Research progress of sodium sulfate decahydrate phase changematerial

doi:10.19799/j.cnki.2095-4239.2021.0007

Abstract

Abstract:

Sodium sulfate decahydrate is a popular inorganic hydrated salt phase change material because of its suitable phase change temperature (32.4 ℃), high latent heat of phase change value (>200 J/g), low price, wide source, safety and non-toxicity. However, there are problems such as large subcooling, severe phase separation and leakage in the application process. This paper reviews the research progress in recent years to solve the above problems, the preparation of eutectic salt phase change materials and related applications, and makes the following outlook on the subsequent research directions: in terms of reducing the subcooling degree, use of borax, preparation of eutectic salts or addition of external field perturbation to improve subcooling; in terms of suppressing phase separation, highly thermally conductive porous materials can be used to adsorb phase change materials, and the method of preparing stereotyped phase change materials by vacuum impregnation can be used to improve or eliminate the phase separation phenomenon; in terms of eutectic salt materials, binary phase diagrams can be drawn to find new eutectic phase change materials for research, especially organic phase change materials that are currently less combined; in terms of applications, focus on researching and broadening the scope of application in conjunction with sodium decahydrate sulfate phase change energy storage devices and systems.

Key words: sodium sulfate decahydrate, supercooling, phase separation, form-stable phase-change materials, eutectic salt

CLC Number:

TQ 050.4

Caimei YU, Xuelai ZHANG, Weisan HUA. Research progress of sodium sulfate decahydrate phase changematerial[J]. Energy Storage Science and Technology, 2021, 10(3): 1016-1024.

