六水氯化钙基无机水合盐相变储能材料的研究进展
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摘要
六水氯化钙具有适宜的相变温度(29℃)、较高的相变焓值(191 J/g左右)、原料廉价易得和安全无毒等诸多优点,在未来中低温物理储能领域有着巨大的应用潜力。但它同时具有过冷、相分离和易泄露等典型缺陷,因而限制了它的应用。一般地,成核剂和相分离剂被用来解决过冷和相分离问题,微胶囊和多孔基吸附用来解决泄露问题,这些研究在抑制缺陷方面取得了良好的进展,但进一步的性能改善仍然有待探索。本文综述了六水氯化钙相变储能材料的过冷,相分离和泄漏问题的原理及其研究现状。并对后续的研究方向做了如下展望:采用高传热纳米粒子,多孔吸附基改善过冷;采用高导热的增稠剂或控制结晶过程改善相分离;采用高导热和高强度的包覆层物质制备微胶囊来改善泄露;改善多孔吸附的工艺制备表面清洁的复合材料来改善泄漏;注重单一添加剂的多种功能的实现。
Calcium chloride hexahydrate, possessing many advantages including suitable operating temperature(29℃), high enthalpy of phase change(around 191 J/g), low price and easy obtaining of raw material, security and non-toxic property, is a promising medium-low temperature phase change material in Physical energy storage. However, it suffers from sugpercooling, phase separation and leakage, which limit its applications. Generally, Nucleating agent and thickening agent can be used to solve the problems of supercooling and phase separation. Microcapsulation and porous adsorption may help to overcome the leakage problem. Although some progresses have been achieved, further explorings of modifying properties still need to be done. In this paper, the mechanisms and recent work on those problems are summarized.In addition, some predictions are presented, including using high thermal conductivity nanoparticles and porous materials to inhibit the supercooling, utilizing high thermal conductivity thickening agents or controlling the process of crystallization to prevent the phase separation, finding high thermal conductivity and high strength package materials to prevent leakage, improving the technology of making porous adsorption composites to prepare surface-clean materials and achieving multiple functions with single addictive.
Calcium chloride hexahydrate, possessing many advantages including suitable operating temperature(29℃), high enthalpy of phase change(around 191 J/g), low price and easy obtaining of raw material, security and non-toxic property, is a promising medium-low temperature phase change material in Physical energy storage. However, it suffers from sugpercooling, phase separation and leakage, which limit its applications. Generally, Nucleating agent and thickening agent can be used to solve the problems of supercooling and phase separation. Microcapsulation and porous adsorption may help to overcome the leakage problem. Although some progresses have been achieved, further explorings of modifying properties still need to be done. In this paper, the mechanisms and recent work on those problems are summarized.In addition, some predictions are presented, including using high thermal conductivity nanoparticles and porous materials to inhibit the supercooling, utilizing high thermal conductivity thickening agents or controlling the process of crystallization to prevent the phase separation, finding high thermal conductivity and high strength package materials to prevent leakage, improving the technology of making porous adsorption composites to prepare surface-clean materials and achieving multiple functions with single addictive.
引文
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[2]于慧生.国外无机盐相变贮热材料及设备[J].无机盐工业,1982(1):26-30.
[3]ZHOU D,ZHAO C Y,TIAN Y.Review on thermal energy storage with phase change materials(PCMs)in building applications[J].Applied Energy,2012,92:593-605.
[4]ZALBA B,MARíN J M,CABEZA L F,et al..Review on thermal energy storage with phase change:Materials,heat transfer analysis and applications[J].Applied Thermal Engineering,2003,23(3):251-283.
[5]GIRO-PALOMA J,MARTíNEZ M,CABEZA L F,et al.Types,methods,techniques,and applications for microencapsulated phase change materials(MPCM):A review[J].Renewable and Sustainable Energy Reviews,2016,53:1059-1075.
[6]KHAN Zakir,KHAN Zulfiqar,GHAFOOR Abdul.A review of performance enhancement of PCM based latent heat storage system within the context of materials,thermal stability and compatibility[J].Energy Conversion and Management,2016,115:132-158.
