Na2HPO4•12H2O相变储能复合材料制备及热物性

doi:10.16085/j.issn.1000-6613.2019-0475

摘要/Abstract

摘要：

十二水磷酸氢二钠的过冷度、相分离以及热导率低等问题影响了其在低温蓄热场合的应用，因此需要对其进行相关的改性研究。本文通过成核剂和增稠剂的筛选实验及添加导热增强剂纳米氧化铁（α-Fe₂O₃），制备了质量分数为Na₂HPO₄·12H₂O+2% Na₄P₂O₇·10H₂O+1%黄原胶（GX）+0.2%α-Fe₂O₃复合相变储能材料，并对其进行了凝固放热测试、热物性测试及循环稳定性测试。结果表明：2%的Na₄P₂O₇·10H₂O抑制过冷效果最好，成核效果不随循环次数的增加而减小，过冷度维持在2℃左右；GX可以有效抑制Na₂HPO₄·12H₂O的相分离现象，且质量分数为0.75%～1.25%是较合适的剂量；α-Fe₂O₃可以有效地提高Na₂HPO₄·12H₂O的热导率，添加0.2%α-Fe₂O₃使热导率提高了90.8%；循环150次后，复合相变储能材料的相变潜热值为252J/g，相比于循环前衰减了7.4%，相变温度为35.4℃，过冷度为1.3℃，热导率为2.054W/(m·K)，相比纯材料提高了100.2%。改性后的复合相变储能材料相变温度适宜，潜热值大，热导率高，热性能稳定，可推广应用到热泵蓄热、温室生产和电子器件散热等领域。

关键词: 相变, 复合材料, 稳定性, 过冷度, 相分离, 热导率

Abstract:

Disodium hydrogen phosphate(Na₂HPO₄·12H₂O) had some problems such as supercooling, phase separation and low thermal conductivity affecting its applications in the low temperature thermal storage. Therefore, it needs to be further improved. By means of the selecting experiment of nucleating agent and thickening agent and adding thermal conductive enhancer nano-iron oxide(α-Fe₂O₃), composite phase change energy storage materials with mass ratio of Na₂HPO₄·12H₂O+2% Na₄P₂O₇·10H₂O+1% xanthan gum(GX)+0.2% α-Fe₂O₃ were prepared，and the solidification exothermic test, thermophysical properties test and cycling stability test were carried out. The results showed that the nucleating effect of adding 2% Na₄P₂O₇·10H₂O was the best and did not decrease with the increase of cycle times, and the degree of supercooling was maintained at about 2℃. GX can effectively control the phase separation of Na₂HPO₄·12H₂O, for which mass ratio of 0.75%～1.25% was much better. α-Fe₂O₃ can effectively improve the thermal conductivity of Na₂HPO₄·12H₂O, and mass ratio of 0.2% can increase by 90.8%. The latent heat of composite phase change energy storage materials was 252J/g after 150 cycles, which decreased by 7.4%. The phase change temperature was 35.4℃, while the supercooling was 1.3℃.The thermal conductivity was 2.054W/(m·K), which was 100.2% higher than that of pure materials. The modified composite materials with the suitable phase change temperature, high latent heat, high thermal conductivity and stable thermal performance can be widely used in heat pump storage, greenhouse production and heat dissipation of electronic devices.

Key words: phase change, composites, stability, supercooling, phase separation, thermal conductivity

中图分类号:

TK02

汪翔,章学来,华维三,郑灵钰,刘璐,喻彩梅. Na₂HPO₄•12H₂O相变储能复合材料制备及热物性[J]. 化工进展, 2019, 38(12): 5457-5464.

Xiang WANG,Xuelai ZHANG,Weisan HUA,Lingyu ZHENG,Lu LIU,Caimei YU. Preparation and thermal properties of Na₂HPO₄·12H₂O composite phase change material for thermal energy storage[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5457-5464.

图/表 14

表1 实验仪器

仪器名称	规格型号	仪器精度	仪器用途
电热恒温水槽	DK-S600	±0.1℃	为测试提供高温环境
低温恒温槽	DC-6515	±0.1℃	为测试提供低温环境
超声波分散仪	SY-300	—	分散振荡纳米材料
安捷伦数据采集仪	34972A	±0.01℃	采集温度信号
热电偶测温线	T型	±0.05℃	传送温度信号
电子天平	FA2004	±0.1mg	材料称重
差示扫描量热仪	DSC204F1	温度0.1℃，热焓0.1J/g	测量相变温度和潜热值
热常数分析仪	Hotdisk TPS 2500S	测量精度±2%	测试热导率
自制相变材料循环寿命测试仪	—	—	测试材料循环稳定性

图1 复合DSP的制备过程

图2 相变材料循环寿命测试系统原理图1—低温恒温槽; 2—控制系统; 3—温控器1; 4—温控器2;5—低温循环泵; 6—高温循环泵; 7—样品换热槽; 8—温度探头;9—样品杯; 10—数据采集仪; 11—电脑; 12—超级恒温槽

图3 添加不同种成核剂的DSP凝固放热曲线

图4 不同质量分数TPD对DSP相变材料的成核效果

图5 DSP相变体系的相分离现象

图6 不同增稠剂的增稠效果

图7 不同质量分数黄原胶（GX）的增稠效果

图8 α-Fe2O3/DSP相变材料的热导率

图9 0.2%α-Fe2O3/DSP相变体系升温对比

图10 纯DSP与复合DSP样品的DSC曲线

表2 纯DSP及复合DSP相变材料的热物性

材料	相变温度/℃	相变潜热/J·g^-1	热导率/W·m^-1·K^-1
纯DSP	36.0	278	1.026
复合DSP	37.0	272	2.054

图11 复合相变材料的循环稳定性测试曲线

图12 相变温度及潜热随循环次数变化曲线

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Na₂HPO₄•12H₂O相变储能复合材料制备及热物性

Preparation and thermal properties of Na₂HPO₄·12H₂O composite phase change material for thermal energy storage

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