Supercooling characteristics of inorganic phase change material CaCl2·6H2O

doi:10.11949/j.issn.0438-1157.20170490

Abstract

Abstract:

As a common room temperature inorganic hydrated salt phase change material(PCM), calcium chloride hexahydrate(CaCl₂·6H₂O) is being widely focused due to its low cost, easy availability and high thermal energy storage. CaCl₂·6H₂O was prepared in terms of mass ratio of anhydrous CaCl₂ and H₂O as 1.027:1, whose crystal structure was characterized by X-ray diffraction(XRD). CaCl₂·6H₂O was modified by adding nucleating agents SrCl2·6H₂O and Ba(OH)₂. The results showed that the combination of SrCl2·6H₂O and Ba(OH)₂ could suppress supercooling phenomenon. The average supercooling degree was 1.07℃ in the process of melting-cooling for 10 cycles. The phase change latent heat of CaCl₂·6H₂O before and after adding nucleating agents, characterized by differential scanning calorimetry(DSC), decreased from 223.54 J·g^-1 to 160.41 J·g^-1. In order to enlarge the scope of phase change temperature of CaCl₂·6H₂O, 5%, 10%, 15%, 20% and 25%(mass) magnesium chloride hexahydrate(MgCl₂·6H₂O) was added into CaCl₂·6H₂O respectively, which indicated the phase change temperature of CaCl₂·6H₂O decreased linearly with the increase of MgCl₂·6H₂O content, however, not exceeding 20%(mass). The modification of CaCl₂·6H₂O-20% MgCl₂·6H₂O binary eutectic salt phase change thermal energy storage material was designed by adding 1% SrCl2·6H₂O and 0.5% CMC, and the results suggested that the degree of supercooling was reduced to 0.57℃. The phase change latent heat of this material was 141.09 J·g^-1, which was lower than that of CaCl₂·6H₂O(223.54 J·g^-1) and MgCl₂·6H₂O(163.35 J·g^-1). The above study showed that inorganic hydrated salt CaCl₂·6H₂O had significant application value as an inorganic PCM.

Key words: CaCl₂·, 6H₂O, phase change, preparation, supercooling, nucleation, latent heat, MgCl₂·, 6H₂O, binary eutectic salt

摘要：

CaCl₂·6H₂O作为一种常见的常温无机水合盐相变材料，由于成本低、易获取、蓄热强而受到广泛的关注。按无水CaCl₂与H₂O的质量比为1.027：1制备了CaCl₂·6H₂O，经X射线衍射（XRD）表征其晶体结构；通过添加成核剂SrCl2·6H₂O和Ba（OH）₂对CaCl₂·6H₂O改性，发现两者的联合作用可抑制过冷，10次熔化-冷却循环平均过冷度1.07℃。采用差示扫描量热仪（DSC）测定CaCl₂·6H₂O添加成核剂前后相变潜热，发现潜热由223.54 J·g^-1降至160.41 J·g^-1；为了扩大CaCl₂·6H₂O相变温度的范围，通过添加质量分数分别为5%、10%、15%、20%和25%的MgCl₂·6H₂O，发现相变温度随MgCl₂·6H₂O质量分数的升高呈线性降低，但不宜超过20%；选取CaCl₂·6H₂O-20% MgCl₂·6H₂O二元共晶盐相变储热体系为改性目标，通过添加1% SrCl2·6H₂O和0.5% CMC，过冷度降至0.57℃，相变潜热为141.09 J·g^-1，低于单独组成盐CaCl₂·6H₂O的潜热223.54 J·g^-1和MgCl₂·6H₂O的潜热163.35 J·g^-1。研究表明，CaCl₂·6H₂O作为无机相变材料具有显著的应用价值。

关键词: CaCl₂·, 6H₂O, 相变, 制备, 过冷, 成核, 潜热, MgCl₂·, 6H₂O, 二元共晶盐

CLC Number:

TK02

HE Meizhi, YANG Luwei, ZHANG Zhentao. Supercooling characteristics of inorganic phase change material CaCl₂·6H₂O[J]. CIESC Journal, 2017, 68(11): 4016-4024.

何媚质, 杨鲁伟, 张振涛. 无机相变材料CaCl₂·6H₂O的过冷特性[J]. 化工学报, 2017, 68(11): 4016-4024.

