Classification, absorbing mechanism and research progress of biomass-derived carbon-based composite absorbing materials
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摘要: 为解决电子信息技术带来的电磁波污染问题，碳基复合吸波材料受到了广泛的关注。生物质衍生碳复合材料不仅具有优异的电磁波吸收能力，还具有密度小、来源广泛和成本低等优点。本文首先阐述了生物质衍生碳的制备方法及过程；其次，依据生物科学分类法系统归纳了植物界类、真菌类、原生生物界类的三种生物质衍生碳的结构形貌特征，对生物质衍生碳基复合吸波材料近些年的研究成果进行了总结与综述；接着，对不同分类的吸波材料的结构形貌与电磁波吸收性能进行了对比，并分析了各类材料的吸波机制。最后，分析了目前生物质衍生碳基复合材料的吸波性能及其缺点，并对未来发展方向进行展望。本文为推进非动物类生物质衍生碳复合吸波材料的研究，提供了较全面的归纳、分类、分析与理论支持，为其未来发展提供了思路。Abstract: In order to solve the electromagnetic wave pollution caused by electronic information technology, carbon-based composite absorbing materials have received extensive attention. Biomass-derived carbon composites not only have excellent electromagnetic wave absorption ability, but also have the advantages of low density, wide source and low cost. Firstly, the preparation method and process of biomass derived carbon are described. Secondly, the structural and morphological characteristics of three kinds of biomass-derived carbon, including plant kingdom, fungus kingdom and protista kingdom, were systematically summarized, and the research results of biomass-derived carbon-based composite absorbing materials in recent years were summarized. Then, the structural morphology and electromagnetic wave absorption properties of different kinds of absorbing materials are compared, and the absorbing mechanism of various materials is analyzed. Finally, the current wave absorbing properties and disadvantages of biomass-derived carbon matrix composites are analyzed, and the future development direction is prospected. This paper provides comprehensive induction, classification, analysis and theoretical support for promoting the research of non-animal biomass derived carbon composite absorbing materials, and provides ideas for its future development.
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表 1 真菌类生物质的结构与成分
Table 1. Structure and composition of fungal biomass
Biomass species Mushroom Agaric Yeast Heteroelement element/(μg·g−1) P: 0.63-1.05
Fe: 27.5-215
Zn: 49.4-85.8P: 1305.35-2430.59
Fe: 83.76-110.62
Zn: 26.58-51.76P: 1.6-3.5% (wt%)
Fe: 90-350
Zn: 100-160Structural molecule Chitin, cellulose, hemicellulose Pore size scope /μm Tissue holes:10-200 μm
Cell wall pit 0.9-2.7 μmPlasmodesma:
30-60 nmPorosity/% 59.0 62.9 — 
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表 2 部分真菌类生物质衍生碳复合材料的结构与成分
Table 2. Structure and composition of partial fungal biomass derived carbon composites
BDC species Mushroom Agaric Yeast Heteroelement species P、Fe Fe Carbonization temperature /℃ 700 800 800 800 800 800 800 900 900 ID/IG 0.92 0.97 — 1.02 1.06 0.89 2.95 0.92 1.05 Pore size scope /nm — 9.10 5.27 5.60 3.93 — 2.6-5.0 6.90 — BET surface area/(m2/g) — 81.6 1631 193 173 — 571 89.6 — Pore volume/(cm3/g) — 0.22 0.07 0.25 — — 0.33 0.04 — Ref. [24] [25] [21] [26] [27] [28] [22] [29] [30] Notes: BDC—Biomass Derived Carbon; BET—Brunauer Emmett Teller
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表 3 真菌生物质衍生碳基复合吸波材料的微波吸收性能
Table 3. Microwave absorption performance of fungal biomass derived carbon-based composite absorbing materials
Precursor material Amount of fill /wt% Abosobers Thickness/
mmFrequence/
GHzRLmin/
dBEAB/
GHzDistribution area of
EAB/GHzRef. Mushroom 50% Fe/Fe4N/BDC 5
44.8 −30.3
6.64
4.00-10.64[24] FeCo@C@BDC 2.9 12.2 −69.5 8.6 9.4-18 [25] Agaric 30% Co/BDC 2.8 8.56 −52.6 5.44 11.84-17.28 [26]
[27]50% BDC@NCO 4.09 −54.6 1.85 5.7 9.9-15.6 50% Fe/Fe3O4/BDC 2.06 9.63 −30.4 2.45 9.58-12.37 [28] Yeast 20% CoNiO2@BDC 4 6.56 −44.0 4.5 7.04 [29] 40% Mo2C@N/P 2.5 12.4 −50.6 5.4 10.5-15.9 [30] Notes: RLmin—Reflection Loss Minimum; EAB—Effective absorption bandwidth.
