Preparation and characterization of paraffin phase change composites reinforced by carbon fiber-graphite nanoplatelets network
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摘要: 以石蜡为代表的固-液相变储能材料存在导热率低和热稳定性差两大问题，为了提高其导热性能，以酚醛树脂为碳质黏结剂前驱体，采用浆料成型法制备碳纤维-纳米石墨片(CF-GNP)复合网络体，并通过真空浸渍石蜡，制得CF-GNP/石蜡复合材料。表征和分析了CF和GNP含量对CF-GNP网络体微观形貌和CF-GNP/石蜡相变储能复合材料导热效率及热稳定性的影响。结果表明，CF-GNP/石蜡复合材料的导热效率较纯石蜡大幅增加。CF-GNP网络体中CF含量越低，GNP导热增强效应越明显。CF-GNP网络体中CF和GNP含量分别为50wt%、10wt%时，CF-GNP/石蜡复合材料的升温时间较CF含量为50wt%的CF/石蜡复合材料缩短了39.9%，当CF含量分别为70wt%和85wt%时，分别缩短了24.5%和9.4%。40次热循环稳定性测试表明，CF-GNP/石蜡复合材料具有良好热稳定性。Abstract: Two main drawbacks of most phase change materials are the low thermal conductivity and thermal stability. To address the above-mentioned problems, carbon bonded carbon fiber-graphite nanoplatelets (CF-GNP) network was first prepared using a slurry molding method. And molten paraffin was infiltrated into the CF-GNP network to form a CF-GNP/paraffin phase change composites. The effects of CF and GNP contents on the structure of the CF-GNP network and thermal properties of the CF-GNP/paraffin composites were systematically studied. The results show that the melting-solidifying rates are greatly accelerated for the CF-GNP/paraffin composites comparing to pure paraffin. The less the CF loading amount is, the more the effect of GNP on heat enhancement is. For the CF-GNP/paraffin composites with 50wt% CF and 10wt% GNP in the CF-GNP network, the melting time is shortened by 39.9% comparing with the CF/paraffin composite with only 50wt% CF in network. The decrements are 24.5% and 9.4% for CF/paraffin composite with CF loading of 70wt% and 85wt%, respectively. The tests of 40 thermal cycles indicate that the CF-GNP/paraffin composites prepared in this study show good thermal stability.
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图 1 碳纤维-纳米石墨片（CF-GNP）/石蜡相变复合材料的制备流程
Figure 1. Preparation process of carbon fiber-graphite nanoplatelets (CF-GNP)/paraffin phase change composites
图 2 EG和GNP的XRD(a)、Raman(b)和FTIR(c)图谱
Figure 2. XRD patterns(a), Raman spectra(b) and FTIR spectra (c) of EG and GNP
图 3 EG(a)和GNP(b)的SEM图像及 GNP的TEM图像(c)
Figure 3. SEM images of EG(a) and GNP(b) and TEM image of GNP(c)
图 4 CF-GNP网络体的SEM图像(未添加GNP，CF含量分别为50wt%(a), 70wt%(b), 85wt%(c)及对应的黏结点放大图(插图)；GNP添加量为10wt%，CF含量分别为50wt%(d), 70wt%(e), 85wt%(f))
Figure 4. SEM images of CF-GNP network (Without GNP, CF content is 50wt%(a), 70wt%(b), 85wt%(c) respectively; With 10wt% GNP, CF content is 50wt%(d), 70wt%(e), 85wt%(f) respectively)
图 5 CF-GNP网络体黏结点处的SEM图像(GNP含量为1wt%，CF含量分别为50wt%(a), 70wt%(b), 85wt%(c)及黏结点放大图((a1), (b1), (c1))；GNP含量为10wt%，CF含量分别为50wt%(d), 70wt%(e), 85wt%(f)及黏结点放大图((d1), (e1), (f1)))
Figure 5. SEM images of carbon bonded CF-GNP network (With 1wt% GNP, CF content is 50wt%(a),70wt%(b), 85wt%(c) and their enlargements((a1), (b1), (c1)) respectively; With 10wt% GNP, CF content is 50wt%(d),70wt%(e), 85wt%(f) and their enlargements((d1), (e1), (f1)) respectively)
图 6 CF-GNP/石蜡相变复合材料储热((a)~(c))和放热((d)~(f))曲线
Figure 6. Charging((a)–(c)) and discharging((d)–(f)) curves of CF-GNP/paraffin phase change composites
图 7 CF-GNP网络体导热模型：(a)CF-酚醛碳-CF； (b)CF-酚醛碳-GNP-CF； (c)GNP-酚醛碳-GNP； (d)碳纤维网络；(e)复合网络
Figure 7. Heat conduction transfer model of CF-GNP network：(a) CF-PR-CF； (b) CF-PR-GNP-CF； (c) GNP-PR-GNP；(d) CF network； (e) Hybrid composite network
图 8 CF-GNP/石蜡相变复合材料冷热循环的质量变化曲线
Figure 8. Mass change curves of CF-GNP/paraffin phase change composites during thermal cycle
图 9 CF-GNP/石蜡相变复合材料的DSC曲线
Figure 9. DSC curves of CF-GNP/paraffin phase change composites
表 1 CF-GNP网络体成分含量
Table 1. Composition of CF-GNP network
Sample Mass fraction of CF/wt% Mass fraction of GNP/wt% Mass fraction of PR/wt% 85-10 85 10 5 85-1 85 1 14 85-0 85 0 15 70-10 70 10 20 70-1 70 1 29 70-0 70 0 30 50-10 50 10 40 50-1 50 1 49 50-0 50 0 50 Note: PR—Phenolic resin. 
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