3D Printing Engineered Multi-porous Cu Microelectrodes with In Situ Electro-Oxidation Growth of CuO Nanosheets for Long Cycle, High Capacity and Large Rate Supercapacitors

doi:10.1007/s40195-020-01097-x

Abstract

Abstract:

Developing excellent pseudocapacitive electrodes with long cycle, high areal capacity and large rate has been challenged. 3D printing is an additive manufacture technique that has been explored to construct microelectrodes of arbitrary geometries for high-energy-density supercapacitors. In comparison with conventional electrodes with uncontrollable geometries and architectures, 3D-printed electrodes possess unique advantage in geometrical shape, mechanical properties, surface area, especially in ion transport and charge transfer. Thus, a desirable 3D electrode with ordered porous structures can be elaborately designed by 3D printing technology for improving electrochemical capacitance and rate capability. In this work, a designed, monolithic and ordered multi-porous 3D Cu conductive skeleton was manufactured through 3D direct ink writing technique and coated with CuO nanosheet arrays by an in situ electro-oxidation treatment. Benefiting from the highly ordered multi-porous nature, the 3D-structured skeleton can effectively enlarge the surface area, enhance the penetration of electrolyte and facilitate fast electron and ion transport. As a result, the 3D-printed Cu deposited with electro-oxidation-generated CuO (3DP Cu@CuO) electrodes demonstrates an ultrahigh areal capacitance of 1.690 F cm ^-2 (38.79 F cm ^-3) at a large current density of 30 mA cm ^-2 (688.59 mA cm ^-3), excellent lifespan of 88.20% capacitance retention after 10,000 cycles at 30 mA cm ^-2 and superior rate capability (94.31% retention, 2-30 mA cm ^-2). This design concept of 3D printing multi-porous current collector with hierarchical active materials provides a novel way to build high-performance 3D microelectrodes.

Key words: 3D printing, Supercapacitor, Microelectrode, Copper oxide, Multi-porous current, High areal specific capacitance

Tao Liu, Yuejiao Chen, Libao Chen. 3D Printing Engineered Multi-porous Cu Microelectrodes with In Situ Electro-Oxidation Growth of CuO Nanosheets for Long Cycle, High Capacity and Large Rate Supercapacitors[J]. Acta Metallurgica Sinica (English Letters), 2021, 34(1): 85-97.

Figures/Tables 9

Fig. 1 Schematic illustration of the preparation process of the 3DP Cu@CuO electrode

Fig. 2 Digital images to show the printing process and the rheological properties of the ink: a pristine PF127 gel, PF127/Cu ink stored in inverted vials to show the viscosity; b Cu current collector printed layer by layer; c scaffold printed with PF127/Cu ink after drying; d different layers of current collector from 3 to 12 printed layers with PF127/Cu ink; e expected and actual heights of PF127/Cu ink as a function of layer number; f apparent viscosity as a function of shear rate; g storage modulus (G′) and loss modulus (G″) as a function of shear stress for the composite ink

Fig. 3 a TGA curve of the PF127 powder; b curve of the heat treatment program; c-f SEM images of top-view of the 3DP Cu lattice after debinding process; SEM images showing the morphology of the 3DP Cu lattice after further sintering process at different views; g, h SEM images of lateral-view; i-l element mapping results of the 3DP Cu lattice after further sintering

Fig. 4 SEM images to show the morphologies of CuO nanosheets on different substrates: a-c 3DP Cu@CuO nanosheet arrays; d-f Cu foam@CuO nanosheet arrays; g-i Cu foil@CuO nanosheet arrays

Fig. 5 a XRD patterns of 3DP Cu and 3DP Cu@CuO; b XPS survey spectrum of 3DP Cu@CuO and high-resolution XPS spectra for c Cu 2p and d O 1s of 3DP Cu@CuO

Fig. 6 a CV curves of 3DP Cu@CuO electrode obtained at different CVO cycles; b GCD curves of 3DP Cu@CuO electrode with different CVO cycles; c CV curves of 3DP Cu@CuO electrode with 1500 CVO cycles at various scan rates; d voltage profiles at various current density from 2 to 30 mA cm-2; e cycling performance of 3DP Cu@CuO electrode at a current density of 30 mA cm-2, the inset showing the SEM image of 3DP Cu@CuO electrode after 10,000 cycles; f GCD curves of the first and 10,000th cycles at a current density of 30 mA cm-2; g Nyquist plots of 3DP Cu@CuO before and after cycle, the inset showing the plots in high-frequency range

Table 1 A comparison of cycle performance with recently reported CuO electrodes

Active material	Current density (mA cm^-2)	Cycle number	Capacitance retention (%)	References
CVO Cu@CuO	20	4000	96.45	[27]
NSA-CuO/Ni-foam	10	500	93	[33]
Lotus-like CuO/Cu(OH)₂	5	5000	85	[36]
3D-CuONA-Cu	30	s4000	88.6	[28]
Cu(OH)₂/Cu/Dacron	2	3000	90	[37]
Cu@CoF-LDH	10	1000	96.2	[38]
3DP Cu@CuO	30	5000/10000	93.11/88.20	This work

Fig. 7 a TEM image and b HRTEM image of the 3DP Cu@CuO, the inset showing the SAED image; c corresponding EDS elemental mapping images; d TEM image and e HRTEM image of the 3DP Cu@CuO after 10,000 cycles, the inset showing the SAED image; f corresponding EDS mapping images for Cu and O in the CuO nanosheet after 10,000 cycles

Fig. 8 a CV curves of 3DP Cu@CuO, Cu foam@CuO and Cu foil@CuO electrodes at a scan rate of 50 mV s-1; b GCD curves of 3DP Cu@CuO, Cu foam@CuO and Cu foil@CuO electrodes at a current density of 2 mA cm-2; c capacitance retention and areal capacitance versus different current densities for 3DP Cu@CuO, Cu foam@CuO and Cu foil@CuO electrodes; d comparison of specific capacitance; e schematic illustration of the advantages of the 3DP Cu@CuO electrode

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