Design of hybridized network structure and photoelectric thermal conversion performance of polyethylene glycol-based phase change composites
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摘要: 为了探究不同结构的纳米粒子对聚乙二醇(PEG)基相变复合材料形状稳定性及光电转换效率的影响，本文将碳纳米管(CNT)分别与BN、Al2O3以及铜粉(Cu)通过物理杂化的方式制备了PEG-聚乳酸(PLA)-CNT-X(y)相变储能复合材料。通过导电数据分析发现，Al2O3和Cu纳米填料的加入对PEG-PLA-CNT-X(y)复合材料的导电性能影响较小，使复合材料仍然具有较高的导电性能；而BN的引入使复合材料的导电性能急剧下降，当BN的质量含量比达到40%时，PEG60-PLA40-CNT0.6-BN(40)复合材料的电导率仅为8.71×10−7 S/m，呈现出明显的绝缘性。通过SEM和EDS能谱发现， Al2O3纳米粒子在复合材料内部均匀分布，当Al2O3质量含量比为40%时，PEG60-PLA40-CNT0.6-Al2O3(40)复合材料热导率和增强因子($ \varPhi $)值分别高达5.81 W/(m·K)和363.6%；相较于PEG60-PLA40-CNT0.6复合材料，PEG60-PLA40-CNT0.6-Al2O3(40)复合材料在160℃时仍具有较高的形状稳定性，没有出现PEG的泄露和塌陷现象。相比于其他纳米粒子，Al2O3的引入能够显著提高PEG60-PLA40-CNT0.6-Al2O3(40) 复合材料的光热转换效率($ \eta $)，$ \eta $值从42.9%提升至79.9%。而且复合材料对光的响应灵敏度更高，响应速度更快，电流变化曲线更加平滑，具有优异的光电转换性能。Abstract: PEG60-polylactic acid (PLA40)-CNT0.6-X(y) phase-change energy storage composites were prepared in this paper by physically hybridizing carbon nanotubes (CNT) with BN, Al2O3, and copper powder (Cu), respectively, to investigate the effects of nanoparticles with different structures on the shape stability and photovoltaic conversion efficiency of polyethylene glycol (PEG) based phase-change composites. The incorporation of Al2O3 and Cu nanofillers has a minor effect on the electrical conductivity of the PEG-PLA-CNT-X(y) composites. However, the introduction of BN drastically reduces the electrical conductivity of the composites. When the mass ratio of BN reaches 40%, the electrical conductivity of the PEG60-PLA40-CNT0.6-BN(40) composites is only 8.71×10−7 S/m, indicating obvious insulating properties. The spherical Al2O3 nanoparticles were found to be uniformly distributed inside the composites by SEM and EDS energy spectroscopy, and the thermal conductivity and enhancement factor ($ \varPhi $) values of PEG60-PLA40-CNT0.6-Al2O3(40) composites were as high as 5.81 W/(m·K) and 363.6%, respectively. Compared to the PEG60-PLA40-CNT0.6 composites, the addition of Al2O3 improves the photothermal conversion efficiency ($ \eta $), photo sensitive response rate, and current stability of PEG60-PLA40-CNT0.6-Al2O3(40) composites, raising the value from 42.9% to 79.9%. Moreover, composite materials exhibit higher sensitivity to light, faster response time, smoother current change curves, and excellent photoelectric conversion performance.
