Next Article in Journal
The Enhancing Effect of Stable Oxygen Functional Groups on Porous-Carbon-Supported Pt Catalysts for Alkaline Hydrogen Evolution
Next Article in Special Issue
Asymmetric Supercapacitors Using Porous Carbons and Iron Oxide Electrodes Derived from a Single Fe Metal-Organic Framework (MIL-100 (Fe))
Previous Article in Journal
Controllable Synthesis of Sheet-Flower ZnO for Low Temperature NO2 Sensor
Previous Article in Special Issue
Carbon Materials as a Conductive Skeleton for Supercapacitor Electrode Applications: A Review
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Nanomaterials
Volume 13
Issue 8
10.3390/nano13081414
nanomaterials-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Hierarchically Developed Ni(OH)2@MgCo2O4 Nanosheet Composites for Boosting Supercapacitor Performance

by
Hammad Mueen Arbi
1,†,
Ganesh Koyyada
2,†,
Yedluri Anil Kumar
3,4,
Dasha Kumar Kulurumotlakatla
5,
Jae Hong Kim
2,
Md Moniruzzaman
6,*,
Salem Alzahmi
3,4,* and
Ihab M. Obaidat
1,4,*
1
Department of Physics, United Arab Emirates University, Al Ain P.O. Box 15551, United Arab Emirates
2
Department of Chemical Engineering, Yeungnam University, 214-1, Daehak-ro 280, Gyeongsan 712-749, Republic of Korea
3
Department of Chemical & Petroleum Engineering, United Arab Emirates University, Al Ain P.O. Box 15551, United Arab Emirates
4
National Water and Energy Center, United Arab Emirates University, Al Ain P.O. Box 15551, United Arab Emirates
5
Graduate School of Convergence Science, Pusan Nationfivel University, San 30 Jangjeon-dong, Geumjeong-gu, Busan 609-735, Republic of Korea
6
Department of Chemical and Biological Engineering, Gachon University, 1342 Seongnam-daero, Seongnam-si 13120, Republic of Korea
*
Authors to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Nanomaterials 2023, 13(8), 1414; https://doi.org/10.3390/nano13081414
Submission received: 17 March 2023 / Revised: 10 April 2023 / Accepted: 13 April 2023 / Published: 19 April 2023
(This article belongs to the Special Issue Nanomaterials for Supercapacitors)
Browse Figures
Versions Notes

Abstract

:
MgCo2O4 nanomaterial is thought to be a promising candidate for renewable energy storage and conversions. Nevertheless, the poor stability performances and small specific areas of transition-metal oxides remain a challenge for supercapacitor (SC) device applications. In this study, sheet-like Ni(OH)2@MgCo2O4 composites were hierarchically developed on nickel foam (NF) using the facile hydrothermal process with calcination technology, under carbonization reactions. The combination of the carbon–amorphous layer and porous Ni(OH)2 nanoparticles was anticipated to enhance the stability performances and energy kinetics. The Ni(OH)2@MgCo2O4 nanosheet composite achieved a superior specific capacitance of 1287 F g−1 at a current value of 1 A g−1, which is higher than that of pure Ni(OH)2 nanoparticles and MgCo2O4 nanoflake samples. At a current density of 5 A g−1, the Ni(OH)2@MgCo2O4 nanosheet composite delivered an outstanding cycling stability of 85.6%, which it retained over 3500 long cycles with an excellent rate of capacity of 74.5% at 20 A g−1. These outcomes indicate that such a Ni(OH)2@MgCo2O4 nanosheet composite is a good contender as a novel battery-type electrode material for high-performance SCs.

1. Introduction

With the increasing demand for future-generation renewable energy storage cells, supercapacitors (SCs) are holding on as one of the most favored electrochemical devices, due to their ability to provide greater charge/discharge rates, prolonged cycling life, and superior power densities [1,2,3]. Nevertheless, most SCs are limited by lower energy densities that significantly hamper their further application. As established by the equation (E = 1/2CV2), work voltage and electrode samples have pivotal roles in determining the energy density [4]. In order to attain greater energy densities, a hybrid SC setup could be designed to increased work voltages [5,6]. SCs possess a battery-type faradaic sample as the energy key and a capacitor nanomaterial as the power initiator [7]. Moreover, constructing unique electrodes to achieve greater specific capacities has been contemplated as a way to enhance energy densities [8,9]. Thus, there is a strong desire to develop unique electrode samples with superior electrochemical activities.
Transition-metal oxides, metal hydroxides, and polymer-based conductors have been extensively utilized as superior electrodes owing to their greater specific theoretical capacities [10,11]. Binary-transition-metal oxides (BTMOs) have gained significant attention as unique sample materials because of their varied oxidation states, cheap prices, and simple preparations, in addition to being eco-friendly. Cobalt-type spinel BTMOs that include CoMnO4 [12], MnCo2O4 [13], CuCo2O4 [14], and MgCo2O4 [15] are being investigated as possible SCs. Because of their excellent theoretical capacitance and sufficient reserves of innate magnesium MgCo2O4 composites have been considered for SCs and Li-ion batteries [16]. Nevertheless, in practical devices, MgCo2O4 electrodes alone hardly exhibit a superior theoretical capacity (~3120 F/g) due to their simple nanostructure, small surface region, and weak conductivities [17,18]. To enhance the performance limit of MgCo2O4 electrodes, it is imperative that a rational and unique design be constructed to improve the energy storage properties of MgCo2O4-type SCs [19,20].
On other hand, nickel hydroxide Ni(OH)2 has been the object of much consideration because of its superior theoretical capacities, superior electrochemical activities, and cheap price [21]. The unique Ni(OH)2 nanoparticle that develops on the electrode interface would extend the specific area with the electrolytes and condense the ion diffusion routes to optimize its energy-storing performance [22,23,24]. Meng et al. prepared a ZnCo2S4/Ni(OH)2 sample with a great capacitance of 2156 F g−1 at 1 A g−1 and solid stability performances (94.3% retained over 3000 cycles) [25]. Liu et al. prepared MnCo-LDHs@Ni(OH)2 via an easier two-step hydrothermal route that provided a specific capacitance of 2320 F g−1 at 3 A g−1 [26]. Therefore, the design of Ni(OH)2 sheets and MgCo2O4 nanoflakes is anticipated to effectively enhance the energy storage activities and impart significant capacities. Meanwhile, it has been shown that electrode materials covered by an amorphous carbon layer display improved stability performances and increased structural stabilities [27,28,29].
To explore extremely effective, unique, and reliable electrode samples, both Ni(OH)2 particles and MgCo2O4 nanoflakes were combined to form a Ni(OH)2@MgCo2O4 nanosheet composite structure. In this study, the novel structure of the Ni(OH)2@MgCo2O4 nanosheet was engineered and developed via a hydrothermal process. This recently discovered Ni(OH)2@MgCo2O4 nanosheet composite displayed a specific capacitance of 1287 F g−1 at a current density of 1 A g−1, which is superior to that of the MgCo2O4 nanoflakes and Ni(OH)2 particles alone. Additionally, the Ni(OH)2@MgCo2O4 nanosheet composite showed a notable cyclic stability of 85.6% over 3500 long cycles. These results demonstrate that the Ni(OH)2@MgCo2O4 nanosheet composite is a potential electrode material candidate for high-performance SCs.

