromagnetic wave absorption[J]. ACS Appl Nano Mater, 2020, 3(9): 8939-8948.
[25] WANG X Y, LU Y K, ZHU T, et al. CoFe₂O₄/N-doped reduced graphene oxide aerogels for high-performance microwave absorption[J]. Chem Eng J, 2020, 388: 124317.
[26] ZHANG Y C, GAO S, XING H L, et al. In situ carbon nanotubes encapsulated metal nickle as high-performance microwave absorber from Ni-Zn metal-organic framework derivative[J]. J Alloys Compd, 2019, 801: 609-618.
[27] ZHANG Z L, LV Y Y, CHEN X Q, et al. Porous flower-like Ni/C composites derived from MOFs toward high-performance electromagnetic wave absorption[J]. J Magn Magn Mater, 2019, 487: 165334-165334.
[28] CAO M S, SONG W L, HOU Z L, et al. The effects of temperature and frequency on the dielectric properties, electromagnetic interference shielding and microwave-absorption of short carbon fiber/silica composites[J]. Carbon, 2009, 48(3): 788.
[29] LI J, LU S Q, HUANG H L, et al. ZIF-67 as continuous self-sacrifice template derived NiCo₂O₄/CoN-CNTs nanocages as efficient bifunctional electrocatalysts for rechargeable Zn-Air batteries[J]. ACS Sustainable Chem Eng, 2018, 6: 10021-10029.
[30] HONG W, KITTA M, XU Q. Bimetallic MOF-derived FeCo-P/C nanocomposites as efficient catalysts for oxygen evolution reaction[J]. Small Methods, 2018, 2(12): 1800214.
[31] WANG L, GUAN Y, QIU X, et al. Efficient ferrite/Co/porous carbon microwave absorbing material based on ferrite@metal-organic framework[J]. Chem Eng J, 2017, 326: 945-955.
[32] YAN J, HUANG Y, YAN Y, et al. The high-performance electromagnetic wave absorbers based on two kinds of nickel-based MOFs-derived Ni@C microspheres[J]. ACS Appl Mater Interfaces, 2019, 11(43): 40781-40792.
[33] GREEN M, LIU Z, XIANG P, et al. Ferric metal-organic framework for microwave absorption[J]. Mater Today Chem, 2018, 9: 140-148.
[34] WU C, CHEN Z, WANG M, et al. Microwaveabsorption: confining tiny MoO₂ clusters into reduced graphene oxide for highly efficient low frequency microwave absorption[J]. Small, 2020, 16(30): 2001686.
[35] CHE R C, PENG L M, DUAN X F, et al. Microwave absorption enhancement and complex permittivity and permeability of Fe encapsulated within carbon nanotubes[J]. Adv Mater, 2004, 16(5): 401-405.
[36] XIANG J, LI J L, ZHANG X H, et al. Magnetic carbon nanofibers containing uniformly dispersed Fe/Co/Ni nanoparticles as stable and high-performance electromagnetic wave absorbers[J]. J Mater Chem A, 2014: 16905-16914.
[37] FU M, JIAO Q, ZHAO Y, et al. Vapor diffusion synthesis of CoFe₂O₄ hollow sphere/graphene composites as absorbing materials[J]. J Mater Chem A, 2013, 2(3): 735-744.
[38] GANDHI N, SINGH K, OHLAN A, et al. Thermal, dielectric and microwave absorption properties of polyaniline-CoFe₂O₄ nanocomposites[J]. Compos Sci Technol, 2011, 71(15): 1754-1760.
[39] WANG W, TANG B, JU B, et al. Fe₃O₄-functionalized graphene nanosheet embedded phase change material composites: efficient magnetic- and sunlight-driven energy conversion and storage[J]. J Mater Chem A, 2017, 5: 958-968.
[40] GUYOMAR D, MATEI D F, GUIFFARD B, et al. Magnetoelectricity in polyurethane films loaded with different magnetic particles[J]. Mater Lett, 2009, 63(6/7): 611-613.
[41] WU W H, HUANG X Y, YAO R M, et al. Synthesis and properties of polyurethane/coal-derived carbon foam phase change composites for thermal energy storage[J]. Acta Phys-Chim Sin, 2017, 33(1): 255-261.
[42] YIN Y, LIU X, WEI X, et al. Magneticallyaligned Co-C/MWCNTs composite derived from MWCNTs interconnected zeolitic imidazolate frameworks for lightweight and highly efficient electromagnetic wave absorber[J]. ACS Appl Mater Interfaces, 2017: 30850.
[43] LIN H, ZHU H, GUO H, et al. Microwave-absorbing properties of Co-filled carbon nanotubes[J]. Mater Res Bull, 2008, 43(10): 2697-2702.
[44] QIANG R, DU Y C, CHEN D T, et al. Electromagnetic functionalized Co/C composites by in situ pyrolysis of metal-organic frameworks (ZIF-67)[J]. J Alloys Compd, 2016, 681: 384-393.