丹宁酸刻蚀ZIF-67制备导热增强型定形相变材料的性能

郭文尧; 王骏驰; 李辉; 李国宁; 郭敏; 崔萍; 陆万鹏; 周守军; 于明志

doi:10.13801/j.cnki.fhclxb.20220830.001

丹宁酸刻蚀ZIF-67制备导热增强型定形相变材料的性能

doi: 10.13801/j.cnki.fhclxb.20220830.001

山东建筑大学　热能工程学院，济南 250101

基金项目: 中国博士后科学基金项目(2021M702017)；山东省博士后创新项目(202102034)

详细信息

通讯作者:
李辉，博士，副教授，硕士生导师，研究方向为生物质能源的开发与利用、储能技术　E-mail: lihui@sdjzu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-05-30
- 修回日期: 2022-07-21
- 录用日期: 2022-08-18
- 网络出版日期: 2022-08-31
- 刊出日期: 2023-05-15

Thermal storage performance of shape stabilized phase change materials with high thermal conductivity derived from ZIF-67 etched via tannic acid

School of Thermal Engineering, Shandong Jianzhu University, Jinan 250101, China

Funds: China Postdoctoral Science Foundation (2021M702017); Shandong Provincial Postdoctoral Innovation Project (202102034)

摘要

摘要: 为解决有机固-液相变材料(PCMs)导热系数低和相变易泄漏的难题，利用丹宁酸刻蚀ZIF-67制备碳基骨架作为支撑体(HX-C)，硬脂酸(SA)为相变芯材，采用真空熔融吸附法构筑导热增强型定形相变材料(SA/HX-C)。为评估其储热能力，对热稳定性、储热性能、导热系数、定形能力及光热转换能力进行研究。同时，借助氮气等温吸附-脱附、傅里叶红外光谱、X-射线衍射和扫描电子显微镜进行表征。结果表明：丹宁酸刻蚀ZIF-67可实现对其碳化衍生物的扩孔作用，提高SA/HX-C的定形能力。所制备的SA/HX-C具有良好的储热性能、导热能力及光热转换性能。其中，刻蚀时间为6 min的复合相变材料(SA/H6-C)的储热效率可达80.84%，光热转化效率高达76.29%，导热系数(0.461 W/(m·K))相比于SA提高了156.11%。SA/H6-C在相变过程中无任何形貌变化和泄漏，重复循环储/放热100次后仍然具有良好的储热能力。
- 相变储热 /
- 定形 /
- ZIF-67 /
- 光热转化 /
- 硬脂酸
Abstract: To solve the defects of low thermal conductivity and leakage of organic solid-liquid phase change materials (PCMs), ZIF-67 was etched by tannin acid to obtain the carbon-based supports (HX-C), stearic acid (SA) was the phase change material and then used to prepare the enhanced thermal conductivity PCMs (SA/HX-C) via vacuum melting adsorption method. In detail, thermal stability, heat storage property, thermal conductivity, shape stability and photo-thermal conversion were investigated to evaluate the thermal storage performance. Meanwhile, characterizations of nitrogen isothermal adsorption-desorption, FTIR, XRD and SEM were conducted. Results revealed that tannic acid can expand the pore size of carbonized ZIF-67 derivatives, thus enhancing the shape stability. The obtained SA/HX-C own favorable heat storage property, thermal conductivity, and photo-thermal conversion. Among them, etching time of 6 min for PCMs (SA/H6-C) exhibits high thermal storage efficiency of 80.84% and photo-thermal conversion of 76.29%. Thermal conductivity is strengthened to 0.461 W/(m·K), which is 156.11% higher than that of SA. No leakage and shape change are observed for SA/H6-C during phase transition, it still shows good thermal storage performance even after recycling 100 times.
- phase change thermal storage /
- shape stability /
- ZIF-67 /
- photo-thermal conversion /
- stearic acid

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图 1 支撑体(HX-C)的氮气等温吸附-脱附曲线(a)和孔径分布曲线(b)

STP—Standard temperature and pressure; dV_p/dD_p—Rate of change of pore volume with aperture

Figure 1. Nitrogen isothermal adsorption-desorption (a) and pore diameter distributions (b) for supports (HX-C)

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图 2 HX-C (a)和复合相变材料(硬脂酸(SA)/HX-C) (b)的FTIR图谱

