水合无机盐及其复合相变储热材料的研究进展
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摘要
水合无机盐具有适宜的相变温度、较大的相变潜热、原料廉价以及热导率较高(相对有机相变材料而言)等优势而有望成为中低温热利用领域理想的储热材料。然而,水合盐具有过冷、相分离和液漏等缺陷,一直以来成为限制其应用的瓶颈缺陷。水合无机盐作为相变储热材料的传统研究主要集中在成核剂和增稠剂的选择上,近几年一些研究者开始研究水合无机盐复合或封装工艺,极大地促进了水合盐性能提升方面的工作。本文综述了常见的几种低温类水合无机盐过冷和相分离现象的解决方法以及基于这几种低温水合无机盐的复合相变储热材料的研究,复合相变材料较单一纯相变材料具有诸多优越的性能,预测采用多孔材料吸附封装技术或微胶囊封装技术来制备水合无机盐复合相变材料可能成为未来解决水合盐液漏问题的研究热点。
With the advantages of proper phase change temperature,high latent heat,cheap raw materials and high thermal conductivity(compared with organic phase change materials),the inorganic hydrated salts are considered as ideal heat storage materials in the field of middle and low temperature heat utilization. However,the hydrated salts have also defects of supercooling,phase separation and leakage,which have significantly limited their applications. The traditional researches on hydrated salts focused on the choice of nucleating agents and thickening agents. Recently,some researchers on the composite or encapsulation of inorganic hydrous salt showed up,greatly promoting the work of improving the performance of hydrated salts. In this paper,the solutions for supercooling and phase separation and the researches on phase change composites of several common inorganic hydrated salts are summarized. Compared with single phase change materials,the phase change composites have many superior properties. Preparing inorganic hydrated salts phase change composites with porous materials package and micro encapsulation technology may become the research hotspots for solving the problem of inorganic hydrated salts leakage in the future.
With the advantages of proper phase change temperature,high latent heat,cheap raw materials and high thermal conductivity(compared with organic phase change materials),the inorganic hydrated salts are considered as ideal heat storage materials in the field of middle and low temperature heat utilization. However,the hydrated salts have also defects of supercooling,phase separation and leakage,which have significantly limited their applications. The traditional researches on hydrated salts focused on the choice of nucleating agents and thickening agents. Recently,some researchers on the composite or encapsulation of inorganic hydrous salt showed up,greatly promoting the work of improving the performance of hydrated salts. In this paper,the solutions for supercooling and phase separation and the researches on phase change composites of several common inorganic hydrated salts are summarized. Compared with single phase change materials,the phase change composites have many superior properties. Preparing inorganic hydrated salts phase change composites with porous materials package and micro encapsulation technology may become the research hotspots for solving the problem of inorganic hydrated salts leakage in the future.
引文
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[3]ZHANG H Z,WANG X D.Fabrication and performances of microencapsulated phase change materials based on n-octadecane core and resorcinol-modified melamine–formaldehyde shell[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,332(2):129-138.
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[6]FANG Y T,KUANG S,GAO X N,et al.Preparation of nanoencapsulated phase change material as latent functionally thermal fluid[J].Journal of Physics D:Applied Physics,2009,42(3):035407.
[7]YUAN K J,WANG H C,LIU J,et al.Novel slurry containing graphene oxide-grafted microencapsulated phase change material with enhanced thermo-physical properties and photo-thermal performance[J].Solar Energy Materials and Solar Cells,2015,143:29-37.
[8]KARAIPEKLI A,SARI A,KAYGUSUZ K.Thermal characteristics of paraffin/expanded perlite composite for latent heat thermal energy storage[J].Energy Sources,Part A,2009,31(10):814-823.
[9]CARLSSON B.Phase change behaviour of some latent heat storage media based on calcium chloride hexahydrate[J].Solar Energy,2009,83(4):485-500.
[10]HUANG J,WANG T Y,ZHU P P,et al.Preparation,characterization,and thermal properties of the microencapsulation of a hydrated salt as phase change energy storage materials[J].Thermochimica Acta,2013,557:1-6.
[11]KOLEVA V,STEFOV V,NAJDOSKI M,et al.Thermal,spectral and microscopic studies of water-rich hydrate of the type Mg2KH(PO4)2·15H2O.Thermal transformations[J].Thermochimica Acta,2015,619:20-25.
