微波辅助合成具有优异电化学性能的rGO/CeO2超级电容器电极材料

doi:10.6023/A21050216

摘要/Abstract

CeO₂具有良好的赝电容, 但有关碳/CeO₂复合材料的电化学性能有待改善. 本工作采用简单的微波辅助合成法, 将氧化石墨烯与Ce(NO₃)₃混合发生氧化还原反应, 获得还原氧化石墨烯(rGO)/CeO₂复合材料. 通过形貌观察, CeO₂以颗粒形式均匀分布在褶皱的rGO上, 且沿着rGO表面仿形生长; 纳米级CeO₂颗粒之间存在微小间隙. N₂吸/脱附测试结果表明, rGO/CeO₂具有大的比表面积和介孔孔径, 有益于与电解液充分接触. 通过电化学测试, rGO/CeO₂的比电容高达468 F•g^-1, 经过10000次充放电循环, 电容保持率高达107.3%. 优异的循环稳定性归因于大表面积的rGO与均匀薄层的CeO₂良好的协同效应减少了离子传输的阻力以及CeO₂颗粒之间微小的间隙, 缓解了Ce⁴⁺还原为Ce³⁺过程中发生的晶格膨胀. 将rGO/CeO₂组装成对称型超级电容器rGO/CeO₂||rGO/CeO₂获得的能量密度达18.16 Wh•kg^-1. rGO/CeO₂作为超级电容器电极材料具有广阔前景.

关键词: 微波, 石墨烯, 二氧化铈, 超级电容器, 电化学

CeO₂ possesses excellent pseudocapacitance, nevertheless the electrochemical properties of carbon/CeO₂ composites need to be improved. In this paper, reduced graphene oxide (rGO)/CeO₂ composite is prepared via a simple microwave-assisted synthesis method. The typical synthesis process is as follows. Firstly, 60 mg of graphene oxide was dissolved into 50 mL of deionized water. Then 20 mL of 0.17 mol•L^-1 Ce(NO₃)₃•6H₂O solution was added under ultrasonic conditions. The electrostatic assembly led to the combination of the graphene oxide and Ce(NO₃)₃. Afterwards, 10 mL of 1.5 mol•L^-1 KOH was added dropwise into the mixed solution until the pH value up to 10. The rGO/CeO₂ was synthesized in the above-mentioned mixed solution by using the microwave heating method. The heating time was set for 45 s. Repeated the microwave heating process for five times after the solution cooled down to the room temperature. Finally, the rGO/CeO₂ was harvested by centrifugation, washing and freeze-drying. The CeO₂, in the form of particles, distributes uniformly and conformally on the surface of the corrugated rGO by the morphology observation. The existence of the tiny gaps is displayed between the nano-scaled CeO₂ particles. N₂ adsorption/desorption analysis suggests that the rGO/CeO₂ has large specific area and pores in the mesoporous size, which is helpful to the sufficient contact with the electrolyte. By the electrochemical measurements, the specific capacitance of the rGO/CeO₂ is as high as 468 F•g^-1 and the capacity retention is up to 107.3% after 10000 charge/discharge cycles. The excellent cycling stability is attributed to the good synergistic effect between the rGO with large specific area and the CeO₂ with uniform and thin layer, which decreases the resistance of ion transport, and the tiny gaps between CeO₂ particles, which mitigates the lattice expansion during the transformation from Ce⁴⁺ to Ce³⁺. The energy density of the assembled symmetrical supercapacitor rGO/CeO₂||rGO/CeO₂ reaches 18.16 Wh•kg^-1. As a supercapacitor electrode material, the rGO/CeO₂ has wide prospect.

Key words: microwave, graphene, cerium oxide, supercapacitor, electrochemistry

引用此文

翟耀, 辛国祥, 王佳琦, 张邦文, 宋金玲, 刘晓旭. 微波辅助合成具有优异电化学性能的rGO/CeO₂超级电容器电极材料[J]. 化学学报, 2021, 79(9): 1129-1137.

Yao Zhai, Guoxiang Xin, Jiaqi Wang, Bangwen Zhang, Jinling Song, Xiaoxu Liu. Microwave-assisted Synthesis of rGO/CeO₂ Supercapacitor Electrode Materials with Excellent Electrochemical Properties[J]. Acta Chimica Sinica, 2021, 79(9): 1129-1137.

