Development and properties of PEG-EG solid-solid phase change materials

doi:10.11949/0438-1157.20230231

Abstract

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

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

CLC Number:

TK 02

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.

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.

Figures/Tables 11

References 45

1	焦敬平, 池砚文. 世界可再生能源发展情况分析[J]. 能源, 2019(12): 59-63.
	Jiao J P, Chi Y W. Analysis on the development of renewable energy in the world[J]. Energy, 2019(12): 59-63.
2	董淑华, 江建飞. 我国可再生能源开发利用对策研究[J]. 现代经济信息, 2019(17): 362.
	Dong S H, Jiang J F. Study on the countermeasures for the development and utilization of renewable energy in China[J]. Modern Economic Information, 2019(17): 362.
3	汪翔, 陈海生, 徐玉杰, 等. 储热技术研究进展与趋势[J]. 科学通报, 2017, 62(15): 1602-1610.
	Wang X, Chen H S, Xu Y J, et al. Advances and prospects in thermal energy storage: a critical review[J]. Chinese Science Bulletin, 2017, 62(15): 1602-1610.
4	Cheng Q J, Cheng X L, Wang X, et al. Supercooling regulation and thermal property optimization of erythritol as phase change material for thermal energy storage[J]. Journal of Energy Storage, 2022, 52: 105000.
5	Li S W, Li J, Liao Y N, et al. Dual-functional polyethylene glycol/graphene aerogel phase change composites with ultrahigh loading for thermal energy storage[J]. Journal of Energy Storage, 2022, 54: 105337.
6	Amin M, Putra N, Kosasih E A, et al. Thermal properties of beeswax/graphene phase change material as energy storage for building applications[J]. Applied Thermal Engineering, 2017, 112: 273-280.
7	Ko J, Jeong J W. Annual performance evaluation of thermoelectric generator-assisted building-integrated photovoltaic system with phase change material[J]. Renewable and Sustainable Energy Reviews, 2021, 145: 111085.
8	Yu C B, Youn J R, Song Y S. Multiple energy harvesting based on reversed temperature difference between graphene aerogel filled phase change materials[J]. Macromolecular Research, 2019, 27(6): 606-613.
9	Zhang Y A, Gurzadyan G G, Umair M M, et al. Ultrafast and efficient photothermal conversion for sunlight-driven thermal-electric system[J]. Chemical Engineering Journal, 2018, 344: 402-409.
10	凌子夜, 张正国, 方晓明, 等. 不同复合相变材料用于电子器件控温性能的研究[J]. 工程热物理学报, 2015, 36(1): 147-150.
	Ling Z Y, Zhang Z G, Fang X M, et al. Performances of a thermal management system using different phase change materials on a simulative electronic chip[J]. Journal of Engineering Thermophysics, 2015, 36(1): 147-150.
11	赖艳华, 吴涛, 魏露露, 等. 基于相变材料的电子元件的散热性能[J]. 化工学报, 2014, 65(S1): 157-161.
	Lai Y H, Wu T, Wei L L, et al. Thermal performance of electronic components based on phase change materials[J]. CIESC Journal, 2014, 65(S1): 157-161.
12	Ling Z Y, Wen X Y, Zhang Z G, et al. Thermal management performance of phase change materials with different thermal conductivities for Li-ion battery packs operated at low temperatures[J]. Energy, 2018, 144: 977-983.
13	Ren Q L, Guo P H, Zhu J J. Thermal management of electronic devices using pin-fin based cascade microencapsulated PCM/expanded graphite composite[J]. International Journal of Heat and Mass Transfer, 2020, 149: 119199.
14	Wu W F, Ye G H, Zhang G Q, et al. Composite phase change material with room-temperature-flexibility for battery thermal management[J]. Chemical Engineering Journal, 2022, 428: 131116.
15	Xiang S X, Liu D J, Jiang C C, et al. Liquid-metal-based dynamic thermoregulating and self-powered electronic skin[J]. Advanced Functional Materials, 2021, 31(26): 2100940.
