High performance flexible energy storage device based on copper foam supported NiMoO4 nanosheets-CNTs-CuO nanowires composites with core-shell holey nanostructure

doi:10.1016/j.jmst.2020.11.076

Abstract

Abstract:

Because of the intensified electrochemical activities, mixed metal oxides as a representative for pseudocapacitive materials play a key role for high performance supercapacitor electrodes. Nevertheless, low ion and electron transfer rate and poor cycling performance in the electrode practically restrict further promotion of their electrochemical performance. In order to offset the defect, a novel copper (Cu) foam-supported nickel molybdate nanosheet decorated carbon nanotube wrapped copper oxide nanowire array (NiMoO₄ NSs-CNTs-CuO NWAs/Cu foam) flexible electrode is constructed. The as-prepared electrode demonstrates a unique core-shell holey nanostructure with a large active surface area, which can provide a large number of active sites for redox reactions. Besides, the CNTs networks supply improved conductivity, which can hasten electron transport. Through this simple and efficient design method, the spatial distribution of each component in the flexible electrode is more orderly, short and fast electron transport path with low intrinsic resistance. As a result, the NiMoO₄ NSs-CNTs-CuO NWAs/Cu foam as an adhesiveless supercapacitor electrode material exhibits excellent energy storage performance with high specific areal capacitance of 23.40 F cm^-2 at a current density of 2 mA cm^-2, which outperforms most of the flexible electrodes reported recently. The assembled asymmetric supercapacitor demonstrates an energy density up to 96.40 mW h cm^-3 and a power density up to 0.4 W cm^-3 under a working voltage window of 1.7 V. In addition, outstanding flexibility of up to 100° bend and good cycling stability with the capacitance retention of 82.53 % after 10,000 cycles can be obtained.

Key words: Supercapacitor, Binary metal oxide, Flexible electrode, Pseudocapacitive material, Core-shell nanostructure

Pingping Yao, Chenyang Li, Jiali Yu, Shuo Zhang, Meng Zhang, Huichao Liu, Muwei Ji, Guangtao Cong, Tao Zhang, Caizhen Zhu, Jian Xu. High performance flexible energy storage device based on copper foam supported NiMoO₄ nanosheets-CNTs-CuO nanowires composites with core-shell holey nanostructure[J]. J. Mater. Sci. Technol., 2021, 85: 87-94.

Figures/Tables 8

Fig. 1. Schematic illustration of the fabrication process of the NiMoO4 NSs-CNTs-CuO NWAs/Cu foam flexible electrode.

Fig. 2. (a, b) SEM images of Cu(OH)2 NWAs at low and high magnifications; the inset shows the SEM image of the pristine Cu foam. (c) SEM image of CNTs-Cu(OH)2 NWAs. (d, e, f) SEM images of NiMoO4 NSs-CNTs-CuO NWAs at different magnifications. (g) EDX mappings of NiMoO4 NSs-CNTs-CuO nanowire.

Fig. 3. (a, b) TEM images of NiMoO4 NSs-CNTs-CuO nanowire at low and high magnifications. (c) EDX mappings of NiMoO4 NSs-CNTs-CuO nanowire. (d, e) HR-TEM images of NiMoO4 nanosheet at low and high magnifications.

Fig. 4. (a) XRD patterns of different samples. High resolution XPS spectra of (b) Cu 2p, (c) Ni 2p, (d) Mo 3d, (e) O 1s and (f) C 1s for NiMoO4 NSs-CNTs-CuO NWAs/Cu foam electrode.

Fig. 5. Raman spectra of Cu foam, CNTs-Cu(OH)2 NWAs/Cu foam, and NiMoO4 NSs-CNTs-CuO NWAs/Cu foam.

Fig. 6. (a) CV curves of different samples at the scan rate of 20 mV s-1. (b) GCD curves of different samples at the current density of 40 mA cm-2. (c) CV curves of NiMoO4 NSs-CNTs-CuO NWAs/Cu foam electrode at different scan rates. (d) Specific capacitances of NiMoO4 NSs-CNTs-CuO NWAs/Cu foam electrode at different current densities.

Fig. 7. (a) Schematic diagram of the asymmetric supercapacitor structure. (b) CV curves of NiMoO4 NSs-CNTs-CuO NWAs/Cu foam and carbon cloth. (c) CV curves of the supercapacitor at different potentials at the scan rate of 50 mV s-1. (d) Relationship of the specific areal capacitance with different voltages. (e) CV curves of the supercapacitor at various scan rates. (f) GCD curves of the device obtained at different current densities. (g) Specific areal and volume capacitances at different scan rates. (h) Log (peak current) versus log (scan rate) based on the CV curves.

Fig. 8. (a) Digital image of the NiMoO4 NSs-CNTs-CuO NWAs/Cu foam flexible electrode at different bending angles. (b) CV curves comparison of the flexible device at different bending angles. (c) Capacitance retention of the flexible supercapacitor with bending different cycles at 90° bending angle. (d) Ragone plot of the as-assembled supercapacitor compared with previously reported work. (e) Capacitance retention during 10,000 cycles. (f) Digital image of a red LED display panel powered by three devices connected in series.

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High performance flexible energy storage device based on copper foam supported NiMoO₄ nanosheets-CNTs-CuO nanowires composites with core-shell holey nanostructure

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