制备方法对纳米熔盐储热性能及形成机理的影响

doi:10.11949/0438-1157.20201406

化工学报 ›› 2021, Vol. 72 ›› Issue (5): 2857-2868.DOI: 10.11949/0438-1157.20201406

• 材料化学工程与纳米技术 • 上一篇下一篇

制备方法对纳米熔盐储热性能及形成机理的影响

熊亚选¹(),钱向瑶¹,李烁¹,孙明远¹,王振宇¹,吴玉庭²,徐鹏¹,丁玉龙³,马重芳²

^1.北京建筑大学供热供燃气通风及空调工程北京市重点实验室，北京 100044
^2.北京工业大学传热强化与过程节能教育部重点实验室，北京 100124
^3.伯明翰大学伯明翰储能中心，英国伯明翰 B15 2TT

收稿日期:2020-10-09 修回日期:2021-01-08 出版日期:2021-05-05 发布日期:2021-05-05
通讯作者: 熊亚选
作者简介:熊亚选(1977—)，男，博士，副教授，xiongyaxuan@bucea.edu.cn
基金资助:
北京市教委科研计划项目(KM201910016011);北京市自然科学基金重点项目(3151001)

Effect of preparation methods on thermal energy storage performance and formation mechanism of molten salt nanofluids

XIONG Yaxuan¹(),QIAN Xiangyao¹,LI Shuo¹,SUN Mingyuan¹,WANG Zhenyu¹,WU Yuting²,XU Peng¹,DING Yulong³,MA Chongfang²

^1.Key Laboratory of HVAC, Beijing University of Civil Engineering and Architecture, Beijing 100044, China
^2.Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, Beijing University of Technology, Beijing 100124, China
^3.Birmingham Center for Energy Storage, University of Birmingham, Birmingham B15 2TT, UK

Received:2020-10-09 Revised:2021-01-08 Online:2021-05-05 Published:2021-05-05
Contact: XIONG Yaxuan

摘要/Abstract

摘要：

纳米材料能够改善高温熔盐的传热储热性能，提升大规模储热系统的储热和热交换效率，但目前仍未找到纳米熔盐的高效大规模制备方法。为优选纳米熔盐的高效大规模制备方法，以二元混合盐为基盐，采用高温熔融法和水溶液法分别制备纳米熔盐，用差示扫描量热法、热重分析法和微观形貌分析法，研究制备方法对纳米熔盐显热和储热性能提升、微观结构的影响，探索纳米熔盐形成机理。结果表明，两种制备方法均在搅拌90 min时制备的纳米熔盐性能达到最优，且高温熔融法制备纳米熔盐的熔化潜热和比热容分别比水溶液法高2.6%和28.18%；两种方法制备纳米熔盐的熔点较小，但对纳米熔盐的微观形貌存在明显影响，云核的形成与结构影响着纳米熔盐的储热性能。相比水溶液法，高温熔融法工艺简单，过程能耗低，纳米熔盐储热性能更好，适用于纳米熔盐的大规模生产和工程应用。

关键词: 纳米熔盐, 大规模生产, 高温熔融法, 水溶液法, 云核, 储热

Abstract:

Nanomaterials could improve the heat transfer and thermal heat storage performance of molten salts and further increase the efficiency of heat transfer and thermal heat storage systems greatly. To find efficient method for large-scale production of molten salt nanofluids, both the high-temperature melting method and the aqueous solution method were employed to prepare molten salt nanofluids by adding SiO₂ nanoparticles to a binary nitrate salt. Then, methods of differential scanning calorimetry, thermogravimetric analysis and micromorphology analysis were used to investigate the enhancement of latent heat and sensible heat, change of micromorphology of molten salt nanofluids prepared by the two methods. Results show that molten salt nanofluids with optimal performance were observed under the mixing time of 90 minutes for both preparation methods when heat of fusion and specific heat of molten salt nanofluid prepared by the high-temperature melting method are 2.6% and 28.18% higher than those by the aqueous solution method; Effect of preparation methods on melting point is weak but is apparent on micromorphology of molten salt nanofluids. Formation process and structure of cloud nuclei determine the thermal storage performance of molten salt nanofluids. In addition, preparation process of the high-temperature melting method is simple and energy-saving, which is suitable for large-scale production and engineering application of molten salt nanofluids.

Key words: molten salt nanofluid, large-scale production, high-temperature melting method, aqueous solution method, cloud nuclei, thermal energy storage

中图分类号:

TB 321

熊亚选, 钱向瑶, 李烁, 孙明远, 王振宇, 吴玉庭, 徐鹏, 丁玉龙, 马重芳. 制备方法对纳米熔盐储热性能及形成机理的影响[J]. 化工学报, 2021, 72(5): 2857-2868.