16	Liu C, Li F, Ma L P, et al. Advanced materials for energy storage[J]. Advanced Materials, 2010, 22(8): E28-E62.
17	Nie B J, Palacios A, Zou B Y, et al. Review on phase change materials for cold thermal energy storage applications[J]. Renewable and Sustainable Energy Reviews, 2020, 134: 110340.
18	Shi J M, Aftab W, Liang Z B, et al. Tuning the flexibility and thermal storage capacity of solid-solid phase change materials towards wearable applications[J]. Journal of Materials Chemistry A, 2020, 8(38): 20133-20140.
19	方昕, 廉刚, 胡亚才, 等. 基于石墨烯气凝胶的定形相变材料储热性能研究[J]. 热科学与技术, 2016, 15(1): 13-18.
	Fang X, Lian G, Hu Y C, et al. Investigation on thermal energy storage characteristics of form-stable phase change materials supported by graphene aerogel[J]. Journal of Thermal Science and Technology, 2016, 15(1): 13-18.
20	罗李娟, 张凯, 杨文彬, 等. 形貌对石蜡/石墨烯气凝胶定形相变材料性能的影响[J]. 高分子材料科学与工程, 2017, 33(5): 93-96, 101.
	Luo L J, Zhang K, Yang W B, et al. Effect of morphology on the properties of paraffin/graphene aerogel shape-stable phase change materials[J]. Polymer Materials Science & Engineering, 2017, 33(5): 93-96, 101.
21	Shchukina E M, Graham M, Zheng Z, et al. Nanoencapsulation of phase change materials for advanced thermal energy storage systems[J]. Chemical Society Reviews, 2018, 47(11): 4156-4175.
22	Zheng Z L, Chang Z, Xu G K, et al. Microencapsulated phase change materials in solar-thermal conversion systems: understanding geometry-dependent heating efficiency and system reliability[J]. ACS Nano, 2017, 11(1): 721-729.
23	Yuan K J, Liu J, Fang X M, et al. Novel facile self-assembly approach to construct graphene oxide-decorated phase-change microcapsules with enhanced photo-to-thermal conversion performance[J]. Journal of Materials Chemistry A, 2018, 6(10): 4535-4543.
24	Kenisarin M M, Kenisarina K M. Form-stable phase change materials for thermal energy storage[J]. Renewable and Sustainable Energy Reviews, 2012, 16(4): 1999-2040.
25	Zeng J L, Zheng S H, Yu S B, et al. Preparation and thermal properties of palmitic acid/polyaniline/exfoliated graphite nanoplatelets form-stable phase change materials[J]. Applied Energy, 2014, 115: 603-609.
26	Alkan C, Sari A. Fatty acid/poly(methyl methacrylate) (PMMA) blends as form-stable phase change materials for latent heat thermal energy storage[J]. Solar Energy, 2008, 82(2): 118-124.
27	高颖, 许子龙, 李晓旭, 等. PEG/EG/SiO₂复合定形相变材料的制备与性能研究[J]. 化工新型材料, 2022, 50(5): 240-244, 249.
	Gao Y, Xu Z L, Li X X, et al. Preparation and property of PEG/EG/SiO₂ composite form-stable PCM[J]. New Chemical Materials, 2022, 50(5): 240-244, 249.
28	杨同伟, 王少奇. PEG/UPR/石墨烯复合相变材料的制备及其在节能建筑中的传热性能研究[J]. 塑料工业, 2020, 48(2): 123-127.
	Yang T W, Wang S Q. Preparation of polyethylene glycol/unsaturated polyester resin/graphene composite phase change material and study on heat transfer performance in energy-saving buildings[J]. China Plastics Industry, 2020, 48(2): 123-127.
29	Cheng Z L, Chang G J, Xue B, et al. Hierarchical Ni-plated melamine sponge and MXene film synergistically supported phase change materials towards integrated shape stability, thermal management and electromagnetic interference shielding[J]. Journal of Materials Science & Technology, 2023, 132: 132-143.
30	Liu Y, Liu H C, Qi H S. High efficiency electro- and photo-thermal conversion cellulose nanofiber-based phase change materials for thermal management[J]. Journal of Colloid and Interface Science, 2023, 629: 478-486.
