石蜡基核壳结构相变储能复合材料的制备及性能

何绪权; 王政华; 张玲; 李春忠

doi:10.14135/j.cnki.1006-3080.20210512001

石蜡基核壳结构相变储能复合材料的制备及性能

doi: 10.14135/j.cnki.1006-3080.20210512001

何绪权^1,,
王政华²,
张玲^1, ,,
李春忠^1, ,

1.
上海多级结构纳米材料工程技术研究中心，华东理工大学材料科学与工程学院，上海 200237
2.
上海汉特工程塑料有限公司，上海 201108

基金项目: 国家自然科学基金(21878092，21838003)，上海市教育委员会科研创新计划项目，上海市优秀学术人(19XD1401400)

详细信息

作者简介:
何绪权(1995—)，男，山东日照人，硕士生，研究方向为相变储能复合材料。E-mail：19921252560@163.com

通讯作者:
张　玲，E-mail：zlingzi@ecust.edu.cn

李春忠，E-mail：czli@ecust.edu.cn

中图分类号: TB33
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- 文章访问数: 87
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- PDF下载量: 8
- 被引次数: 0
出版历程
- 收稿日期: 2021-05-12
- 网络出版日期: 2021-07-12

Preparation and properties of paraffin-based core-shell phase change energy storage composites

HE Xuquan^1
,,
WANG Zhenghua²,
ZHANG Ling^{1
, ,},
LI Chunzhong^{1
, ,}

1.
Shanghai Engineering Research Center of Hierarchical Nanomaterials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science & Technology, Shanghai 200237
2.
Shanghai Hunt Engineering Plastics Co., Ltd, Shanghai 201108

摘要

摘要: 将石蜡熔融浸渍在膨胀石墨(EG)中得到核组分(EG-Paraffin)，将制得的Paraffin@SiO₂微胶囊填充在环氧树脂(Ep)中得到壳组分(Ep-Paraffin@SiO₂)，然后通过简单的模压成型制备了具有宏观核-壳结构的相变复合材料(EG-Paraffin/Ep-Paraffin@SiO₂)。实验结果表明，这种宏观的核-壳结构赋予了相变复合材料优异的防泄漏性能和形状稳定性。壳组分中的微胶囊使相变复合材料保持较高的焓值(大于144 J/g)。而核组分中的膨胀石墨一方面能够有效封装石蜡，另一方面可以大大提升相变复合材料的传热速率。优异的综合性能使此相变复合材料在热能储存和热管理领域具有巨大的应用潜力。
- 相变储能复合材料 /
- 微胶囊 /
- 模压成型 /
- 宏观核-壳结构
Abstract: The core component (EG-Paraffin) was obtained by impregnation of Paraffin in expanded graphite (EG), and the shell component (EP-Paraffin@SiO₂) was obtained by filling the obtained Paraffin@SiO₂ microcapsules into epoxy resin. The EG-Paraffin/EP-Paraffin@SiO₂ phase change composite with macroscopic core-shell structure was prepared by simple molding. The experimental results show that the macroscopic core-shell structure gave the phase change composite excellent leak-proof performance and shape stability. The microcapsules in the shell component maintained a high enthalpy (greater than 144 J/g) of the phase change composite. On the one hand, EG in the core component can encapsulate the paraffin effectively, and on the other hand, the heat transfer rate of the phase change composites can be greatly improved. The excellent comprehensive performance of this phase change composite has great application potential in the field of thermal energy storage and thermal management.
- Phase change energy storage composites /
- Microcapsule /
- Pressure forming /
- Macroscopic core-shell structure

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图 1 Paraffin@SiO₂微胶囊的制备流程图

Figure 1. Preparation process of Paraffin@SiO₂ microcapsules

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图 2 EG-paraffin/Ep-Paraffin@SiO₂相变复合材料的制备流程图

Figure 2. Preparation process diagram of EG-paraffin/Ep-Paraffin@SiO₂

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图 5 (a, d) EG的SEM图像；(b) EG-Paraffin/Ep-Paraffin@SiO₂相变复合材料的断面图；(c) 核组分(EG-Paraffin)， (e) 壳组分(Ep-Paraffin@SiO₂)以及(f) 核-壳界面处的SEM图像

Figure 5. (a, d) SEM image of EG; (b) cross-sectional view of EG-Paraffin/Ep-Paraffin@SiO₂ composite; (c) SEM image of the core component (EG-Paraffin); (e) SEM image of the shell component (Ep-Paraffin@SiO₂); (f) SEM image at the core-shell interface

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图 3 微胶囊的(a) SEM图像和(b) TEM图像；(c) SiO₂颗粒对比样的SEM图像；石蜡、SiO₂对比样和Paraffin@SiO₂微胶囊的(d)XRD图谱和(e) FTIR图谱

Figure 3. (a) SEM images and (b) the TEM image of the microcapsules; (c) the SEM image of the SiO₂ contrast sample; (d) the XRD patterns and (e) the FTIR spectra of paraffin, SiO₂ contrast sample and paraffin@SiO₂ microcapsules

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图 4 含有(a, d) 3% EG, (b, e) 5% EG和(c, f) 8% EG的EG-Paraffin在60 ℃下加热1 h前后的泄露图片

