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摘要: 树脂炭具有良好的力学、电学以及热物理性能,是广泛应用于航空、航天、能源等领域的结构功能一体化材料。树脂固有的分子结构特性导致树脂炭难石墨化,限制了树脂炭的广泛应用。本文综述了近年来改性树脂炭石墨化及应用的研究进展,系统介绍了催化剂、碳纳米材料、易石墨化共炭化剂三类树脂改性剂,可提高树脂炭的石墨化炭含量并降低其石墨化温度。其中催化剂和碳纳米材料改性剂方面的研究较多,催化剂改性剂在较低温度下(低于1400 °C)便能使树脂炭的石墨化度达74%,而碳纳米材料改性剂需要在2000 °C以上才能较明显地提高树脂炭的石墨化度。相比前两种改性剂,易石墨化的共炭化改性剂不仅能提高树脂炭的石墨化度,还能提高树脂的残炭率。在应用方面,提高树脂炭的石墨化度能提高炭/炭复合材料的导热和导电性能,也能提高超级电容器材料和二次电池电极材料的导电性能、倍率性能和功率密度。最后探讨了改性树脂炭的石墨化及应用面临的挑战和发展方向。Abstract: Resin carbons have favorable mechanical, electrical and thermal properties, and are widely used as structural and functional materials in aviation, aerospace and energy storage, etc. The inherent molecular structures of resins make their graphitization difficult, which greatly limits wide applications. Research progress on the graphitization and applications of resin carbons in recent years are reviewed. Their graphitized carbon content can be increased and their graphitization temperature reduced by adding catalysts, carbon nanomaterials and easily graphitized co-carbonization agents. Most studies have been devoted to increasing their graphitized carbon content using catalysts and carbon nanomaterials. The degree of graphitization of resin carbons at temperatures below 1400 °C can reach 74% by adding a catalyst, and above 2000 °C by adding carbon nanomaterials. Co-carbonization agents may increase their degree of graphitization and also their carbon yield. The thermal and electrical conductivities of carbon/carbon composites could be improved by increasing the degree of graphitization of resin carbons, and this would improve the conductivity, rate performance and power density of supercapacitors and secondary batteries. Challenges and research prospects for the graphitization of resin carbons and their applications are discussed.
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Key words:
- Modification resin carbon /
- Graphitization /
- Catalyst /
- Carbon nanomaterials /
- Co-carbonizing agents /
- Applications
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图 2 (a)800 °C炭化1 h后的每平方厘米1015 Fe+离子改性酚醛树脂炭TEM,(b)不同离子束强度改性后800 °C炭化1 h的酚醛树脂炭Raman[12],(c1)焦耳加热镍改性的非晶炭纤维,(c2和c3)多孔和管状石墨化炭纤维的TEM和HRTEM[19],(d)60%的Co(NO3)2·6H2O在800 °C炭化1 h催化形成多孔石墨炭纤维过程[20]
Figure 2. TEM images of the obtained carbon materials with the ion implantation (1×1015 ions/cm2): typical results of measurement of interlayer distance (a), Proportion of raman spectra peak area obtained by the peak with the ion implantation (b) after carbonization at 800 °C for 1 h [12], Nickel modification amorphous carbon fiber modified by Joule heat (c1), TEM and HRTEM of porous and tubular graphitization carbon fibers (c2 and c3)[19], Porous graphite carbon fibers prepared by carbonization of 60% Co(NO3)2·6H2O and phenolic resin at 800 °C for 1 h[20]. Reprinted with permission
图 4 (a)煤沥青和片状酚醛树脂为前体驱体合成多孔炭制备工艺,(b)75 wt%的煤沥青改性酚醛树脂800 °C炭化2 h的TEM,(c,d)不同质量分数(0、50 wt%、75 wt%、85 wt%、100 wt%)的煤沥青改性酚醛树脂800 °C炭化2 h的XRD和Raman[31]
