高溫相變儲能微膠囊研究進展

江羽; 王倩; 王冬; 趙彤

doi:10.13374/j.issn2095-9389.2020.07.21.004

高溫相變儲能微膠囊研究進展

doi: 10.13374/j.issn2095-9389.2020.07.21.004

江羽^{1, 2},
王倩^2, ,,
王冬¹,
趙彤²

1.
北京科技大學材料科學與工程學院，北京 100083
2.
中國科學院化學研究所，中國科學院極端環境高分子材料重點實驗室，北京 100190

基金項目: 中國科學院化學研究所創新培育項目（CXPY-17）

詳細信息

通訊作者:
E-mail: wangqian@iccas.ac.cn

中圖分類號: TQ316.3
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- 文章訪問數: 1748
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- 被引次數: 0
出版歷程
- 收稿日期: 2020-07-21
- 刊出日期: 2021-01-25

Research progress of high-temperature phase change energy storage microcapsules

JIANG Yu^{1, 2},
WANG Qian^{2
, ,},
WANG Dong¹,
ZHAO Tong²

1.
School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
Key Laboratory of Science and Technology on High-tech Polymer Materials, Chinese Academy of Sciences, Beijing 100190, China

More Information

Corresponding author: E-mail: wangqian@iccas.ac.cn

摘要

摘要: 相變材料的微膠囊化能解決相變材料在相變過程中的熔融滲出問題，提高相變材料的環境適應性、拓展其應用。本文主要對300 ℃以上的高溫相變微膠囊材料的制備及其應用進行闡述，主要論述了相變材料的分類，微膠囊的合成方法，以及高溫微膠囊的研究現狀。且通過研究表明，具有高熔點、高焓值的氟化物微膠囊是一種非常有應用前景的相變材料。
- 相變材料 /
- 高溫 /
- 微膠囊 /
- 儲能 /
- 熱防護 /
- 熱管理
Abstract: In today’s world, global problems such as a shortage of fossil fuel energy, environmental pollution, and global warming are becoming increasingly serious. For the development of human society, sustainability is particularly important. Energy is the basis for human survival and promotes the development of human society. However, rapid growth in population and the global economy has led to a significant increase in energy demand. At the same time, extensive use of fossil fuels has polluted the environment and led to a shortage of fossil energy. Currently, with the continuous increase in energy consumption and development of human society, there is a pressing need to develop energy storage technology. Latent heat storage, using phase change materials that play a vital role in the field of energy storage, has been widely accepted as an effective way to improve heat energy utilization. Phase change materials provide a type of thermal energy storage that can store a large amount of latent heat through physical phase change. This heat is then released in a controlled manner within a small temperature change based on thermal energy requirements. At present, phase change materials have important applications in aerospace, industrial and agricultural production, building materials, energy and power, textile materials, highway transportation, and engine technology. Most current research on phase change materials focuses on medium- and low-temperature materials, especially those materials whose phase change temperature is lower than 100 ℃. There is less research on high-temperature phase change materials owing to the encapsulation and corrosion of such materials. The problem of performance is difficult to solve, yet high temperature phase change materials are in urgent need in some extreme high temperature environments. High-temperature phase change materials (HTPCM) can control thermal energy under extremely high temperatures. They have important prospects for application in the fields of thermal protection and thermal management in high-temperature environments such as aerospace, solar energy, etc. The microencapsulation of phase change materials can solve the problem of melt exudation of these materials during the phase change process, improve the environmental adaptability of these materials, and expand their applications. This article mainly reviewed the preparation and application of HTPCM above 300 ℃. The classification of phase change materials, the method of synthesis of microcapsules, and the preparation of high temperature microcapsules were discussed. Through research, it is found that fluoride microcapsules, with their high melting point and enthalpy value, are a promising material in the field of HTPCMs.
- phase change materials /
- high temperature /
- microcapsules /
- energy storage /
- thermal protection /
- thermal management