Figure 4. Leakage pictures of EG-Paraffin with (a, d) 3% EG, (b, e) 5% EG and (c, f) 8% EG before and after heating at 60 ℃ for 1 h

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图 6 核组分(EG-Paraffin)和壳组分(Ep-Paraffin@SiO₂)的DSC曲线

Figure 6. DSC curves of core component (EG-Paraffin) and shell component (Ep-Paraffin@SiO₂)

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图 7 在加热受力前(a) EG-Paraffin和(b) EG-Paraffin/Ep-Paraffin@SiO₂的泄露图像；在加热受力后(c) EG-Paraffin and (d) EG-Paraffin/Ep-Paraffin@SiO₂的泄露图像；(e) 经过泄露测试后两样品的泄露率；(f) 泄露测试示意图

Figure 7. Leakage images of (a) EG-Paraffin and (b) EG-Paraffin/Ep-Paraffin@SiO₂ before heating under load; Leakage images of (c) EG-Paraffin and (d) EG-Paraffin/Ep-Paraffin@SiO₂ after heating under load; (e) Leakage rate of the two samples; (f) Schematic diagram of leakage test

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图 8 EG-Paraffin, Ep-Paraffin@SiO₂和EG-Paraffin/Ep-Paraffin@SiO₂的温度（上表面）-时间曲线

Figure 8. Temperature (the upper surface)-time curves of EG-Paraffin, Ep-Paraffin@SiO₂ and EG-Paraffin/Ep-Paraffin@SiO₂

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图 9 100个热循环前后(a) EG-Paraffin和(b) Ep-Paraffin@SiO₂的DSC曲线

Figure 9. DSC curves of (a) EG-Paraffin and (b) Ep-Paraffin@SiO₂ before and after 100 thermal cycles

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图 10 相变复合材料板

Figure 10. Phase change composite board

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表 1 核组分（EG-Paraffin）和壳组分（Ep-Paraffin@SiO₂）的组成配方

Table 1. Formulation of the core component (EG-Paraffin) and the shell component (Ep-Paraffin@SiO₂)

The core component	w(EG-Paraffin)		w(Ep-Paraffin@SiO₂)
The core component	EG	Paraffin	Ep	Paraffin@SiO₂
EG-Paraffin	8.00t%	92.00t%	60%	40%

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表 2 石蜡、核组分（EG-Paraffin）和壳组分（Ep-Paraffin@SiO₂）的DSC数据

Table 2. DSC data of paraffin, core component (EG-Paraffin) and shell component (Ep-Paraffin@SiO₂)

Sample	Melting process		Solidifying process
Sample	H_m/ J·g⁻¹	T_m/ ℃	H_s/ J·g⁻¹	T_s/ ℃
Paraffin	227.87	45.22/47.02	224.85	38.66/42.56
EG-Paraffin	205.46	45.47/48.07	207.65	37.60/42.08
Ep-Paraffin@SiO₂	53.64	44.84/47.04	53.75	36.95/43.13

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表 3 EG-Paraffin/Ep-Paraffin@SiO₂和对比样（EG-Paraffin/Ep）的核/壳比重和热焓值

Table 3. The core/shell ratio and enthalpy of EG-Paraffin/Ep-Paraffin@SiO₂ and the comparison sample

Sample ^a	w (core component)^c/ （%）	w (shell component)^d/ （%）	ΔH_{m,theoretical}/ （J·g⁻¹）
EG-Paraffin/Ep-Paraffin@SiO₂	55.00	45.00	137.14
EG-Paraffin/Ep ^b	50.90	49.10	104.58
a−The sample is a cylinder with a base diameter of 14.65-14.80 mm and a height of 6.20-6.30 mm; b−Contrast sample. The shell component is pure epoxy resin (Ep); c−The nuclear component is EG-paraffin; d−The shell components of the two samples are Ep-Paraffin@SiO₂ and Ep, respectively; And the thickness of the shell is 0.85-1.00 mm.

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表 4 100个热循环前后核组分（EG-Paraffin）和壳组分（Ep-Paraffin@SiO₂）的DSC数据

Table 4. DSC data of the core component (EG-Paraffin) and the shell component (Ep-Paraffin@SiO₂) before and after 100 thermal cycles

Sample		Melting process		Solidifying process
Sample		H_m/J·g⁻¹	T_m/℃	H_s/ J·g⁻¹	T_s/℃
EG-Paraffin	1^st cycle	206.46	45.47/48.07	207.65	37.60/42.08
EG-Paraffin	100^th cycle	205.86	45.32/48.03	206.52	37.73/42.08
Ep-Paraffin@SiO₂	1^st cycle	53.64	44.84/47.04	54.65	36.95/43.13
Ep-Paraffin@SiO₂	100^th cycle	53.15	44.62/47.09	53.93	32.19/38.54

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表 5 相变复合材料板的相关参数

Table 5. Related parameters of the phase change composite board.

w (core component)^a/%	w (shell component)^b/%	Total weight/g	Size/cm	ΔH_m,_theoretical/ J·g⁻¹
59.6 t	40.40 t	73.00	10×10×1	144.12

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