2. Experimental Section

2.1. Synthesis of MgCo2O4 Nanoflakes Grown on Ni Foam

MgCo2O4 nanoflakes were prepared using a hydrothermal method. NF (2 × 4 cm−2) pieces were handled with ultrasonication to detach oxide impurities on their interface. Clear solutions were optimized through fully dissolving 0.964 g of Co(NO3)2⋅6H2O, 0.494 g of Mg(NO3)2⋅6H2O, 0.45 g of CO(NH2)2, 0.083 g of NH4F, in 60 mL of distilled water (DI water). After that, the mixed solution and the reacted NF were moved to a well-sealed 150 mL autoclave and held in an oven at 140 °C for 8 h. Then, the autoclave was cooled down to a normal temperature, and the NF pieces were removed from the precursors, washed 3 times with DI water and ethanol, and then heated at 60 °C for 12 h, accompanied by annealing at 350 °C for 2 h at a rate of 6 °C min−1. Eventually, the products were acquired and denoted as MgCo2O4 nanoflakes.

2.2. Preparation of Ni(OH)2@MgCo2O4 Nanosheet Composite

Following a typical procedure, 2 mmol NiCl2·6H2O and 4 mmol urea were put into 20 mL of DI water and stirred for 30 min to obtain a clear solution. The mixed precursor with pieces of MgCo2O4 nanoflakes loaded on Ni foam was then moved to a 40 mL autoclave and maintained at 110 °C for 3 h. After being cooled down to a normal temperature, the samples were rinsed with ethanol and DI water several times and dried at 70 °C for 5 h in a vacuum. The mass loading of the Ni(OH)2@MgCo2O4 nanosheet composites was 3.7 mg cm−2. For comparison, Ni(OH)2 was fabricated on Ni foams using a similar procedure. The mass loading of the MgCo2O4 nanoflake electrode and Ni(OH)2 electrode was 3.7 mg cm−2 and 1.9 mg cm−2, respectively.

2.3. Measurements and Characterizations

X-ray powder diffraction (XRD, Bruker D8 Advance with Cu Kα radiation) was used to characterize the crystalline phases of the samples. Field emission scanning electron microscopy (FE-SEM, JSM-7800F) was used to study the morphologies. High-resolution transmission electron microscopy (HRTEM, JEM-2100F at 200 kV) was used to study the microstructures and the elemental compositions. Photoelectron X-ray spectroscopy (XPS; ESCCALAB 250Xi, Busan, Republic of Korea) was used to study the chemical valence states and compositions of samples.

2.4. Measurements and Characterizations

All electrochemical measurements were conducted using a 3-electrode configuration in a 3 M KOH aqueous electrolyte. The fabricated samples, a Ag/AgCl electrode, and a platinum wire were utilized as working electrodes, reference electrodes, and counter electrodes, respectively. Galvanostatic charge–discharge (GCD) and cyclic voltammetry (CV) were acquired on a Bio-Logic- SP-150C electrochemical workstation. Electrochemical impedance spectroscopy (EIS) was employed in the frequency width from 0.01 to 100 kHz. The specific capacitance (Cs, F g−1) was calculated from the GCD plots using the following equation [30]:
C S = I × ∆ t m × ∆ V
where I (A), Δt (s), and m (g) have their conventional meanings.

