Research progress of lignin modification method and its application in preparation of carbon fiber
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摘要: 木质素作为自然界最丰富的芳香族化合物，其含碳量达30%~40%，是制备碳纤维的优质原料。然而由于存在非晶态化学结构、低分子量、宽分子量分布和排列不良等特性，其复杂的非均质结构和固有的易絮凝特质需通过改性以克服。本文介绍了木质素的基本结构单元与特征，并在此基础上详细描述了物理混合、化学改性、生物作用等改性过程工艺条件及其对木质素结构及木质素基碳纤维的强度、电化学、过滤、透气等性能影响，并在此基础上对碳纤维在交通建筑、航空航天、生命健康及新能源等领域应用进行了拓展探讨。此外，拓展概述了木质素的定向官能团改性、绿色改性方法及改性过程表达等可行性，为木质素基碳纤维复合材料的进一步研究和开发提供思考，并推动其实现工业化应用。Abstract: Lignin, as the most abundant aromatic compound in nature, has a carbon content of 30%-40% and is a high-quality raw material for preparing carbon fiber. However, due to the characteristics of amorphous chemical structure, low molecular weight, wide molecular weight distribution and poor arrangement, its complex heterogeneous structure and inherent flocculation characteristics need to be overcome by modification. In this paper, the basic structural units and characteristics of lignin were introduced, and on this basis, the modification process conditions such as physical mixing, chemical modification and biological action were described in detail, and their effects on the lignin structure and the strength, electrochemistry, filtration and air permeability of lignin-based carbon fibers were also described. On this basis, the application of carbon fiber in the fields of transportation, construction, aerospace, life and health and new energy was discussed. In addition, the feasibility of directional functional group modification, green modification method and modification process expression of lignin were summarized, which provided thinking for further research and development of lignin-based carbon fiber composites and promoted their industrial application.
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Key words:
- lignin /
- physicochemical modification /
- carbon fiber /
- mechanical property /
- electrochemical property
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图 7 纳米纤维垫预氧化及不同温度下碳化的SEM图像：(a) 250℃预氧化；(b) 600℃碳化；(c) 800℃碳化；(d) 1000℃碳化；(e) 1200℃碳化；(f) 1400℃碳化[32]
Figure 7. SEM images of nanofiber mat preoxidation and carbonization at different temperatures: (a) 250℃ preoxidation; (b) 600℃ carbonization; (c) 800℃ carbonization; (d) 1000℃ carbonization; (e) 1200℃ carbonization; (f) 1400℃ carbonization[32]
图 11 纯聚丙烯腈(PAN)纤维和添加0.2wt%木质素的DMSO-水凝结剂纺成的L/P纤维的SEM图像：(a) PAN；(b) L25/P75；(c) L35/ P65；(d) L45/P55；(e) L50/P50[26]
Figure 11. SEM images of pure polyacrylonitrile (PAN) fiber and L/P fibers spun in DMSO-water coagulant with additional 0.2wt% lignin: (a) PAN; (b) L25/P75; (c) L35/P65; (d) L45/P55; (e) L50/P50[26]
图 15 基于氮硫共掺杂石墨烯(GNs-N-S)共掺杂活性木质素基碳纳米纤维生产超级电容器的工艺示意图[52]
Figure 15. Process diagram of supercapacitor production based on GNs-N-S co-doped active lignin-based carbon nanofibers[52]
VE:VW—Volume ratio of ethanol and water; DMF—N, N-dimethylformamide; PAN—Polyacrylonitrile; GNs—Graphene; HVPS—High voltage power supply; ACNFs—Nitorgen and sulphur co-doped graphene modified lignin/polyacrylonitrile-based carbon nanofiber
表 1 木质素基碳纤维原料及其处理方式和碳纤维性能
Table 1. Lignin-based carbon fiber raw materials, treatment methods and properties of carbon fiber
Material Aids Treatment Carbon fiber properties Calcium lignosulfonate[20] Acrylonitrile, itaconic acid Copolymerization Tensile strength: 1.74 GPa
Tensile modulus: 210 GPaPyrolytic lignin[21] Polyethylene terephthalate Copolymerization Average diameter: 12.6 μm
Tensile strength: 1220 MPaPyrolytic lignin[22] Acryloyl chloride Modified Tensile strength: 1.70 GPa
Tensile modulus: 182 GPaSoftwood kraft lignin[23] Acetic anhydride Modified Tensile strength: 1.04 GPa
Tensile modulus: 52 GPaSoftwood lignin[24] Stearic acid Modified Average diameter: 48.6 μm
Tensile strength: 640 MPa
Tensile modulus: 70.7 GPaOrganosolv lignin from
Alamo switchgrass[25]Organosolv lignin from yellow poplar Mix Average diameter: 15.7 μm
Tensile strength: 747 MPa
Tensile modulus: 41.8 GPaSoftwood kraft lignin[26] Polyacrylonitrile Mix Tensile strength: 1.2 GPa
Tensile modulus: 130 GPaSoftwood kraft lignin[27] Polyvinyl alcohol Mix Average diameter: 12.6 μm
Tensile strength: 351 MPa
Tensile modulus: 44.5 GPaKraft lignin[28] Cellulose Mix Tensile strength: 780 MPa
Tensile modulus: 68 GPa
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