空气能蓄冷用相变材料研制及热物性表征

doi:10.16085/j.issn.1000-6613.2020-1660

摘要/Abstract

摘要：

针对自然冷源在建筑空气调节中的应用，以癸酸-月桂酸（CA-LA）低共熔混酸为相变材料，纳米Fe₂O₃为添加剂，膨胀石墨（EG）为基质材料，采用化学分散、超声振荡和物理吸附的方法制备CA-LAFe₂O₃/EG复合相变材料，并对材料进行性能表征。结果表明纳米Fe₂O₃质量分数为0.8%时与CA-LA混合均匀性较好，具有成核作用，消除了CA-LA的过冷度；EG质量分数为5.88%时，对CA-LAFe₂O₃（质量分数0.8%）具有较好的包覆效果，傅里叶变换红外光谱（FTIR）显示复合材料内部未发生化学反应，各物质之间属于物理吸附；纳米Fe₂O₃粒子和EG可加快材料相变过程，较CA-LA、CA-LA Fe₂O₃（质量分数0.8%）的冷却与结晶过程总时间缩短了39.4%，CA-LA Fe₂O₃（质量分数0.8%）/EG（质量分数5.88%）对应时间缩短78.2%，有利于空气能蓄冷过程的顺利进行；CA-LA Fe₂O₃（质量分数0.8%）/EG（质量分数5.88%）的相变焓为124.70kJ/kg，融化初始温度为18.66℃，结晶起始温度为19.87℃，较CA-LA的焓降低3.4%，融化与结晶过程温度区间均增大，材料的导热性能增强。定型复合相变材料热响应与受压方向有关，受压面切向方向温度响应速度远大于受压面法向方向，相变储能换热器设计时应考虑材料导热的各向异性特点。

关键词: 空气能蓄冷, 癸酸, 月桂酸, 纳米三氧化二铁, 膨胀石墨, 热物性, 定型相变材料

Abstract:

Phase change materials with excellent performance are very important for the application of natural cooling source in building air conditioning. Composite phase change materials CA-LAFe₂O₃/EG was prepared using the CA-LA eutectic acid as phase change materials, nano-Fe₂O₃as additive, and expanded graphite(EG) as matrix materials by chemical dispersion, ultrasonic oscillation and physical adsorption. The properties of the materials were characterized. The results showed that it was better mixing uniformity with CA-LA when the mass fraction of nano-Fe₂O₃ was 0.8%, which eliminated the supercooling of CA-LA. When the mass fraction of EG was 5.88%, it had a good adsorption on CA-LA Fe₂O₃(0.8%). FTIR spectrum revealed that there was no chemical reaction in CA-LAFe₂O₃/EG. The crystallization process showed that adding nano-Fe₂O₃ particles and EG can accelerate the cooling and crystallization process. The cooling and crystallization time was reduced 39.4% by adding only nano-Fe₂O₃ particles and 78.2% by adding nano-Fe₂O₃ and EG, which was conducive to the cold storage process. DSC results indicated that the enthalpy of CA-LAFe₂O₃(0.8%)/EG (5.88%)/EG was 124.70kJ/kg, which was 3.4% lower than that of pure CA-LA. The oneset melting temperature was 18.66℃ and the oneset crystallization temperature was 19.87℃. Compared with CA-LA the temperature range during melting and crystallization was increased and the thermal conductivity of the material was enhanced. The thermal response of shape stabilized composite phase change materials was affected by the anisotropy of expanded graphite and its thermal response was related to the compression direction. The temperature response speed in the tangential direction of compression was far greater than that in the normal direction. The anisotropy of the materials should be considered in the design of phase change energy storage heat exchangers.

Key words: natural cold storage, capric acid, lauric acid, nano-ferric oxide(Fe₂O₃), expanded graphite, thermophysical properties, shaped phase change material

中图分类号:

TK02

张润霞, 顾兆林, 王赞社, 康彦青, 白梦梦. 空气能蓄冷用相变材料研制及热物性表征[J]. 化工进展, 2021, 40(7): 3892-3899.

ZHANG Runxia, GU Zhaolin, WANG Zanshe, KANG Yanqing, BAI Mengmeng. Preparation and characterization of phase change materials for air energy storage[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3892-3899.