Figures/Tables 6

Table 1

Fig. 1

Table 2

Fig. 2

Fig. 3

Fig. 4

References 57

1	GOODMAN J. Researching climate crisis and energy transitions: Some issues for ethnography[J]. Energy Research & Social Science, 2018, 45: 340-347.
2	WAQAS A, DIN Z U. Phase change material (PCM) storage for free cooling of buildings—A review[J]. Renewable and Sustainable Energy Reviews, 2013, 18: 607-625.
3	GUNDERSON R, STUART D, PETERSEN B. The fossil fuel industry's framing of carbon capture and storage: Faith in innovation, value instrumentalization, and status quo maintenance[J]. Journal of Cleaner Production, 2020, doi: 10.1016/j.jclepr o.2019.119767.
4	FERRER G, BARRENECHE C, SOLÉ A, et al. New proposed methodology for specific heat capacity determination of materials for thermal energy storage (TES) by DSC[J]. Journal of Energy Storage, 2017, 11: 1-6.
5	BOUHAL T, EL RHAFIKI T, KOUSKSOU T, et al. PCM addition inside solar water heaters: Numerical comparative approach[J]. Journal of Energy Storage, 2018, 19: 232-246.
6	BARRENECHE C, ELENA N M, CABEZA L F, et al. New database to select phase change materials: Chemical nature, properties, and applications[J]. Journal of Energy Storage, 2015, 3: 18-24.
7	AGYENIM F, HEWITT N, EAMES P, et al. A review of materials, heat transfer and phase change problem formulation for latent heat thermal energy storage systems (LHTESS)[J]. Renewable and Sustainable Energy Reviews, 2010, 14(2): 615-628.
8	LI Y, DING Z, DU Y. Techno-economic optimization of open-air swimming pool heating system with PCM storage tank for winter applications[J]. Renewable Energy, 2020, 150: 878-890.
9	HARIKRISHNAN S, DEENADHAYALAN M, KALAISELVAM S. Experimental investigation of solidification and melting charac teristics of composite PCMs for building heating application[J]. Energy Conversion and Management, 2014, 86: 864-872.
10	HUANG R, LI Z, HONG W, et al. Experimental and numerical study of PCM thermophysical parameters on lithium-ion battery thermal management[J]. Energy Reports, 2020, 6: 8-19.
11	FONSECA A, MAYOR T S, CAMPOS J B. Guidelines for the specification of a PCM layer in firefighting protective clothing ensembles[J]. Applied Thermal Engineering, 2018, 133: 81-96.
12	蔡作乾. 陶瓷材料辞典[M]. 北京: 化学工业出版社, 2002.
13	马江生.相变储热材料——Na₂SO₄·10H₂O的研制[J]. 海湖盐与化工, 1994, 23(1): 37-39.
	MA J S. Phase change heat storage material—Preparation of Na₂SO₄·10H₂O[J]. Journal of Salt Science and Chemical Industry, 1994, 23(1): 37-39.
14	张寅平. 相变贮能: 理论和应用[M]. 合肥: 中国科学技术大学出版社, 1996.
15	杨绪强, 潘毅, 封银平, 等. 十水硫酸钠低共熔混合物储热的实验研究[J]. 太阳能学报,1982(2): 212-215.
	YAN X Q, PAN Y, FENG Y P, et al. Experimental study on heat storage of low eutectic mixture of sodium sulfate decahydrate[J]. Acta Energiae Solaris Sinica, 1982(2): 212-215.
16	张仁元. 相变材料与相变储能技术[M]. 北京: 科学出版社, 2009.
17	丁益民, 阎立诚. 水合盐储热材料的成核作用[J]. 化学物理学报, 1996(1): 83-86.
	DING Y M, YAN L C. Nucleation of salt-hydrates as the thermal energy storage material[J]. Chinese Journal of Chemical Physics, 1996(1): 83-86.
18	TELKES M. Nucleation of supersaturated inorganic salt solutions[J]. Industrial and Engineering Chemistry, 1952, 44(6): 1308-1310.
19	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(sup5): S5-972-S5-977.
20	HOU P, MAO J, CHEN F, et al. Preparation and thermal performance enhancement of low temperature eutectic composit e phase change materials based on Na₂SO₄·10H₂O[J]. Materials, 2018, 11(11): doi: 10.3390/ma11112230.
