水热法制备三维导电石墨烯气凝胶及其焦耳热性能研究

doi:10.11949/0438-1157.20210198

摘要/Abstract

摘要：

采用水热法将氧化石墨烯（GO）组装成三维圆柱状结构，通过冷冻干燥和高温热还原法成功制备三维导电的还原氧化石墨烯气凝胶。该气凝胶内部的高度交联和多孔道网状结构为电子传输提供有效路径，利于系统的焦耳热研究。结果表明，通过对其进行电流加热，石墨烯气凝胶表现出高功率-温度线性相关性、高电热转换效率、超快升温和降温速率、长时间且稳定的循环加热能力。通过不同模型验证了气凝胶内部可进行焦耳热传导，其高电导率主要由材料自身较低的活化能所决定。石墨烯气凝胶超高的热导率赋予其超快的自然降温速率（456 K?min^-1），远高于传统的热传导加热装置。此外，所制备的气凝胶还可被广泛应用于焦耳热辅助的催化剂温度可控的载体。

关键词: 水热法制备氧化石墨烯, 气凝胶, 多孔材料, 焦耳热, 电热响应

Abstract:

Joule-heating studies of different electric-conducting nanocarbon aerogels have been extensively exploited, however, there are no systematic investigations on the Joule-heating characteristics of reduced graphene oxide (rGO) aerogels prepared via the hydrothermal approach. Therefore, this work adopted the hydrothermal and freeze-drying methods, followed by thermal reduction to fabricate three-dimensional, cylindrical, and electric-conducting reduced hydrothermal graphene oxide aerogel, i.e., rHT-GO aerogel. Electron microscopic analysis showed that the aerogel interior presented a high density of nanocarbon interconnectivity and multiscale porosity, providing numerous paths for electrons to transport, hence available for systematic Joule-heating studies. The results demonstrated that the power input and Joule-heating temperature exhibited a good linear correlation with R² > 0.999, high electrothermal transformation efficiency (reaching up to 128℃ with only 2 W energy consumption), ultrafast heating/cooling capacities, long-duration electrothermal performance and excellent cycling capability. The 3D variable range hopping (3D VRH) model elucidated that the Joule-heating effects can reach the entire rHT-GO aerogel. The high electrical conductivity (9.0 S?m^-1) was originated from the small bandgap (E_a= 0.015 eV). Additionally, the radial temperature gradient fitting results corroborated that the as-prepared rHT-GO aerogels also displayed distinct thermal conductivity (0.222 W?m^-1?K^-1), resulting in their ultrafast cooling rates (456 K?min^-1) and consequently outperforming traditional external radiative heating modes. Importantly, the as-prepared cylindrical rHT-GO aerogels in this study can also be potentially utilized as Joule-heating-assisted adsorption/desorption agents, energy-efficient heaters, temperature-controllable catalyst supports, highly accurate sensors, and solar water evaporators.

Key words: graphene oxide prepared by hydrothermal method, aerogel, porous materials, Joule-heating, electrothermal response

中图分类号:

O 69

夏东, 黄朋, 李恒. 水热法制备三维导电石墨烯气凝胶及其焦耳热性能研究[J]. 化工学报, 2021, 72(7): 3839-3848.

XIA Dong, HUANG Peng, LI Heng. Joule-heating studies of electrically conducting three-dimensional graphene aerogels prepared by hydrothermal assembly[J]. CIESC Journal, 2021, 72(7): 3839-3848.

图/表 9

表1 原材料与试剂

Table 1 Chemical and reagents

名称	规格	生产厂家
氧化石墨烯	直径为0.3~0.7 cm的薄片	William Blythe Limited
抗坏血酸	AR	Sigma-Aldrich
水	HPLC	Fisher Scientific, UK

图1 制备导电还原氧化石墨烯气凝胶的示意图和焦耳热实验的示意图

Fig.1 Schematic representation of preparing electrically-conducting rHT-GO aerogels and Joule-heating measurements

图2 氧化还原石墨烯气凝胶的焦耳热测量

Fig.2 Electrically-conducting rHT-GO aerogels

图3 还原氧化石墨烯气凝胶的拉曼谱图(a)和还原氧化石墨烯气凝胶在空气中的热重分析(b)

Fig.3 Raman spectroscopy (a) of the rHT-GO aerogel and thermogravimetric analysis (b) of the rHT-GO aerogel in air

图4 还原氧化石墨烯气凝胶不同分辨率的扫描电镜图[(a)、(b)]和还原氧化石墨烯气凝胶的透射电镜图(c)

Fig.4 SEM images of rHT-GO aerogels[(a),(b)] and TEM image (c) of rHT-GO aerogels

表2 氧化还原石墨烯气凝胶的物理以及电热性质参数

Table 2 Physical and electrothermal parameters of the as-prepared rHT-GO aerogel

直径/m

高度/m

密度/

(mg?cm^-3)

电导率，σ/

(S·m^-1)

热导率，κ/

(W?(m^-1?K^-1))

图5 还原氧化石墨烯气凝胶的电热性质

Fig.5 Electrothermal characteristics of rHT-GO aerogels under Joule-heating

图6 还原氧化石墨烯气凝胶的循环升降温曲线

Fig.6 Heating and cooling kinetics of rHT-GO aerogels

图7 参数线性拟合，气凝胶温度测量示意图和获得热传导数值的一维径向温度梯度拟合图

Fig.7 Fitted curve of models, description of the temperature record at different position and thermal temperature gradient fitting method and curve of the rHT-GO aerogel

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