Joule-heating studies of electrically conducting three-dimensional graphene aerogels prepared by hydrothermal assembly

doi:10.11949/0438-1157.20210198

Abstract

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

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

CLC Number:

O 69

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.

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.

Figures/Tables 9

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

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

Fig.2 Electrically-conducting rHT-GO aerogels

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

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

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))

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

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

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

References 33

1	刘海波, 王成辉, 周茜, 等. 石墨烯在金属基复合材料中的应用研究与进展[J]. 热加工工艺, 2020, 49(24): 8-14, 20.
	Liu H B, Wang C H, Zhou Q, et al. Application research and progress of graphene in metal matrix composite[J]. Hot Working Technology, 2020, 49(24): 8-14, 20.
2	陈站, 刘晓国, 宋松林, 等. 石墨烯及氧化石墨烯应用在电性能涂料中的研究进展[J]. 电镀与涂饰, 2020, 39(10): 660-664.
	Chen Z, Liu X G, Song S L, et al. Research progress on applications of graphene and graphene oxide in electrical coatings[J]. Electroplating & Finishing, 2020, 39(10): 660-664.
3	覃荣华, 曾丹林, 王荣, 等. 石墨烯基催化材料的制备及其应用研究进展[J]. 化工新型材料, 2020, 48(12): 29-33.
	Qin R H, Zeng D L, Wang R, et al. Review in preparation and application of rGO-based catalytic material[J]. New Chemical Materials, 2020, 48(12): 29-33.
4	Xia D, Li H, Mannering J, et al. Electrically heatable graphene aerogels as nanoparticle supports in adsorptive desulfurization and high-pressure CO₂ capture[J]. Advanced Functional Materials, 2020, 30(40): 2002788.
5	Cheng C, Li S, Thomas A, et al. Functional graphene nanomaterials based architectures: biointeractions, fabrications, and emerging biological applications[J]. Chemical Reviews, 2017, 117(3): 1826-1914.
6	Li J S, Wang Y, Liu C H, et al. Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution[J]. Nature Communications, 2016, 7: 11204.
7	Sriwong C, Choojun K, Kongtaweelert S. Investigation of the influences of reaction temperature and time on the chemical reduction of graphene oxide by conventional method using vitamin C as a reducing agent[J]. Materials Science Forum, 2017, 909: 225-230.
8	Liu Y J, Li P, Wang F, et al. Rapid roll-to-roll production of graphene films using intensive Joule heating[J]. Carbon, 2019, 155: 462-468.
9	Ren L, Wang M, Lu S, et al. Tailoring thermal transport properties of graphene paper by structural engineering[J]. Scientific Reports, 2019, 9(1): 4549.
10	安飞, 孙冰, 李娜, 等. 三维石墨烯的制备及其在电阻型气体传感器领域的应用[J]. 材料工程, 2020, 48(12): 24-35.
	An F, Sun B, Li N, et al. Research on the fabrication of 3D graphene and its application in chemiresistive gas sensors[J]. Journal of Materials Engineering, 2020, 48(12): 24-35.
11	Shehzad K, Xu Y, Gao C, et al. Three-dimensional macro-structures of two-dimensional nanomaterials[J]. Chemical Society Reviews, 2016, 45(20): 5541-5588.
12	Perreault F, Fonseca de Faria A, Elimelech M. Environmental applications of graphene-based nanomaterials[J]. Chemical Society Reviews, 2015, 44(16): 5861-5896.
13	Yousefi N, Lu X L, Elimelech M, et al. Environmental performance of graphene-based 3D macrostructures[J]. Nature Nanotechnology, 2019, 14(2): 107-119.