3. Results and Discussion

The synthesis procedure of Ni(OH)2@MgCo2O4 is demonstrated in Figure 1. Initially, MgCo2O4 nanoflakes were developed on Ni foam under simple hydrothermal and annealing technologies. After that, MgCo2O4 nanoflakes were directly engaged as a skeleton to construct Ni(OH)2@MgCo2O4 through secondary hydrothermal procedures. As an outcome, MgCo2O4 nanoflakes gradually dissolved and generated fresh Ni(OH)2, manifesting a uniform sheet-like Ni(OH)2@MgCo2O4 composite.
The XRD patterns of the Ni(OH)2, MgCo2O4, and Ni(OH)2@MgCo2O4 nanosheet electrodes are displayed in Figure 2. In the XRD tests of MgCo2O4, except for the diffraction angles from the nickel foam matrixes that remained, long peaks could be clearly identified in the MgCo2O4 phases [14]. The diffraction peaks positioned at 31°, 36.8°, 44.6°, 58.89°, and 64.98° were attributed to the (2 2 0), (3 1 1), (4 0 0), (4 2 2), and (4 4 0) lattice planes of MgCo2O4 (JCPDS NO. 02–1073) [12,16,29]. Additionally, three longer peaks were identified at 2θ = 44.5°, 51.85°, and 76.37° that came from the Ni foam skeleton (JCPDS NO. 04–0850). Meanwhile, the line angles at 11.4°, 23.7°, and 33.4° were matched to Ni(OH)2 (JCPDS No. 38-0715) [31,32]. In general, the diffraction angles of the Ni(OH)2@MgCo2O4 nanosheet composite were in good agreement with Ni(OH)2 and MgCo2O4 [28].
XPS was utilized to detect the chemical valence states and compositions of each element in the developed Ni(OH)2@MgCo2O4 nanosheet composites. Figure 3a depicts the survey spectra, which illustrate the coexistence of Ni, Mg, Co, and O in the composite sample. The Ni 2p XPS spectra are shown in Figure 3b. The angles situated at 873.5 eV in Ni 2p1/2 and 855.6 eV in Ni 2p3/2 were ascribed to the Ni2+ states, and those located at 876.6 eV in Ni 2p1/2 and 858.76 eV in Ni 2p3/2 were attributed to the Ni3+ states [33,34,35]. The straight spectra of Mg 2p seen in the XPS results are shown in Figure 3c, where the peaks in the binding source at 51.2 eV confirm the existence of magnesium oxides. The Co 2p XPS spectra (Figure 3d) possess two spin orbits and two shake-up satellites (denoted as “Sat.”). The phases at 794.2 eV and 779.4 eV were attributed to Co3+, whereas the remaining peaks at 798.4 eV and 782.5 eV were ascribed to Co2+ [34]. The percentage of oxidation of cobalt ions was calculated based on the fitted peak areas of all the individual peaks in the Co 2p XPS spectra for the Ni(OH)2@MgCo2O4 nanosheet composites, and was determined to be 41:59 (Co2+:Co3+). As depicted in Figure 3e, the O 1 s XPS spectra are composed of three different peaks labeled as O1, O2, and O3 [36,37]. The O1 peak at 531.2 eV was assigned to metal-oxidized bonds. The O2 peak at 532.8 eV was attributed to the OH− groups procured from Ni(OH)2. The O3 peak at 535.2 eV was ascribed to the chemisorbed oxidized atoms on the interface. In addition, Figure S1 of XPS full spectra of MgCo2O4 nanoflakes grown on Ni foam.
The intrinsic nanostructures and morphologies of the Ni(OH)2@MgCo2O4 nanosheet composite were analyzed via FE-SEM. The morphological structure of the MgCo2O4 nanoflake electrode is shown in Figure 4a–c from lower to higher magnifications. Uniform nanoflakes were grown at the edge of the surface, as shown in Figure 4a. Figure 4b,c indicate that the nanoflakes nearly uniformly covered the initial micro-morphology, and their formation was followed by an annealing process. Figure 4d demonstrates that the nanosheets were grown perpendicular to the skeleton. As illustrated in Figure 4e,f, it is obvious that the interface of the MgCo2O4 nanoflakes was covered with Ni(OH)2 nanoparticles. The buildup of Ni(OH)2 nanoparticles did not demolish the intrinsically ordered nanostructure. The nanoflakes and nanosheets would supply efficient transfer channels for the electrolytes during the charge storage procedures. The MgCo2O4 nanoflakes were fully positioned on Ni(OH)2 nanoflakes, which favored the effective conductive, preservative furnishing of MgCo2O4 nanoflakes with ion transportations in the electrolyte, and also provided safe structural stabilities. In addition, the Ni(OH)2@MgCo2O4 nanosheet composite supplied abundant active sites for the faradic redox process.
The specific microstructures and morphology of the MgCo2O4 nanoflakes (Figure 5a) and Ni(OH)2@MgCo2O4 nanosheet composite (Figure 5b,c) were obtained using TEM and HRTEM. Figure 5a shows that the MgCo2O4 nanoflakes existed as the array type, and the nanoflake could be clearly seen. Figure 5b shows the TEM images of a Ni(OH)2@MgCo2O4 nanosheet composite, demonstrating MgCo2O4 has a sheet-type construction with a diameter range of 50 nm [34]. The HRTEM image of the Ni(OH)2@MgCo2O4 nanosheet composite illustrates well-defined lattice spacings with interplanar fringes of 0.288 nm and 0.244 nm, which were assigned to the (2 2 0) and (3 1 1) planes of MgCo2O4 [18,29]. The SAED image (inset in Figure 5c) obtained from the nanosheets reveals their polycrystalline characteristic, which greatly enhances the active sites needed for the Faraday capacity process. As shown in Figure 5d–g, the elements of Ni, Mg, and Co were homogeneously coated in the whole nanosheet, indicating the uniform coexistence of a Ni(OH)2@MgCo2O4 nanosheet composite.

