Controllable synthesis of 2D mesoporous nitrogen-doped carbon/graphene nanosheets for high-performance micro-supercapacitors
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摘要: 石墨烯基二维介孔材料能够有效耦合石墨烯基底、功能化材料和介孔结构的优势，被认为是一种理想的微型超级电容器电极材料。基于此，本文以苯胺为前驱体，氧化石墨烯为二维导向剂，二氧化硅纳米球为介孔模板，采用双模板界面诱导自组装法制备介孔氮掺杂炭/石墨烯（mNC/G）纳米片，并实现了其介孔孔径的精确调控和电化学性能的优化。研究表明，7 nm孔径的介孔氮掺杂炭/石墨烯（mNC/G-7）展现出267 F g−1的高比电容，且应用于准固态平面微型超级电容器表现出21.0 F cm−3的体积比电容和1.9 mWh cm−3的体积能量密度，证明了该二维介孔氮掺杂炭/石墨烯纳米片在微型超级电容器应用方面具有良好的前景。Abstract: Graphene-based 2D mesoporous materials have been considered ideal electrode materials for micro-supercapacitors (MSCs). 2D mesoporous nitrogen-doped carbon/graphene (mNC/G) nanosheets were prepared by the solution polymerization of aniline as the carbon and nitrogen precursor, in mixtures of graphene oxide as a guide for the 2D structure and silica nanospheres as a mesopore template. This was followed by leaching with dilute NaOH to remove the silica, freeze drying and carbonization. The nanosheets were formed from the templated mesoporous nitrogen-doped carbon decorating both sides of the graphene sheets. Precise regulation of the mesopore size and optimization of the electrochemical performance of the material were achieved. mNC/G with a pore size of 7 nm (mNC/G-7) had a specific capacitance of 267 F g−1, and quasi-solid-state planar MSCs based on it had a high volumetric capacitance of 21.0 F cm−3 and an energy density of 1.9 mWh cm−3, indicating the tremendous potential of 2D mNC/G for MSCs.
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图 1 2D mNC/G纳米片的合成示意图
Figure 1. Schematic illustration of the synthesis of 2D mNC/G nanosheets.
图 2 2D mNC/G的结构与形貌表征图:（a-c）mNC/G-7、mNC/G-12和mNC/G-22的TEM图，（d-f）mNC/G-7、mNC/G-12和mNC/G-22的HRTEM图，（g）mNC/G-7的等温吸附线（插图为孔径分布曲线），（h）mNC/G-7的AFM图像，（i）mNC/G-7的XPS N1s拟合谱图
Figure 2. Characterization of 2D mNC/G. (a-c) TEM images of mNC/G-7, mNC/G-12 and mNC/G-22, (d-f) HRTEM images of mNC/G-7, mNC/G-12 and mNC/G-22, (g) nitrogen adsorption-desorption isotherm of mNC/G-7 (Inset: pore size distribution profile), (h) AFM image and thickness of mNC/G-7, (i) XPS spectrum of N 1s for mNC/G-7.
图 3 2D mNC/G的电化学性能:（a）mNC/G-7的CV曲线，（b）mNC/G-7的GCD曲线，（c）mNC/G-7、mNC/G-12和mNC/G-22在1 A g−1时的GCD曲线，（d）mNC/G-7、mNC/G-12和mNC/G-22比电容随电流密度变化的曲线，（e）mNC/G-7、mNC/G-12和mNC/G-22的EIS图，（f）mNC/G-7、mNC/G-12和mNC/G-22的循环性能
Figure 3. Electrochemical performance of 2D mNC/G. (a) CV curves and (b) GCD profiles of mNC/G-7, (c) GCD profiles obtained at 1 A g−1, (d) specific capacity versus current density, (e) EIS plots and (f) cycling stability of mNC/G-7, mNC/G-12 and mNC/G-22.
图 4 mNC/G-MSCs的电化学性能:（a）微电极的俯视SEM和（b）横截面SEM图,（c）mNC/G-MSCs在5~100 mV s−1下的CV曲线，（d）mNC/G-MSCs在0.05~1 mA cm−2下的GCD曲线，（e）mNC/G-MSCs比电容随扫描速率的变化曲线，（f，g）1~3个器件并联的CV和GCD曲线，（h，i）是1~3个器件串联的CV和GCD曲线
Figure 4. Electrochemical performance of mNC/G-MSCs. (a) Top-view and (b) cross-section SEM images of microelectrodes, (c) CV curves measured at scan rates of 5-100 mV s−1, (d) GCD profiles tested at current density of 0.05-1 mA cm−2, and (e) specific capacity versus scan rates of mNC/G-MSCs, (f-i) CV curves and GCD profiles of three mNC/G-MSCs connected (f, g) in parallel, and (h, i) in series.
图 5 mNC/G-MSCs的Ragone图和展示图:（a）mNC/G-MSCs的面积能量密度和功率密度曲线，（b）mNC/G-MSCs体积能量密度和功率密度曲线；（c，d）串联mNC/G-MSCs点亮LCD的光学照片
Figure 5. Ragone plot and application photographs of mNC/G-MSCs. (a) Ragone plot of areal energy density and power density of mNC/G-MSCs, (b) Ragone plot of volumetric energy density and power density of mNC/G-MSCs, (c,d) optical images of LCDs powered by three serially-connected mNC/G-MSCs.
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