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表 4 植物类生物质的结构与成分
Table 4. Structure and composition of plant biomass
Biomass Heteroelement element/(μg/g) Structural molecule Pore size scope Porosity/% Part Species Leaf Ginkgo Fe: 340; Zn: 30; P: 250 Lignin
Cellulose
HemicelluloseCell pit 1.2 μm
Capillary: 0.1-25 μm— Peatmoss P: 1.04; Zn: 415.8; — Shell Pinecone N: 3.78%(wt%) Cell pit 1.2 μm
Pore: 2.41 nm— Rice-hull P: 289; Fe: 37;
Zn: 14; Si: 40— Stems Fir N：0.1~0.2% (wt%)
Ash content：0.2~1.7(wt%)26.03 μm 58.46 Pine Capillary:1-10 nm
Cell pit: 0.1-0.7 μm
average:1.466 nm78.39 Wheat-straw N：1.12% (wt%)
S：0.25% (wt%)14.79 nm 27.2 Purslane Fe: 154.5; Zn: 177.1 Cell pit 1.2 μm —
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表 5 植物类生物质衍生碳复合材料的结构与成分
Table 5. Structure and composition of plant biomass derived carbon composites
BDC Heteroelement element Carbonization
temperature /℃ID/IG Pore size
scope/nmBET surface
area/(m2/g)Ref. Part Species Leaf Ginkgo S
P700 1.08 — — [36] 800 1.10 1.4-1.6
/2.2/42103 [35] Peatmoss Fe
Zn:
P800 1.01 1.1/1.7-3.5 350 [32] 800 0.98 5/7/15/25 1861 [33] Shell Pinecone N 800 0.85 1.07 — [45] Rice-hull P 600 — 1.7-2.6/4 941.98 [53] 600 0.41 4-10 82.23 [54] 600 1.75 3.5 666.14 [56] Stems Fir N 1000 1.66 19.2-24.8μm — [41] 1000 1.01 — [42] 900 1.06 — 681.63 [37] Pine 670 — 10-20μm — [40] 1400 1.58 2 — [43] Purslane Fe、Zn 650 1.82 — — [49] Wheat-straw N 600 0.95 12.5–30 654.23 [48]
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表 6 植物生物质衍生碳基复合吸波材料的微波吸收性能
Table 6. Microwave absorption performance of plant biomass-derived carbon-based composite absorbing materials
Precursor material Amount of fill /wt% Abosober Thickness/
mmFrequence/
GHzRLmin/
dBEAB/
GHzDistribution area of
EAB/GHzRef Peatmoss 40% Ni/BDC 2.4 8.7 −52 2.6 7.3-9.9 [32] 40% Ni/BDC 2.4 9.4 −52 2.6 [33] Fe3O4/BDC 1.6 14.2 −51.6 4.1 Ginkgo-leaf 30% CaS/BDC 2.0 9.6 −15.47 2.08 [36] Fir 10% CoFe/BDC 2.4 12.2 −54.4 2.6 9.7-12.3 [41] 2.2 1.9 −53.6 4.2 8.2-12.4 [42] Pine 20% Fe3O4/BDC 3.2 12.16 −49.5 6.24 9.04-15.28 [40] 20% Ni/BDC 5.7 6.00 −50.38 3.76 6.4-10.16 [43] Pinecone 16.7% BDC 2.1 15.36 −76.0 [45] 2.3 5.92 11.92-17.84 Purslane 10% Co@BDC/CoO 2.5 14.0 −43.09 6.75 11.25-18 [49] Wheat-straw 10% BDC 2.5 12.1 −37 8.8 7.2-16 [48] 40% (Fe,Ni)/ BDC 1 0.81 −46.36 1.92 0.89-2.81 [50] Rice-hull 40% Fe3O4/ BDC 2.39 10.8 −51.73 [53] 30% NiCo2/BDC 3.57 6.32 −55.62 [54] 10% BDC 2.8 9.796 −47.46 3.40 8.47-11.87 [55] Coconut shell 10% BDC 2.5 −30.5 5.20 [56]
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表 7 部分原生生物类生物质的结构与成分
Table 7. Structure and composition of partial protist biomass
Biomass species Spirulina Nori Kelp Heteroelement element/wt% P: 1.2
S: 1.1P: 5.097-7038
Fe: 0.025-0.119N: 1.7-3.0
P: 0.25-0.42Structural molecule Cellulose, hemicellulose, pectin Pore size scope /μm Plasmodesma: 30-60 nm；Air hole 0.2-1.0 μm surface area/(m2/g) 214.4 — 68.3
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表 8 原生生物类生物质衍生碳复合材料的结构与成分
Table 8. Structure and composition of protist biomass derived carbon composites
BDC species Spirulina Nori Kelp Heteroelement species P、S P P、N Carbonization temperature /℃ 650 650 650 650 800 ID/IG 1.09 0.99 1.13 0.98 1.01 Pore size scope /nm 30-200 2 — 200-1000 3.50 BET surface area/(m2/g) 2400 1145 — 1145 1085.9 Pore volume/(cm3/g) — 0.58 — 0.58 — Ref. [59] [61] [62] [63] [64]
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表 9 原生生物质衍生碳基复合吸波材料的微波吸收性能
Table 9. Microwave absorption properties of carbon based composite absorbing materials derived from primary biomass
Precursor
materialAmount of