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[8]POMIANOWSKI Michal,HEISELBERG Per,ZHANG Yinping.Review of thermal energy storage technologies based on PCM application in buildings[J].Energy and Buildings,2013,67:56-69.
[9]VEERAKUMAR C,SREEKUMAR A.Phase change material based cold thermal energy storage:Materials,techniques and applications—A review[J].International Journal of Refrigeration,2016,67:271-289.
[10]ZHANG P,XIAO X,MA Z W.A review of the composite phase change materials:Fabrication,characterization,mathematical modeling and application to performance enhancement[J].Applied Energy,2016,165:472-510.
[11]USHAK S,CRUZ M,CABEZA L,et al.Preparation and characterization of inorganic PCM microcapsules by fluidized bed method[J].Materials,2016,9(1):doi:10.3390/ma9010024.
[12]LANE G A.Phase change materials for energy storage nucleation to prevent supercooling[J].Solar Energy Materials and Solar Cells,1992,27:135-160.
[13]KENISARIN M,MAHKAMOV K.Salt hydrates as latent heat storage materials:Thermophysical properties and costs[J].Solar Energy Materials and Solar Cells,2016,145:255-286.
[14]AYHAN T,KAYGUSUZ K,GüLTEKI?N N.Heat-storage chemical materials which can be used for domestic heating by heat-pumps[J].Energy Conversion and Management,1991,32(4):311-317.
[15]KHALIFA A J,ABBAS E F.A comparative performance study of some thermal storage materials used for solar space heating[J].Energy and Buildings,2009,41(4):407-415.
[16]朱孝钦,陆建生,孙加林,等.用六水氯化钙作为相变材料的换热器储热性能研究[J].无机盐工业,2007,39(8):56-58.ZHU Xiaoqin,LU Jiansheng,SUN Jialin,et al.Research on heat storage performances of the heat exchanger using calcium chloride hexahydrate as phase-change material[J].Inorganic Chemicals Industry,2007,39(8):56-58.
[17]BRANDSTE'ITER A.On the stability of calcium-chloride hexahydrate in thermal storage-systems[J].Solar Energy,1988,41(2):183-191.
[18]阮北,刘鹏.结晶动力学研究进展[J].河北化工,2006,29(8):13-16.RUAN Bei,LIU Peng.The development of crystallization kinetics[J].Heibei Chemical Engineering and Industry,2006,29(8):13-16.
[19]MEWES D F,MAYINGER HARALD MEHLING,LUISA F CABEZA.Heat and cold storage with PCM[M].deblik,Berlin,Germany:Springer-Verlag Berlin Heidelberg,2008:29-31.
[20]CARLSSON B,STYMNE H,WETTERMARK G.An incongruent heat-of-fusion system-Ca Cl2·6H2O-made congruent through modification of the chemical composition of the system[J].Solar Energy,1979,23(4):343-350.
[21]TYAGI V V,BUDDHI D.Thermal cycle testing of calcium chloride hexahydrate as a possible PCM for latent heat storage[J].Solar Energy Materials and Solar Cells,2008,92(8):891-899.
[22]LI Xiang,ZHOU Yuan,NIAN Hongen.Phase change behavior of latent heat storage media based on calcium chloride hexahydrate composites containing strontium chloride hexahydrate and oxidation expandable graphite[J].Applied Thermal Engineering,2016,102:38-44.
[23]刘栋,徐云龙.成核剂对Ca Cl2?6H2O相变材料储热性能的影响[J].太阳能学报,2007,28(7):732-738.LIU Dong,XU Yunlong.Thermoproperties research on nucleators-Ca Cl2?6H2O-composites under distictive systems[J].Acta Energiae Solaris Sinica,2007,28(7):732-738.
[24]李志广,徐雷,黄红军,等.相变恒温材料六水氯化钙的研究[J].功能材料,2007,38:3162-3163.LI Zhiguang,XU Lei,Huang Hongjun,et al.The study of phase change constant temperature material calcium chloride hexahydrate[J].Journal of Functional Materials,2007,38:3162-3163.
