Recent advances in thermosetting resin-based composite phase change materials and enhanced phase change energy storage
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摘要: 热固性树脂是一种能够在加热或辐射条件下发生交联反应而固化,逐渐硬化成型的树脂类材料,具有耐热性高,受压不易变形等优点,广泛应用于涂料、胶粘剂、电子封装等领域。现有研究表明,由于热固性树脂受热后的固化成型,可有效解决固-液相变材料相变储能过程中泄漏问题。本文从热固性树脂的分类出发,首次系统综述其在相变储能领域的应用研究现状,包括:(1) 基于酚醛树脂封装的定型相变材料研究进展;(2) 基于环氧树脂封装的定型相变材料研究进展;(3) 双环戊二烯石油树脂在相变储能领域应用的可能性。同时,从制备时改性与废弃时处置回收的角度,对热固性树脂强化的相变储能复合材料未来研究重点和发展趋势进行了展望,旨在为拓宽热固性树脂在相变储能领域的应用范围提供有益参考,为制备性能优异的定型相变材料提供更多研究思路。Abstract: Thermosetting resin is a kind of resin material that can be cured by cross-linking reaction under the condition of heating or radiation, and gradually hardened and molded, which has the advantages of high heat resistance and not easily deformed by pressure, and it was widely used in the fields of coating, adhesive and electronic packaging. Existing studies have shown that the problem of leakage during phase change energy storage of solid-liquid phase change materials can be effectively solved due to the curing and molding of thermosetting resin by heat. This paper presents the first review of the current research status of thermosetting resins in the field of phase change energy storage from the classification of thermosetting resins, including: (1) Research progress of stereotyped phase change materials based on phenolic resin encapsulation; (2) Research progress of stereotyped phase change materials based on epoxy resin encapsulation; (3) Possibilities of dicyclopentadiene petroleum resin for phase change energy storage applications. At the same time, the future research focus and development trend of thermoset resin-reinforced phase change energy storage materials are prospected from the perspectives of modification at preparation and disposal and recycling at disposal, aiming to provide useful references for broadening the application scope of thermoset resin in the field of phase change energy storage and to provide more research ideas for the preparation of stereotyped phase change materials with excellent performance.
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Key words:
- phase change /
- renewable energy /
- polymers /
- thermosetting resin /
- energy storage
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图 4 PEG/EP复合相变材料的相关研究[43]:(a) EP、PEG、PEG/EP的FTIR图谱;(b) PEG/EP的SEM图像;(c) PEG和PEG/EP的DSC曲线;(d) PEG和PEG/EP的静态热机械分析(TMA)曲线
Figure 4. Research related to PEG/EP composite phase change materials[43]: (a) FTIR spectra of EP, PEG and PEG/EP; (b) SEM image of PEG/EP composite; (c) DSC curves of PEG and PEG/EP; (d) Thermomechanicanalysis (TMA) curves of PEG/EP composite
图 6 PEG/改性环氧树脂(DMEP)复合材料的相关研究[48]:(a) PEG和不同PEG质量分数的PEG/DMEP的稳型性能;(b) PEG和PEG/DMEP的TG曲线;(c) DMEPPEG-70 100次热循环前(实线)和后(虚线)的DSC曲线;(d) PEG和PEG/DMEP的DTG曲线
Figure 6. Correlation study on PEG/modified epoxy resin (DMEP) composites[48]: (a) Shape-stable properties of pristine PEG and PEG/DMEP with different mass fraction of PEG; (b) TG curves of pristine PEG and PEG/DMEP; (c) DCS curves of DMEPPEG-70 before (solid line) and after (dash dot line) 100 times thermal cycles; (d) DTG curves of pristine PEG and PEG/DMEP
x in DMEPPEG-x—Mass fraction of PEG
图 8 石蜡/EP复合材料中石蜡颗粒的相关研究[56-57]:(a) 乳化法制备石蜡颗粒的SEM图像;(b) 石蜡颗粒的SEM图像;(c) 石蜡颗粒的制备过程
Figure 8. Correlation study of paraffin particles in paraffin/EP composites materials[56-57]: (a) SEM image of paraffin particles produced by the emulsification method; (b) SEM image of paraffin particles; (c) Scheme representing synthesis of paraffin particles
图 9 费托蜡(FT蜡)/环氧树脂复合材料相关研究[62]:(a) 70/30 w/w环氧树脂/FT蜡断裂表面的SEM图像;(b) 70/30 w/w环氧树脂/FT蜡加热至140℃冷却后断裂表面的SEM图像;(c) 研究样品的DSC加热曲线;(d) 研究样品的DSC冷却曲线;(e) 研究样品的热重曲线(表内的T20wt%为质量损失20wt%时温度的平均值,括号内为标准差);(f) 储存模量随温度的变化
Figure 9. Correlation study on Fischer-Tropsch paraffin wax (wax FT)/epoxy resin composites[62]: (a) SEM image of fractured surfaces of 70/30 w/w wax FT/epoxy; (b) SEM image of fractured surfaces of 70/30 w/w wax FT/epoxy after heating to 140℃ and cooling; (c) DSC heating curves of the investigated samples; (d) DSC cooling curves of the investigated samples; (e) TGA curves of the investigated samples (T20wt% in table inset gives average values, with standard deviations in brackets, of temperatures at 20wt% mass loss); (f) Storage modulus as function of temperature of the investigated samples
图 10 正十四烷-二甲苯@环氧树脂相变微胶囊的热性能[25]:(a) 样品A、B、C、D、E和G的SEM图像;(b) 微相变材料粉碎后(样品C)的SEM图像;样品A、B、C、D和E的DSC曲线 (c) 和TGA曲线 (d)
Figure 10. Thermal properties of n-tetradecane- dimethylbenzene@epoxy resin phase change microcapsules[25]: (a) SEM images of samples A, B, C, D, E and G; (b) SEM image of crushed micro phase change materials (sample C); DSC curves (c) and TGA curves (d) of samples A, B, C, D and E
图 11 新戊二醇(NPG)/环氧树脂复合相变储能材料的性能图[26]:(a) EP、NPG、NPG/EP复合材料的FTIR图谱;(b) NPG/EP复合材料的SEM图像;(c) NPG/EP复合材料的DSC曲线;(d) NPG/EP复合材料经过100次热循环试验后的DSC曲线
Figure 11. Performance diagram of neopentyl glycol (NPG)/epoxy resin composite phase change energy storage material[26]: (a) FTIR spectra of EP, NPG, NPG/EP composite; (b) SEM image of NPG/EP composite; (c) DSC curve of NPG/EP composite; (d) DSC curve of NPG/EP composite after 100 times thermal cycling test
△H—Latent heat of phase change; Te—Melting temperature
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