Controllable preparation method and performance of three-dimensional reduced graphene oxide aerogel under mild conditions
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摘要: 为了实现石墨烯类三维气凝胶在温和环境条件下的大面积可控制备和高性能化，本文应用水合肼作为还原剂，通过低温预冷冻结合室温自然干燥，实现了室温还原自组装法可控制备直径30 cm的大面积三维还原氧化石墨烯(3D-RGO)气凝胶。该方法制备条件温和，不需任何加热条件和特殊冷冻干燥设备。通过对气凝胶制备过程中还原时间、预冷冻时间、预冷冻温度和反应容器进行控制，可以有效调节气凝胶的形状、表面浸润性、体积收缩率等，实现3D-RGO气凝胶的可控制备。该气凝胶不会出现明显的体积收缩和结构破裂，为具有约500 μm的稳定孔径和3.8 mg/cm3的低密度的蜂窝状结构，并能够从90%的压缩应变下快速地恢复到初始状态，其干燥过程体积收缩率<5%；同时该石墨烯气凝胶展现良好稳定的导电性，在压缩应变从0%增加到90%时，其导电率从17.3 S/m增加至115.2 S/m。这种方法经济高效且易于制备出大面积的3D-RGO。Abstract: In order to realize the large-area controllable preparation and high performance of graphene-based three-dimensional aerogels under mild environmental conditions, hydrazine hydrate is used as reducing agent in this paper. Through low-temperature pre-frozen combined with natural drying at room temperature, large-area three-dimensional reduced graphene oxide (3D-RGO) aerogels with a diameter of 30 cm can be prepared effectively and controlled. The method has mild preparation conditions and does not need any heating conditions or special freeze-drying equipment. By controlling the reduction time, pre-frozen time, pre-frozen temperature and reaction vessel during the preparation of 3D-RGO aerogel, the shape, surface wettability, volume shrinkage aerogel can be effectively adjusted to achieve controllable preparation of 3D-RGO aerogel. The 3D-RGO aerogel has no obvious volume shrinkage and structural cracks. The aerogels exhibit a stable honeycomb-like structure with a stable pore size of about 500 μm and a low density of 3.8 mg/cm3, and it can quickly undergo a compression strain of 90% and return to the initial state. The volume shrinkage rate of the aerogels is <5% in the drying process. At the same time, the graphene aerogel exhibits good and stable conductivity. When the compressive strain increases from 0% to 90%, its conductivity increases from 17.3 S/m to 115.2 S/m. This method is suitable for the cost-effective preparation of large-area graphene aerogels.
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图 1 氧化石墨烯(GO)和三维还原氧化石墨烯(3D-RGO)的FTIR图谱
Figure 1. FTIR spectra of graphene oxide (GO) and three-dimensional reduced graphene oxide (3D-RGO)
图 3 3D-RGO的数码照片 (a) 和SEM图像 (b)
Figure 3. Digital photo (a) and SEM image (b) of 3D-RGO
图 4 GO和3D-RGO的Raman图谱
Figure 4. Raman spectra of GO and 3D-RGO
ID/IG—Intensity ratio between the D band and the G band
图 6 不同类型反应容器制备得到的气凝胶
Figure 6. Aerogels prepared according to different types of reaction vessel
图 7 不同工艺条件对3D-RGO气凝胶的体积收缩率的影响：(a) 还原时间；(b) 预冷冻时间；(c) 预冷冻温度；(d) GO溶液浓度
Figure 7. Volume shrinkage of 3D-RGO aerogel prepared with different process conditions: (a) Reduction time; (b) Pre-freeze time; (c) Pre-freeze temperature; (d) Concentrations of GO solution
图 8 不同还原时间制备得到3D-RGO气凝胶的水接触角
Figure 8. Water contact angle of 3D-RGO aerogel prepared under different reduction time
图 9 3D-RGO气凝胶在不同应变下的循环压缩曲线 (a) 和70%应变下的10个循环压缩曲线 (b)
Figure 9. 3D-RGO aerogel cyclic compression curves at different strains (a) and 10 cyclic compression curves at 70% strain (b)
图 10 3D-RGO多次吸水-干燥的循环压缩性能曲线
Figure 10. 3D-RGO repeated water absorption-drying cycle compression performance curves
图 11 不同浓度GO溶液制得的3D-RGO气凝胶的电导率
Figure 11. 3D-RGO aerogel conductivity diagrams prepared with different concentrations of GO solutions
图 12 通过3D-RGO气凝胶压缩应变控制二极管亮度
Figure 12. Controlling diode brightness by compressive strain of 3D-RGO aerogels
图 13 3D-RGO气凝胶压缩过程导电性能变化 (a) 及其归一化电阻变化 (b) 与稳定性曲线 (c)
Figure 13. Change in conductivity of 3D-RGO aerogel during compression (a) and its normalized resistance change (b) and stability curve (c)
Rt/R0—Normalized resistance; Rt—Resistance at time t; R0—Initial resistance
图 14 3D-RGO气凝胶的相对电阻变化随压缩应变的响应曲线
Figure 14. Response curve of 3D-RGO aerogel relative resistance change with compressive strain
ΔR/R0—Relative resistance change
表 1 不同方法制备的3D-RGO气凝胶密度、压缩应变与尺寸比较
Table 1. Density, compressive strain and size ratio of 3D-RGO aerogel prepared by various methods
Sample Method Density/
(mg·cm−3)Compression strain Size/cm GFs[29] CVD ca. 5 No 17×22 Graphene aerogel[30] Supercritical drying 12-96 40% < 5 GF[31] Freeze-drying ca. 2.1 No < 5 UFAs[32] Freeze-drying 0.16 82% ca. 21 MGM[33] Freeze-drying 6.73 50% < 5 CMG-CNs[34] Freeze-drying 2.0 50% < 5 Graphene sponge [35] Freeze-drying 1.7 98% < 5 GFs [36] Sintering 11.3 10% ca. 10 Graphene aerogel [19] Vacuum-/air-drying 5.3 80% < 5 NDGA[2] Air-drying 6.7 99% ca. 10 ADGA[1] Air-drying 2.5 93% ca. 5 RGO/GNP[37] Air-drying ca. 100 50% < 5 GAB[38] Air-drying 2.8 99% >100 CNTS-GR[39] Freeze-drying 1.06 72% 5 3D-RGO
( This work)Air-drying 3.8 90% 30 Notes: GFs, GF—Graphene foams; UFAs—Ultra-flyweight aerogels; MGM—Macroporous graphene monoliths; CMG-CNs—Chemically modified graphene-cellular networks; NDGA—Naturally dried graphene aerogels; ADGA—Ambient pressure dried graphene aerogels; RGO/GNP—Reduced graphene oxide/graphene nanoplatelets; GAB—Graphene aerogel bulk; CNTS-GR—Carbon nanotubes-graphene aerogel; CVD—Chemical vapor deposition; ca.—About. 
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