References 30

[1]	FANG G Y, CHEN Z, LI H. Synthesis and properties of microencapsulated paraffin composites with SiO2 shell as thermal energy storage materials[J]. Chem. Eng. J., 2010, 163:154-159.
[2]	?AHAN N, PAKSOY H. Determining influences of SiO2 encapsulation on thermal energy storage properties of different phase change materials[J]. Sol. Energy Mater. Sol. Cells, 2017, 159:1-7.
[3]	MAZMAN M, CABEZA L F, MEHLING H, et al. Utilization of phase change materials in solar domestic hot water systems[J]. Renew. Energy, 2009, 34:1639-1643.
[4]	XU B, LI P W, CHAN C. Application of phase change materials for thermal energy storage in concentrated solar thermal power plants:a review to recent developments[J]. Appl. Energy, 2015, 160:286-307.
[5]	WANG T, MANTHA D, REDDY R G. Novel low melting point quaternary eutectic system for solar thermal energy storage[J]. Appl. Energy, 2013, 102:1422-1429.
[6]	KENISARIN M, MAHKAMOV K. Solar energy storage using phase change materials[J]. Renew. Sustain. Energy Rev., 2007, 11:1913-1965.
[7]	SOARES N, COSTA J J, GASPAR A R, et al. Review of passive PCM latent heat thermal energy storage systems towards buildings' energy efficiency[J]. Energy Build., 2013, 59:82-103.
[8]	KENISARIN M, MAHKAMOV K. Passive thermal control in residential buildings using phase change materials[J]. Renew. Sustain. Energy Rev., 2016, 55:371-398.
[9]	TYAGI V V, PANDEY A K, BUDDHI D, et al. Thermal performance assessment of encapsulated PCM based thermal management system to reduce peak energy demand in buildings[J]. Energy Build, 2016, 117:44-52.
[10]	BENLI H, DURMUS A. Performance analysis of a latent heat storage system with phase change material for new designed solar collectors in greenhouse heating[J]. Sol. Energy, 2009, 83:2109-2119.
[11]	WANG X L, DENNIS M. An experimental study on the formation behavior of single and binary hydrates of TBAB, TBAF and TBPB for cold storage air conditioning applications[J]. Chem. Eng. Sci., 2015, 137:938-946.
[12]	AL-ABIDI A A, MAT S B, SOPIAN K, et al. Review of thermal energy storage for air conditioning systems[J]. Renew. Sustain. Energy Rev., 2012, 16:5802-5819.
[13]	GIL A, ORO E, MIRO L, et al. Experimental analysis of hydroquinone used as phase change material (PCM) to be applied in solar cooling refrigeration[J]. Int. J. Refrig., 2014, 39:95-103.
[14]	TAN F L, TSO C P. Cooling of mobile electronic devices using phase change materials[J]. Appl. Therm. Eng., 2004, 24:159-169.
[15]	ALAY S, GODE F, ALKAN C. Synthesis and thermal properties of poly(n-butylacrylate)/n-hexadecane microcapsules using different cross-linkers and their application to textile fabrics[J]. J. Appl. Polym. Sci., 2011, 120(5):2821-2829.
[16]	SARIER N, ONDER E. Organic phase change materials and their textile applications:an overview[J]. Thermochimica Acta, 2012, 540:7-60.
[17]	?AHAN N, FOIS M, PAKSOY H. The effects of various carbon derivative additives on the thermal properties of paraffin as a phase change material[J]. Int. J. Energy Res., 2016, 40:198-206.
[18]	LI G, ZHANG B B, LI X, et al. The preparation, characterization and modification of a new phase change material:CaCl2·6H2O-MgCl2·6H2O eutectic hydrate salt[J]. Sol. Energy Mater. Sol. Cells, 2014, 126:51-55.
[19]	DUAN Z J, ZHANG H Z, SUN L X, et al. CaCl2·6H2O/expanded graphite composite as form-stable phase change materials for thermal energy storage[J]. J. Therm. Anal. Calorim., 2014, 115:111-117.
[20]	LANE G A. Adding strontium chloride or calcium hydroxide to calcium chloride hexahydrate heat storage material[J]. Sol. Energy, 1981, 1:73-75.
[21]	BILEN K, TAKGIL F, KAYGUSUZ K. Thermal energy storage behavior of CaCl2·6H2O during melting and solidification[J]. Energy Sources, Part A, 2008, 30:775-787.
[22]	LI X, ZHOU Y, NIAN H G, et al. Phase change behavior of latent heat storage media based on calcium chloride hexahydrate composites containing strontium chloride hexahydrate and oxidation expandable graphite[J]. Appl. Therm. Eng., 2016, 102:38-44.
[23]	TYAGI V V, KAUSHIK S C, PANDEY A K, et al. Experimental study of the supercooling and pH behavior of a typical phase change material for thermal energy storage[J]. Indian J. Pure Appl. Phys., 2011, 49:117-125.
[24]	TYAGI V V, BUDDHI D. Thermal cycle testing of calcium chloride hexahydrate as a possible PCM for latent heat storage[J]. Sol. Energy Mater. Sol. Cells, 2008, 92:891-899.
[25]	张仁元. 相变材料与相变储能技术[M]. 北京:科学出版社, 2008. ZHANG R Y. Phase Change Materials and Phase Change Energy Storage Technology[M]. Beijing:Science Press, 2008.
[26]	GUNTHER E, LI H, MEHLING H, et al. Subcooling in PCM emulsions(part 2):Interpretation in terms of nucleation theory[J]. Thermochimica Acta, 2011, 522:199-204.
[27]	RHAFIKI T E, KOUSKSOU T, JAMIL A, et al. Crystallization of PCMs inside an emulsion:supercooling phenomenon[J]. Sol. Energy Mater. Sol. Cells, 2011, 95:2588-2597.
[28]	CABEZA L F, SVENSSON G, HIEBLER S, et al. Thermal performance of sodium acetate trihydrate thickened with different materials as phase change energy storage material[J]. Appl. Therm. Eng., 2003, 23:1697-1704.
[29]	HU P, LU D J, FAN X Y, et al. Phase change performance of sodium acetate trihydrate with AlN nanoparticles and CMC[J]. Sol. Energy Mater. Sol. Cells, 2011, 95:2645-2649.
[30]	SHIN H K, PARK M, KIM H Y, et al. Thermal property and latent heat energy storage behavior of sodium acetate trihydrate composites containing expanded graphite and carboxymethyl cellulose for phase change materials[J]. Appl. Therm. Eng., 2015, 75:978-983.

Supercooling characteristics of inorganic phase change material CaCl₂·6H₂O

无机相变材料CaCl₂·6H₂O的过冷特性

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