石墨烯增强的生物炭/正十八烷定型复合相变材料制备及性能研究

doi:10.11949/0438-1157.20250984

摘要/Abstract

摘要：

以农产品废弃物玉米秸秆为生物质前体，经高温热解、KOH刻蚀得到富含多孔结构的生物炭（KBC），利用改进的Hummers法制备氧化石墨烯。通过水热自组装将二者结合，构建了生物炭/还原氧化石墨烯杂化气凝胶（KBC/r-GO），再将有机相变材料正十八烷（ODE）通过真空熔融浸渍的方式封装于杂化气凝胶中，得到石墨烯增强的生物炭/正十八烷定型复合相变材料（KBC/r-GO/ODE）。通过SEM、FT-IR、TGA、DSC等表征手段对其微观结构、形貌和储热性能以及热稳定性进行了研究，发现当KBC/r-GO与ODE的质量比为1：2时，所制备的定型复合相变材料呈现出高负载、无渗漏的特点，其熔融焓高达104.3 J/g，经100次吸、放热循环后仍保持了结构稳定，未出现液体泄露现象，表现出良好的储热性能和热稳定性。此外，由于石墨烯优异的导热、导电性和光热捕获能力，赋予KBC/r-GO/ODE优异的光热、电热转换能力和良好的红外伪装性能。因此KBC/r-GO/ODE在清洁能源转化和存储利用、热管理、红外隐身等方面具有应用前景。

关键词: 生物炭, 石墨烯, 正十八烷, 定型复合相变材料, 光热、电热转换, 红外隐身

Abstract:

In this work, porous biochar (KBC) was synthesized using corn straw as a biomass precursor, through high-temperature pyrolysis and KOH etching. Graphene oxide was prepared using the modified Hummers method synchronously. Afterward, the two materials were combined via hydrothermal self-assembly to construct a biochar/reduced graphene oxide hybrid aerogel (KBC/r-GO). Subsequently, the organic phase change material octadecane (ODE) was encapsulated into the KBC/r-GO by vacuum melting impregnation, yielding a graphene-enhanced biochar/octadecane composite shaped phase change material (KBC/r-GO/ODE). The microstructure, morphology, thermal storage performance, and thermal stability of the KBC/r-GO/ODE were investigated using SEM, FT-IR, TGA, and DSC methods. It was found that as the mass ratio of KBC/r-GO to ODE was 1:2, the resulting composite exhibited high loading capacity and no leakage, with a melting enthalpy as high as 104.3 J/g. After 100 cycles of heat absorption and release, the composite maintained structural stability and no liquid leakage, demonstrating excellent thermal storage and thermal stability. Moreover, due to the superior thermal conductivity, electrical conductivity, and photothermal capture ability of graphene, the KBC/r-GO/ODE composite exhibited excellent photothermal and electrothermal conversion capabilities and good infrared stealth performance. Thus, the prepared KBC/r-GO/ODE has potential applications in clean energy conversion and storage, thermal management, and infrared stealth fields.

Key words: biochar, graphene, n-Octadecane, composite shaped phase change material, photothermal and electrothermal conversion, infrared stealth

中图分类号:

TK02

禹兴海, 张永文, 李艳安, 李月文, 邵文辉. 石墨烯增强的生物炭/正十八烷定型复合相变材料制备及性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20250984.

Xinghai YU, Yongwen ZHANG, Yan'an LI, Yuewen LI, Wenhui SHAO. Preparation and properties of graphene enhanced biochar/ n-octadecane composite phase change materials[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250984.