Electrochemical Properties of Electrode Materials

To better evaluate the electrochemical behaviors of Ni(OH)2 nanoparticle electrodes, MgCo2O4 nanoflake electrodes, and Ni(OH)2@MgCo2O4 nanosheet composites, CV, GCD, and EIS measurements were conducted using a three-electrode configuration in a 2 M KOH aqueous electrolyte solution (Figure 6). Figure 6a shows the results of the CV tests of as-developed electrodes of the Ni(OH)2 nanoparticle, MgCo2O4 nanoflake electrodes, and Ni(OH)2@MgCo2O4 nanosheet composites at a scanning rate of 5 mV s−1. All electrode samples possessed an obvious couple of reversible redox peaks, demonstrating that active electrodes have typical battery-type characteristics. Particularly, as depicted in the CV test results shown in Figure 6a, the specific area of the Ni(OH)2@MgCo2O4 nanosheet composite was much bigger than that of the Ni(OH)2 nanoparticle electrode and MgCo2O4 nanoflake electrode at similar scan rates, revealing the notable capacitance of Ni(OH)2@MgCo2O4 nanosheet composites. Figure 6b depicts the GCD plots of the Ni(OH)2 nanoparticle electrode, MgCo2O4 nanoflake electrode, and Ni(OH)2@MgCo2O4 nanosheet composites at an identical current density of 1 A g−1. Figure 6d,f display the GCD curves of the Ni(OH)2@MgCo2O4 nanosheet composite and MgCo2O4 nanoflake electrodes at different current densities. Based on the GCD tests in Figure 6d,f, the Cs of the Ni(OH)2@MgCo2O4 nanosheet composites was measured as 1287 F g−1 at 1 A g−1. At higher current density values of 2, 5, 10, and 20 A g−1, the Ni(OH)2@MgCo2O4 nanosheet composites also reached good capacitances of 1071, 926, 661, and 459 F g−1, respectively (Figure 6d), which were attributed to the large specific area and excellent ion interlayer exchanges of the composites.
Figure 6c,e display the CV test results for the MgCo2O4 nanoflake electrode and Ni(OH)2@MgCo2O4 nanosheet composites at scanning rates ranging from 5 to 25 mV s−1. The CV tests show that the specific area of the Ni(OH)2@MgCo2O4 nanosheet composites was larger, indicating the Cs of the Ni(OH)2@MgCo2O4 nanosheet composites was higher.
The specific capacitances of the Ni(OH)2@MgCo2O4 nanosheet composites, MgCo2O4 nanoflake electrodes, and Ni(OH)2 nanoparticle electrodes based on the GCD tests were determined to be 1287 F g−1, 1084 F g−1, and 531 F g−1, respectively, at a current density of 1 A g−1 (Figure 7a). Importantly, the Ni(OH)2@MgCo2O4 nanosheet composite electrode was found to exhibit notable rate capabilities with 74.5% retention of the starting capacitances at 20 A g−1.
EIS measurements were conducted on the samples, and the corresponding Nyquist plots are presented in Figure 7b. The outline of the impedance spectra possesses three parts. In the high-frequency area, the real axis with intersections reveals the electrolyte’s resistances (Rs), including the internal resistance, the interface resistance, and ionic resistance of the electrolytes between the working electrodes and current collector [38]. The semicircle diameters give the charge transfer impedances (Rct) [39]. The line slope in the lower-frequency region is attributed to the Warburg resistance (Rw), which is close to OH− in the aqueous solution [40,41]. We can see that the Ni(OH)2@MgCo2O4 nanosheet composite sample has abundant vertical lines and semicircles with a smaller diameter than those of the MgCo2O4 nanoflake electrodes and Ni(OH)2 nanoparticle electrodes, indicating rapid electron transportation kinetics and high diffusion ion rates. The EIS outcomes reveal that the Ni(OH)2@MgCo2O4 nanosheet composites had lower Rs (0.59 Ω) and Rct (0.07 Ω) compared to the MgCo2O4 nanoflake electrode (Rs was 0.81 Ω and Rct was 0.36 Ω) and Ni(OH)2 nanoparticle electrode (Rs was 0.93 Ω and Rct was 0.51 Ω), indicating superior electrical conductivities and fast electron transportation kinetics.
Cycling stability is also a crucial factor in studying the characteristics of SCs. Thus, continuous charge/discharge procedures were maintained for Ni(OH)2@MgCo2O4 nanosheet composites, MgCo2O4 nanoflake electrodes, and Ni(OH)2 nanoparticle electrodes at a current density of 2 A g−1 over 3500 long cycles. As illustrated in Figure 7c, the Ni(OH)2 nanoparticles and MgCo2O4 nanoflake electrodes retained 78.3% and 81.2% of their starting capacitances, respectively, over 3500 cycles. However, the hybrid Ni(OH)2@MgCo2O4 nanosheet composite electrode (with an initial specific capacitance of 1071 F g−1) retained 85.6% of its initial capacitance after 3500 long cycles. The unique hybrid constructions achieved outstanding cycling stability results. The specific capacitance values of the Ni(OH)2@ MgCo2O4 electrode were compared with those found in previous studies, as shown in Table 1.

4. Conclusions

In summary, we successfully fabricated a Ni(OH)2@MgCo2O4 nanosheet composite electrode on Ni foam using a facile two-step hydrothermal route followed by annealing techniques. The as-synthesized sample electrodes achieved notable electrochemical activities due to their synergistic effects. Combining the synergistic effects of the outstandingly aligned MgCo2O4 nanoflakes and unique specific area of Ni(OH)2 nanoparticles, the as-developed Ni(OH)2@MgCo2O4 nanosheet composite demonstrated a superior Cs of 1287 F g−1 at a current density of 1 A g−1 and rate capabilities superior to those of MgCo2O4 nanoflakes and Ni(OH)2 nanoparticle electrodes alone. Moreover, the Ni(OH)2@MgCo2O4 nanosheet composite showed a notable cyclic stability of 85.6% over 3500 long cycles. These features of battery-type electrode materials with outstanding electrochemical performances demonstrate their promise as high-performance SCs.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/nano13081414/s1, Figure S1: XPS full spectra of MgCo2O4 nanoflakes grown on Ni foam.

Author Contributions

Conceptualization, I.M.O., Y.A.K. and S.A.; supervision and validation, I.M.O. and S.A.; investigation and writing, H.M.A., Y.A.K., G.K. and D.K.K.; investigation, visualization, and validation, H.M.A., M.M. and J.H.K. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the UAEU SUREPLUS Program under grant No. 31S277 and the UAEU Strategic Research Program under grant No. 12R128.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

No new data were created or analyzed in this study. Data sharing is not applicable to this article.