31	Gök Ö, Alkan C, Konuklu Y. Developing a poly(ethylene glycol)/cellulose phase change reactive composite for cooling application[J]. Solar Energy Materials and Solar Cells, 2019, 191: 345-349.
32	Li C C, Zhang B, Liu Q X. N-eicosane/expanded graphite as composite phase change materials for electro-driven thermal energy storage[J]. Journal of Energy Storage, 2020, 29: 101339.
33	Chen W C, Liang X H, Wang S F, et al. SiO₂ hydrophilic modification of expanded graphite to fabricate form-stable ternary nitrate composite room temperature phase change material for thermal energy storage[J]. Chemical Engineering Journal, 2021, 413: 127549.
34	Wei B J, Zhang L, Yang S Q. Polymer composites with expanded graphite network with superior thermal conductivity and electromagnetic interference shielding performance[J]. Chemical Engineering Journal, 2021, 404: 126437.
35	Xu T, Wang D, Qiu P, et al. In situ synthesis of porous Si dispersed in carbon nanotube intertwined expanded graphite for high-energy lithium-ion batteries[J]. Nanoscale, 2018, 10(35): 16638-16644.
36	Zhao Q, Hao X G, Su S M, et al. Expanded-graphite embedded in lithium metal as dendrite-free anode of lithium metal batteries[J]. Journal of Materials Chemistry A, 2019, 7(26): 15871-15879.
37	Shen J W, Huang W Y, Zuo S W, et al. Polyethylene/grafted polyethylene/graphite nanocomposites: preparation, structure, and electrical properties[J]. Journal of Applied Polymer Science, 2005, 97(1): 51-59.
38	Wang J W, Wu Z H, Xie H Q, et al. Graphene oxide/polyurethane-based composite solid-solid phase change materials with enhanced energy storage capacity and photothermal performance[J]. International Journal of Energy Research, 2022, 46(15): 22744-22756.
39	仝仓, 李祥立, 端木琳. 聚乙二醇/二氧化硅/膨胀石墨相变储能材料的制备与性能研究[J]. 区域供热, 2018(3): 100-104.
	Tong C, Li X L, Duanmu L. Preparation and properties of polyethylene glycol/silica/expanded graphite phase change energy storage materials[J]. District Heating, 2018(3): 100-104.
40	王浩, 何丽红, 杨帆, 等. 聚乙二醇/石墨烯纳米片复合相变材料的制备及其性能研究[J]. 应用化工, 2018, 47(6): 1119-1122, 1126.
	Wang H, He L H, Yang F, et al. Preparation and properties of polyethylene glycol/graphene nanoplates composite phase change materials[J]. Applied Chemical Industry, 2018, 47(6): 1119-1122, 1126.
41	Wang F, Zhang P, Mou Y R, et al. Synthesis of the polyethylene glycol solid-solid phase change materials with a functionalized graphene oxide for thermal energy storage[J]. Polymer Testing, 2017, 63: 494-504.
42	Shen J, Zhang P, Song L X, et al. Polyethylene glycol supported by phosphorylated polyvinyl alcohol/graphene aerogel as a high thermal stability phase change material[J]. Composites Part B-Engineering, 2019, 179: 107545.
43	Qian T T, Zhu S K, Wang H L, et al. Comparative study of carbon nanoparticles and single-walled carbon nanotube for light-heat conversion and thermal conductivity enhancement of the multifunctional PEG/diatomite composite phase change material[J]. ACS Applied Materials & Interfaces, 2019, 11(33): 29698-29707.
44	Mu B Y, Li M. Fabrication and characterization of polyurethane-grafted reduced graphene oxide as solid-solid phase change materials for solar energy conversion and storage[J]. Solar Energy, 2019, 188: 230-238.
45	Yang J, Tang L S, Bao R Y, et al. Largely enhanced thermal conductivity of poly (ethylene glycol)/boron nitride composite phase change materials for solar-thermal-electric energy conversion and storage with very low content of graphene nanoplatelets[J]. Chemical Engineering Journal, 2017, 315: 481-490.