HTML全文

圖 1 相變材料的相變溫度(T_m)與焓值(ΔH)圖

Figure 1. Diagram of phase change temperature (T_m) and enthalpy (ΔH) of phase change materials

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圖 2 SEM圖像顯示通過勃姆石涂層和1130 ℃的熱氧化處理組合制備的MEPCM的表面形態（a～c）和橫截面（d）^[39]

Figure 2. SEM images showing the surface morphology (a–c) and cross-section (d) of the MEPCM prepared by the combination of boehmite coating and heat oxidation treatment at 1130 ℃^[39]

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圖 3 金屬包殼高溫相變儲熱微膠囊的光學顯微圖^[43]

Figure 3. Optical micrograph of metal cladding high-temperature phase change heat storage microcapsules^[43]

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圖 4 高溫加熱之前和之后的NaNO₃（a）、（b）、（e）、（f）和MCP-NaNO₃（c）、（d）、（g）、（h）的照片圖像和顯微圖像^[47]

Figure 4. Photo images and micrograph images of NaNO₃ (a)(b)(e)(f), and MCP-NaNO₃ (c)(d)(g)(h) before and after heating at high temperature^[47]

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圖 5 加熱后的微膠囊的SEM照片。（a）將沒有GO防腐蝕防漏層的LiF @ PDA @ SiO₂微膠囊從35 ℃加熱至1000 ℃；（b）將沒有SiO₂耐熱強度層的LiF @ PDA @ GO微膠囊從35 ℃加熱到1000 ℃；（c）將LiF @ GO @ SiO₂微囊從35 ℃加熱到1000 ℃；（d）從35 ℃到900 ℃進行10次熱重循環后，LiF @ GO @ SiO₂微膠囊^[50]

Figure 5. SEM micrographs of microcapsules after heating: (a) LiF@PDA@SiO₂ microcapsules without GO anti-corrosion leakage-proof layer being heated from 35 ℃ to 1000 ℃; (b) LiF@PDA@GO microcapsules without SiO₂ heat-resistant strength layer being heated from 35 ℃ to 1000 ℃; (c) LiF@GO@SiO₂ microcapsules being heated from 35 ℃ to 1000 ℃; (d) LiF@GO@SiO₂ microcapsules after thermo-gravimetric circulation 10 times from 35 ℃ to 900 ℃^[50]

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圖 6 1050~1150 ℃ 220次充放電循環后銅膠囊橫截面形態的SEM圖像^[52]

Figure 6. SEM image of the cross-sectional morphology of the copper capsule after 220 charge–discharge cycles from 1050–1150 ℃^[52]

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表 1 高溫相變材料的熔點和焓值

Table 1. Melting temperature and heat of fusion of high-temperature phase change materials

Material	Melting temperature / ℃	Heat of fusion / (J·g^–1)	Material	Melting temperature / ℃	Heat of fusion / (J·g^–1)
NaNO₃	307	172	Mg	651	372.6
RbNO₃	312	31	Al	660.1	393.6
Cd	320.9	54	FeCl₂	677	337.9
NaOH	323	170	LiH	688	2678
KNO₃	333	266	Li₂MoO₄	703	281
Zn/Mg（52/48）	340	180	MgCl₂	714	454
KOH	380	149.7	Li₂CO₃	732	509
Zn/Al（96/4）	381	138	K	759	60.7
CsNO₃	409	71	KCl	771	353
Zn	419	113	NaCl	800	492
AgBr	432	48.8	LiBO₂	845	504.7
Mg/Cu/Zn（60/25/15）	452	254	LiF	848	1080
LiI	458	109	Cu/P/Si(83/10/7)	840	92
LiOH	462	433.4	Na₂CO₃	854	275.7
PbCl₂	501	78.7	KF	857	452
Al/Cu/Mg/Zn(54/22/18/6)	520	305	ZnF₂	872	400
SrI₂	527	57	K₂CO₃	897	235.8
Al/Cu(66.92/33.08)	548	372	Si/Mg(56/44)	946	757
LiBr	550	203	NaF	996	794
Ca(NO₃)₂	560	145	NaMgF₃	1022	670
Al/Cu/Si(65/30/5)	571	422	KCaF₃	1070	460
Ba(NO₃)₂	594	209	KMgF₃	1072	710
Sr(NO₃)₂	608	221	Cu	1083	205.2
LiCl	610	441	Na₂SiO₃	1088	424
CsI	629	96	MgF₂	1263	930
MgI₂	633	93	CaF₂	1418	391
CsBr	638	105	CaSO₄	1460	203
RbI	646	104	Fe	1535	314
SrBr₂	650	41	SrSO₄	1605	196

