蓄热用纳米相变微胶囊制备与性能

doi:10.16085/j.issn.1000-6613.2022-2330

摘要/Abstract

摘要：

防止相变材料的泄漏和提高热导率是相变材料储能的两大关键问题。本文以钛酸四丁酯（TBT）为前体，通过细乳液界面聚合法制备了nano-TiO₂@n-docosane微胶囊。采用生物显微镜对其形成过程进行观察，利用扫描电子显微镜（SEM）、差示扫描量热仪（DSC）、热导率测定仪和热重分析仪对nano-TiO₂@n-docosane微胶囊的性能进行了表征。研究结果表明，nano-TiO₂@n-docosane微胶囊形成过程表现为纳米微胶囊数量由少变多、粒径由小变大、微观溶液界面由模糊变清晰的过程，溶液陈化放冷过程表现为由胶凝悬浮状态逐渐转变为粉末沉淀状态。nano-TiO₂@n-docosane微胶囊粒径与转速显著相关，外貌形态与TBT、盐酸（HCl）和十二烷基硫酸钠（SDS）用量密切相关。纳米相变微胶囊的融化和凝固温度分别为41.3℃和42.4℃，相变焓为178J/g，包覆率和包覆效率达到70.7%和69.0%，蓄热能力为97.6%。nano-TiO₂@n-docosane微胶囊平均热导率是n-docosane的215%。红外光谱测试结果表明，n-docosane和TiO₂物理结合，n-docosane成功被TiO₂包覆。热重分析表明TiO₂形成了一个物理保护屏障，减缓了n-docosane向胶囊外的扩散。

关键词: 相变, 焓, 稳定性, 纳米微胶囊, 正二十二烷, 二氧化钛

Abstract:

Leakage prevention and thermal conductivity improvement of phase change materials are two key issues for energy storage of phase change materials. In this work, nano-TiO₂@n-docosane microcapsules were prepared by fine emulsion interfacial polymerization using tetrabutyl titanate (TBT) as precursor. The formation process was observed by biomicroscopy, and the properties of nano-TiO₂@n-docosane microcapsules were characterized by scanning electron microscope (SEM), differential scanning calorimeter (DSC), thermal conductivity meter and thermogravimetric analyzer. The experimental results showed that the formation process of nano-TiO₂@n-docosane microcapsules was that the number of nano-microcapsules changed from less to more, the particle size from small to large, the interface of microscopic solution from blurred to clear, and the aging and cooling process of solution was gradually from gelation suspension state to powder precipitation state. The results of SEM test indicated that the particle size of nano-TiO₂@n-docosane microcapsules was significantly related to rotational speed, and the appearance was closely related to the dosage of TBT, hydrochloric acid (HCl) and sodium dodecyl sulfate (SDS). The DSC results showed that the melting and solidification temperatures were 41.3℃ and 42.4℃, respectively. The latent heat of nano-TiO₂@n-docosane was 178J/g. The coating rate and the coating efficiency were 70.7% and 69.0%, respectively with the heat storage capacity of 97.6%. The average thermal conductivity of nano-TiO₂@n-docosane microcapsules was 215% of n-docosane. It was found from the infrared spectrum test that there was no chemical reaction when n-docosane and TiO₂ were physically combined. The results of thermogravimetric analysis indicated that TiO₂formed a physical protective barrier and slowed down the diffusion of n-docosane outside the capsule.

Key words: phase change, enthalpy, stability, nano microcapsules, n-docosane, titanium dioxide

中图分类号:

TK02

黄志国, 孙志高. 蓄热用纳米相变微胶囊制备与性能[J]. 化工进展, 2023, 42(11): 5842-5851.

HUANG Zhiguo, SUN Zhigao. Preparation and properties of nano phase change microcapsules for heat storage[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5842-5851.