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

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

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

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

[1]	Jiahao SONG, Wen WANG. Study on coupling operation characteristics of Stirling engine and high temperature heat pipe [J]. CIESC Journal, 2023, 74(S1): 287-294.
[2]	Shuangxing ZHANG, Fangchen LIU, Yifei ZHANG, Wenjing DU. Experimental study on phase change heat storage and release performance of R-134a pulsating heat pipe [J]. CIESC Journal, 2023, 74(S1): 165-171.
[3]	He JIANG, Junfei YUAN, Lin WANG, Guyu XING. Experimental study on the effect of flow sharing cavity structure on phase change flow characteristics in microchannels [J]. CIESC Journal, 2023, 74(S1): 235-244.
[4]	Yanpeng WU, Qianlong LIU, Dongmin TIAN, Fengjun CHEN. A review of coupling PCM modules with heat pipes for electronic thermal management [J]. CIESC Journal, 2023, 74(S1): 25-31.
[5]	Yuanchao LIU, Bin GUAN, Jianbin ZHONG, Yifan XU, Xuhao JIANG, Duan LI. Investigation of thermoelectric transport properties of single-layer XSe₂(X=Zr/Hf) [J]. CIESC Journal, 2023, 74(9): 3968-3978.
[6]	Jie WANG, Xiaolin QIU, Ye ZHAO, Xinyang LIU, Zhongqiang HAN, Yong XU, Wenhan JIANG. Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films [J]. CIESC Journal, 2023, 74(7): 3068-3078.
[7]	Haopeng SHI, Dawen ZHONG, Xuexin LIAN, Junfeng ZHANG. Experimental study on the downward-facing surface enhanced boiling heat transfer of multiscale groove-fin structures [J]. CIESC Journal, 2023, 74(7): 2880-2888.
[8]	Fangzhe SHI, Yunhua GAN. Numerical simulation of start-up characteristics and heat transfer performance of ultra-thin heat pipe [J]. CIESC Journal, 2023, 74(7): 2814-2823.
[9]	Meibo XING, Zhongtian ZHANG, Dongliang JING, Hongfa ZHANG. Enhanced phase change energy storage/release properties by combining porous materials and water-based carbon nanotube under magnetic regulation [J]. CIESC Journal, 2023, 74(7): 3093-3102.
[10]	Yuanchao LIU, Xuhao JIANG, Ke SHAO, Yifan XU, Jianbin ZHONG, Zhuan LI. Influence of geometrical dimensions and defects on the thermal transport properties of graphyne nanoribbons [J]. CIESC Journal, 2023, 74(6): 2708-2716.
[11]	Jialin DAI, Weidong BI, Yumei YONG, Wenqiang CHEN, Hanyang MO, Bing SUN, Chao YANG. Effect of thermophysical properties on the heat transfer characteristics of solid-liquid phase change for composite PCMs [J]. CIESC Journal, 2023, 74(5): 1914-1927.
[12]	Xuehong WU, Linlin LUAN, Yanan CHEN, Min ZHAO, Cai LYU, Yong LIU. Preparation and thermal properties of degradable flexible phase change films [J]. CIESC Journal, 2023, 74(4): 1818-1826.
[13]	Mingchuan LI, Shuanshi FAN, Fuhai XU, Huidong LU, Xiaojun LI. Existence and Laplace transform of the solution to Stefan phase change model in thermal dissociation hydrate [J]. CIESC Journal, 2023, 74(4): 1746-1754.
[14]	Chi YIN, Zhengguo ZHANG, Ziye LING, Xiaoming FANG. Combining paraffin@silica nanocapsules with carbon fiber to develop a phase change thermal interface material for efficient heat dissipation [J]. CIESC Journal, 2023, 74(4): 1795-1804.
[15]	Huizhu YANG, Jingling LAN, Yue YANG, Jialin LIANG, Chuanwen LYU, Yonggang ZHU. Experimental study on thermal performance of high power flat heat pipe [J]. CIESC Journal, 2023, 74(4): 1561-1569.