21	DONG X, MAO J F, GENG S B, et al. Study on performance optimization of sodium sulfate decahydrate phase change energy storage materials[J]. Journal of Thermal Analysis and Calorimetry, 2021, 143(6): 3923-3934.
22	李凤艳, 王鹏, 袁亚东, 等. 相变温度为室温的Na₂SO₄·10H₂O相变储热材料的制备研究[J]. 合成材料老化与应用, 2015, 44(1): 39-41, 46.
	LI F Y, WANG P, YUAN Y D, et al. The preparation of phase change material Na₂SO₄·10H₂O with the phase transition temperature at room temperature[J]. Synthetic Materials Aging and Application, 2015, 44(1): 39-41, 46.
23	柳馨, 铁健, 铁生年. 纳米粉体对Na₂SO₄·10H₂O过冷及相分层现象的影响[J]. 人工晶体学报, 2015, 44(11): 3072-3078.
	LIU X, TIE J, TIE S N. Effect of nano powder addition on the subcooling and phase stratification of sodium sulfate decahydrate[J]. Journal of Synthetic Crystals, 2015, 44(11): 3072-3078.
24	BISWAS D R. Thermal energy storage using sodium sulfate decahydrate and water[J]. Solar Energy, 1977, 19: 99-100.
25	徐玲玲, 沈艳华, 梁斌斌, 等. Na₂SO₄·10H₂O和Na₂HPO₄·12H₂O体系的相变特性[J]. 南京工业大学学报(自然科学版), 2005, 27(4): 27-31.
	XU L L, SHEN Y H, LIANG B B, et al. Study on phase transfer characteristics of systems Na₂SO₄·10H₂O and Na₂HPO₄·12H₂O[J]. Journal of Nanjing University of Technology (Natural Science Edition), 2005, 27(4): 27-31.
26	汪意, 杨睿, 张寅平, 等. 定形相变材料的研究进展[J]. 储能科学与技术, 2013, 2(4): 362-368.
	WANG Y, YANG R, ZHANG Y P, et al. Recent progress in shape-stabilized phase change materials[J]. Energy Storage Science and Technology, 2013, 2(4): 362-368.
27	刘欣, 徐涛, 高学农, 等. 十水硫酸钠的过冷和相分离探究[J]. 化工进展, 2011, 30(S1): 755-758.
	LIU X, XU T, GAO X N, et al. Study on supercooling and phase separation of Na₂SO₄·10H₂O[J]. Chemical Industry Engineering Progress, 2011, 30(S1): 755-758.
28	刘欣. 十水硫酸钠相变蓄热材料的改性及其在模拟机房中的应用[D]. 广州: 华南理工大学, 2013.
29	李凤艳, 袁亚东, 杨雅君, 等. 相变储能材料在建筑节能材料上的应用研究[J]. 新型建筑材料, 2014, 41(7): 87-91.
	LI F Y, YUAN Y D, YANG Y J, et al. Study and application of phase change materials on building energy conservation materials[J]. New Building Materials, 2014, 41(7): 87-91.
30	卢铁梅, 朱紫璇, 胡湖, 等. 聚丙烯酸钠/十水合硫酸钠复合相变材料[J]. 功能高分子学报, 2020, 33(2): 157-164.
	LU T M, ZHU Z X, HU H, et al. Sodium polyacrylate/sodium sulfate decahydrate phase change composites[J]. Journal of Functional Polymers, 2020, 33(2): 157-164.
31	OH K, KWON S, XU W Y, et al. Effect of micro- and nanofibrillated cellulose on the phase stability of sodium sulfate decahydrate based phase change material[J]. Cellulose, 2020, 27(9): 5003-5016.
32	LI C, ZHANG B, XIE B, et al. Tailored phase change behavior of Na₂SO₄·10H₂O/expanded graphite composite for thermal energy storage[J]. Energ Convers Manage, 2020, doi: 10.1016/j.enconman.2020.112586.
33	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.
34	汤瑜凤. 十水硫酸钠—十二水磷酸氢二钠室温共晶盐定形复合吸附剂的微波复合相变材料的制备及性能研究[D]. 广州: 华南理工大学, 2019.
35	FANG Y, SU J, TANG Y, et al. Form-stable Na₂SO₄·10H₂O-Na₂HPO₄·12H₂O eutectic/hydrophilic fumed silica composite pha se change material with low supercooling and low thermal conductivity for indoor thermal comfort improvement[J]. International Journal of Energy Research, 2020, 44 (4): 3171-3182.
36	ZHANG Z, LIAN Y, XU X, et al. Synthesis and characterization of microencapsulated sodium sulfate decahydrate as phase change energy storage materials[J]. Applied Energy, 2019, 255: doi: 10.1016/j.apenergy.2019.113830.
37	WANG Y, GE S, HUANG B, et al.A simple route to PVC encapsulated Na₂SO₄·10H₂O nano/micro-composite with excellent energy storage performance[J]. Materials Chemistry and Physics, 2019, 223: 723-726.
38	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[J]. Advanced Powder Technology, 2016, 27(5): 2032-2038.