图/表 13

参考文献 37

1	王灿, 张雅欣. 碳中和愿景的实现路径与政策体系[J]. 中国环境管理, 2020, 12(6): 58-64.
	WANG Can, ZHANG Yaxin. Implementation pathway and policy system of carbon neutrality vision[J]. Chinese Journal of Environmental Management, 2020, 12(6): 58-64.
2	姜竹, 邹博杨, 丛琳, 等. 储热技术研究进展与展望[J]. 储能科学与技术, 2022, 11(9): 2746-2771.
	JIANG Zhu, ZOU Boyang, CONG Lin, et al. Recent progress and outlook of thermal energy storage technologies[J]. Energy Storage Science and Technology, 2022, 11(9): 2746-2771.
3	YUAN Mengdi, XU Chao, WANG Tieying, et al. Supercooling suppression and crystallization behaviour of erythritol/expanded graphite as form-stable phase change material[J]. Chemical Engineering Journal, 2021, 413: 127394.
4	GUO Xi, ZHANG Shaodi, CAO Jinzhen. An energy-efficient composite by using expanded graphite stabilized paraffin as phase change material[J]. Composites Part A: Applied Science and Manufacturing, 2018, 107: 83-93.
5	ZHOU Sunxi, ZHANG Xuelai, LIU Sheng, et al. Performance study on expand graphite/organic composite phase change material for cold thermal energy storage[J]. Energy Procedia, 2019, 158: 5305-5310.
6	TAYLOR Peter G, BOLTON Ronan, STONE Dave, et al. Developing pathways for energy storage in the UK using a coevolutionary framework[J]. Energy Policy, 2013, 63: 230-243.
7	MASSON-DELMOTTE V, ZHAI P, PÖRTNER H O, et al. Intergovernmental panel on climate change (IPCC). Global warming of 1.5℃: an IPCC special report on the impacts of global warming of 1.5℃ above pre-industrial levels and related global greenhouse gas emission pathways, in the context of strengthening the global response to the threat of climate change[EB/OL]. Sustainable Development and Efforts to Eradicate Poverty. (2021-10-18)..
8	GE Zhiwei, LI Yongliang, LI Dacheng, et al. Thermal energy storage: Challenges and the role of particle technology[J]. Particuology, 2014, 15: 2-8.
9	DUAN Zhenya, ZHANG Zhuang, WANG Jingtao, et al. Thermal performance of structured packed bed with encapsulated phase change materials[J]. International Journal of Heat and Mass Transfer, 2020, 158: 120066.
10	SHIN Donghyun, BANERJEE Debjyoti. 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.
11	PACHECO James E, SHOWALTER Steven K, KOLB William J. Development of a molten-salt thermocline thermal storage system for parabolic trough plants[J]. Journal of Solar Energy Engineering, 2002, 124(2): 153-159.
12	FARID Mohammed M, KHUDHAIR Amar M, RAZACK Siddique Ali K, et al. A review on phase change energy storage: materials and applications[J]. Energy Conversion and Management, 2004, 45(9/10): 1597-1615.
13	THIRUGNANAM C, KARTHIKEYAN S, KALAIMURUGAN K. Study of phase change materials and its application in solar cooker[J]. Materials Today: Proceedings, 2020, 33: 2890-2896.
14	HUANG Zhanhua. Research progress in organic/composite phase change materials for energy storage[J]. ES Energy & Environment, 2020, 9: 28-40.
15	刘庆祎, 肖桐, 孙文杰, 等. 纳米二氧化钛强化的相变储能研究进展[J]. 化工学报, 2022, 73(5): 1863-1882.
	LIU Qingyi, XIAO Tong, SUN Wenjie, et al. Progress in the research of phase change energy storage enhanced by titanium dioxide nanoparticles[J]. CIESC Journal, 2022, 73(5): 1863-1882.
16	李昭, 李宝让, 陈豪志, 等. 相变储热技术研究进展[J]. 化工进展, 2020, 39(12): 5066-5085.
	LI Zhao, LI Baorang, CHEN Haozhi, et al. State of the art review on phase change thermal energy storage technology[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5066-5085.
17	XIAO X, ZHANG P, LI M. Preparation and thermal characterization of paraffin/metal foam composite phase change material[J]. Applied Energy, 2013, 112: 1357-1366.
18	GEORGE Mathew, PANDEY A K, RAHIM Nasrudin ABD, et al. A novel polyaniline (PANI)/paraffin wax nano composite phase change material: Superior transition heat storage capacity, thermal conductivity and thermal reliability[J]. Solar Energy, 2020, 204: 448-458.
19	LI Min, WU Zhishen, TAN Jinmiao. Heat storage properties of the cement mortar incorporated with composite phase change material[J]. Applied Energy, 2013, 103: 393-399.