图/表 17

图1 氮气吸附-脱附等温线（a）（b）及孔径分布曲线（c）（d）

Fig.1 Adsorption-desorption isotherm (a) (b) and pore size distribution curves (c) (d)

表1 比表面积及孔径数据对比

Table 1 Comparison of specific surface area and pore size data

	BC	KBC（1:3）	KBC（1:4）	KBC（1:5）	r-GO	KBC/r-GO
BET surface（m²/g）	3.62	1279.14	1507.41	1976.48	1.81	1993.81
Total volume in pores（cm³/g）	0.004	0.71	0.83	1.03	0.002	1.07
DFT pore size（nm）	2.15	28.30	31.66	37.84	1.26	38.73
Micropore volume（cm³/g）	0.000	0.22	0.12	0.09	0.00	0.14
Mesoporous volume（cm³/g）	0.002	0.37	0.53	0.92	0.001	0.87

图2 BC（a）（b）、KBC（c）（d）的SEM图

Fig.2 SEM images of BC (a) (b) and KBC (c) (d)

图3 r-GO（a）（b）、KBC/r-GO（c）（d）和KBC/r-GO/ODE（e）（f）的SEM图

Fig.3 SEM images of r-GO (a) (b)、KBC/r-GO (c) (d) and KBC/r-GO/ODE (e) (f)

图4 KBC、r-GO、KBC/r-GO、ODE及KBC/r-GO/ODE的FT-IR图

Fig.4 Infrared spectrogram of KBC、r-GO、KBC/r-GO、ODE and KBC/r-GO/ODE

图5 KBC、r-GO、KBC/r-GO、KBC/r-GO/ODE及ODE的XRD谱图

Fig.5 XRD patterns of KBC、r-GO、KBC/r-GO、KBC/r-GO/ODE and ODE

图6 KBC、GO、r-GO、KBC/r-GO的Raman光谱图

Fig.6 Raman spectra of KBC、GO、r-GO、KBC/r-GO

图7 KBC、r-GO、KBC/r-GO、KBC/r-GO/ODE、ODE的TGA图

Fig.7 TGA curves of KBC、r-GO、KBC/r-GO、KBC/r-GO/ODE and ODE

图8 ODE和KBC/r-GO/ODE的渗露测试图

Fig.8 Leakage text images of ODE and KBC/r-GO/ODE

图 9 KBC、KBC/r-GO、KBC/r-GO/ODE、ODE的DSC曲线

Fig. 9 DSC curves of KBC、KBC/r-GO、KBC/r-GO/ODE and ODE

表2 纯ODE与KBC/r-GO/ODE的DSC数据

Tab.2 The DSC data of pure ODE and KBC/r-GO/ODE

样品	熔融温度T_m（℃）	熔融焓值ΔH_m（J/g）	结晶温度T_f（℃）
纯ODE	28.0	190.9	25.6	190.3
1:1	27.1	24.15	25.0	23.83
1:1.5	27.7	63.06	25.4	61.58
1:2	27.9	104.3	26.0	103.5

图10 KBC/r-GO/ODE循环前后的DSC曲线（a）和FT-IR（b）

Fig.10 DSC curves (a) and infrared spectrogram (b) of KBC/r-GO/ODE before and after cycling

图11 KBC/r-GO/ODE电传导测试（a）（b）及U-I曲线（c）

Fig.11 KBC/r-GO/ODE electrical conductivity test (a) (b) and U-I curve (c)

图12 KBC/r-GO/ODE光热转换热成像图及光热转换测试曲线

Fig.12 Infrared thermograms and photothermal conversion test curves of KBC/r-GO/ODE photothermal conversion

图13 KBC/r-GO/ODE电热转换热成像图及电热转换测试曲线

Fig.13 Infrared thermograms and photothermal conversion test curves of KBC/r-GO/ODE electrothermal conversion

图14 50 ℃下KBC/r-GO/ODE的热成像图及温度变化曲线

Fig.14 Infrared thermography and temperature-time response curves of KBC/r-GO/ODE at 50 ℃

图15 体温下KBC/r-GO/ODE的热成像图及温度变化曲线

Fig.15 Infrared thermography and temperature-time response curves of KBC/r-GO/ODE at human body temperature

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