Acknowledgments

This work was financially supported by the UAEU SUREPLUS Program under grant No. 31S277 and the UAEU Strategic Research Program under grant No. 12R128.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Yoon, J.H.; Kumar, Y.A.; Sambasivam, S.; Hira, S.A.; Krishna, T.N.V.; Zeb, K.; Uddin, W.; Kumar, K.D.; Obaidat, I.M.; Kim, S.; et al. Highly efficient copper-cobalt sulfide nano-reeds array with simplistic fabrication strategy for battery-type supercapacitors. J. Energy Storage 2020, 32, 101988. [Google Scholar] [CrossRef]
  2. Mun, C.H.; Gopi, C.V.V.M.; Vinodh, R.; Sambasivam, S.; Obaidat, I.M.; Kim, H.J. Microflower-like nickel sulfide-lead sulfide hierarchical composites as binder-free electrodes for high-performance supercapacitors. J. Energy Storage 2019, 26, 100925. [Google Scholar] [CrossRef]
  3. Gopi, C.V.V.M.; Vinodh, R.; Sambasivam, S.; Obaidat, I.M.; Kalla, R.M.N.; Kim, H.J. One-pot synthesis of copper oxide–cobalt oxide core–shell nanocactus-like heterostructures as binder-free electrode materials for high-rate hybrid supercapacitors. Mater. Today Energy 2019, 14, 100358. [Google Scholar] [CrossRef]
  4. Kumar, Y.A.; Sambasivam, S.; Hira, S.A.; Zeb, K.; Uddin, W.; Krishna, T.N.V.; Kumar, K.D.; Obaidat, I.M.; Kim, H.J. Boosting the energy density of highly efficient flexible hybrid supercapacitors via selective integration of hierarchical nanostructured energy materials. Electrochim. Acta 2020, 364, 137318. [Google Scholar] [CrossRef]
  5. Bhat, V.S.; Hegde, G.; Nasrollahzadeh, M. A sustainable technique to solve growing energy demand: Porous carbon nanoparticles as electrode materials for high-performance supercapacitors. J. Appl. Electrochem. 2020, 50, 1243–1255. [Google Scholar] [CrossRef]
  6. Huang, Y.; Zhao, Y.; Bao, J.; Lian, J.; Cheng, M.; Li, H. Lawn-like FeCo2S4 hollow nanoneedle arrays on flexible carbon nanofiber film as binder-free electrodes for high-performance asymmetric pseudocapacitors. J. Alloys Compd. 2019, 772, 337–347. [Google Scholar] [CrossRef]
  7. Elshahawy, A.M.; Li, X.; Zhang, H.; Hu, Y.T.; Ho, K.H.; Guan, C.; Wang, J. Controllable MnCo2S4 nanostructures for high performance hybrid supercapacitors. J. Mater. Chem. A 2017, 5, 7494–7506. [Google Scholar] [CrossRef]
  8. Sun, W.; Du, Y.; Wu, G.; Gao, G.; Zhu, H.; Shen, J.; Zhang, K.; Cao, G. Constructing metallic zinc–cobalt sulfide hierarchical core–shell nanosheet arrays derived from 2D metal–organic-frameworks for flexible asymmetric supercapacitors with ultrahigh specific capacitance and performance. J. Mater. Chem. A 2019, 7, 7138–7150. [Google Scholar] [CrossRef]
  9. Yang, Y.; Huang, W.; Li, S.; Ci, L.; Si, P. Surfactant-dependent flower- and grass-like Zn0.76Co0.24S/Co3S4 for high-performance all-solid-state asymmetric supercapacitors. J. Mater. Chem. A 2018, 6, 22830–22839. [Google Scholar] [CrossRef]
  10. Li, H.; He, Y.; Dai, Y.; Ren, Y.; Gao, T.; Zhou, G. Bimetallic SnS2/NiS2@S-rGO nanocomposite with hierarchical flower-like architecture for superior high rate and ultra-stable half/full sodium-ion batteries. Chem. Eng. J. 2022, 427, 131784. [Google Scholar] [CrossRef]
  11. Li, Y.; Qian, J.; Zhang, M.; Wang, S.; Wang, Z.; Li, M.; Bai, Y.; An, Q.; Xu, H.; Wu, F.; et al. Co-Construction of Sulfur Vacancies and Heterojunctions in Tungsten Disulfide to Induce Fast Electronic/Ionic Diffusion Kinetics for Sodium-Ion Batteries. Adv. Mater. 2020, 32, 2005802. [Google Scholar] [CrossRef] [PubMed]
  12. Niu, L.; Wu, T.; Chen, M.; Yang, L.; Yang, J.; Wang, Z.; Kornyshev, A.A.; Jiang, H.; Bi, S.; Feng, G. Conductive Metal-Organic Frameworks for Supercapacitors. Adv. Mater. 2022, 34, e2200999. [Google Scholar] [CrossRef] [PubMed]
  13. Lee, Y.S.; Kumar, Y.K.; Sambasivam, S.; Hira, S.A.; Zeb, K.; Uddin, W.; Reddy, S.P.R.; Kumar, K.D.; Obaidat, I.M.; Kim, H.J.; et al. CoCu2O4 nanoflowers architecture as an electrode material for battery type supercapacitor with improved electrochemical performance. Nano-Struct. Nano-Objects 2020, 24, 100618. [Google Scholar] [CrossRef]
  14. Priya, M.S.; Divya, P.; Rajalakshmi, R. A review status on characterization and electrochemical behaviour of biomass derived carbon materials for energy storage supercapacitors. Sustain. Chem. Pharm. 2020, 16, 100243. [Google Scholar] [CrossRef]
