聚乙二醇基聚合物固固相变材料的研究进展

doi:10.19799/j.cnki.2095-4239.2024.0733

摘要/Abstract

摘要：

固固相变材料(SSPCMs)是一类能够通过可逆相变过程高效吸收与释放热能，同时保持固态特性的新型材料，具有相变期间体积变化微小、高温下使用无泄漏和力学性能好等优点，吸引了科技界的广泛瞩目。其中，以聚乙二醇(PEG)为相变单元的聚合物SSPCMs凭借其高储能密度、优异的循环稳定性以及可调控相变温度等独特优势，在能量储存、温度调节及热管理等多个关键领域展现出了巨大的应用潜力。本文围绕近几年PEG基SSPCMs的研究进展，归纳总结其分类和化学制备方法。根据其存在的导热、阻燃、可回收利用差等缺陷，重点讨论了如何对其进行性能优化和改性，以拓宽PEG基SSPCMs的应用，同时总结了在电池、电子设备和柔性可穿戴设备的热管理以及太阳能热能储存等领域的潜在应用研究进展。最后，分析了PEG基SSPCMs目前所面临的挑战，指出未来的研究应致力于环境友好型和多功能化的SSPCMs研发，提高SSPCMs的综合性能、降低成本和增强可行性等，并探索其在更广泛领域的应用潜力，进一步推动其实际应用。

关键词: 聚乙二醇, 固固相变, 相变材料, 聚氨酯, 复合材料

Abstract:

Solid-solid phase change materials (SSPCMs) are a new class of materials capable of efficiently absorbing and releasing thermal energy through a reversible phase change process while maintaining solid-state properties. These materials have attracted extensive attention from the scientific research community owing to their small volume change during phase change, absence of any leakage phenomenon at high temperatures, and excellent mechanical properties. Polymeric SSPCMs with polyethylene glycol (PEG) as the phase-transition unit have shown great potential for applications in various key areas such as energy storage, temperature regulation, and thermal management. This is because they possess unique advantages such as high energy storage density, excellent cycling stability, and tunable phase transition temperature. This study focuses on the research progress of PEG-based SSPCMs in recent years, summarizing their classification and chemical preparation methods. Considering their defects such as thermal conductivity, flame retardancy, and poor recyclability, we focus on optimizing and modifying their properties to broaden their applications. This study also summarizes the research progress on their potential applications in the fields of thermal management of batteries, electronic devices, and flexible wearables, as well as the thermal energy storage of solar energy. Finally, the current challenges affecting PEG-based SSPCMs were analyzed. Future research should be devoted to the research and development of environmentally friendly and multifunctional SSPCMs, as well as to improving the comprehensive performance, reducing the cost, and enhancing the feasibility of SSPCMs. Another research avenue is to explore the potential of their application in a wider range of fields to further promote their practical applications.

Key words: polyethylene glycol, solid-solid phase change, phase change materials, polyurethane, composites

中图分类号:

TB 34

陈艳, 黎子琦, 陈南豪, 张一弛, 吴晓鸿, 陈大柱. 聚乙二醇基聚合物固固相变材料的研究进展[J]. 储能科学与技术, 2025, 14(1): 124-139.

Yan CHEN, Ziqi LI, Nanhao CHEN, Yichi ZHANG, Xiaohong WU, Dazhu CHEN. Advances in polymeric solid-solid phase change materials based on polyethylene glycol[J]. Energy Storage Science and Technology, 2025, 14(1): 124-139.