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參考文獻(56)

[1]	Dresselhaus M S, Thomas I L. Alternative energy technologies. Nature, 2001, 414(6861): 332 doi: 10.1038/35104599
[2]	Zalba B, Marin J M, Cabeza L F, et al. Review on thermal energy storage with phase change: materials, heat transfer analysis and applications. Appl Therm Eng, 2003, 23(3): 251 doi: 10.1016/S1359-4311(02)00192-8
[3]	Tuncbilek K, Sari A, Tarhan S, et al. Lauric and palmitic acids eutectic mixture as latent heat storage material for low temperature heating applications. Energy, 2005, 30(5): 677 doi: 10.1016/j.energy.2004.05.017
[4]	Tan F L, Tso C P. Cooling of mobile electronic devices using phase change materials. Appl Therm Eng, 2004, 24(2-3): 159 doi: 10.1016/j.applthermaleng.2003.09.005
[5]	Mondal S. Phase change materials for smart textiles–an overview. Appl Therm Eng, 2008, 28(11-12): 1536 doi: 10.1016/j.applthermaleng.2007.08.009
[6]	Alva G, Lin Y X, Liu L K, et al. Synthesis, characterization and applications of microencapsulated phase change materials in thermal energy storage: a review. Energy Build, 2017, 144: 276 doi: 10.1016/j.enbuild.2017.03.063
[7]	Schossig P, Henning H M, Gschwander S, et al. Micro-encapsulated phase-change materials integrated into construction materials. Sol Energy Mater Sol Cells, 2005, 89(2-3): 297 doi: 10.1016/j.solmat.2005.01.017
[8]	Zhang X X, Tao X M, Yick K L, et al. Structure and thermal stability of microencapsulated phase change materials. Colloid Polym Sci, 2004, 282(4): 330 doi: 10.1007/s00396-003-0925-y
[9]	Sari A, Alkan C, Karaipekli A, et al. Micro-encapsulated n-octacosane as phase change material for thermal energy storage. Sol Energy, 2009, 83(10): 1757 doi: 10.1016/j.solener.2009.05.008
[10]	De Luca M, Ferraro M M, Hartmann R, et al. Advances in use of capsule-based fluorescent sensors for measuring acidification of endocytic compartments in cells with altered expression of V-ATPase subunitV₁G₁. ACS Appl Mater Interfaces, 2015, 7(27): 15052 doi: 10.1021/acsami.5b04375
[11]	Guo P J, Weimer M S, Emery J D, et al. Conformal coating of a phase change material on ordered plasmonic nanorod arrays for broadband all-optical switching. ACS Nano, 2017, 11(1): 693 doi: 10.1021/acsnano.6b07042
[12]	Ling Z Y, Zhang Z G, Shi G Q, et al. Review on thermal management systems using phase change materials for electronic components, Li-ion batteries and photovoltaic modules. Renew Sust Energ Rev, 2014, 31: 427 doi: 10.1016/j.rser.2013.12.017
[13]	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. Appl Energ, 2015, 160: 286 doi: 10.1016/j.apenergy.2015.09.016
[14]	Zhong Y J, Zhao B C, Lin J, et al. Encapsulation of high-temperature inorganic phase change materials using graphite as heat transfer enhancer. Renew Energ, 2019, 133: 240 doi: 10.1016/j.renene.2018.09.107
[15]	Liu M, Bell S, Segarra M, et al. A eutectic salt high temperature phase change material: Thermal stability and corrosion of SS316 with respect to thermal cycling. Sol Energy Mater Sol Cells, 2017, 170: 1 doi: 10.1016/j.solmat.2017.05.047