39	PUROHIT B K, SISTLA V S. Studies on solution crystallization of Na₂SO₄·10H₂O embedded in porous polyurethane foam for thermal energy storage application[J]. Thermochimica Acta, 2018, 668: 9-18.
40	WANG T, WU N, LI H, et al. Preparation and properties of a form-stable phase-change hydrogel for thermal energy storage[J]. Journal of Applied Polymer Science, 2016, 133 (34): doi: 10.1002/app.43836.
41	XIE N, LUO J, LI Z, et al. Salt hydrate/expanded vermiculite composite as a form-stable phase change material for building energy storage[J]. Solar Energy Materials and Solar Cells, 2019, 189: 33-42.
42	KARTHICK A, KALIDASA M K, GHOSH A, et al. Investigation of a binary eutectic mixture of phase change material for building integrated photovoltaic (BIPV) system[J]. Solar Energy Materials and Solar Cells, 2020, 207: doi: 10.1016/j.solmat.2019.110360.
43	XIAO L, ZHAO M. Modification and secondary packaging of Na₂SO₄·10H₂O[J]. Earth and Environmental Science, 2017, 81: doi: 10.1088/1755-1315/81/1/012032.
44	ZHENG M, XIE C, LIU J, et al. Composite hydrate salt Na₂HPO₄·12H₂O-Na₂SO₄·10H₂O and its thermal storage properties[J]. Emerging Materials Research, 2019, 8 (1): 68-76.
45	路丽婷. 七水硫酸镁/十水硫酸钠复合相变储热复合材料的性能分析[D]. 西安: 西北大学, 2018.
46	罗建文. MgSO₄-Na₂SO₄、KAl(SO₄)₂-Na₂SO₄水合盐相变储热材料优化及在太阳能蓄热器中的应用[D]. 西安: 西北大学, 2017.
47	ZHENG M, LUO J W, ZHANG Y H, et al. Preparation and characterization of composite material Na₂SO₄·10H₂O-KAl(SO₄)₂·12H₂O for thermal storage[J]. Materials Science and Engineering, 2017, 167: doi: 10.1088/1757-899X/167/1/012007.
48	LIU Y, LIU W, ZHANG S, et al. Preparation and characterization of new nano-particle mixed as thermal storage material[J]. Applied Thermal Engineering, 2019, 163: doi: 10.1016/j.applthermaleng.2019.114386.
49	孙相宇. 混合无机水合盐储热性能及其定型相变墙体的研究[D]. 北京: 北京建筑大学, 2018.
50	TAYEB A M. Organic-inorganic mixtures for solar energy storage systems[J]. Energy Conversion and Management, 1995, 36(10): 969-974.
51	NDUKWU M C, BENNAMOUN L, ABAM F I, et al. Energy and exergy analysis of a solar dryer integrated with sodium sulfate decahydrate and sodium chloride as thermal storage medium[J]. Renewable Energy, 2017, 113: 1182-1192.
52	蒋自鹏, 铁生年. 芒硝基相变材料性能及其在简易温室中升温效果试验[J]. 农业工程学报, 2016, 32(20): 209-216.
	JIANG Z P, TIE S N. Property and heat storage performances of Glauber's salt-based phase change materials for solar greenhouse in Qinghai-Tibet plateau[J]. Transaction of the Chinese Society of Agriculture Engineering, 2016, 32(20): 209-216.
53	徐燕, 刘伟, 于观成, 等. 十水硫酸钠储热材料在农业大棚中的应用[J]. 郑州轻工业学院学报(自然科学版), 2011, 26(2): 98-100,110.
	XU Y, LIU W, YU G C, et al. Application of Na₂SO₄·10H₂O thermal energy storage materials in the vegetable greenhouse[J]. Journal of Zhengzhou University of Light Industry (Natural Science Edition), 2011, 26(2): 98-100,110.
54	韩丽蓉. 相变蓄热材料十水硫酸钠的改性及应用研究[D]. 杨凌: 西北农林科技大学, 2014.
55	鲁义, 刘艺伦, 施式亮, 等. 用于消防服的无机相变材料改进试验研究[J]. 中国安全科学学报, 2020, 30(8): 171-176.
	LU Y, LIU Y L, SHI S L, et al. Improvement experiments on inorganic phase change material for fire-fighting clothing[J]. China Safety Science Journal, 2020, 30(8): 171-176.
56	徐笑锋, 章学来, MUNYALO J M, 等. 十水硫酸钠相变蓄冷保温箱保冷特性的试验研究[J]. 农业工程学报, 2017, 33(22): 308-314.
	XU X F, ZHANG X L, JOTHAM M, et al. Experimental study on cold retention characteristics of cold storage incubator using Na₂SO₄·10H₂O as PCMs[J]. Transactions of the Chinese Society of Agricultural Engineering, 2017, 33(22): 308-314.
57	ALKAN C, DÖĞÜŞCÜ D K, GOTTSCHALK A, et al. Polyvinyl alcohol-salt hydrate mixtures as passive thermal energy storage systems[J]. Energy Procedia, 2016, 91: 1012-1017.