20	CUI Wenlong, YUAN Yanping, SUN Liangliang, et al. Experimental studies on the supercooling and melting/freezing characteristics of nano-copper/sodium acetate trihydrate composite phase change materials[J]. Renewable Energy, 2016, 99: 1029-1037.
21	WANG Jifen, XIE Huaqing, XIN Zhong. Thermal properties of heat storage composites containing multiwalled carbon nanotubes[J]. Journal of Applied Physics, 2008, 104(11): 113537.
22	CHOI Da Hee, LEE Juhyuk, HONG Hiki, et al. Thermal conductivity and heat transfer performance enhancement of phase change materials (PCM) containing carbon additives for heat storage application[J]. International Journal of Refrigeration, 2014, 42: 112-120.
23	MYERS Philip DJr, ALAM Tanvir E, KAMAL Rajeev, et al. Nitrate salts doped with CuO nanoparticles for thermal energy storage with improved heat transfer[J]. Applied Energy, 2016, 165: 225-233.
24	MADATHIL Pramod Kandoth, BALAGI Nagaraj, SAHA Priyanka, et al. Preparation and characterization of molten salt based nanothermic fluids with enhanced thermal properties for solar thermal applications[J]. Applied Thermal Engineering, 2016, 109: 901-905.
25	BABAPOOR Aziz, KARIMI Gholamreza. Thermal properties measurement and heat storage analysis of paraffinnanoparticles composites phase change material: Comparison and optimization[J]. Applied Thermal Engineering, 2015, 90: 945-951.
26	LIU Zhengxuan, YU Zhun, YANG Tingting, et al. A review on macro-encapsulated phase change material for building envelope applications[J]. Building and Environment, 2018, 144: 281-294.
27	PRAJAPATI Deepak G, KANDASUBRAMANIAN Balasubramanian. A review on polymeric-based phase change material for thermo-regulating fabric application[J]. Polymer Reviews, 2020, 60(3): 389-419.
28	CHANG Yanghui, SUN Zhigao. Synthesis and thermal properties of n-tetradecane phase change microcapsules for cold storage[J]. Journal of Energy Storage, 2022, 52: 104959.
29	SARI Ahmet, ALKAN Cemil, DÖĞÜŞCÜ Derya Kahraman, et al. Micro/nano encapsulated n-tetracosane and n-octadecane eutectic mixture with polystyrene shell for low-temperature latent heat thermal energy storage applications[J]. Solar Energy, 2015, 115: 195-203.
30	尉菁华, 刘欢, 连慧琴, 等. 棕榈酸/二氧化硅相变微胶囊的制备及性能研究[J]. 中国塑料, 2020, 34(2): 1-8.
	YU Jinghua, LIU Huan, LIAN Huiqin, et al. Preparation and performance of phase-change microcapsules based on palmitic acid core and silica shell[J]. China Plastics, 2020, 34(2): 1-8.
31	GENG Lixia, WANG Shuangfeng, WANG Tingyu, et al. Facile synthesis and thermal properties of nanoencapsulated n-dodecanol with SiO₂ shell as shape-formed thermal energy storage material[J]. Energy & Fuels, 2016, 30(7): 6153-6160.
32	Hafiz Muhammad ALI, JANJUA Muhammad Mansoor, SAJJAD Uzair, et al. A critical review on heat transfer augmentation of phase change materials embedded with porous materials/foams[J]. International Journal of Heat and Mass Transfer, 2019, 135: 649-673.
33	LIU Huan, WANG Xiaodong, WU Dezhen. Fabrication of graphene/TiO₂/paraffin composite phase change materials for enhancement of solar energy efficiency in photocatalysis and latent heat storage[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 4906-4915.
34	JI Wei, CHENG Xiaomin, CHEN Sihong, et al. Self-assembly fabrication of GO/TiO₂@paraffin microcapsules for enhancement of thermal energy storage[J]. Powder Technology, 2021, 385: 546-556.
35	ZHAO Liang, WANG Hao, LUO Jie, et al. Fabrication and properties of microencapsulated n-octadecane with TiO₂ shell as thermal energy storage materials[J]. Solar Energy, 2016, 127: 28-35.
36	ABDI Amir, IGNATOWICZ Monika, GUNASEKARA Saman Nimali, et al. Experimental investigation of thermo-physical properties of n-octadecane and n-eicosane[J]. International Journal of Heat and Mass Transfer, 2020, 161: 120285.
37	LIANG Shuen, LI Qianbiao, ZHU Yalin, et al. Nanoencapsulation of n-octadecane phase change material with silica shell through interfacial hydrolysis and polycondensation in miniemulsion[J]. Energy, 2015, 93: 1684-1692.