[12]CABEZA L,CASTELL A,BARRENECHE C,et al.Materials used as PCM in thermal energy storage in buildings:a review[J].Renewable and Sustainable Energy Reviews,2011,15(3):1675-1695
[13]VERMA P,SINGAL S.Review of mathematical modeling on latent heat thermal energy storage systems using phase-change material[J].Renewable and Sustainable Energy Reviews,2008,12(4):999-1031
[14]FARID M M,KHUDHAIR A M,RAZACK S A K,et al.A review on phase change energy storage:materials and applications[J].Energy Conversion and Management,2004,45(9):1597-1615.
[15]徐祖耀.相变原理[M].北京:科学出版社,1988.
[16]DUKEK W,GRAYSON M.Kirk-othmer encyclopedia of chemical technology Vol.3[M].New York:John Wiley,1978:328-351.
[17]TORII T,OSSAKA J.Antarcticite:a new mineral,calcium chloride hexahydrate,discovered in Antarctica[J].Science,1965,149(3687):975-977.
[18]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.
[19]KIMURA H,KAI J.Mixtures of calcium chloride hexahydrate with some salt hydrates or anhydrous salts as latent heat storage materials[J].Energy conversion and management,1988,28(3):197-200.
[20]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.
[21]PARIS J,JOLLY R.Calcium chloride hexahydrate fusion-solidification behavior[J].Thermochimica Acta,1989,152(2):271-278.
[22]GU X B,NIU J J,QIN S.Antarcticite:a phase change material for thermal energy storage––experiments and simulation[C]//In Proceedings of the 11th International Congress for Applied Mineralogy(ICAM).2015:125-135.
[23]朱孝钦,胡劲,陆建生,等.相变储能材料Ca Cl2·6H2O相变温度调节的实验研究[J].材料工程,2010(s2):334-336.
[24]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.
[25]罗庆,夏煦,刘红,等.定形相变材料(壁纸)在高于相变温度下的调温性能分析[J].材料导报:纳米与新材料专辑,2009(2):319-321.
[26]徐云龙,刘栋.六水氯化钙相变材料过冷性质的研究[J].材料工程,2006(s1):218-221.
[27]叶锋,曲江兰,仲俊瑜,等.相变储热材料研究进展[J].过程工程学报,2010,10(6):1231-1241.
[28]黄金,柯秀芳.无机水合盐相变材料Na2SO4·10H2O的研究进展[J].材料导报,2008,22(3):63-67.
[29]黄保军,何琴,杨风岭,等.微纳米水合盐相变材料Na2SO4·10H2O的仿生合成与表征[J].化工新型材料,2011,39(1):52-54.
[30]王鹏,史晨曦,李凤艳,等.以十水硫酸钠为主体的相变材料体系防分层剂研究[J].可持续能源,2015,5:11-16.
[31]FENG G,XU X,HE N,et al.Testing research of energy storage system during Na2SO4·10H2O phase change[J].Materials Research Innovations,2015,19(5):972-977.
[32]FENG G,XU X,LI G,et al.Application of Na2SO4·10H2O thermal storage in air-conditioning cooling water system[J].Materials Research Innovations,2015,19(s5):983-987.
[33]LI G.,ZHANG B B,LI X,et al.The preparation,characterization and modification of a new phase change material:Ca Cl2·6H2O-Mg Cl2·6H2O eutectic hydrate salt[J].Solar Energy Materials and Solar Cells,2014,126:51-55.
[34]李卫萍,阮德水,胡起柱.Ca Cl2·6H2O-Ba Cl2·2H2O体系相图的研究[J].化学世界,1996(s1):216-217.
[35]李卫萍,阮德水,胡起柱,等.Ca Cl2·6H2O–Mg Cl2·6H2O多温截面的研究[J].华中师范大学学报(自然科学版),1998,32 74-76.
[36]王智平,田禾青,王克振,等.钾明矾基低共熔相变储热材料的制备与研究[J].人工晶体学报,2013,42(3):491-496.
[37]张勇,邹志荣,李建明,等.日光温室相变空心砌块的制备及功效[J].农业工程学报,2010,26(2):263-267.
[38]陈娇,张焕芝,孙立贤,等.Ca Cl2·6H2O/多孔Al2O3复合相变材料的制备与热性能[J].应用化工,2014,43(4):590-593.
[39]DUAN Z J,ZHANG H Z,SUN L X.,et al.Ca Cl2·6H2O/Expanded graphite composite as form-stable phase change materials for thermal energy storage[J].Journal of Thermal Analysis and Calorimetry,2014,115(1):111-117.
[40]雷琳,宋贝.硅藻土负载型复合相变材料的制备与表征[J].河南科技,2015,556(2):131-134.
[41]WU Y P,WANG T.Hydrated salts/expanded graphite composite with high thermal conductivity as a shape-stabilized phase change material for thermal energy storage[J].Energy Conversion and Management,2015,101:164-171.
