Preparation and investigation of quaternary nitrates/halloysites/graphite shape-stable composite phase change material with low melting temperature for thermal energy storage

doi:10.19799/j.cnki.2095-4239.2021.0599

Abstract

Abstract:

Herein, a shape-stable molten salt-based composite phase change material with low melting temperature and large temperature range was fabricated by cold compression-hot sintering approach and investigated. A eutectic quaternary nitrate of Ca(NO₃)₂-KNO₃-NaNO₃-NaNO₂ is used as the phase change material (PCM), and halloysite and graphite are respectively employed as the structure supporting material and thermal conductivity enhancer. Several characterizations, including differential scanning calorimetry, laser thermal conductivity test, scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy were conducted to investigate the microstructure, chemical compatibility, and thermal properties of the composite. The results show that a fairly low melting point about 91.3 ℃ and relatively high decomposition temperature of 627.5 ℃ were observed, giving the composite a large energy storage density exceeding 630.15 kJ/kg at a temperature range of 25—625 ℃. For the composite containing 10% graphite, the material's thermal conductivity can be increased by 44.8% from 0.58 to 1.18 W·(m·K)^-1. Due to the special hollow structure of the halloysite nanotube, the molten salt can be absorbed by the halloysite, and hence the issues of salt corrosion, leakage, and decomposition can be effectively addressed. No chemical reaction occurs among the salt, halloysite, and graphite, including good chemical stability achieved in the composite. After 100 heating-cooling cycles, the fluctuation of the phase change temperature and latent heat is less than 3.5%, demonstrating the excellent cycling stability of the composites. The present results indicate that such salt-based composite with low melting temperature and high thermal performance could be an effective alternative to organic-based PCMs used in low-mid thermal energy storage systems.

Key words: halloysite nanotubes, quaternary nitrates, composite phase change materials, thermal energy storage

CLC Number:

TK 512

Yuying LI, Wenzhen WEI, Qi LI, Yuting WU. Preparation and investigation of quaternary nitrates/halloysites/graphite shape-stable composite phase change material with low melting temperature for thermal energy storage[J]. Energy Storage Science and Technology, 2022, 11(3): 1044-1051.

Figures/Tables 12

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样品	A1	A2	A3	A4	A5
共晶盐/%	30	40	50	60	70
埃洛石/%	70	60	50	40	30
有无泄漏	无	无	无	轻微	严重

样品	T_onset/℃	T_Peak/℃	T_end/℃	c_p /[J/(g·K)]	?H_mea/(kJ/kg)	?H_cal/(kJ/kg)
四元硝酸盐	90.9	96.7	100.8	1.414	78.52	78.52
埃洛石				0.714
50QN-50HNTs	90.0	93.7	100.2	0.752	35.85	39.26
石墨				0.710
复合材料	91.3	94.1	99.8	0.932	31.86	35.33

相变特性	复合相变材料	循环30次	循环100次
起始温度/℃	91.3	92.3	91.7
峰值温度/℃	94.1	94.3	94
终止温度/℃	99.5	98.2	96.7
潜热/(kJ/kg)	31.86	32.37	30.83

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