[25]马江伟,王宏丽,李凯,等.适于温室应用的六水氯化钙的性能研究[J].农机化研究,2013(7):211-216.MA Jiangwei,WANG Hongli,LI Kai,et al.Study on properties of calcium chloride hexahydrate suitable for greenhouse application[J].Journal of Agricultural Mechanization Research,2013(7):211-216.
[26]周彦同,张文昭,韦雪骐.六水合氯化钙蓄热材料制备的研究[J].江苏广播电视大学学报,1994(4):12-16.
[27]PARIS J,JOLLY R.Observations sur le comportement a la fusion-solidification du chlorure de calcium hexahydrate[J].Thermochimica Acta,1989,152:271-278.
[28]FEILCHENFELD H,FUCHS J,KAHANA F,et al.The melting point adjustment of calcium chloride hexahydrate by addition of potassium chloride or calcium bromide hexahydrate[J].Solar Energy,1985,34(2):199-201.
[29]ZHU X Q,HU J,ZHAO H Y,et al.Phase transformation temperature adjustment of calcium chloride hexahydrate[J].Key Engineering Materials,2012,512-515:386-389.
[30]刘超.六水氯化钙重结晶的相分层机理和控制研究[J].中国建材科技,2015,24(3):52-53.LIU Chao,Study on stratiifcation mechanism and conformity of calcium chloride hexahydrate during recrystallization[J].China Building Materials Science&Technology,2015,24(3):52-53.
[31]KIMURA H,KAI J.Phase change stability of Ca Cl2·6H2O[J].Solar Energy,1984,33(1):49-55.
[32]GU Xiaobin,NIU Jingjing,QIN Shan.Antarcticite,a phase change material for thermalenergy storage—Experiments and simulation[J].Acta Mineralogica Sinica,2013(S1):28.
[33]USHAK S,SUáREZ M,VéLIZ S,et al.Characterization of calcium chloride tetrahydrate as a phase change material and thermodynamic analysis of the results[J].Renewable Energy,2016,95:213-224.
[34]KENISARIN M M,KENISARINA K M.Form-stable phase change materials for thermal energy storage[J].Renewable and Sustainable Energy Reviews,2012,16(4):1999-2040.
[35]BAYéS-GARCíA L,VENTOLA L,CORDOBILLA R,et al.Phase change materials(PCM)microcapsules with different shell compositions:preparation,characterization and thermal stability[J].Solar Energy Materials and Solar Cells,2010,94(7):1235-1240.
[36]JAMEKHORSHID A,SADRAMELI S M,FARID M.A review of microencapsulation methods of phase change materials(PCMs)as a thermal energy storage(TES)medium[J].Renewable and Sustainable Energy Reviews,2014,31:531-542.
[37]KHUDHAIR A M,FARID M M.A review on energy conservation in building applications with thermal storage by latent heat using phase change materials[J].Energy Conversion and Management,2004,45(2):263-275.
[38]TYAGI V V,KAUSHIK S C,TYAGI S K,et al.Development of phase change materials based microencapsulated technology for buildings:A review[J].Renewable and Sustainable Energy Reviews,2011,15(2):1373-1391.
[39]方贵银,李辉.具有多孔基体复合相变储能材料研究[J].材料科学与工程学报,2003,21(6):842-844.FANG Guiyin,LI Hui.Study on the thermal energy storage phase change compositem aterial with porous skeleton[J].Journal of Materials Science&Engineering,2003,21(6):842-844.
[40]GU Xiaobin,QIN Shan,WU Xiang,et al.Preparation and thermal characterization of sodium acetate trihydrate/expanded graphite composite phase change material[J].Journal of Thermal Analysis and Calorimetry,2016,125(2):831-838.
[41]LI Ruguang,ZHU Jiaoqun,ZHOU Weibing,et al.Thermal properties of sodium nitrate-expanded vermiculite form-stable composite phase change materials[J].Materials&Design,2016,104:190-196.
[42]LI Xiangqi,WEI Haiting,LIN Xingshui,et al.Preparation of stearic acid/modified expanded vermiculite composite phase change material with simultaneously enhanced thermal conductivity and latent heat[J].Solar Energy Materials and Solar Cells,2016,155:9-13.
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