定向生物质多孔碳复合相变材料的制备及其热性能研究

doi:10.11949/0438-1157.20211852

摘要/Abstract

摘要：

针对石蜡热导率低以及易泄漏等问题，以生物质木头多孔碳作为导热填料骨架，利用壳聚糖改性木头多孔碳在其竖向孔道中生长碳薄片形成分级多孔网络结构，并与石蜡复合制成定形复合相变材料（PCC）。结果表明，由于分级多孔网络骨架的引入，PCC的定形效果好，无明显泄漏，其相变焓值为126.9 J/g，经100次熔化凝固循环测试，其相变温度和焓值均无明显变化，具有良好的循环稳定性。PCC的导热性能具有较大提高，且呈现明显的各向导热异性，平面外和平面内热导率分别为0.67和0.41 W/(m·K)。此外，通过模拟太阳光进行光热实验，发现PCC具有良好的光热转换性能。本复合相变材料在储热以及热管理领域具有应用前景。

关键词: 复合材料, 生物质多孔碳, 相变储热, 传热, 太阳能

Abstract:

The low thermal conductivity and poor shape-stability of organic paraffin as phase change material have limited their applications. In order to improve the thermal conductivity and anti-leakage performance of paraffin, wood was modified by chitosan and carbonized at high temperature to prepare hierarchical porous carbon skeleton, which can not only firmly adsorb paraffin but also greatly improve the thermal conductivity of phase change composite (PCC). The morphology, phase change cycling stability, thermal conductivity and photothermal conversion performance were tested. The results show that with the introduction of multi-scaled porous structure, PCCs have good shape-stability without obvious leakage. The phase change enthalpy of the PCC is 126.9 J/g. The phase-transition temperature and enthalpy of the PCC have no obvious change over the 100 cycles of melting and solidification, indicating that the PCC has good cyclic stability. The thermal conductivity of PCC is also greatly improved and presents obvious anisotropic thermal conductivity. The out-of-plane and in-plane thermal conductivity of PCC are 0.67 and 0.41 W/(m·K), respectively. The great improvement of the out-of-plane thermal conductivity is conducive to improve the thermal management application of PCC. In addition, it is also found that PCC has good photothermal conversion performance. The composite phase change materials developed in this paper have application prospects in the fields of heat storage and thermal management.

Key words: composites, biomass porous carbon, phase change thermal storage, heat transfer, solar energy

中图分类号:

TK 02

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.

Zihe CHEN, Chengzhi ZHAO, Wenli MAO, Nan SHENG, Chunyu ZHU. Preparation and thermal properties of phase change composites supported by oriented biomass porous carbon[J]. CIESC Journal, 2022, 73(4): 1817-1825.

图/表 12

图1 壳聚糖改性木头碳骨架及其定形复合相变材料的制备流程

Fig.1 Preparation process of carbon skeleton modified by chitosan and the phase change composite

表1 样品命名及实验条件

Table 1 Name of samples and experimental condition

填料骨架命名	石蜡复合物	实验条件
无填料	Paraffin	石蜡空白样品
C-1200	C/P-1200	未改性，1200℃热处理
Ch/C-1200	Ch/C/P-1200	壳聚糖改性，1200℃热处理

图2 1200℃热处理后木头碳骨架改性前后的XRD谱图

Fig.2 XRD patterns of wood carbon skeleton after 1200℃ heat treatment with/without the modification

图3 木头碳及其相变复合物的SEM形貌图

Fig.3 SEM images of the wood carbons and the corresponding phase change composites

图4 样品DSC数据分析

Fig.4 DSC data analysis of the samples

表2 复合相变材料熔化和凝固过程的相变温度及焓值

Table 2 Temperature and enthalpy of PCC during melting and solidification

样品	熔化过程		凝固过程
样品	T_mp/℃	ΔH_m /(J/g)	T_sp/℃	ΔH_s/(J/g)
Paraffin	58.0	203.9	49.8	204.0
C/P-1200	58.4	130.2	48.9	129.3
Ch/C/P-1200	59.1	126.9	48.5	126.6

图5 纯石蜡以及样品Ch/C/P-1200循环前后的红外光谱图

Fig.5 Infrared spectroscopy of paraffin and sample Ch/C/P-1200 before and after cycling

图6 相变复合材料泄漏实验测试

Fig.6 Leakage test of phase change composites

图7 泄漏实验前后样品质量变化

Fig.7 Sample mass change before and after leakage test

图8 复合相变材料的热导率

Fig.8 Thermal conductivity of phase change composites

图9 复合相变材料样品的红外热像图

Fig.9 Infrared thermal response of the composite samples

图10 光热转换实验分析 (模拟1.2个太阳光光强)

Fig.10 Experimental analysis of photothermal conversion (1.2 solar light intensity)

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