熔点/℃	相变潜热值 /J?g^-1	固体导热系数 /W?( m?℃)^-1	固相比热容 /kJ?(kg?K)^-1	参考文献
32.4	251.2	0.5	—	[13]
32.4	241	0.544	1.7	[14]

十水硫酸钠相变储热体系 (不同增稠剂体系)	体系增稠效果 (关于使用效果的描述)
丙烯酸系	收集产品后，静置，1 h后明显分层
聚丙烯酸系	收集产品后，静置，5 h后明显分层，效果不理想
丙烯酰胺系	不同时间取样，48 h后普遍有沉淀现象出现
聚丙烯酸/丙烯酰胺系	不同质量配比，收集产品静置，短时间内没有明显分层，能一定程度上解决分层现象，经熔冻循环后比较容易分层
丙烯酸/丙烯酰胺系	没有黏稠感，分层，效果不理想
聚丙烯酸/聚丙烯酰胺系	刚收集的样品外观上浓稠均匀，经熔冻循环后易分层
明胶系	明胶难溶解，收集产品放置，溶液上下层不均匀，上层液稍清，下层黏稠，第二天明显分层
CMC 系	收集产品放置稳定，经熔冻循环后轻微分层
聚丙烯酰胺系	样品外观上浓稠、均匀，经熔冻循环后不分层，比较理想
可溶性淀粉系	放置几天不分层，经熔冻循环后微微分层
蔗糖系	不稳定，静置几天后出现分层
活性白土系	样品均匀黏稠，经熔冻循环后不分层

[1]	FENG Jinxin, LING Ziye, FANG Xiaoming, ZHANG Zhengguo. Research progress on phase-change emulsions [J]. Energy Storage Science and Technology, 2022, 11(6): 1968-1979.
[2]	Yingying WANG, Dekun FU, Mingbiao CHEN, Wenji SONG, Ziping FENG. Economy of ice source heat pump clean heating system in cold winter zone [J]. Energy Storage Science and Technology, 2021, 10(4): 1380-1387.
[3]	Xianwei ZHU, Zhigao SUN. Preparation and properties of dodecane microemulsion ice slurry [J]. Energy Storage Science and Technology, 2021, 10(2): 506-513.
[4]	Jianjun WANG, Yuxia SHEN, Yu ZHANG, Tuodi ZHANG, Yong LI, Yi WANG. T-history method and its application in the determination of thermophysical properties of phase change materials [J]. Energy Storage Science and Technology, 2021, 10(1): 280-286.
[5]	FANG Manting, ZHANG Xuelai, JI Jun, HUA Weisan, LIU Biao, WANG Xuzhe. Progress in hydrated salt based composite phase change materials [J]. Energy Storage Science and Technology, 2019, 8(4): 709-717.
[6]	LIU Lum, ZHANG Xuelai, CHEN Yue, ZHANG Yongyichuan. Supercooling characteristics of a mannitol based phase change system under a ultrasonic action [J]. Energy Storage Science and Technology, 2019, 8(2): 326-332.
[7]	LI Jintian, MAO Jinfeng. Recent progress in salt hydrate sodium acetate based phase change materials for heat storage [J]. Energy Storage Science and Technology, 2018, 7(5): 881-887.
[8]	ZHANG Xinxing, ZHOU Yuan, LI Xiang, SHEN Yue, HAI Chunxi, DONG Ouyang,REN Xiufeng, . Research progress of calcium chloride hexahydrate phase change material [J]. Energy Storage Science and Technology, 2018, 7(1): 40-.
[9]	LI Chuan1, LI Qi2, JIANG Zhu1, CAO Hui1, QIAO Geng3, LI Yongliang1, LEI Xianzhang3, DING Yulong1. Charging and discharging behavior of carbonate-based salt composite phase change material modules [J]. Energy Storage Science and Technology, 2017, 6(4): 655-661.
[10]	WANG Huichun, LING Ziye, FANG Xiaoming, YUAN Kunjie, ZHANG Zhengguo. Recent progress in the use of magnesium chloride hexahydrate used as a phase change material#br# [J]. Energy Storage Science and Technology, 2017, 6(2): 204-212.
[11]	WANG Xiao, HOU Jianfeng, WU Yuyue, FAN Liwu, XU Xu, YU Zitao, HU Yacai. Supercooling behaviour and non-isothermal crystallization processes of aqueous suspensions of carbon nanotubes [J]. Energy Storage Science and Technology, 2014, 3(3): 256-261.
[12]	ZHANG Xiyao, NIU Jianlei, WU Jianyong, ZHANG Shuo. Suppression of supercooling of PCM-water emulsions using nano-additives [J]. Energy Storage Science and Technology, 2014, 3(2): 133-136.
[13]	WANG Linsheng, DING Xuejia, HE Jinying, SU Leijing, LI Xiran, LEI Xiaohui. Recent progress in thermo-stimulative shape memory polyurethane materials [J]. Energy Storage Science and Technology, 2013, 2(2): 126-131.