XIONG Yaxuan, QIAN Xiangyao, LI Shuo, SUN Mingyuan, WANG Zhenyu, WU Yuting, XU Peng, DING Yulong, MA Chongfang. Effect of preparation methods on thermal energy storage performance and formation mechanism of molten salt nanofluids[J]. CIESC Journal, 2021, 72(5): 2857-2868.

图/表 10

表1 组分盐和纳米材料的基本特性

Table 1 Basic characteristics of component salts and nanoparticles

材料	纯度/%	生产商	粒径/nm	单价/(CNY/t)
NaNO₃	≥ 99	Sinopharm Chemical Reagent Co., Ltd., China	—	3500
KNO₃	≥ 99	Sinopharm Chemical Reagent Co., Ltd., China	—	5200
SiO₂	≥ 99.8	Shen Zhen Nanolly Chemical Reagent Co., Ltd., China	20	25000

图1 改后的纳米熔盐工程现场制备工艺

Fig.1 Improved preparation processes for in-situ preparation of molten salt nanofluids

表2 纳米熔盐的熔点和相变潜热

Table 2 Melting point and latent heat of molten salt nanofluids

材料	水溶液法				高温熔融法
材料	熔化潜热/(J/g)	升高/%	熔点/℃	升高/℃	熔化潜热/(J/g)	升高/%	熔点/℃	升高/℃
base salt	113.6	0.00	217.6	0	113.6	0.00	217.6	0
+1% SiO₂ 30 min	111.9	-1.52	210.4	-7.2	118.3	3.97	210.7	-6.9
+1% SiO₂ 45 min	112.3	-1.16	210.8	-6.8	118.4	4.05	210.6	-7
+1% SiO₂ 60 min	114.7	0.96	210.3	-7.3	120.1	5.41	209.7	-7.9
+1% SiO₂ 75 min	116.6	2.57	209.6	-8	118.6	4.22	210.2	-7.4
+1% SiO₂ 90 min	117.6	3.40	210.7	-6.9	120.6	5.80	210.5	-7.1
+1% SiO₂ 105 min	118.5	4.14	210.2	-7.4	118.4	4.05	210.3	-7.3
+1% SiO₂ 120 min	115.5	1.65	209.6	-8	116.6	2.57	210.3	-7.3
+1% SiO₂ 135 min	119.4	4.86	209.3	-8.3	118.3	3.97	210.3	-7.3
+1% SiO₂ 150 min	117.3	3.15	209.6	-8	117.4	3.24	210.1	-7.5
+1% SiO₂ 165 min	114.9	1.13	209.3	-8.3	116.9	2.82	210.5	-7.1

图2 纳米熔盐的热流曲线

Fig.2 Heat flow of molten salt nanofluids prepared by both methods

图3 两种方法制备纳米熔盐的平均比热容

Fig.3 Average specific heat of molten salt nanofluids by both methods

图4 两种方法制备纳米熔盐的比热容随温度变化

Fig.4 Specific heat of molten salt nanofluids by both methods

图5 搅拌90 min制备纳米熔盐的微观形貌

Fig.5 Micromorphology of molten salt nanofluids prepared by mixing for 90 min

图6 水溶液法制备纳米熔盐的形成机理

Fig.6 Formation mechanism of molten salt nanofluids prepared by aqueous solution method

图7 高温熔融法制备纳米熔盐中形成的颗粒云核结构

Fig.7 Structure of cloud nuclei formed in molten salt nanofluids prepared by high-temperature melting method