图/表 12

图1 CA-LA Fe2O3复合相变材料分层现象（初选）

图2 不同Fe2O3质量分数下复合相变材料分层现象

图3 复合相变材料渗漏率测试实验

图4 定型材料密度及Fe2O3质量分数对复合材料渗漏率的影响

图5 CA-LA、CA-LA/EG(5.88%)与CA-LA Fe2O3(0.8%)/EG(5.88%)的FTIR谱图对比

图6 膨胀石墨、CA-LA/EG(5.88%)与CA-LA Fe2O3(0.8%)/EG(5.88%)复合相变材料SEM微观结构

图7 纳米Fe2O3粒子的质量分数对CA-LA Fe2O3融化过程的影响

图8 不同质量分数的Fe2O3和EG复合相变材料步冷曲线

图9 CA-LA与不同质量比的CA-LA Fe2O3/EG的DSC曲线

表1 CA-LA与不同质量比的CA-LAFe2O3/EG的DSC测试结果 (℃)

材料规格	熔化过程			结晶过程
材料规格	初始温度	尖峰温度	终熔温度	初始温度	尖峰温度	终了温度
CA-LA	19.15	21.89	23.24	18.92	18.17	16.68
CA-LA/EG(5.88%)	18.65	22.46	25.04	19.93	15.44	12.17
CA-LA/EG(6.70%)	18.75	22.69	25.12	19.78	15.22	11.91
CA-LA Fe₂O₃(1.0%)/EG(5.88%)	18.72	22.61	25.47	19.81	15.05	11.57
CA-LA Fe₂O₃(0.8%)/EG(5.88%)	18.74	22.69	25.34	19.77	15.04	11.68
CA-LA Fe₂O₃(0.6%)/EG(5.88%)	18.66	21.91	24.16	19.87	15.65	12.75
CA-LA Fe₂O₃(0.4%)/EG(5.88%)	18.72	22.50	25.10	19.81	15.25	12.01