[42]刘太奇,操彬彬,张成,等.物理法制备微胶囊无机芯相变材料及其表征[J].新技术新工艺,2010(3):81-84.
[43]ZHANG J,WANG S S,ZHANG S D,et al.In situ synthesis and phase change properties of Na2SO4·10H2O@Si O2 solid nanobowls toward smart heat storage[J].The Journal of Physical Chemistry C,2011,115(41):20061-20066.
[44]HASSABO A G,MOHAMED A L,WANG H,et al.Metal salts rented in silica microcapsules as inorganic phase change materials for textile usage[J].Indian Journal of Chemistry(Sec A),2015,10:59-65.
[45]黄金,王婷玉.无机芯微胶囊相变储能材料制备,表征及其热物性研究[J].功能材料,2013,44(12):1758-1762.
[46]SALAüN F,DEVAUX E,BOURBIGOT S,et al.Influence of the solvent on the microencapsulation of an hydrated salt[J].Carbohydrate Polymers,2010,79(4):964-974.
[2]SHARMA A,TYAGI V V,CHEN C R,et al.Review on thermal energy storage with phase change materials and applications[J].Renewable and Sustainable Energy Reviews,2009,13(2):318-345
[3]ZHANG H Z,WANG X D.Fabrication and performances of microencapsulated phase change materials based on n-octadecane core and resorcinol-modified melamine–formaldehyde shell[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,332(2):129-138.
[4]ZHANG H Z,WANG X D.Synthesis and properties of microencapsulated n-octadecane with polyurea shells containing different soft segments for heat energy storage and thermal regulation[J].Solar Energy Materials and Solar Cells,2009,93(8):1366-1376.
[5]SHI X M,XU S M,LIN J T,et al.Synthesis of Si O2-polyacrylic acid hybrid hydrogel with high mechanical properties and salt tolerance using sodium silicate precursor through sol-gel process[J].Materials Letters,2009,63(5):527-529.
[6]FANG Y T,KUANG S,GAO X N,et al.Preparation of nanoencapsulated phase change material as latent functionally thermal fluid[J].Journal of Physics D:Applied Physics,2009,42(3):035407.
[7]YUAN K J,WANG H C,LIU J,et al.Novel slurry containing graphene oxide-grafted microencapsulated phase change material with enhanced thermo-physical properties and photo-thermal performance[J].Solar Energy Materials and Solar Cells,2015,143:29-37.
[8]KARAIPEKLI A,SARI A,KAYGUSUZ K.Thermal characteristics of paraffin/expanded perlite composite for latent heat thermal energy storage[J].Energy Sources,Part A,2009,31(10):814-823.
[9]CARLSSON B.Phase change behaviour of some latent heat storage media based on calcium chloride hexahydrate[J].Solar Energy,2009,83(4):485-500.
[10]HUANG J,WANG T Y,ZHU P P,et al.Preparation,characterization,and thermal properties of the microencapsulation of a hydrated salt as phase change energy storage materials[J].Thermochimica Acta,2013,557:1-6.
[11]KOLEVA V,STEFOV V,NAJDOSKI M,et al.Thermal,spectral and microscopic studies of water-rich hydrate of the type Mg2KH(PO4)2·15H2O.Thermal transformations[J].Thermochimica Acta,2015,619:20-25.
[12]CABEZA L,CASTELL A,BARRENECHE C,et al.Materials used as PCM in thermal energy storage in buildings:a review[J].Renewable and Sustainable Energy Reviews,2011,15(3):1675-1695
[13]VERMA P,SINGAL S.Review of mathematical modeling on latent heat thermal energy storage systems using phase-change material[J].Renewable and Sustainable Energy Reviews,2008,12(4):999-1031
[14]FARID M M,KHUDHAIR A M,RAZACK S A K,et al.A review on phase change energy storage:materials and applications[J].Energy Conversion and Management,2004,45(9):1597-1615.
[15]徐祖耀.相变原理[M].北京:科学出版社,1988.
[16]DUKEK W,GRAYSON M.Kirk-othmer encyclopedia of chemical technology Vol.3[M].New York:John Wiley,1978:328-351.
[17]TORII T,OSSAKA J.Antarcticite:a new mineral,calcium chloride hexahydrate,discovered in Antarctica[J].Science,1965,149(3687):975-977.
[18]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.
[19]KIMURA H,KAI J.Mixtures of calcium chloride hexahydrate with some salt hydrates or anhydrous salts as latent heat storage materials[J].Energy conversion and management,1988,28(3):197-200.
[20]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.