  15. Chen, X.; Chen, D.; Guao, X.; Wang, R.; Zhang, H. Facile Growth of Caterpillar-like NiCo2S4 Nanocrystal Arrays on Nickle Foam for High-Performance Supercapacitors. ACS Appl. Mater. Interfaces 2017, 9, 18774–18781. [Google Scholar] [CrossRef]
  16. Zhou, X.; Yue, X.; Dong, Y.; Zheng, Q.; Lin, D.; Du, X.; Qu, G. Enhancing electrochemical performance of electrode material via combining defect and heterojunction engineering for supercapacitors. J. Colloid Interface Sci. 2021, 599, 68–78. [Google Scholar] [CrossRef]
  17. Huang, C.; Gao, A.; Yi, F.; Wang, Y.; Shu, D.; Liang, Y.; Zhu, Z.; Ling, J.; Hao, J. Metal organic framework derived hollow NiS@C with S-vacancies to boost high-performance supercapacitors. Chem. Eng. J. 2021, 419, 129643. [Google Scholar] [CrossRef]
  18. Zhu, Y.; Wu, Z.; Jing, M.; Xuming, J.; Xuming, Y.; Song, W.; Ji, X. Mesoporous NiCo2S4 nanoparticles as high-performance electrode materials for supercapacitors. J. Power Source 2015, 273, 584–590. [Google Scholar] [CrossRef]
  19. Arbi, H.M.; Yadav, A.A.; Anil Kumar, Y.; Moniruzzaman, M.; Alzahmi, S.; Obaidat, I.M. Polypyrrole-Assisted Ag Doping Strategy to Boost Co(OH)2 Nanosheets on Ni Foam as a Novel Electrode for High-Performance Hybrid Supercapacitors. Nanomaterials 2022, 12, 3982. [Google Scholar] [CrossRef]
  20. Moniruzzaman, M.; Anil Kumar, Y.; Pallavolu, M.R.; Arbi, H.M.; Alzahmi, S.; Obaidat, I.M. Two-Dimensional Core-Shell Structure of Cobalt-Doped@MnO2 Nanosheets Grown on Nickel Foam as a Binder-Free Battery-Type Electrode for Supercapacitor Application. Nanomaterials 2022, 12, 3187. [Google Scholar] [CrossRef]
  21. Zhang, X.; Wang, Y.; Yu, X.; Tu, J.; Ruan, D.; Qiao, Z.J. High-performance discarded separator-based activated carbon for the application of supercapacitors. J. Energy Storage 2021, 44, 103378. [Google Scholar] [CrossRef]
  22. Li, J.; Yun, S.; Han, F.; Si, Y.; Arshad, A.; Zhang, Y.; Chidambaram, B.; Zafar, N.; Qiao, X. Biomass-derived carbon boosted catalytic properties of tungsten-based nanohybrids for accelerating the triiodide reduction in dye-sensitized solar cells. J. Colloid Interface Sci. 2020, 578, 184–194. [Google Scholar] [CrossRef]
  23. Ariharan, A.; Ramesh, K.; Vinayagamoorthi, R.; Rani, M.S.; Viswanathan, B.; Ramaprabhu, S.; Nandhakumar, V. Biomass derived phosphorous containing porous carbon material for hydrogen storage and high-performance supercapacitor applications. J. Energy Storage 2021, 35, 102185. [Google Scholar] [CrossRef]
  24. Mallesh, D.; Anbarasan, J.; Kumar, P.M.; Upendar, K.; Chandrashekar, P.; Rao, B.V.S.K.; Lingaiah, N. Synthesis, characterization of carbon adsorbents derived from waste biomass and its application to CO2 capture. Appl. Surf. Sci. 2020, 530, 147226. [Google Scholar] [CrossRef]
  25. Jiang, J.; Zhang, Y.; Nie, P.; Xu, G.; Shi, M.; Wang, J.; Wu, Y.; Fu, R.; Dou, H.; Zhang, X. Progress of nanostructured electrode materials for supercapacitors. Adv. Sustain. Syst. 2018, 2, 1700110. [Google Scholar] [CrossRef]
  26. Xie, P.; Yuan, W.; Liu, X.; Peng, Y.; Yin, Y.; Li, Y.; Wu, Z. Multifunctional surfactants for synthesizing high-performance energy storage materials. Energy Storage Mater. 2021, 36, 56–76. [Google Scholar] [CrossRef]
  27. Lobato, B.; Suárez, L.; Guardia, L.; Centeno, T.A. Capacitance and surface of carbons in supercapacitors. Carbon 2017, 122, 434–445. [Google Scholar] [CrossRef]
  28. Sharma, K.; Arora, A.; Tripathi, S.; Storage, J.E. Review of supercapacitors: Materials and devices. J. Energy Storage 2019, 21, 801–825. [Google Scholar]
  29. Lin, L.; Liu, J.; Liu, T.; Hao, J.; Ji, K.; Sun, R.; Zeng, W.; Wang, Z. Growth-controlled NiCo2S4 nanosheet arrays with self-decorated nanoneedles for high-performance pseudocapacitors. J. Mater. Chem. A 2015, 3, 17652–17658. [Google Scholar] [CrossRef]
  30. Wan, H.; Jiang, J.; Yu, J.; Xu, K.; Miao, L.; Zhang, L.; Chen, H.; Ruan, Y. NiCo2S4 porous nanotubes synthesis via sacrificial templates: High-performance electrode materials of supercapacitors. CrystEngComm 2013, 15, 7649–7651. [Google Scholar] [CrossRef]
  31. Wang, H.; Ren, Q.; Brett, D.J.L.; He, G.; Wang, R.; Key, J.; Ji, S. Double-shelled tremella-like NiO@Co3O4@MnO2 as a high-performance cathode material for alkaline supercapacitors. J. Power Source 2017, 343, 76–82. [Google Scholar] [CrossRef]
  32. Zeng, Z.; Wang, D.; Zhu, J.; Xiao, F.; Li, Y.; Zhu, X. NiCo2S4 nanoparticles//activated balsam pear pulp for asymmetric hybrid capacitors. CrystEngComm 2016, 18, 2363–2374. [Google Scholar] [CrossRef]