[16]	Jiang Y F, Sun Y P, Bruno F, et al. Thermal stability of Na₂CO₃?Li₂CO₃ as a high temperature phase change material for thermal energy storage. Thermochim Acta, 2017, 650: 88 doi: 10.1016/j.tca.2017.01.002
[17]	Huang Z W, Xie N, Luo Z G, et al. Characterization of medium-temperature phase change materials for solar thermal energy storage using temperature history method. Sol Energy Mater Sol Cells, 2018, 179: 152 doi: 10.1016/j.solmat.2017.11.006
[18]	Kenisarin M M. High-temperature phase change materials for thermal energy storage. Renew Sust Energ Rev, 2010, 14(3): 955 doi: 10.1016/j.rser.2009.11.011
[19]	Hoshi A, Mills D R, Bittar A, et al. Screening of high melting point phase change materials (PCM) in solar thermal concentrating technology based on CLFR. Sol Energy, 2005, 79(3): 332 doi: 10.1016/j.solener.2004.04.023
[20]	Nazir H, Batool M, Osorio F J B, et al. Recent developments in phase change materials for energy storage applications: a review. Int J Heat Mass Transfer, 2019, 129: 491 doi: 10.1016/j.ijheatmasstransfer.2018.09.126
[21]	Nardin G, Meneghetti A, Dal Magro F, et al. PCM-based energy recovery from electric arc furnaces. Appl Energ, 2014, 136: 947 doi: 10.1016/j.apenergy.2014.07.052
[22]	Fukahori R, Nomura T, Zhu C Y, et al. Thermal analysis of Al–Si alloys as high-temperature phase-change material and their corrosion properties with ceramic materials. Appl Energ, 2016, 163: 1 doi: 10.1016/j.apenergy.2015.10.164
[23]	Sun J Q, Zhang R Y, Liu Z P, et al. Thermal reliability test of Al–34% Mg–6% Zn alloy as latent heat storage material and corrosion of metal with respect to thermal cycling. Energy Convers Manage, 2007, 48(2): 619 doi: 10.1016/j.enconman.2006.05.017
[24]	Maruoka N, Akiyama T. Exergy recovery from steelmaking off-gas by latent heat storage for methanol production. Energy, 2006, 31(10-11): 1632 doi: 10.1016/j.energy.2005.05.023
[25]	Jiang Y F, Sun Y P, Liu M, et al. Eutectic Na₂CO₃–NaCl salt: a new phase change material for high temperature thermal storage. Sol Energy Mater Sol Cells, 2016, 152: 155 doi: 10.1016/j.solmat.2016.04.002
[26]	Jacob R, Liu M, Sun Y P, et al. Characterisation of promising phase change materials for high temperature thermal energy storage. J Energy Storage, 2019, 24: 100801 doi: 10.1016/j.est.2019.100801
[27]	Misra A K, Whittenberger J D. Fluoride salts and container materials for thermal energy storage applications in the temperature range 973 to 1400 K // 22nd Intersociety Energy Conversion Engineering Conference. Philadelphia, Pennsylvania, 1987: 188
[28]	Lund K O. Analysis of radiative and phase-change phenomena with application to space-based thermal energy storage. NASA Rep, 1991: 92
[29]	Shi T J, Hu P, Wang J T. Preparation of polyurea microcapsules containing phase change materials using microfluidics. Chem Select, 2020, 5(7): 2342
[30]	Feng L, Dong S P, Zhou H. n-Dodecanol nanocapsules with supramolecular lock shell layer for thermal energy storage. Chem Eng J, 2020, 389: 124483 doi: 10.1016/j.cej.2020.124483