[21]PARIS J,JOLLY R.Calcium chloride hexahydrate fusion-solidification behavior[J].Thermochimica Acta,1989,152(2):271-278.
[22]GU X B,NIU J J,QIN S.Antarcticite:a phase change material for thermal energy storage––experiments and simulation[C]//In Proceedings of the 11th International Congress for Applied Mineralogy(ICAM).2015:125-135.
[23]朱孝钦,胡劲,陆建生,等.相变储能材料Ca Cl2·6H2O相变温度调节的实验研究[J].材料工程,2010(s2):334-336.
[24]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.
[25]罗庆,夏煦,刘红,等.定形相变材料(壁纸)在高于相变温度下的调温性能分析[J].材料导报:纳米与新材料专辑,2009(2):319-321.
[26]徐云龙,刘栋.六水氯化钙相变材料过冷性质的研究[J].材料工程,2006(s1):218-221.
[27]叶锋,曲江兰,仲俊瑜,等.相变储热材料研究进展[J].过程工程学报,2010,10(6):1231-1241.
[28]黄金,柯秀芳.无机水合盐相变材料Na2SO4·10H2O的研究进展[J].材料导报,2008,22(3):63-67.
[29]黄保军,何琴,杨风岭,等.微纳米水合盐相变材料Na2SO4·10H2O的仿生合成与表征[J].化工新型材料,2011,39(1):52-54.
[30]王鹏,史晨曦,李凤艳,等.以十水硫酸钠为主体的相变材料体系防分层剂研究[J].可持续能源,2015,5:11-16.
[31]FENG G,XU X,HE N,et al.Testing research of energy storage system during Na2SO4·10H2O phase change[J].Materials Research Innovations,2015,19(5):972-977.
[32]FENG G,XU X,LI G,et al.Application of Na2SO4·10H2O thermal storage in air-conditioning cooling water system[J].Materials Research Innovations,2015,19(s5):983-987.
[33]LI G.,ZHANG B B,LI X,et al.The preparation,characterization and modification of a new phase change material:Ca Cl2·6H2O-Mg Cl2·6H2O eutectic hydrate salt[J].Solar Energy Materials and Solar Cells,2014,126:51-55.
[34]李卫萍,阮德水,胡起柱.Ca Cl2·6H2O-Ba Cl2·2H2O体系相图的研究[J].化学世界,1996(s1):216-217.
[35]李卫萍,阮德水,胡起柱,等.Ca Cl2·6H2O–Mg Cl2·6H2O多温截面的研究[J].华中师范大学学报(自然科学版),1998,32 74-76.
[36]王智平,田禾青,王克振,等.钾明矾基低共熔相变储热材料的制备与研究[J].人工晶体学报,2013,42(3):491-496.
[37]张勇,邹志荣,李建明,等.日光温室相变空心砌块的制备及功效[J].农业工程学报,2010,26(2):263-267.
[38]陈娇,张焕芝,孙立贤,等.Ca Cl2·6H2O/多孔Al2O3复合相变材料的制备与热性能[J].应用化工,2014,43(4):590-593.
[39]DUAN Z J,ZHANG H Z,SUN L X.,et al.Ca Cl2·6H2O/Expanded graphite composite as form-stable phase change materials for thermal energy storage[J].Journal of Thermal Analysis and Calorimetry,2014,115(1):111-117.
[40]雷琳,宋贝.硅藻土负载型复合相变材料的制备与表征[J].河南科技,2015,556(2):131-134.
[41]WU Y P,WANG T.Hydrated salts/expanded graphite composite with high thermal conductivity as a shape-stabilized phase change material for thermal energy storage[J].Energy Conversion and Management,2015,101:164-171.
[42]刘太奇,操彬彬,张成,等.物理法制备微胶囊无机芯相变材料及其表征[J].新技术新工艺,2010(3):81-84.
[43]ZHANG J,WANG S S,ZHANG S D,et al.In situ synthesis and phase change properties of Na2SO4·10H2O@Si O2 solid nanobowls toward smart heat storage[J].The Journal of Physical Chemistry C,2011,115(41):20061-20066.
[44]HASSABO A G,MOHAMED A L,WANG H,et al.Metal salts rented in silica microcapsules as inorganic phase change materials for textile usage[J].Indian Journal of Chemistry(Sec A),2015,10:59-65.
[45]黄金,王婷玉.无机芯微胶囊相变储能材料制备,表征及其热物性研究[J].功能材料,2013,44(12):1758-1762.
[46]SALAüN F,DEVAUX E,BOURBIGOT S,et al.Influence of the solvent on the microencapsulation of an hydrated salt[J].Carbohydrate Polymers,2010,79(4):964-974.