图8 水溶液法颗粒云核直径随温度的变化

Fig.8 Change of cloud nuclei diameter over temperature

参考文献 30

1	Alva G, Lin Y X, Fang G Y. An overview of thermal energy storage systems[J]. Energy, 2018, 144: 341-378.
2	Xuan Y M, Roetzel W. Conceptions for heat transfer correlation of nanofluids[J]. International Journal of Heat and Mass Transfer, 2000, 43(19): 3701-3707.
3	Shin D. Molten salt nanomaterials for thermal energy storage and concentrated solar power applications[D]. Texas: Texas A & M University, 2011.
4	Chieruzzi M, Cerritelli G F, Miliozzi A, et al. Heat capacity of nanofluids for solar energy storage produced by dispersing oxide nanoparticles in nitrate salt mixture directly at high temperature[J]. Solar Energy Materials and Solar Cells, 2017, 167: 60-69.
5	Hu Y W, He Y R, Zhang Z D, et al. Effect of Al₂O₃ nanoparticle dispersion on the specific heat capacity of a eutectic binary nitrate salt for solar power applications[J]. Energy Conversion and Management, 2017, 142: 366-373.
6	Jo B, Banerjee D. Enhanced specific heat capacity of molten salt-based carbon nanotubes nanomaterials[J]. Journal of Heat Transfer, 2015, 137(9): 091013-091017.
7	Sang L X, Liu T. The enhanced specific heat capacity of ternary carbonates nanofluids with different nanoparticles[J]. Solar Energy Materials and Solar Cells, 2017, 169: 297-303.
8	Tian H Q, Du L C, Wei X L, et al. Enhanced thermal conductivity of ternary carbonate salt phase change material with Mg particles for solar thermal energy storage[J]. Applied Energy, 2017, 204: 525-530.
9	Singh R P, Kaushik S C, Rakshit D. Solidification behavior of binary eutectic phase change material in a vertical finned thermal storage system dispersed with graphene nano-plates[J]. Energy Conversion and Management, 2018, 171: 825-838.
10	Chieruzzi M, Cerritelli G F, Miliozzi A, et al. Effect of nanoparticles on heat capacity of nanofluids based on molten salts as PCM for thermal energy storage[J]. Nanoscale Res Lett, 2013, 8(1): 448.
11	Shin D, Banerjee D. Effects of silica nanoparticles on enhancing the specific heat capacity of carbonate salt eutectic [J]. International Journal of Structural Changes in Solids, 2010, 2(2): 25-31.
12	Zhang L D, Chen X, Wu Y T, et al. Effect of nanoparticle dispersion on enhancing the specific heat capacity of quaternary nitrate for solar thermal energy storage application[J]. Solar Energy Materials and Solar Cells, 2016, 157: 808-813.
13	Kim H, Jo B. Anomalous increase in specific heat of binary molten salt-based graphite nanofluids for thermal energy storage[J]. Applied Sciences, 2018, 8(8): 1305.
14	Xiong Y X, Wang Z Y, Wu Y T, et al. Performance enhancement of bromide salt by nano-particle dispersion for high-temperature heat pipes in concentrated solar power plants[J]. Applied Energy, 2019, 237: 171-179.
15	Schuller M, Little F, Malik D, et al. Molten salt-carbon nanotube thermal energy storage for concentrating solar power systems final report[R]. Office of Scientific and Technical Information (OSTI), 2012.
16	Lasfargues M. Nitrate based high temperature nano-heat-transfer-fluids: formulation & characterisation[D]. Leeds: The University of Leeds, 2014.
17	Luo Y, Du X Z, Awad A, et al. Thermal energy storage enhancement of a binary molten salt viain situ produced nanoparticles[J]. International Journal of Heat and Mass Transfer, 2017, 104: 658-664.
18	Awad A, Burns A, Waleed M, et al. Latent and sensible energy storage enhancement of nano-nitrate molten salt[J]. Solar Energy, 2018, 172: 191-197.
19	Song W L, Lu Y W, Wu Y T, et al. Effect of SiO₂ nanoparticles on specific heat capacity of low-melting-point eutectic quaternary nitrate salt[J]. Solar Energy Materials and Solar Cells, 2018, 179: 66-71.
20	张璐迪, 吴玉庭, 任楠, 等. 纳米粒子的分散对提高LMPS盐比热容的影响[J]. 太阳能学报, 2017, 38(11): 3018-3021.
	Zhang L D, Wu Y T, Ren N, et al. Effects of nanoparticle dispersion on enhancing specific heat capacity of lmps salt[J]. Acta Energiae Solaris Sinica, 2017, 38(11): 3018-3021.
21	熊亚选, 王振宇, 徐鹏, 等. 添加纳米SiO₂对单组分及二元硝酸盐热物性的影响[J]. 化工学报, 2018, 69(10): 4418-4426.
	Xiong Y X, Wang Z Y, Xu P, et al. Eenhancing thermal properties of mono and binary nitrates by adding SiO₂ nanoparticles[J]. CIESC Journal, 2018, 69(10): 4418-4426.
22	Oh S H, Kauffmann Y, Scheu C, et al. Ordered liquid aluminum at the interface with sapphire[J]. Science, 2005, 310(5748): 661-663.
23	Thoms M W. Adsorption at the nanoparticle interface for increased thermal capacity in solar thermal systems[D]. Cambridge Massachusetts: MIT, 2012.
24	Keblinski P, Phillpot S R, Choi S U S, et al. Mechanisms of heat flow in suspensions of nano-sized particles (nanofluids)[J]. International Journal of Heat and Mass Transfer, 2002, 45(4): 855-863.
25	Xue L, Keblinski P, Phillpot S R, et al. Two regimes of thermal resistance at a liquid–solid interface[J]. The Journal of Chemical Physics, 2003, 118(1): 337-339.
26	Xue L, Keblinski P, Phillpot S R, et al. Effect of liquid layering at the liquid-solid interface on thermal transport[J]. International Journal of Heat and Mass Transfer, 2004, 47(19/20): 4277-4284.
27	Rizvi S M M, Shin D. Mechanism of heat capacity enhancement in molten salt nanofluids[J]. International Journal of Heat and Mass Transfer, 2020, 161: 120260.
28	Shin D, Banerjee D. Enhancement of specific heat capacity of high-temperature silica-nanofluids synthesized in alkali chloride salt eutectics for solar thermal-energy storage applications[J]. International Journal of Heat and Mass Transfer, 2011, 54(5/6): 1064-1070.
29	Wang W, Wu Z, Li B X, et al. A review on molten-salt-based and ionic-liquid-based nanofluids for medium-to-high temperature heat transfer[J]. Journal of Thermal Analysis and Calorimetry, 2019, 136(3): 1037-1051.
30	Muñoz-Sánchez B, Nieto-Maestre J, Iparraguirre-Torres I, et al. Molten salt-based nanofluids as efficient heat transfer and storage materials at high temperatures. An overview of the literature[J]. Renewable and Sustainable Energy Reviews, 2018, 82: 3924-3945.