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参考文献 64

1	LI M, MA Q G. Performance improvement of phase change materials encapsulated with graphene oxide for thermal storage[J]. Journal of Energy Storage, 2024, 80: 110315. DOI: 10.1016/j.est.2023.110315.
2	SHARMA A, TYAGI V V, CHEN C R, et al. Review on thermal energy storage with phase change materials and applications[J]. Renewable and Sustainable Energy Reviews, 2009, 13(2): 318-345. DOI: 10.1016/j.rser.2007.10.005.
3	YANG Z P, MA Y Y, JIA S M, et al. 3D-printed flexible phase-change nonwoven fabrics toward multifunctional clothing[J]. ACS Applied Materials & Interfaces, 2022, 14(5): 7283-7291. DOI: 10.1021/acsami.1c21778.
4	周建华, 刘庚, 刘晨, 等. 聚氨酯固-固相变储能材料的制备及应用[J]. 印染, 2020, 46(12): 61-65.
	ZHOU J H, LIU G, LIU C, et al. Preparation and application of polyurethane solid-solid phase change energy storage material[J]. China Dyeing & Finishing, 2020, 46(12): 61-65.
5	CHEN M Y, CUI Y L, OUYANG D X, et al. Experimental study on the hybrid carbon based phase change materials for thermal management performance of lithium-ion battery module[J]. International Journal of Energy Research, 2022, 46(12): 17247-17261. DOI: 10.1002/er.8388.
6	FREEMAN T B, FOSTER K E O, TROXLER C J, et al. Advanced materials and additive manufacturing for phase change thermal energy storage and management: A review[J]. Advanced Energy Materials, 2023, 13(24): 2204208. DOI: 10.1002/aenm.202204208.
7	REDDY V J, GHAZALI M F, KUMARASAMY S. Advancements in phase change materials for energy-efficient building construction: A comprehensive review[J]. Journal of Energy Storage, 2024, 81: 110494. DOI: 10.1016/j.est.2024.110494.
8	折晓会, 王星宇, 郭晓龙, 等. 超低温-高温跨温区相变材料制备及物性调控综述[J]. 储能科学与技术, 2023, 12(12): 3818-3835. DOI: 10.19799/j.cnki.2095-4239.2023.0726.
	SHE X H, WANG X Y, GUO X L, et al. A review on the preparation of ultra-low-temperature, high-temperature, and cross-temperature zone phase change materials and the regulation of physical properties[J]. Energy Storage Science and Technology, 2023, 12(12): 3818-3835. DOI: 10.19799/j.cnki.2095-4239.2023.0726.
9	SU W G, DARKWA J, KOKOGIANNAKIS G. Review of solid-liquid phase change materials and their encapsulation technologies[J]. Renewable and Sustainable Energy Reviews, 2015, 48: 373-391. DOI: 10.1016/j.rser.2015.04.044.
10	SARı A, BIÇER A, ALKAN C. Thermal energy storage properties of polyethylene glycol grafted styrenic copolymer as novel solid-solid phase change materials[J]. International Journal of Energy Research, 2020, 44(5): 3976-3989. DOI: 10.1002/er.5208.
11	LEE J J C, SUGIARTO S, ONG P J, et al. Lignin-g-polycaprolactone as a form-stable phase change material for thermal energy storage application[J]. Journal of Energy Storage, 2022, 56: 106118. DOI: 10.1016/j.est.2022.106118.
12	XIAO C R, ZHANG G Q, LI Z H, et al. Custom design of solid-solid phase change material with ultra-high thermal stability for battery thermal management[J]. Journal of Materials Chemistry A, 2020, 8(29): 14624-14633. DOI: 10.1039/D0TA05247G.
13	LEE W, LEE J, YANG W, et al. Fabrication of biobased advanced phase change material and multifunctional composites for efficient thermal management[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(3): 1178-1189. DOI: 10.1021/acssuschemeng. 2c06598.
14	XIAO Q Q, XU Y, LI X Q, et al. Enhanced solar-thermal and electro-thermal storage performance of solid-solid composite phase change material[J]. Composites Communications, 2024, 45: 101818. DOI: 10.1016/j.coco.2024.101818.
15	ZHANG N, YUAN Y P, CAO X L, et al. Latent heat thermal energy storage systems with solid-liquid phase change materials: A review[J]. Advanced Engineering Materials, 2018, 20(6): DOI: 10.1002/adem.201700753.