fill/wt%Abosober Thickness/mm Frequence/GHz RLmin/dB EAB/GHz Distribution Area
of EAB/GHzRef. Spirulina 18.6 Fe3O4@BDC 1.49 14.68 −45.54 5.14 12.45-17.59 [59] 60 Ni/BDC 3 8.9 −19.2 4 [60] Nori 30 NiCo2O4/BDC 5.5 6.24 −43.20 3.3 [61] 28.6 Ni@BDC 3.0 9.25 −35.73 [62] 2.5 6.37 10.35-16.72 30 MnO2/BDC 5.5 5.04 −40.16 [63] 3.5 5.12 6.72-11.84 Kelp 30 NiO-NixSy/BDC 3 7.28 −38.2 2.05 6.33–8.38 [64]
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表 10 真菌类、植物类、原生生物类生物质组成成分及吸波机制特点总结
Table 10. Summarizes the composition and absorbing mechanism characteristics of fungi, plants and protists.
Biomass species Structural components Characteristics of absorbing mechanism Fungus Chitin, cellulose Natural heteroatoms P and Fe produce more defects; Phosphorus atoms form a polarization center, which increases the dipole polarization loss. Natural iron ions give magnetic loss Plants Lignin, cellulose, hemicellulose Lignin, cellulose decomposition, and diaryl ether bond cleavage produce a large amount of CO, and the framework cell wall begins to become rough and fluffy, forming more pore structures Protista Cellulose, hemicellulose, pectin After the cellulose reticulum is carbonized, a network of extensive aromatic porous carbon with a macroporous structure is formed. After the pyrolysis of a large number of nitrogen-containing proteins, nitrogen enters the crystal lattice, forming lattice defects and dipoles, forming polarization centers and increasing polarization losses
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表 11 真菌类、植物类、原生生物类生物质微观结构及吸波机制特点总结
Table 11. Summary of microscopic structure and wave absorbing mechanism of fungi, plants and protists
Types of BDC Carbon structure Pore size/nm Absorbing mechanism Microstructure and mechanistic characteristics Fungus Multicellular Bulk porous carbon combined with a honeycomb carbon fiber mesh 0.5-5 1. A large number of polarization sites and structural defects;
2. Pore structure to improve impedance matching;
3. Charge polarization due to the gas/solid interface;
4. The lattice defect becomes the polarization center and improves the dipole polarization;
5. Three-dimensional conductive network to improve conductive loss;
6. Magnetic particles provide magnetic loss;
7. The heterogeneous interface provides interfacial polarization lossThe internal pores provide a large number of magnetic particle adsorption sites; Natural heteroatoms form polarization centers to enhance dipole polarization Unicellular Carbon microspheres, cellular efflux, and chitin pyrolysis form micropores 5-15 Plants Leaf Honeycomb hexagonal pores 1.2-2 /4 The internal inorganic salts act as templates, and the surface patterns of the blades form a rough undulating surface Stem/trunk Hollow frame three-dimensional carbon fiber layer, internal vascular and tracheid carbon channels 2/2-50 The wavelength of the incident electromagnetic wave is smaller than the size of the cell and tracheid to be absorbed, and some carbonized stems have a threaded structure Fruit/seed shell Honeycomb porous layered pores with natural mass transfer channels and multi-level pore structures inside 1.4-4/4-50 Amorphous soft carbon with low crystallinity and small grain size Protista Phaeophyta Flaked/filamentous porous carbon with numerous porous folds on the surface 1-3 Hard carbon, which is difficult to graphitize, retains its original shape more stably and completely after heat treatment Spirulina Spiral structure porous carbon 2-5 The spiral structure creates multiple areas of eddy current loss
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