Figure 2. FTIR spectra of HX-C (a) and composite phase change materials (Stearic acid (SA)/HX-C) (b)

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图 3 HX-C (a)、HX-C的5°~40°窄范围(b)和SA/HX-C (c)的XRD图谱

Figure 3. XRD patterns of HX-C (a), narrow range 5°-40° of HX-C (b) and SA/HX-C (c)

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图 4 ZIF-67 (a)、H0-C (b)、H6 (c)、H6-C (d)和SA/H6-C (e)的SEM图像

Figure 4. SEM images of ZIF-67 (a), H0-C (b), H6 (c), H6-C (d) and SA/H6-C (e)

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图 5 SA和SA/HX-C的热稳定性

Figure 5. Thermal stability of SA and SA/HX-C

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图 6 SA/HX-C的DSC曲线

Figure 6. DSC curves of SA/HX-C

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图 7 SA和SA/HX-C加热前后图像及泄漏率记录

Figure 7. Images of leakage rate for SA and SA/HX-C before and after heating

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图 8 SA/H6-C循环储/放热100次的形貌和质量记录

Figure 8. Shape and quality records of SA/H6-C cyclic storage/exhaust heat 100 times

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图 9 SA/H6-C循环储/放热100次前后的DSC曲线

Figure 9. DSC curves of SA/H6-C before and after 100 cycles of storage/exhaust heat

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图 10 SA/H6-C循环储/放热100次前后的XRD图谱(a)和FTIR图谱(b)

Figure 10. XRD patterns (a) and FTIR spectra (b) of SA/H6-C before and after 100 cycles of storage/exhaust heat

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图 11 SA和SA/H6-C的光热转换曲线

Figure 11. Photo-thermal conversion curves of SA and SA/H6-C

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图 12 SA/H6-C加热过程红外热成像记录

Figure 12. IR images of heating process for SA/H6-C

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表 1 SA/HX-C制备参数

Table 1. Preparation parameters of SA/HX-C

Precursor	Etching time/min	Support	Carbonization temperature/℃	Composite PCM	SA mass fraction/wt%
ZIF-67	0	H0-C	700	SA/H0-C	60
ZIF-H3	3	H3-C		SA/H3-C
ZIF-H4	4	H4-C		SA/H4-C
ZIF-H6	6	H6-C		SA/H6-C
ZIF-H8	8	H8-C		SA/H8-C
ZIF-H10	10	H10-C		SA/H10-C
Notes: PCM—Phase change material; SA—Stearic acid.

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表 2 HX-C的比表面积、孔容和平均孔径

Table 2. Surface area, pore volume and average pore diameter of HX-C

Sample	Surface area/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Average pore diameter/nm
H0-C	357.63	0.240	2.63
H3-C	259.74	0.337	6.02
H4-C	247.11	0.381	7.43
H6-C	249.13	0.386	7.46
H8-C	238.53	0.432	9.43
H10-C	267.30	0.498	9.69

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表 3 SA和SA/HX-C的热性能

Table 3. Thermal properties of SA and SA/HX-C

Sample	T_m/T_f /℃	ΔH_m/ΔH_f/(J·g⁻¹)	ΔT/℃	λ/(W·(m·K)⁻¹)
SA	68.53/65.01	220.28/221.48	3.52	0.180
SA/H0-C	67.72/67.12	109.52/110.48	0.60	0.452
SA/H3-C	67.53/66.70	106.80/101.43	0.77	0.453
SA/H4-C	67.53/66.84	109.34/103.21	0.69	0.457
SA/H6-C	67.38/66.70	109.93/104.35	0.68	0.461
SA/H8-C	67.25/66.55	109.09/100.27	0.70	0.456
SA/H10-C	67.17/66.32	109.67/99.80	0.75	0.458
Notes: T_m, T_f and ΔT—Melting temperature, solidification temperature and supercooling; ΔH_m and ΔH_f—Latent heat of melting and latent heat of solidification; λ—Thermal conductivity.

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表 4 SA/H6-C循环储/放热100次前后的热性能

Table 4. Thermal properties of SA/H6-C before and after 100 cycles of storage/exhaust heat

Cycle time	T_m/T_f/℃	ΔH_m/ΔH_f/(J·g⁻¹)	ΔT/℃
Before the cycle	67.38/66.70	109.93/104.35	0.68
After 100 cycles	67.39/66.71	109.25/103.72	0.68

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