16	KOU Y, WANG S Y, LUO J P, et al. Thermal analysis and heat capacity study of polyethylene glycol (PEG) phase change materials for thermal energy storage applications[J]. The Journal of Chemical Thermodynamics, 2019, 128: 259-274. DOI: 10.1016/j.jct.2018.08.031.
17	ALVA G, LIN Y X, FANG G Y. Synthesis and characterization of chain-extended and branched polyurethane copolymers as form stable phase change materials for solar thermal conversion storage[J]. Solar Energy Materials and Solar Cells, 2018, 186: 14-28. DOI: 10.1016/j.solmat.2018.06.023.
18	张雪丽, 孙伟清, 郑君华. 聚氨酯型固-固相变储能材料对沥青调温效果的影响研究[J]. 储能科学与技术, 2024, 13(3): 841-843. DOI: 10.19799/j.cnki.2095-4239.2024.0125.
	ZHANG X L, SUN W Q, ZHENG J H. Study on the influence of polyurethane-type solid-solid phase change energy storage materials on the temperature control effect of asphalt[J]. Energy Storage Science and Technology, 2024, 13(3): 841-843. DOI: 10.19799/j.cnki.2095-4239.2024.0125.
19	CUI M L, TIAN C, YANG Y Y, et al. Intrinsic photothermal phase change materials with enhanced toughness and flexibility for thermal management in extreme environments[J]. Chemical Engineering Journal, 2023, 475: 146091. DOI: 10.1016/j.cej.2023.146091.
20	TIAN C, NING J Y, YANG Y Y, et al. Super tough and stable solid-solid phase change material based on π-π stacking[J]. Chemical Engineering Journal, 2022, 429: 132447. DOI: 10.1016/j.cej.2021.132447.
21	YUAN Y, WU B, JIANG L, et al. Nonconstant enthalpy of thermosetting solid-solid phase change materials controlled by light[J]. Energy and Buildings, 2020, 214: 109894. DOI: 10.1016/j.enbuild.2020.109894.
22	SOO X Y D, MUIRURI J K, YEO J C C, et al. Polyethylene glycol/polylactic acid block co-polymers as solid-solid phase change materials[J]. SmartMat, 2023, 4(3): e1188. DOI: 10.1002/smm2.1188.
23	OKTAY B, KAYAMAN-APOHAN N. Biodegradable polyurethane solid-solid phase change materials[J]. ChemistrySelect, 2021, 6(24): 6280-6285. DOI: 10.1002/slct.202100590.
24	YAN D G, FENG B B, ZHAO S L, et al. Robust phase change materials based on PBAT-block-PEG multiblock copolymers with novel thermostability prepared via facile melt transesterification[J]. Journal of Energy Storage, 2024, 84: 110895. DOI: 10.1016/j.est.2024.110895.
25	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. DOI: 10.1016/j.solmat.2018.11.038.
26	YAN D G, ZHAO S L, GE C, et al. PBT/adipic acid modified PEG solid-solid phase change composites[J]. Journal of Energy Storage, 2022, 52: 104753. DOI: 10.1016/j.est.2022.104753.
27	WU Y H, CHEN M S, ZHAO G Z, et al. Recyclable solid-solid phase change materials with superior latent heat via reversible anhydride-alcohol crosslinking for efficient thermal storage[J]. Advanced Materials, 2024, 36(16): e2311717. DOI: 10.1002/adma.202311717.
28	LIAO Y N, LI J, LI S W, et al. Super-elastic and shape-stable solid-solid phase change materials for thermal management of electronics[J]. Journal of Energy Storage, 2022, 52: 104751. DOI: 10.1016/j.est.2022.104751.
29	ZHU G Y, ZOU M M, LUO W X, et al. A polyurethane solid–solid phase change material for flexible use in thermal management[J]. Chemical Engineering Journal, 2024, 488: 150930. DOI: 10.1016/j.cej.2024.150930.
30	ZHAO P P, LU P, ZHAO Z Y, et al. Aromatic schiff base-based polymeric phase change materials for safe, leak-free, and efficient thermal energy management[J]. Chemical Engineering Journal, 2022, 437: 135461. DOI: 10.1016/j.cej.2022.135461.
31	HARLÉ T, NGUYEN G T M, LEDESERT B, et al. Cross-linked polyurethane as solid-solid phase change material for low temperature thermal energy storage[J]. Thermochimica Acta, 2020, 685: 178191. DOI: 10.1016/j.tca.2019.01.007.
32	HUANG L, YANG Y Y, YUAN D D, et al. Solid-solid phase-change materials with excellent mechanical property and solid state plasticity based on dynamic urethane bonds for Thermal Energy Storage[J]. Journal of Energy Storage, 2021, 36: 102343. DOI: 10.1016/j.est.2021.102343.