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图/表 14

图1. GO, rGO和rGO/CeO2的TG曲线

Figure 1. TG curves of GO, rGO and rGO/CeO2

图2. rGO/CeO2和CeO2的XRD衍射谱

Figure 2. XRD patterns of rGO/CeO2 and CeO2

图3. (a) rGO和 (b, c) rGO/CeO2的FESEM图, (d)为(c)的能谱图

Figure 3. FESEM images of (a) rGO and (b, c) rGO/CeO2, (d) shows the energy spectra of (c)

图4. (a, b) CeO2的低倍TEM图, (c, d) rGO/CeO2的低倍TEM图, (e) rGO/CeO2的高分辨TEM图, (f) rGO/CeO2的选择区域电子衍射图

Figure 4. TEM images of (a, b) low-magnification for CeO2, TEM images of (c, d) low-magnification and (e) of high-resolution for rGO/CeO2, (f) selected area electron diffraction pattern of rGO/CeO2

图5. (a) rGO/CeO2的N2吸/脱附曲线, (b) rGO/CeO2孔径分布图

Figure 5. (a) N2 adsorption/desorption isotherm and (b) pore size distribution curve for rGO/CeO2

图6. (a) rGO/CeO2的XPS全谱图, (b) Ce 3d, (c) O 1s和(d) C 1s的分峰图

Figure 6. XPS spectra and fitting peaks for rGO/CeO2: (a) survey spectrum, (b) Ce 3d, (c) O 1s and (d) C 1s

图7. (a) rGO、CeO2和rGO/CeO2在100 mV•s-1扫描速率下的CV曲线, (b) rGO/CeO2在2~100 mV•s-1扫描速率下的CV曲线

Figure 7. (a) CV curves of rGO, CeO2 and rGO/CeO2 at a scan rate of 100 mV•s-1, (b) CV curves of rGO/CeO2 at a scan rate of 2~100 mV•s-1

材料	比电容/ (F•g^-1)	电流密度/扫速	电解液^a	参考文献
CeO₂/C	125	1 A•g^-1	6 M KOH	[12]
CeO₂/rGO	282	2 A•g^-1	3 M KOH	[13]
Graphene oxide/CeO₂	265	5 mV•s^-1	3 M KOH	[28]
CeO₂/activated carbon	162	10 mV•s^-1	1 M H₂SO₄	[31]
CeO₂/rGO	114	0.5 A•g^-1	6 M KOH	[33]
Hollow CeO₂ spheres/graphitic carbon	501	1 A•g^-1	6 M KOH	[34]
rGO/CeO₂	468	0.5 A•g^-1	3 M KOH	This work

表1. 氧化铈/碳基复合材料及其电容值对比

Table 1. CeO2/carbon-based composites and their capacitance values

图8. (a) rGO、CeO2和rGO/CeO2在0.5 A•g-1电流密度下的GCD曲线, (b) rGO/CeO2在0.5~10 A•g-1电流密度下的GCD曲线

Figure 8. (a) GCD curves of rGO, CeO2 and rGO/CeO2 at a current density of 0.5 A•g-1, (b) GCD curve of rGO/CeO2 at 0.5~10 A•g-1 current density

图9. rGO、CeO2和rGO/CeO2的EIS谱, 右下方插图为高频区的放大部分, 左上方插图为rGO/CeO2的等效电路图

Figure 9. EIS spectra of rGO, CeO2 and rGO/CeO2. Inset at the lower right shows magnified high frequency regions, and inset at the higher left shows electrical equivalent circuit

图10. rGO、CeO2和rGO/CeO2经10000次循环后的比电容保持率

Figure 10. Capacitance retention of rGO, CeO2 and rGO/CeO2 for 10000 cycles

图11. 对称型超级电容器rGO/CeO2||rGO/CeO2的电化学性能: (a)装配示意图, (b) 在2~100 mV•s-1扫描速率下的CV曲线, (c) 在0.2~10 A·g-1电流密度下的GCD曲线, (d) EIS谱(插图为高频区的放大部分), (e) 10000次循环后的电容保持率曲线(插图为最后八圈GCD曲线), (f) Ragone图

Figure 11. Electrochemical properties of the rGO/CeO2||rGO/CeO2: (a) Assembly diagram, (b) CV curves at different scan rates of 2~100 mV•s-1, (c) GCD curves at the current densities of 0.2~10A·g-1, (d) EIS spectrum, (inset shows the magnified high frequency region), (e) Capacity retention for 10000 cycles (inset shows the last eight curves of the GCD curves), (f) Ragone plot

图12. 四个rGO/CeO2||rGO/CeO2串联点亮LED灯前后的照片

Figure 12. Photographs of an LED light turned on by four rGO/CeO2||rGO/CeO2 connected in a series

图13. 微波辅助合成法制备rGO/CeO2过程示意图

Figure 13. Schematic illustration for the preparation process of rGO/CeO2 by microwave-assisted synthesis method

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微波辅助合成具有优异电化学性能的rGO/CeO₂超级电容器电极材料

Microwave-assisted Synthesis of rGO/CeO₂ Supercapacitor Electrode Materials with Excellent Electrochemical Properties

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