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图 1 添加不同导热粒子的PEG基复合材料的电导率曲线
Figure 1. Conductivity curves of PEG composites with different thermally conductive particles
图 2 不同导热填料的PEG基复合材料的热导率图(a)和热协同效率(b)
Figure 2. Thermal conductivity maps (a) and thermal synergy efficiency (b) of PEG composites with different thermally conductive fillers
图 3 PEG60-PLA40-CNT0.6-Al2O3(y)复合材料的SEM图像
Figure 3. SEM images of PEG60-PLA40-CNT0.6-Al2O3(y) composites
图 4 PEG60-PLA40-CNT0.6-X(40)复合材料的SEM-EDS图像
Figure 4. SEM with EDS images of PEG60-PLA40-CNT0.6-X(40) composites
图 5 PEG60-PLA40-CNT0.6-X(40)复合材料在150 mW/cm2光照强度下的温度变化曲线
Figure 5. Temperature profiles of PEG60-PLA40-CNT0.6-X(40) composites at 150 mW/cm2 light intensity
η—Photothermal conversion efficiency
图 6 PEG60-PLA40-CNT0.6-Al2O3(40)复合材料在150 mW/cm2光照强度下的升降温热红外成像图
Figure 6. Lift-off thermal infrared imaging of PEG60-PLA40-CNT0.6-Al2O3(40) composite at 150 mW/cm2 light intensity
图 7 复合材料降温结晶曲线(a)和升温熔融曲线(b)
Figure 7. Cooling crystallization curves (a) and heating melting curves (b) of composites
图 8 PEG60-PLA40-CNT0.6-X(40)复合材料在不同光照强度下的电流变化曲线
Figure 8. Current variation curves of PEG60-PLA40-CNT0.6-X(40) composites under different light intensities
图 9 PEG60-PLA40-CNT0.6-Al2O3(40)复合材料的循环DSC曲线(a)和循环前后的FTIR图谱(b)
Figure 9. Circular DSC curves (a) and FTIR spectra (b) of PEG60-PLA40-CNT0.6-Al2O3(40) composites
图 10 PEG60-PLA40-CNT0.6-Al2O3(y)复合材料在不同温度下的形状稳定图(其中S1代表PEG，S2代表PEG60-PLA40-CNT0.6和S3代表PEG60-PLA40-CNT0.6-Al2O3(40))
Figure 10. Shape stabilization images of PEG60-PLA40-CNT0.6-Al2O3(y) composites (S1, S2 and S3 represent PEG, PEG60-PLA40-CNT0.6 and PEG60-PLA40-CNT0.6-Al2O3(40), respectively)
表 1 聚乙二醇(PEG)60-聚乳酸(PLA)40-碳纳米管(CNT)0.6-X(y)复合材料质量配比表
Table 1. Mass ration of polyethylene glycol (PEG)60-polylactic acid (PLA)40-carbon nanotubes (CNT)0.6-X(y) composites
Sample PLA/% CNT/% PEG/% y/% PEG60-PLA40-CNT0.6 40 0.6 60 — PEG60-PLA40-CNT0.6-X(5) 40 0.6 60 5 PEG60-PLA40-CNT0.6-X(10) 40 0.6 60 10 PEG60-PLA40-CNT0.6-X(20) 40 0.6 60 20 PEG60-PLA40-CNT0.6-X(30) 40 0.6 60 30 PEG60-PLA40-CNT0.6-X(40) 40 0.6 60 40 Notes: "X" represents the thermally conductive particles; "y" represents the mass ratio of thermally conductive particles in PEG60-PLA40 composites. 
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表 2 复合材料中PEG相的DSC参数
Table 2. DSC parameters of PEG phase in composites
Sample T0/℃ Tp/℃ ΔHm/(J·g−1) PEG60-PLA40-CNT0.6 43.4 41.9 100.5 PEG60-PLA40-CNT0.6-Al2O3(5) 39.6 36.6 95.6 PEG60-PLA40-CNT0.6-Al2O3(20) 43.4 40.6 88.9 PEG60-PLA40-CNT0.6-Al2O3(40) 46.0 44.7 85.2 Notes: T0—Onset crystalline temperature; Tp—Peak crystalline temperature; ΔHm—Melting enthalpy.
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表 3 复合材料中PLA相的DSC参数
Table 3. DSC parameters of PLA phase in composites
Sample T0/℃ Tp/℃ ΔHm/(J·g−1) PEG60-PLA40-CNT0.6 120.2 115.5 16.4 PEG60-PLA40-CNT0.6-Al2O3(5) 119.3 112.7 17.1 PEG60-PLA40-CNT0.6-Al2O3(20) 121.5 114.4 16.4 PEG60-PLA40-CNT0.6-Al2O3(40) 127.1 122.5 16.7
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