33	XU Z P, CHEN W H, WU T T, et al. Thermal management system study of flame retardant solid-solid phase change material battery[J]. Surfaces and Interfaces, 2023, 36: 102558. DOI: 10.1016/j.surfin.2022.102558.
34	DU X S, ZHOU M, DENG S, et al. Poly(ethylene glycol)-grafted nanofibrillated cellulose/graphene hybrid aerogels supported phase change composites with superior energy storage capacity and solar-thermal conversion efficiency[J]. Cellulose, 2020, 27(8): 4679-4690. DOI: 10.1007/s10570-020-03110-z.
35	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. DOI: 10.1016/j.polymertesting. 2017.09.005.
36	CHENG M, QIN J W, YU H Y, et al. Solvent-free synthesis of cellulose nanocrystal-graft-poly (ethylene glycol) as solid-solid phase change nanoparticles[J]. Cellulose, 2022, 29(15): 8165-8176. DOI: 10.1007/s10570-022-04782-5.
37	DU X S, WANG H B, WU Y, et al. Solid-solid phase-change materials based on hyperbranched polyurethane for thermal energy storage[J]. Journal of Applied Polymer Science, 2017, 134(26): e45014. DOI: 10.1002/app.45014.
38	LEE J H, KIM S H. Synthesis and characterization of biopolyurethane crosslinked with castor oil-based hyperbranched polyols as polymeric solid-solid phase change materials[J]. Scientific Reports, 2022, 12(1): 14646. DOI: 10.1038/s41598-022-17390-x.
39	ZHOU J H, LIU G, NIU Z L, et al. Hyperbranched waterborne polyurethane solid-solid phase change material for thermal energy storage in thermal management fabric[J]. Fibers and Polymers, 2023, 24(2): 413-422. DOI: 10.1007/s12221-023-00081-3.
40	XIA Y P, ZHANG H Z, HUANG P R, et al. Graphene-oxide-induced lamellar structures used to fabricate novel composite solid-solid phase change materials for thermal energy storage[J]. Chemical Engineering Journal, 2019, 362: 909-920. DOI: 10.1016/j.cej.2019.01.097.
41	WU T T, WANG C H, HU Y X, et al. Flexible solid-solid phase change materials with high stability for thermal management[J]. International Journal of Heat and Mass Transfer, 2023, 211: 124202. DOI: 10.1016/j.ijheatmasstransfer.2023.124202.
42	WANG K, LIU C, XIE W X, et al. Effects of ammonium polyphosphate and organic modified montmorillonite on flame retardancy of polyethylene glycol/wood-flour-based phase change composites[J]. Molecules, 2023, 28(8): 3464. DOI: 10.3390/molecules28083464.
43	XU H L, JIANG L, YUAN A Q, et al. Thermally-stable, solid-solid phase change materials based on dynamic metal-ligand coordination for efficient thermal energy storage[J]. Chemical Engineering Journal, 2021, 421: 129833. DOI: 10.1016/j.cej. 2021.129833.
44	LIU Z L, TANG B T, ZHANG S F. Novel network structural PEG/PAA/SiO₂ composite phase change materials with strong shape stability for storing thermal energy[J]. Solar Energy Materials and Solar Cells, 2020, 216: 110678. DOI: 10.1016/j.solmat. 2020.110678.
45	DENG J, LI X X, LI C B, et al. Multifunctional flexible composite phase change material with high anti-leakage and thermal conductivity performances for battery thermal management[J]. Journal of Energy Storage, 2023, 72: 108313. DOI: 10.1016/j.est.2023.108313.
46	ZHOU J D, FANG M, YANG K, et al. A novel MOF/RGO-based composite phase change material for battery thermal management[J]. Applied Thermal Engineering, 2023, 227: 120383. DOI: 10.1016/j.applthermaleng.2023.120383.
47	LIN X D, SHAO D, JIANG L Q, et al. Low-temperature preparation of solid-solid phase change polymer for thermal management modules[J]. Chemical Engineering Science, 2021, 246: 116985. DOI: 10.1016/j.ces.2021.116985.
48	LI Z C, ZHANG Y A, WANG X, et al. Thermally-induced flexible composite phase change material with enhanced thermal conductivity[J]. Journal of Power Sources, 2024, 603: 234447. DOI: 10.1016/j.jpowsour.2024.234447.