  33. Wang, C.; Wang, J.; Wu, W.; Qian, J.; Song, S.; Yue, Z.J. Feasibility of activated carbon derived from anaerobic digester residues for supercapacitors. J. Power Source 2019, 412, 683–688. [Google Scholar] [CrossRef]
  34. Ramachandran, T.; Natarajan, S.; Hamed, F. The role of dysprosium levels in the formation of mixed oxidation states within spinel MnCo2−xDyxO4 nanocrystalline powders. J. Electron Spectrosc. Relat. Phenom. 2020, 242, 146952. [Google Scholar] [CrossRef]
  35. Gu, C.; Ge, X.; Wang, X.; Tu, J. Cation–anion double hydrolysis derived layered single metal hydroxide superstructures for boosted supercapacitive energy storage. J. Mater. Chem. A 2015, 3, 14228–14238. [Google Scholar] [CrossRef]
  36. Chhetri, K.; Tiwari, A.P.; Dahal, B.; Ojha, G.P.; Mukhiya, T.; Lee, M.; Kim, T.; Chae, S.; Muthurasu, A.; Kim, H.Y. A ZIF-8-derived nanoporous carbon nanocomposite wrapped with Co3O4-polyaniline as an efficient electrode material for an asymmetric supercapacitor. J. Electroanal. Chem. 2020, 856, 113670. [Google Scholar] [CrossRef]
  37. Chhetri, K.; Dahal, B.; Mukhiya, T.; Tiwari, A.P.; Muthurasu, A.; Kim, H.Y. Integrated hybrid of graphitic carbon-encapsulated CuxO on multilayered mesoporous carbon from copper MOFs and polyaniline for asymmetric supercapacitor and oxygen reduction reactions. Carbon 2021, 179, 89–99. [Google Scholar] [CrossRef]
  38. Xu, J.; Wang, L. Fabrication of hierarchical core/shell MgCo2O4@MnO2 nanowall arrays on Ni-foam as high–rate electrodes for asymmetric supercapacitors. Sci. Rep. 2019, 9, 12557. [Google Scholar] [CrossRef]
  39. Zhu, S.J.; Jia, J.Q.; Wang, T.; Zhao, D.; Yang, J.; Dong, F.; Shang, Z.G.; Zhang, Y.X. Rational design of octahedron and nanowire CeO2@MnO2 core–shell heterostructures with outstanding rate capability for asymmetric supercapacitors†. Chem. Commun. 2015, 51, 14840–14843. [Google Scholar] [CrossRef]
  40. Vijaykumar, S.; Nagamuthu, S.; Ryu, K.S. In situ preparation of MgCo2O4 nanosheets on Ni-foam as a binder-free electrode for high performance hybrid supercapacitors. Dalton Trans. 2018, 47, 6722–6728. [Google Scholar] [CrossRef] [PubMed]
  41. Xu, J.; Wang, L.; Zhang, J.; Qian, J.; Liu, J.; Zhang, Z.; Zhang, H.; Liu, X. Fabrication of porous double-urchin-like MgCo2O4 hierarchical architectures for high-rate supercapacitors. J. Alloys Compd. 2016, 688, 933–938. [Google Scholar] [CrossRef]
  42. Silambarasan, M.; Ramesh, P.S.; Geetha, D.; Venkatachalam, V. A report on 1D MgCo2O4 with enhanced structural, morphological and electrochemical properties. J. Mater. Sci. Mater. Electron. 2017, 28, 6880–6888. [Google Scholar] [CrossRef]
  43. Cui, L.; Huang, L.; Ji, M.; Wang, Y.; Shi, H.; Zuo, Y.; Kang, S. High-performance MgCo2O4 nanocone arrays grown on three-dimensional nickel foams: Preparation and application as binder-free electrode for pseudo-supercapacitor. J. Power Source 2016, 333, 118–124. [Google Scholar] [CrossRef]
  44. Xu, J.; Wang, L.; Sun, Y.; Zhang, J.; Zhang, C.; Zhang, M. Fabrication of porous MgCo2O4 nanoneedle arrays/Ni foam as an advanced electrode material for asymmetric supercapacitors. J. Alloys Compd. 2019, 779, 100–107. [Google Scholar] [CrossRef]
  45. Krishnan, S.G.; Reddy, M.V.; Harilal, M.; Vidyadharan, B.; Misnon, I.I.; Rahim, M.H.A.; Ismail, J.; Jose, R. Characterization of MgCo2O4 as an electrode for high performance supercapacitors. Electrochim. Acta 2015, 161, 312–321. [Google Scholar] [CrossRef]
  46. Gao, H.; Wang, X.; Wang, G.; Hao, C.; Zhou, S.; Huang, C. An urchin-like MgCo2O4@PPy core–shell composite grown on Ni foam for a high-performance all-solid-state asymmetric supercapacitor. Nanoscale 2018, 10, 10190–10202. [Google Scholar] [CrossRef]
Nanomaterials 13 01414 g001 550
Figure 1. Schematic illustration of the synthesis preparation of Ni(OH)2@MgCo2O4 nanosheet composite grown on Ni foam.
Figure 1. Schematic illustration of the synthesis preparation of Ni(OH)2@MgCo2O4 nanosheet composite grown on Ni foam.
Nanomaterials 13 01414 g001
Nanomaterials 13 01414 g002 550
Figure 2. XRD patterns of Ni(OH)2 nanoparticle electrode, MgCo2O4 nanoflake electrode, and Ni(OH)2@MgCo2O4 nanosheet composites grown on Ni foam.
Figure 2. XRD patterns of Ni(OH)2 nanoparticle electrode, MgCo2O4 nanoflake electrode, and Ni(OH)2@MgCo2O4 nanosheet composites grown on Ni foam.
Nanomaterials 13 01414 g002
Nanomaterials 13 01414 g003 550
