PEG-EG固-固相变材料的制备和性能研究

doi:10.11949/0438-1157.20230231

摘要/Abstract

摘要：

针对固-液相变材料易泄漏和热导率较低的问题，提出了聚乙二醇(PEG)固-固相变的复合材料。复合材料由不同比例、热导率较大的膨胀石墨(EG)骨架与PEG化学枝接得到。研究结果表明，EG质量分数为10%时，复合相变材料仍存在泄漏现象，而EG质量分数为20%、30%时不再有泄漏现象，复合材料表现为固-固相变。另外，复合材料的热导率随EG含量的增加而增大，其中EG质量分数为30%时，复合材料的热导率最高，为8.031 W·m^-1·K^-1，是纯相变材料热导率(0.289 W·m^-1·K^-1)的27.79倍。经历50次循环后，所有复合相变材料的相变温度和相变焓均未有明显变化，证明其具有良好的热稳定性。考虑综合性能，EG的质量分数为20%时，复合相变材料性能最佳，定形效果良好，相变焓(138.30 J·g^-1)和结晶度(88.6%)较高，热导率也可以达到6.870 W·m^-1·K^-1。

关键词: 膨胀石墨, 聚乙二醇, 相变, 化学枝接, 热传导, 复合材料

Abstract:

Aiming at the problems of easy leakage and low thermal conductivity of solid-liquid phase change materials, a polyethylene glycol (PEG) solid-solid phase change composite material was proposed. The composite material is obtained by chemical grafting of expanded graphite (EG) framework with different proportions and high thermal conductivity and PEG. The results show that the composite phase change material has a leakage phenomenon when the mass fraction of EG is 10%, while there is no more leakage phenomenon when the mass fraction of EG is 20% and 30%. In addition, the thermal conductivity of the composites increased with the increment of EG content. The highest thermal conductivity of 8.031 W·m^-1·K^-1 was obtained with the EG mass fraction of 30%, which was 27.79 times that of the pure phase change material (0.289 W·m^-1·K^-1). After 50 cycles, the phase change temperature and enthalpy of all composite materials did not change significantly, which proved the excellent thermal stability. Considering the comprehensive performance, under the condition of the optimal EG mass fraction of 20%, the phase change composite is form-stable and own high phase change enthalpy (138.30 J·g^-1), high crystallinity (88.6%), and high thermal conductivity (6.870 W·m^-1·K^-1).

Key words: expanded graphite, polyethylene glycol, phase change, chemical graft, heat conduction, composite material

中图分类号:

TK 02

李振, 张博, 王丽伟. PEG-EG固-固相变材料的制备和性能研究[J]. 化工学报, 2023, 74(6): 2680-2688.

Zhen LI, Bo ZHANG, Liwei WANG. Development and properties of PEG-EG solid-solid phase change materials[J]. CIESC Journal, 2023, 74(6): 2680-2688.

图/表 11

图1 化学枝接反应原理图

Fig.1 Principle diagram of chemical grafting reaction

图2 EG和PEG-EG30%的SEM图

Fig.2 SEM images of EG and PEG-EG30%

图3 EG、PEG和PEG-EG的FTIR谱图

Fig.3 FTIR spectra of EG, PEG and PEG-EG

图4 EG、PEG和PEG-EG的XRD谱图

Fig.4 XRD pattern of EG, PEG and PEG-EG

图5 复合相变材料定形效果

Fig.5 Shape change of composite phase change materials

图6 PEG和PEG-EG的DSC图

Fig.6 DSC diagram of PEG and PEG-EG

图7 PEG-EG复合相变材料熔化过程相变焓及温度

Fig.7 Phase change enthalpy and temperature of the melting process of PEG-EG composite phase change materials

表1 PEG-EG复合相变材料的DSC数据

Table 1 DSC data of PEG-EG composite phase change materials

材料	熔化温度T_m/℃	熔化焓ΔH_m/(J·g^-1)	凝固温度T_c/℃	凝固焓ΔH_c/(J·g^-1)	过冷度ΔT/℃	结晶度η/%
PEG	59.02	203.60	43.39	190.43	15.63	100
PEG-EG10%	57.35	156.19	36.72	141.89	20.63	89.3
PEG-EG20%	54.79	138.30	35.98	131.99	18.81	88.6
PEG-EG30%	53.76	111.13	37.92	104.04	15.84	80.9

图8 PEG-EG复合相变材料50次循环DSC图

Fig.8 DSC diagram of PEG-EG composite phase change materials after 50 cycles

图9 PEG-EG复合相变材料热导率

Fig.9 Thermal conductivity of PEG-EG composite phase change materials

表2 文献报道PEG复合相变材料对比

Table 2 Comparison of PEG composite phase change materials reported in literature

复合相变材料成分	比例	制备方法	相变形式	相变焓/ (J·g^-1)	热导率/ (W·m^-1·K^-1)	文献
氧化石墨烯/PEG	1.72%/89%	化学枝接	固-固	150.7	0.972	[38]
EG/PEG/二氧化硅	6%/84%/10%	物理真空浸渍	固-液	129	1.867	[39]
石墨烯纳米片/PEG	2%/98%	物理吸附	固-液	170.2	0.784	[40]
氧化石墨烯/PEG	9.6%/90.4%	化学枝接	固-固	157.6	0.983	[41]
磷酸化聚乙烯醇/石墨烯气凝胶/PEG	15%/1.6%/83.4%	物理溶胶-凝胶法	固-液	119.6	0.61	[42]
碳纳米管/硅藻土/PEG	3.2%/36.8%/60%	物理浸渍	固-液	107.4	1.52	[43]
rGO/PEG	5%/95%	化学枝接	固-固	138.7	0.696	[44]
石墨烯纳希片/氮化硼/PEG	1%/30%/69%	物理共混	固-液	123.8	1.33	[45]
EG/PEG	20%/80%	化学枝接	固-固	138.30	6.870	本文

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