14	Zhang X T, Sui Z Y, Xu B, et al. Mechanically strong and highly conductive graphene aerogel and its use as electrodes for electrochemical power sources[J]. Journal of Materials Chemistry, 2011, 21(18): 6494-6497.
15	Zhou G H, Kim N R, Chun S E, et al. Highly porous and easy shapeable poly-dopamine derived graphene-coated single walled carbon nanotube aerogels for stretchable wire-type supercapacitors[J]. Carbon, 2018, 130: 137-144.
16	Han Z, Tang Z, Li P, et al. Ammonia solution strengthened three-dimensional macro-porous graphene aerogel[J]. Nanoscale, 2013, 5(12): 5462-5467.
17	Zhang Q Q, Wang Y, Zhang B Q, et al. 3D superelastic graphene aerogel-nanosheet hybrid hierarchical nanostructures as high-performance supercapacitor electrodes[J]. Carbon, 2018, 127: 449-458.
18	Fu Y, Wang G, Mei T, et al. Accessible graphene aerogel for efficiently harvesting solar energy[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 4665-4671.
19	Deerattrakul V, Yigit N, Rupprechter G, et al. The roles of nitrogen species on graphene aerogel supported Cu-Zn as efficient catalysts for CO₂ hydrogenation to methanol[J]. Applied Catalysis A: General, 2019, 580: 46-52.
20	Barg S, Perez F M, Ni N, et al. Mesoscale assembly of chemically modified graphene into complex cellular networks[J]. Nature Communications, 2014, 5: 4328.
21	Zhu C, Han T Y, Duoss E B, et al. Highly compressible 3D periodic graphene aerogel microlattices[J]. Nature Communications, 2015, 6: 6962.
22	Wu Z S, Winter A, Chen L, et al. Three-dimensional nitrogen and boron co-doped graphene for high-performance all-solid-state supercapacitors[J]. Advanced Materials, 2012, 24(37): 5130-5135.
23	Li J, Li J, Meng H, et al. Ultra-light, compressible and fire-resistant graphene aerogel as a highly efficient and recyclable absorbent for organic liquids[J]. Journal of Materials Chemistry A, 2014, 2(9): 2934-2941.
24	Menzel R, Barg S, Miranda M, et al. Joule heating characteristics of emulsion-templated graphene aerogels[J]. Advanced Functional Materials, 2015, 25(1): 28-35.
25	Xia D, Li H, Huang P. Understanding the Joule-heating behaviours of electrically-heatable carbon-nanotube aerogels[J]. Nanoscale Advances, 2021, 3(3): 647-652.
26	Xia D, Li H, Huang P, et al. Boron-nitride/carbon-nanotube hybrid aerogels as multifunctional desulfurisation agents[J]. Journal of Materials Chemistry A, 2019, 7(41): 24027-24037.
27	Liu T, Huang M L, Li X F, et al. Highly compressible anisotropic graphene aerogels fabricated by directional freezing for efficient absorption of organic liquids[J]. Carbon, 2016, 100: 456-464.
28	Li T, Pickel A D, Yao Y G, et al. Thermoelectric properties and performance of flexible reduced graphene oxide films up to 3, 000 K[J]. Nature Energy, 2018, 3(2): 148-156.
29	Hong J Y, Sohn E H, Park S, et al. Highly-efficient and recyclable oil absorbing performance of functionalized graphene aerogel[J]. Chemical Engineering Journal, 2015, 269: 229-235.
30	Xia D, Huang P, Li H, et al. Fast and efficient electrical-thermal responses of functional nanoparticle decorated nanocarbon aerogels[J]. Chemical Communications, 2020, 56(92): 14393-14396.
31	Bao W Z, Pickel A D, Zhang Q, et al. Flexible, high temperature, planar lighting with large scale printable nanocarbon paper[J]. Advanced Materials, 2016, 28(23): 4684-4691.
32	Wang K, Zeng Y J, Lin W Z, et al. Energy-efficient catalytic removal of formaldehyde enabled by precisely Joule-heated Ag/Co₃O₄@mesoporous-carbon monoliths[J]. Carbon, 2020, 167: 709-717.
33	Xia D, Xu Y F, Mannering J, et al. Tuning the electrical and solar thermal heating efficiencies of nanocarbon aerogels[J]. Chemistry of Materials, 2021, 33(1): 392-402.