49	ZENG X X, YE L S, WANG C H, et al. Highly stable solid-solid phase change materials for battery thermal management systems[J]. Journal of Energy Storage, 2024, 88: 111495. DOI: 10.1016/j.est.2024.111495.
50	DU X S, JIN L Z, DENG S, et al. Recyclable, self-healing, and flame-retardant solid-solid phase change materials based on thermally reversible cross-links for sustainable thermal energy storage[J]. ACS Applied Materials & Interfaces, 2021, 13(36): 42991-43001. DOI: 10.1021/acsami.1c14862.
51	BAI S J, ZHANG K X, ZHANG Q, et al. Intrinsic flame retardancy and flexible solid-solid phase change materials with self-healing and recyclability[J]. ACS Applied Materials & Interfaces, 2023, 15(41): 48613-48622. DOI: 10.1021/acsami.3c09722.
52	NI X P, WU L J. Preparation and performance study of a novel flame retardant polyurethane phase change materials[J]. Journal of Polymers and the Environment, 2024, 32(3): 1314-1325. DOI: 10.1007/s10924-023-03047-x.
53	WU B, WANG Y, LIU Z M, et al. Thermally reliable, recyclable and malleable solid-solid phase-change materials through the classical Diels-Alder reaction for sustainable thermal energy storage[J]. Journal of Materials Chemistry A, 2019, 7(38): 21802-21811. DOI: 10.1039/C9TA08368E.
54	MEVAWALLA A, PANCHAL S, TRAN M K, et al. One dimensional fast computational partial differential model for heat transfer in lithium-ion batteries[J]. Journal of Energy Storage, 2021, 37: 102471. DOI: 10.1016/j.est.2021.102471.
55	MURALI G, SRAVYA G S N, JAYA J, et al. A review on hybrid thermal management of battery packs and it's cooling performance by enhanced PCM[J]. Renewable and Sustainable Energy Reviews, 2021, 150: 111513. DOI: 10.1016/j.rser. 2021.111513.
56	LI Y M, WANG T Y, LI X X, et al. Experimental investigation on thermal management system with flame retardant flexible phase change material for retired battery module[J]. Applied Energy, 2022, 327: 120109. DOI: 10.1016/j.apenergy.2022.120109.
57	ZHANG Y A, WU P, MENG Y, et al. Flexible phase change films with enhanced thermal conductivity and low electrical conductivity for thermal management[J]. Chemical Engineering Journal, 2023, 464: 142650. DOI: 10.1016/j.cej.2023.142650.
58	LV S S, LIU X L, WANG J G, et al. Flexible highly thermally conductive biphasic composite films for multifunctional solar/electro-thermal conversion energy storage and thermal management[J]. Journal of Cleaner Production, 2023, 426: 139004. DOI: 10.1016/j.jclepro.2023.139004.
59	FANG Y, LI Z L, LI X L, et al. A novel covalent polymerized phase change composite with integrated shape memory, self-healing, electromagnetic shielding and multi-drive thermal management functions[J]. Chemical Engineering Journal, 2023, 459: 141600. DOI: 10.1016/j.cej.2023.141600.
60	GAO S Y, DING J, WANG W L, et al. MXene based flexible composite phase change material with shape memory, self-healing and flame retardant for thermal management[J]. Composites Science and Technology, 2023, 234: 109945. DOI: 10.1016/j.compscitech.2023.109945.
61	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. DOI: 10.1002/er.8576.
62	PAKDEL E, NAEBE M, SUN L, et al. Advanced functional fibrous materials for enhanced thermoregulating performance[J]. ACS Applied Materials & Interfaces, 2019, 11(14): 13039-13057. DOI: 10.1021/acsami.8b19067.
63	DONG J K, SHI W Z, LIU J S, et al. Flexibility and thermal storage properties of polyurethane adhesive supported phase change composites based on polyurethane phase change materials[J]. Fibers and Polymers, 2023, 24(9): 3061-3074. DOI: 10.1007/s12221-023-00300-x.
64	LIANG C B, ZHANG W, LIU C L, et al. Multifunctional phase change textiles with electromagnetic interference shielding and multiple thermal response characteristics[J]. Chemical Engineering Journal, 2023, 471: 144500. DOI: 10.1016/j.cej. 2023.144500.

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