[1]	郑玉圆, 葛志伟, 韩翔宇, 王亮, 陈海生. 中高温钙基材料热化学储热的研究进展与展望[J]. 化工学报, 2023, 74(8): 3171-3192.
[2]	宋超宇, 熊亚选, 张金花, 金宇贺, 药晨华, 王辉祥, 丁玉龙. 污泥焚烧炉渣基定型复合相变储热材料的制备和性能[J]. 化工学报, 2022, 73(5): 2279-2287.
[3]	陈子禾, 赵呈志, 冒文莉, 盛楠, 朱春宇. 定向生物质多孔碳复合相变材料的制备及其热性能研究[J]. 化工学报, 2022, 73(4): 1817-1825.
[4]	孔昕山, 黄仁星, 康丽霞, 刘永忠. 甲醇模块化生产中分时储热系统的优化设计[J]. 化工学报, 2022, 73(2): 770-781.
[5]	沈永亮, 张朋威, 刘淑丽. 肋片和多孔介质强化梯级相变储热系统性能的对比研究[J]. 化工学报, 2022, 73(10): 4366-4376.
[6]	张欣宇, 杨晓宏, 张燕楠, 徐佳锟, 郭枭, 田瑞. 基于二维梯度树状肋相变储热系统强化传热机理[J]. 化工学报, 2022, 73(10): 4399-4409.
[7]	罗伟莉, 王雯雯, 潘权稳, 葛天舒, 王如竹. 基于活性碳纤维毡复合吸附剂的储热性能[J]. 化工学报, 2021, 72(S1): 554-559.
[8]	高剑晨, 赵炳晨, 何峰, 李廷贤. 六水硝酸镁相变储热复合材料改性制备及储/放热性能研究[J]. 化工学报, 2021, 72(6): 3328-3337.
[9]	李威, 王秋旺, 曾敏. 水合盐基中低温热化学储热材料性能测试及数值研究[J]. 化工学报, 2021, 72(5): 2763-2772.
[10]	王琴, 徐会金, 韩兴超, 赵长颖. MgO/Mg（OH）₂热化学储热反应的第一性原理研究[J]. 化工学报, 2021, 72(3): 1242-1252.
[11]	徐祥贵, 王丽琼, 王君雷, 王燕, 黄巧, 黄云. 泡沫金属复合PCM微结构传热储热过程模拟[J]. 化工学报, 2021, 72(2): 956-964.
[12]	张文波, 凌子夜, 方晓明, 张正国. 新型六水氯化镁-六水硝酸镁/石墨相氮化碳复合相变材料的制备及其热性能研究[J]. 化工学报, 2021, 72(12): 6399-6406.
[13]	郭枭,邱云峰,史志国,王亚辉,宋力,田瑞. 储热型太阳能供暖系统热输送全过程特性研究[J]. 化工学报, 2021, 72(10): 5384-5395.
[14]	刘亮, 吴爱枝, 黄云, 黄剑. 两类复合无机相变储热材料高温热稳定性和安全性研究[J]. 化工学报, 2020, 71(S2): 314-320.
[15]	刘华, 彭佳杰, 余凯, 倪毅, 王芳, 潘权稳, 葛天舒, 王如竹. 活性氧化铝基质新型复合吸附剂的制备和储热性能[J]. 化工学报, 2020, 71(7): 3354-3361.

制备方法对纳米熔盐储热性能及形成机理的影响

Effect of preparation methods on thermal energy storage performance and formation mechanism of molten salt nanofluids

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价