图10 定型复合相变材料

图11 定型复合相变材料受压法向面与切向面加热时热响应

参考文献 19

20	武卫东, 唐恒博, 苗朋柯, 等. 空调用纳米有机复合相变蓄冷材料制备与热物性[J]. 化工学报, 2015, 66(3): 1208-1214.
	WU Weidong, TANG Hengbo, MIAO Pengke, et al. Preparation and thermal properties of nano-organic composite phase change materials for cool storage in air-conditioning[J]. CIESC Journal, 2015, 66(3): 1208-1214.
21	王海宁, 郑永平, 康飞宇. 膨胀石墨孔结构的定量研究[J]. 无机材料学报, 2003, 18(3): 606-612.
	WANG Haining, ZHENG Yongping, KANG Feiyu. Quantitative analysis of the pore structure of expanded graphite[J]. Journal of Inorganic Materials, 2003, 18(3): 606-612.
22	曾涑源. α-Fe₂O₃纳米结构的液相合成及性能表征[D]. 合肥: 中国科学技术大学, 2008.
	ZENG Suyuan. Synthesis of α-Fe₂O₃ by the solution-based method and its characterizations[D]. Hefei: University of Science and Technology of China, 2008.
23	贾蒲悦, 武卫东, 王益聪, 等. 新型复合低温相变蓄冷材料的研制及热物性优化[J]. 化工学报, 2019, 70(7): 2758-2765.
	JIA Puyue, WU Weidong, WANG Yicong，et al. Preparation and thermophysical property optimization of a new compositephase change material for cold storage [J]. CIESC Journal, 2019, 70(7): 2758-2765.
24	吴韶飞, 闫霆, 蒯子函, 等. 高导热膨胀石墨/棕榈酸定形复合相变材料的制备及储热性能研究[J]. 化工学报, 2019, 70(9): 3553-3564, 3207.
	WU Shaofei, YAN Ting, KUAI Zihan, et al. Preparation and thermal energy storage properties of high heat conduction expanded graphite/palmitic acid form-stable phase change materials[J]. CIESC Journal, 2019, 70(9): 3553-3564, 3207.
25	翟天尧, 李廷贤, 仵斯, 等. 高导热膨胀石墨/硬脂酸定形相变储能复合材料的制备及储/放热特性[J]. 科学通报, 2018, 63(7): 674-683.
	ZHAI Tianyao, LI Tingxian, WU Si, et al. Preparation and thermal performance of form-stable expanded graphite/stearic acid composite phase change materials with high thermal conductivity[J]. Chinese Science Bulletin, 2018, 63(7): 674-683.
1	WAQAS A, DIN Z U. Phase change material (PCM) storage for free cooling of buildings—A review[J]. Renewable and Sustainable Energy Reviews, 2013, 18: 607-625.
2	THAMBIDURAI M, PANCHABIKESAN K, KRISHNAMOHAN N, et al. Review on phase change material based free cooling of buildings—The way toward sustainability[J]. Journal of Energy Storage, 2015, 4: 74-88.
3	FARAJ K, KHALED M, FARAJ J, et al. Phase change material thermal energy storage systems for cooling applications in buildings: a review[J]. Renewable and Sustainable Energy Reviews, 2020, 119: 1-18.
4	ELISA C N, STATHOBOULOS S N. A comprehensive review of recent advances in materials aspects of phase change materials in thermal energy storage[J]. Energy Procedia, 2019, 161: 385-394.
5	STRITIH U, BUTALA V. Energy saving in building with PCM cold storage[J]. International Journal of Energy Research, 2007, 31(15): 1532-1544.
6	SARI A. Eutectic mixtures of some fatty acids for low temperature solar heating applications: thermal properties and thermal reliability[J]. Applied Thermal Engineering, 2005, 25(14): 2100-2107.
7	SARI A, BICER A, KARAIPEKLI A, et al. Synthesis, thermal energy storage properties and thermal reliability of some fatty acid esters with glycerol as novel solid-liquid phase change materials[J]. Solar Energy Materials and Solar Cells, 2010, 94(10): 1711-1715.
8	张奕, 王朋, 戴征舒, 等. 月桂酸-癸酸二元体系的固-液相平衡特性[J]. 哈尔滨工业大学学报, 2009, 41(11): 201-204.
	ZHANG Yi, WANG Peng, DAI Zhengshu，et al. Solid-liquid phase behavior of lauric acid and capric acid binary mixtures[J]. Journal of Harbin Institute of Technology, 2009, 41(11): 201-204.
9	华建社, 张娇, 张焱, 等. 膨胀石墨/石蜡复合相变蓄热材料的热性能及定形性研究[J]. 材料导报, 2016, 30(12): 61-64，75.
	HUA Jianshe, ZHANG Jiao, ZHANG Yan, et al. Study on thermal properties and shape-stabilizing of expanded graphite/paraffin composite phase change material[J]. Materials Review, 2016, 30(12): 61-64, 75.
10	李云涛, 晏华, 汪宏涛, 等. 膨胀石墨基复合相变材料的结构与性能研究[J]. 材料研究学报, 2016, 30(7): 545-552.
	LI Yuntao, YAN Hua, WANG Hongtao, et al. Characterization of microstructure and property for phase change materials of expanded graphite matrix composite[J]. Chinese Journal of Materials Research, 2016, 30(7): 545-552.
11	周孙希, 章学来, 刘升, 等. 癸醇-棕榈酸/膨胀石墨低温复合相变材料的制备与性能[J]. 化工学报, 2019, 70(1): 290-297.
	ZHOU Sunxi, ZHANG Xuelai, LIU Sheng, et al. Preparation and properties of decyl alcohol-palmitic acid/expanded graphite low temperature composite phase change material[J]. CIESC Journal, 2019, 70(1): 290-297.
12	SHARAM R K, GANESAN P, TYAGI V V, et al. Developments in organic solid-liquid phase change materials and their applications in thermal eneygy storage[J]. Energy Conversion and Managemnet, 2015, 95: 193-228.
13	IBRAHIM I, Al-SAIMAN F A, RAHMAN S, et al. Heat transfer enhancement of phase change materials for thermal energy storage applications: a critical review[J]. Renewable and Sustainable Energy Reviews, 2017, 74: 26-50.
14	孙晓璐, 苏婧, 宋肖飞, 等. 月桂酸-棕榈酸/Al₂O₃复合定形相变材料的制备与热性能研究[J]. 化工新型材料, 2019, 47(6): 171-175.
	SUN Xiaolu, SU Jing, SONG Xiaofei, et al. Preparation and thermal property of LA-PA/Al₂O₃ shape-stable phase change material[J]. New Chemical Materials, 2019, 47(6): 171-175.
15	TANG Y, SU D, HUANG X, et al. Synthesis and thermal properties of the MA/HDPE composites with nano-additives as form-stable PCM with improved thermal conductivity[J]. Apply Energy, 2016, 180: 116-129.
16	李云涛, 晏华, 汪宏涛, 等. 正癸酸-月桂酸-硬脂酸三元低共熔体系/膨胀石墨复合相变材料的制备与表征[J]. 材料导报, 2017, 31(4): 94-99.
	LI Yuntao, YAN Hua, WANG Hongtao, et al. Preparation and characterization of decanoic acid-lauric acid-stearic acid ternary eutectic mixture/expanded grapheme composite phase change material with a low eutectic temperature[J]. Materials Reports, 2017, 31(4): 94-99.
17	张正飞, 秦紫依, 李勇, 等. 相变材料的过冷现象及其抑制方法的研究进展[J]. 材料导报, 2019, 33(21): 3613-3619.
	ZHANG Zhengfei, QIN Ziyi, LI Yong, et al. Progress in supercooling and suppression methods of phase change materials[J]. Materials Reports, 2019, 33(21): 3613-3619.
18	ZHANG X Y, NIU J L, WU J Y, et al. Suppression of supercooling of PCM-water emulsions using nano-additives[J]. Energy Storage Science and Technology, 2014, 3(2): 133-136.
19	洪欢喜, 武卫东, 盛伟, 等. 纳米流体制备的研究进展[J]. 化工进展, 2008, 27(12): 1926 -1931.
	HONG Huanxi, WU Weidong, SHENG Wei, et al. Research progress of preparation of nanofluids[J]. Chemical Industry and Engineering Progress, 2008, 27(12): 1926 -1931.

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