[31]	Xu R, Xia X M, Wang W, et al. Infrared camouflage fabric prepared by paraffin phase change microcapsule with Good thermal insulting properties. Colloids Surf A, 2020, 591: 124591
[32]	Sahan N, Paksoy H. Designing behenic acid microcapsules as novel phase change material for thermal energy storage applications at medium temperature. Int J Energy Res, 2020, 44(5): 3922 doi: 10.1002/er.5193
[33]	Wang X G, Chen Z F, Xu W, et al. Capric acid phase change microcapsules modified with graphene oxide for energy storage. J Mater Sci, 2019, 54(24): 14834 doi: 10.1007/s10853-019-03954-2
[34]	Zhang H Z, Wang X D, Wu D Z. Silica encapsulation of n-octadecane via sol-gel process: a novel microencapsulated phase-change material with enhanced thermal conductivity and performance. J Colloid Interf Sci, 2010, 343(1): 246 doi: 10.1016/j.jcis.2009.11.036
[35]	Liu Z F, Chen Z H, Yu F. Preparation and characterization of microencapsulated phase change materials containing inorganic hydrated salt with silica shell for thermal energy storage. Sol Energy Mater Sol Cells, 2019, 200: art. No. 110004 doi: 10.1016/j.solmat.2019.110004
[36]	He F, Wang X D, Wu D Z. New approach for sol-gel synthesis of microencapsulated n-octadecane phase change material with silica wall using sodium silicate precursor. Energy, 2014, 67: 223 doi: 10.1016/j.energy.2013.11.088
[37]	Li F N, Wang X D, Wu D Z. Fabrication of multifunctional microcapsules containing n-eicosane core and zinc oxide shell for low-temperature energy storage, photocatalysis, and antibiosis. Energy Convers Manage, 2015, 106: 873 doi: 10.1016/j.enconman.2015.10.026
[38]	Sakai H, Sheng N, Kurniawan A, et al. Fabrication of heat storage pellets composed of microencapsulated phase change material for high-temperature applications. Appl Energ, 2020, 265: 114673 doi: 10.1016/j.apenergy.2020.114673
[39]	Nomura T, Sheng N, Zhu C Y, et al. Microencapsulated phase change materials with high heat capacity and high cyclic durability for high-temperature thermal energy storage and transportation. Appl Energ, 2017, 188: 9 doi: 10.1016/j.apenergy.2016.11.025
[40]	He F, Chao S, He X D, et al. Inorganic microencapsulated core/shell structure of Al?Si alloy micro-particles with silane coupling agent. Ceram Int, 2014, 40(5): 6865 doi: 10.1016/j.ceramint.2013.12.006
[41]	Nomura T, Zhu C Y, Sheng N, et al. Microencapsulation of metal-based phase change material for high-temperature thermal energy storage. Sci Rep, 2015, 5: 9117 doi: 10.1038/srep09117
[42]	Zhang M J, Han Z J, Gu H Z, et al. High Temperature Phase Change Thermal Storage Microcapsule of Dense Alumina Shell and Its Preparation Method: China Patent, CN201810202184.8. 2018-08-10 張美杰, 韓藏娟, 顧華志, 等. 致密氧化鋁殼層高溫相變蓄熱微膠囊及其制備方法: 中國專利, CN201810202184.8. 2018-08-10
[43]	Zhang F, Lin J, Yang X, et al. The Invention Relates to a Method for Preparing Metal Coated High-Temperature Phase Change Thermal Storage Microcapsule and the Thermal Storage Microcapsule Obtained Therefrom: China Patent, CN201811197058.4. 2019-02-12 張鋒, 林俊, 楊旭, 等. 一種制備金屬包殼高溫相變儲熱微膠囊的方法以及由此得到的儲熱微膠囊: 中國專利, CN201811197058.4. 2019-02-12