[1]	Wenjie XU, Xianfeng JIA, Jitong WANG, Wenming QIAO, Licheng LING, Renping WANG, Zijian YU, Yinxu ZHANG. Preparation and properties of silicone/phenolic hybrid aerogel [J]. CIESC Journal, 2023, 74(8): 3572-3583.
[2]	Kunyang FAN, Jingxing YANG, Haibo XU, Xingrong LIAN, Fengmei HE, Conghui CHEN, Zengyao LI. A unified lattice Boltzmann model for heat transfer in opacifiers-doped silica aerogel [J]. CIESC Journal, 2023, 74(5): 1974-1981.
[3]	Jinlin MENG, Yu WANG, Qunfeng ZHANG, Guanghua YE, Xinggui ZHOU. Pore network model of low-temperature nitrogen adsorption-desorption in mesoporous materials [J]. CIESC Journal, 2023, 74(2): 893-903.
[4]	Xuemei LANG, Liumei YAO, Shuanshi FAN, Gang LI, Yanhong WANG. Numerical simulation of methane hydrate formation and heat transfer in porous materials [J]. CIESC Journal, 2022, 73(9): 3851-3860.
[5]	Duanhui GAO, Weiqiang XIAO, Feng GAO, Qian XIA, Manqiu WANG, Xinbo LU, Xiaoli ZHAN, Qinghua ZHANG. Preparation and application of polyimide-based aerogels [J]. CIESC Journal, 2022, 73(7): 2757-2773.
[6]	Huifang NIU, Lunjing YAN, Peng LYU, Xufeng ZHANG, Meijun WANG, Jiao KONG, Weiren BAO, Liping CHANG. Preparation and analysis of carbon aerogel microspheres based on coal tar pitch [J]. CIESC Journal, 2022, 73(12): 5605-5614.
[7]	Qingling QIAN, Qing ZHU, Zhengjin YANG, Tongwen XU. Microporous Noria polymer for selective adsorption and separation of xylene isomers [J]. CIESC Journal, 2022, 73(12): 5438-5448.
[8]	WANG Shaoyu, MA Hanze, WU Hong, LIANG Xu, WANG Hongjian, ZHU Ziting, JIANG Zhongyi. Research advances of organic framework membranes in gas separation [J]. CIESC Journal, 2021, 72(7): 3488-3510.
[9]	WANG Yanqiu,ZHONG Zhaoxiang,XING Weihong. Progress in three-dimensional metal oxide nanomaterials [J]. CIESC Journal, 2021, 72(5): 2339-2353.
[10]	Chunjie XIE, Ran HE, Xinlin TUO, Wantai YANG. Preparation and performance of para-aramid aerogel powders [J]. CIESC Journal, 2021, 72(12): 6361-6370.
[11]	Yun ZHAO, Zhonghua XIANG. Progress of microfluidic synthesis of metal/covalent organic frameworks [J]. CIESC Journal, 2020, 71(6): 2547-2563.
[12]	Li CHEN, Cailong ZHOU, Jingcheng DU, Wei ZHOU, Luxi TAN, Lichun DONG. Progress of superhydrophobic porous materials [J]. CIESC Journal, 2020, 71(10): 4502-4519.
[13]	Qiuhui YAN,Xiaoyang SUN,Jieren LUO,Zhiju WU. Study on modification of glass wool/SiO₂ aerogel combined board [J]. CIESC Journal, 2019, 70(S2): 363-368.
[14]	Xuan ZHANG, Jiaxing YANG, Qiuyang JIN, Mingxing TONG, Junxi ZHOU, Jing GAO, Guohua LI. Preparation of nitrogen-doped carbon aerogel under hypersaline condition and its application for supercapacitors [J]. CIESC Journal, 2019, 70(7): 2748-2757.
[15]	Yuhan ZHOU, Xiaoyu CHEN, Cheng ZUO, Qingjie GUO, Jun ZHAO. Performances of waste paper cellulose/SiO₂ composite aerogel [J]. CIESC Journal, 2019, 70(3): 1120-1126.