Building a high-performance supercapacitor with α-MnO2@nitrided TiO2/carbon fiber paper porous structure
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摘要: MnO2由于价格低廉、资源丰富、理论比电容高和环境友好等优点而成为理想的超级电容器电极材料。然而，如何通过成本低的合成方法获得高负载量和高性能的MnO2电极材料，仍是一项重大的挑战。因此，通过晶种辅助水热合成及氮化处理，在预处理碳纤维纸(CFP)表面生长了氮掺杂TiO2(N-TiO2)纳米棒阵列，然后再通过水热合成在N-TiO2上生长了新颖的纳米带缠绕纳米花分级混合结构的α-MnO2(α-MnO2@N-TiO2/CFP)。这种分级多孔纳米带缠绕纳米花及纳米棒阵列混合结构能够提供合适的几何空间和电子结构，有助于抑制高质量负载下的活性物质堆积，提高了电极材料的比电容。在α-MnO2负载量高达20.9 mg·cm−2的情况下，该电极材料在电流密度为1 mA·cm−2时的面积比容量高达3.0 F·cm−2，且循环5000次后无电容衰减，具有优异的循环稳定性。因此，α-MnO2@N-TiO2/CFP电极材料是一种极具应用潜力的超级电容器电极材料。Abstract: MnO2 is considered as a promising electrode material for supercapacitors because of its low cost, high abundance, large theoretical specific capacitance and environmentally friendly nature. How to obtain high-performance MnO2 electrode material with high mass loading via a low-cost synthesis method has attracted considerable attention and still remained a huge challenge. Herein, nitrided TiO2 nanorod arrays (N-TiO2) were successfully prepared on carbon fiber paper (CFP) by a novel seeded hydrothermal synthesis and thermal nitridation, and then hierarchical porous α-MnO2 nanoflowers entwined with nanoribbons were grown on the nitrided TiO2/CFP electrode. Hierarchical porous nanoflowers entwined with nanoribbons and nanorod arrays provide appropriate geometries and electronic structures, helping suppress stack tendency at high mass loading and improve the specific capacitance of electrode. The α-MnO2@N-TiO2/CFP electrode with high mass-loading of 20.9 mg·cm−2 shows a high areal capacitance of 3.0 F·cm−2 at 1 mA·cm−2 and excellent cycling stability with no capacitance reduction after 5000 cycles. The high performance makes the α-MnO2@N-TiO2/CFP electrode a promising electrode material for supercapacitor applications.
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图 1 α-MnO2@氮掺杂 TiO2(N-TiO2)/碳纤维纸(CFP)和α-MnO2/CFP合电极材料的合成示意图
Figure 1. Schematic of the synthesis procedure of α-MnO2@nitrided TiO2 (N-TiO2)/carbon fiber paper (CFP) and α-MnO2/CFP composite electrode materials
SDS—Sodium dodecyl sulfate
图 2 N-TiO2/CFP、α-MnO2@N-TiO2/CFP和α-MnO2/CFP的XRD图谱(a)和拉曼图谱(b)
Figure 2. XRD patterns (a) and Raman spectra of N-TiO2/CFP, α-MnO2@N-TiO2/CFP and MnO2/CFP
图 3 N-TiO2/CFP((a)、(b))、α-MnO2/ CFP((c)、(d))、α-MnO2@N-TiO2/CFP((e)、(f))在低倍率下 及高倍率下的SEM图像
Figure 3. SEM images of N-TiO2/CFP ((a), (b)), α-MnO2/CFP ((c), (d)) and α-MnO2@N-TiO2/CFP ((e), (f)) at lower and higher-magnification
图 4 α-MnO2@N-TiO2/CFP的SEM图像及EDS图谱
Figure 4. SEM image and EDS mapping of α-MnO2@N-TiO2/CFP
图 5 N-TiO2/CFP、α-MnO2/ CFP和α-MnO2@N-TiO2/CFP复合电极材料在50 mV·s−1下的CV曲线 (a) 和复合材料的交流阻抗谱 (d)；α-MnO2/CFP (b) 和α-MnO2@N-TiO2/CFP/CFP (c) 在不同扫速下的CV曲线
Figure 5. Cyclic voltammograms of the N-TiO2/CFP, α-MnO2/CFP and α-MnO2@N-TiO2/CFP electrode at a scan rate of 50 mV s−1 (a) and nyquist plots of the electrodes (d); Cyclic voltammograms of the α-MnO2/CFP (b) and α-MnO2@N-TiO2/CFP (c) electrodes at different scan rates
图 6 N-TiO2/CFP、α-MnO2/ CFP和α-MnO2@N-TiO2/CFP在2 mA·cm−2下的充放电曲线(a)、α-MnO2/CFP(b)和α-MnO2@N-TiO2/CFP(c)的充放电曲线、α-MnO2/CFP和α-MnO2@N-TiO2/CFP在不同的电流密度下的面积比电容(d)
Figure 6. Galvanostatic charge-discharge profiles of N-TiO2/CFP, α-MnO2/ CFP and α-MnO2@N-TiO2/CFP electrodes at a current density of 2 mA·cm−2 (a), galvanostatic charge-discharge profiles of α-MnO2/CFP (b) and α-MnO2@N-TiO2/CFP (c) electrodes at different charge/discharge current densities, areal capacitance of α-MnO2/ CFP and α-MnO2@N-TiO2/CFP electrodes at different charge/discharge current densities (d)
图 7 α-MnO2/ CFP和α-MnO2@N-TiO2/CFP在16 mA·cm−2的电流密度下的循环性能(a)、α-MnO2@N-TiO2/CFP ((b)、(c)) 和α-MnO2/ CFP ((d)、(e)) 5000次循环后的SEM图像、α-MnO2@N-TiO2/CFP在5000次循环前后的交流阻抗图(f)
Figure 7. Cycle life of α-MnO2/CFP and α-MnO2@N-TiO2/CFP electrodes at a current density of 16 mA·cm-2 (a), SEM images of α-MnO2@N-TiO2/CFP ((b), (c)) and α-MnO2/CFP ((d), (e)) after 5000 cycles, nyquist plots of α-MnO2@N-TiO2/CFP electrode before and after 5000 cycles (f)
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