[44]	Yang Z Z, Zhang X, Wang Q. Metal and Alloy Phase Change Energy Storage Microcapsules and Their Preparation Methods: China Patent, CN201710129236.9. 2017-07-04 楊振忠, 張行, 王倩. 金屬及合金相變儲能微膠囊及其制備方法: 中國專利, CN201710129236.9. 2017-07-04
[45]	Li J F, Lu W, Luo Z P, et al. Thermal stability of sodium nitrate microcapsules for high-temperature thermal energy storage. Sol Energy Mater Sol Cells, 2017, 171: 106 doi: 10.1016/j.solmat.2017.06.028
[46]	Takai-Yamashita C, Shinkai I, Fuji M, et al. Effect of water soluble polymers on formation of Na₂SO₄ contained SiO₂ microcapsules by W/O emulsion for latent heat storage. Adv Powder Technol, 2016, 27(5): 2032 doi: 10.1016/j.apt.2016.07.012
[47]	Li J F, Lu W, Luo Z P, et al. Synthesis and thermal properties of novel sodium nitrate microcapsules for high-temperature thermal energy storage. Sol Energy Mater Sol Cells, 2017, 159: 440 doi: 10.1016/j.solmat.2016.09.051
[48]	Li J F, Luo Z P, Sun L L. The Invention Relates to an Inorganic Salt High-Temperature Phase Change Microcapsule and A Preparation Method Thereof: China Patent, CN201811091919.0. 2018-12-21 李俊峰, 羅正平, 孫理理. 一種無機鹽高溫相變微膠囊及其制備方法: 中國專利, CN201811091919.0. 2018-12-21
[49]	Li J F, Luo Z P, Wang M, et al. The Invention Relates to A Phase Change Thermal Control Coating and A Preparation Method Thereof: China Patent, CN201910569905.3. 2019-11-05 李俊峰, 羅正平, 王萌, 等. 一種相變熱控涂層及其制備方法: 中國專利, CN201910569905.3. 2019-11-05
[50]	Liu J, Li J F, Luo Z P, et al. A novel multiwalled LiF@GO@SiO₂ microcapsule with high phase change temperature. Sol Energy Mater Sol Cells, 2019, 203: art. No. 110188 doi: 10.1016/j.solmat.2019.110188
[51]	Zhang Q Y, Liu J, Liu Y B, et al. A Kind of High Temperature and High Enthalpy Phase Change Material Multi-Wall Microcapsule and Its Preparation Method: China Patent, CN201910483692.2. 2019-08-16 張秋禹, 劉錦, 劉毅彬, 等. 一種高溫高焓值相變材料多壁結構微膠囊及制備方法: 中國專利, CN201910483692.2. 2019-08-16
[52]	Zhang G C, Li J Q, Chen Y F, et al. Encapsulation of copper-based phase change materials for high temperature thermal energy storage. Sol Energy Mater Sol Cells, 2014, 128: 131 doi: 10.1016/j.solmat.2014.05.012
[53]	He F, Song G P, He X D, et al. Structural and phase change characteristics of inorganic microencapsulated core/shell Al-Si/Al₂O₃ micro-particles during thermal cycling. Ceram Int, 2015, 41(9): 10689 doi: 10.1016/j.ceramint.2015.05.001
[54]	Sheng N, Zhu C Y, Sakai H, et al. Synthesis of Al–25 wt% Si@Al₂O₃@Cu microcapsules as phase change materials for high temperature thermal energy storage. Sol Energy Mater Sol Cells, 2019, 191: 141 doi: 10.1016/j.solmat.2018.11.013
[55]	Wang X F, Li C H, Zhao T. Fabrication and characterization of poly(melamine-formaldehyde)/silicon carbide hybrid microencapsulated phase change materials with enhanced thermal conductivity and light-heat performance. Sol Energy Mater Sol Cells, 2018, 183: 82 doi: 10.1016/j.solmat.2018.03.019
[56]	Liao H H, Chen W H, Liu Y, et al. A phase change material encapsulated in a mechanically strong graphene aerogel with high thermal conductivity and excellent shape stability. Compos Sci Technol, 2020, 189: 108010 doi: 10.1016/j.compscitech.2020.108010