Mitigation on self-discharge behaviors via morphological control of hierarchical Ni-sulfides/Ni-oxides electrodes for long-life-supercapacitors

doi:10.1016/j.jmst.2021.10.028

Abstract

Abstract:

To cope up with the sustainable energy storage goals for supercapacitors (SCs), the self-discharge in SC electrodes is a significant hurdle, and thereby, nickel sulfide (NS) with high conductivity is adopted as a test vehicle for understanding the morphological evolution effects for long-life SCs. Herein, honeycomb-like NS is hierarchically formed over hydrothermally grown nickel oxide (NO) via successive ionic layer adsorption reaction (SILAR) method. Their heterostructure shows a fivefold improvement in specific capacitance from 348 F g^-1 to 2077 F g^-1 at 1 mV s^-1 over bare NO. Furthermore, the remarkable upliftment of capacitance retention is achieved from 60.7% to 92.3% even after 3000 cycles via morphological control of NS/NO hetero-structure with the help of highly conductive NS. More importantly, the self-discharge behaviors and synergistic role of leakage current associated with morphological evolution via NS overcoating are studied in detail. In particular, the self-discharge mitigation from 45% (NO) to 35% (NS20/NO) due to the NS/NO heterostructure and the behind mechanism are ascribed to the activated-controlled Faradaic reaction coupled with a charge redistribution. This study emphasizes the potential importance of composite heterostructure by tuning the electrical conductivity and morphological adjustment NO via consecutive overcoating of NS through SILAR as a novel strategy. This enhances charge storage, redox kinetics, and the mitigation of self-discharge properties of the active electrode materials. For practical validation on sustainable energy storage, NS20/NO supercapacitors illuminate the LED for 35% longer than NO after one-time charging, potentially beneficial for the next generation SCs.

Key words: Morphological evolution, Self-discharge, SILAR overcoating, Supercapacitors, Heterostructure

Dhananjay Mishra, Niraj Kumar, Ajit Kumar, Seung Gi Seo, Sung Hun Jin. Mitigation on self-discharge behaviors via morphological control of hierarchical Ni-sulfides/Ni-oxides electrodes for long-life-supercapacitors[J]. J. Mater. Sci. Technol., 2022, 113: 217-228.

Figures/Tables 9

Fig. 1. (a) Schematic of the fabrication process for composite electrodes NS/NO via hydrothermal growth of nickel oxide on Ni-foam; (b) SILAR overcoating cycles: (i) adsorption, (ii) rinsing, (iii) reaction, and (iv) second rinsing. Schematic cartoons for nickel sulfide composites on the top of nickel oxides prepared by the SILAR process, corresponding to the overcoating from 10 to 30 cycles (NS10, NS20, and NS30).

Fig. 2. FE-SEM morphological transformation from marigold-like nanostructure to honeycomb-like nanostructure. FE-SEM images of NO, NS10/NO, NS20/NO, and NS30/NO on Ni-foam at (a-d) lower magnifications and (e-h) higher magnification; elemental analysis of (i) NO/Ni foam and (j) NS20/NO/Ni.

Fig. 3. (a) XRD pattern of NO and NS20/NO on Ni-foam, (b-f) XPS spectra of NO and NS20/NO in the full range of the binding energy from 0 to 1100 eV.

Fig. 4. Electrochemical properties of binder-free electrodes measured in 1 M KOH electrolyte with a three-electrode system. (a-d) CV curves, (e-h) Galvanostatic charge-discharge curves at different current densities of NO, NS10/NO, NS20/NO, and NS30/NO.

Fig. 5. Comparison of electrochemical performance in a three-electrode system. (a) CV, (b) Galvanostatic discharge, (c) calculated specific capacitance as a function of current density, (d) EIS analysis, (e) Ragone plot, (f) cycling stability of NO, NS10/NO, NS20/NO, NS30/NO electrodes. The inset of (d) shows the magnified EIS spectrum and the fitted circuit element.

Table 1. Electrochemical performance for various NiO and NiO-centered heterostructure-based active electrode materials in aqueous electrolytes in the literature.

Electrode material	Specific capacitance	Cycling stability	Ref.
NiO nanoflakes	327 F g^-1 at 1 A g^-1	92% after 500 cycles	[7]
Ce-doped NiO	1775 F g^-1 at 1 A g^-1	93% after 2000 cycles	[28]
NiO nano/micro sphere	565 F g^-1 at 1 A g^-1	97% after 2000 cycles	[29]
NiO aerogel	797 F g^-1 at 10 mV s^-1	93% after 1000 cycles	[30]
NiO quantum dots	1181.1 F g^-1 at 2.1 A g^-1	87.2% after 5000 cycles	[31]
NiCo₂O₄/ rGO	1305 F g^-1 at mV s^-1	89% after 3000 cycles	[32]
Ni-NiO micro flower	1828 F g^-1 at 0.5 A g^-1	80% after 10,000 cycles	[33]
NiO hydrothermal Growth	348.21 F g^-1 at 1 A g^-1	78.5% after 3000 cycles	This work
NS20/NiO	2077.2 F g^-1 at 1 A g^-1	95% after 10,000 cycles	This work

Fig. 6. Symmetric supercapacitor device performance. (a, b) CV curves at different scan rates from 5 to 50 mV s-1, (c, d) the Galvanostatic charge-discharge curves at different current densities, (e) the EIS curves, and (f) cycling performance of NO- and NS20/NO-based SSC device, respectively.

Fig. 7. Self-discharge and leakage current Study. (a) Galvanostatic charge-discharge (100 cycles) + voltage holding (2 h) + self-discharge (2 h), (b) GCD + VHT + SD at normalized voltage potential; (c) leakage current during voltage holding measured at OCP for NO-based SSC device. (d) Galvanostatic charge-discharge (100 cycles) + voltage holding (2 h) + self-discharge (2 h), (e) GCD+VHT+SD at normalized voltage potential; (f) leakage current during voltage holding measured at OCP for NS20/NO-based SSC device. Normalized self-discharge voltage potential (g) as a function of linear self-discharge time [(V/Vo) vs t], (h) as a function of log self-discharge time [(V/Vo) vs log t], (i) as a function of the square root of self-discharge time (V/V0) vs t (1/2) for both NO- and NS20/NO-based SC device. [Inset of Fig. 7 (g, h, i) shows the initial period with a similar discharge profile].

Fig. 8. Photographic images of LED demonstration powered by (a) NO-based SSC device and (b) NS20/NO-based SSC device.

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