名称	型号	精度	测量范围
生物显微镜	XSP-BM-3C	—	40~1600倍
赛多利斯电子天平	BSA224S	±0.1mg	0~220g
数控超声波清洗器	KQ100DE	—	RT+10~80℃
微电热恒温水槽	THD-2015	±0.1℃	-20~99℃
差示扫描量热仪	NETZSCH DSC 200F3	—	-180~725℃
傅里叶红外光谱仪	Thermo Scientific Nicolet iS20	—	4000~400cm^-1
真空干燥箱	BZF-30	±0.5℃	RT+2~250℃
扫描电子显微镜	蔡司Gemini300/Nova NanoSEM450	—	—
热导率测定仪	DRE-Ⅲ	≤3%	0.005~50W/(m•K)

名称	型号	精度	测量范围
生物显微镜	XSP-BM-3C	—	40~1600倍
赛多利斯电子天平	BSA224S	±0.1mg	0~220g
数控超声波清洗器	KQ100DE	—	RT+10~80℃
微电热恒温水槽	THD-2015	±0.1℃	-20~99℃
差示扫描量热仪	NETZSCH DSC 200F3	—	-180~725℃
傅里叶红外光谱仪	Thermo Scientific Nicolet iS20	—	4000~400cm^-1
真空干燥箱	BZF-30	±0.5℃	RT+2~250℃
扫描电子显微镜	蔡司Gemini300/Nova NanoSEM450	—	—
热导率测定仪	DRE-Ⅲ	≤3%	0.005~50W/(m•K)

样品	蒸馏水/mL	无水乙醇/mL	SDS/g	HCl/mL	n-docosane/g	TBT/g
S1	72.0	36.0	0.5	0.10	5.0	5.0
S2	72.0	36.0	0.5	0.10	5.0	10.0
S3	72.0	36.0	0.5	0.25	5.0	5.0
S4	72.0	36.0	1.0	0.10	5.0	5.0

样品	蒸馏水/mL	无水乙醇/mL	SDS/g	HCl/mL	n-docosane/g	TBT/g
S1	72.0	36.0	0.5	0.10	5.0	5.0
S2	72.0	36.0	0.5	0.10	5.0	10.0
S3	72.0	36.0	0.5	0.25	5.0	5.0
S4	72.0	36.0	1.0	0.10	5.0	5.0

材料	融化温度/℃	融化焓值/J·g^-1	凝固温度/℃	凝固焓值/J·g^-1	融化峰值温度/℃	凝固峰值温度/℃	R/%	E/%	η/%
n-docosane	42.9	251.6	42.7	254.15	45.7	40	—	—	—
TiO₂@n-docosane	41.3	178	42.4	171	44.7	35.4	70.7	69.0	97.6