Figure 4. (a) Preparation porous carbon using coal tar pitch and flake phenolic resin as precursors, (b) TEM of 75 wt% coal tar pitch modification phenolic resin carbonization at 800 °C for 2 h, (c, d) XRD and Raman of different mass fractions (0, 50 wt%, 75 wt%, 85 wt%, 100 wt%) coal tar pitch modification phenolic resin carbonization at 800 °C for 2 h[31]. Reprinted with permission
图 6 (a)PGCFs-0.3M的详细制备工艺,(b)PGCFs-0 g,PGCFs-O-0.25 g,和PGCFs-0.25 g的XRD图,(c)PGCFs 的Raman光谱图,(d)10-300 A·g−1电流密度范围的比容量图,(e) PGCFs-0.3M 在6 mol.L−1 KOH和1 mol.L−1 Na2SO4电解液中的Ragone图[46]
Figure 6. (a) The detailed preparation process of PGCFs-0.3M, (b) XRD patterns of PGCFs-0g, PGCFs-O-0.25g, and PGCFs-0.25g, (c) Raman spectra image of the PGCFs, (d) Specific capacitance at current density of 10-300 A·g−1, (e) Ragone plots of PGCFs-0.3M in 6 mol.L−1 KOH and 1 mol.L−1 Na2SO4[46]. Reprinted with permission
图 7 (a,b)C9树脂和萘沥青共炭化炭的比容量和库仑效率随温度变化,(c,d,e)900、2000、2800 °C热处理过程中的比容量-循环稳定性曲线,(f)电极材料的微观结构与电化学性能之间的关系[51]
Figure 7. (a, b) Specific capacity and coulomb efficiency for C9 resin and naphthalene pitch co-carbonization during temperature variation, (c, d, e) Specific volume-cyclic stability during heat treatment at 900, 2000 and 2800 °C, (f) Relationship between electrode material microstructure and electrochemical performance[51]. Reprinted with permission
表 1 改性树脂炭的石墨结构
Table 1. Graphitization structure of modified resin carbon
Modifier agent Precursor resin Preparation method Structure Ref. Fe nanoparticles Phenolic resin Ion Implantation, 800 °C Nanosized turbostratic graphite [12] 3 wt% ferrocene Novolak resin Ultrasonic mixing, 1000 °C for 5 h Onion-like hollow carbon [13] 3 wt% ferrocene Novolak and resole resins Vertical and ultrasonic mix, 1000 °C for 5 h Graphitization level, 70% [14] 1.5 wt% Ni(NO3)2 Phenolic resin Solution mixing, 1200 °C for 3 h Cystalline carbon observed [16] 15 wt% Ni-Zn-B alloy Phenolic resin 1400 °C 28.42% ordered graphite [17] 6 wt% Ni(NO3)2 Phenolic resin Magnetic stirrer mixing, 1250 °C for 3 h Graphitization level, 74.41% [18] 60 wt% Co(NO3)2.6H2O Phenolic resin Electrospinning technique, 800°C for 3 h Thin graphitic nanoshells [20] Cobalt acetate Phenolic resin One-pot hydrothermal synthesis, First at 350 °C
for 2 h, then at 700°C for 2 hPresence of graphitic domains [22] 10 wt% H3BO3 Novolac resin Mechanical mixer and ultrasonic mixing
1000 °C for 5 hGraphitization level, 49% [23] Boron powder Polyacrylonitrile Solution method, 2100 °C for 1 h Graphitization level, 88.1% [25] 1.5 wt% MWNTs Furan resin as C/C composite matrix Ultrasound dispersion, 2300 °C Graphitization level, 88% [26] 0.5 wt% carbon nanotubes Phenolic resin Ultrasonic vibration, 1400 °C for 3 h Increased graphitization degree [27] Three-dimensional graphene Phenolic resin In situ polymerization, 800 °C for 3 h IG/ID (1.15) [28] 26 wt% Graphite oxide Furan resin Ultrasonic vibration, 2400 °C Graphitization level, 66% [30] -
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