Figure 3. (a) XPS full spectra of Ni(OH)2@MgCo2O4 nanosheet composite, and high-resolution XPS spectra of Ni(OH)2@MgCo2O4 nanosheet composite for (b) Ni 2p, (c) Mg 2p, (d) Co 2p, and (e) O 1 s.
Figure 3. (a) XPS full spectra of Ni(OH)2@MgCo2O4 nanosheet composite, and high-resolution XPS spectra of Ni(OH)2@MgCo2O4 nanosheet composite for (b) Ni 2p, (c) Mg 2p, (d) Co 2p, and (e) O 1 s.
Nanomaterials 13 01414 g003
Nanomaterials 13 01414 g004 550
Figure 4. SEM images of the prepared MgCo2O4 nanoflakes (a–c) and Ni(OH)2@MgCo2O4 nanosheet composite (d–f).
Figure 4. SEM images of the prepared MgCo2O4 nanoflakes (a–c) and Ni(OH)2@MgCo2O4 nanosheet composite (d–f).
Nanomaterials 13 01414 g004
Nanomaterials 13 01414 g005 550
Figure 5. Low-magnification and high-magnification TEM images. (a) TEM images of MgCo2O4 nanoflake electrode; (b) TEM images of Ni(OH)2@MgCo2O4 nanosheet composite; (c) the HRTEM images of the Ni(OH)2@MgCo2O4 nanosheet composite (the insets of the selected area show the electron diffraction (SAED) patterns); (d–g) EDS element mapping images of Ni(OH)2@MgCo2O4 nanosheet composite.
Figure 5. Low-magnification and high-magnification TEM images. (a) TEM images of MgCo2O4 nanoflake electrode; (b) TEM images of Ni(OH)2@MgCo2O4 nanosheet composite; (c) the HRTEM images of the Ni(OH)2@MgCo2O4 nanosheet composite (the insets of the selected area show the electron diffraction (SAED) patterns); (d–g) EDS element mapping images of Ni(OH)2@MgCo2O4 nanosheet composite.
Nanomaterials 13 01414 g005
Nanomaterials 13 01414 g006 550
Figure 6. (a) Comparison of the CV plots of Ni(OH)2 nanoparticle electrode, MgCo2O4 nanoflake electrode, and Ni(OH)2@MgCo2O4 nanosheet composites at a scan rate of 5 mV s−1; (b) comparison of the GCD curves of the electrodes at a current density of 1 A g−1; (c,e) CV curves of the Ni(OH)2@MgCo2O4 nanosheet composites and MgCo2O4 nanoflake electrodes at varied scan rates; (d,f) GCD curves of the Ni(OH)2@MgCo2O4 nanosheet composite and MgCo2O4 nanoflake electrodes at different current densities.
Figure 6. (a) Comparison of the CV plots of Ni(OH)2 nanoparticle electrode, MgCo2O4 nanoflake electrode, and Ni(OH)2@MgCo2O4 nanosheet composites at a scan rate of 5 mV s−1; (b) comparison of the GCD curves of the electrodes at a current density of 1 A g−1; (c,e) CV curves of the Ni(OH)2@MgCo2O4 nanosheet composites and MgCo2O4 nanoflake electrodes at varied scan rates; (d,f) GCD curves of the Ni(OH)2@MgCo2O4 nanosheet composite and MgCo2O4 nanoflake electrodes at different current densities.
Nanomaterials 13 01414 g006
Nanomaterials 13 01414 g007 550
Figure 7. Electrochemical characterization of Ni(OH)2 nanoparticle electrode, MgCo2O4 nanoflake electrode, and Ni(OH)2@MgCo2O4 nanosheet composites: (a) specific capacitances of as-developed active electrodes at different current densities; (b) Nyquist plots of EIS; (c) cycling performance tests over 3500 long cycles at a current density of 2 A g−1.
Figure 7. Electrochemical characterization of Ni(OH)2 nanoparticle electrode, MgCo2O4 nanoflake electrode, and Ni(OH)2@MgCo2O4 nanosheet composites: (a) specific capacitances of as-developed active electrodes at different current densities; (b) Nyquist plots of EIS; (c) cycling performance tests over 3500 long cycles at a current density of 2 A g−1.
Nanomaterials 13 01414 g007
Table
Table 1. Comparison of electrochemical performance of Ni(OH)2@ MgCo2O4 electrode with earlier reported studies on a three-electrode system.
Table 1. Comparison of electrochemical performance of Ni(OH)2@ MgCo2O4 electrode with earlier reported studies on a three-electrode system.
Electrode MaterialsElectrolyteSpecific Capacitance (F g−1)/Current DensityCycles (Stability)Ref.
MgCo2O4@MnO22 M KOH852.5 F g−1 at (1 A g−1)-[38]
CeO2@MnO21 M Na2SO4255 F g−1 at (1 A g−1)3000 (90.1%)[39]
MgCo2O4 nanosheets2 M KOH947 C g−1 (2 A g−1)5000 (96%)[40]
Double-urchin-like MgCo2O43 M KOH508 F g−1 (2 A g−1)2000 (95.9%)[41]
1D MgCo2O4-752 F g−1 (2 mA cm−2)-[42]
MgCo2O4 nanocone arrays1 M Na2SO4750 F g−1 (1 A g−1)1000 (84%)[43]
Porous MgCo2O4 nanoneedle-804 F g−1 (1 A g−1)2000 (87%)[44]
MgCo2O42 M KOH321 F g−1 (0.5 A g−1)-[45]
Urchin-like MgCo2O4@PPy-1076.9 F g−1 (1 A g−1)1000 (97.4%)[46]
Ni(OH)2@MgCo2O42 M KOH1287 F g−1 at 1 A g−13500 (85.6%)This work
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Arbi, H.M.; Koyyada, G.; Anil Kumar, Y.; Kumar Kulurumotlakatla, D.; Kim, J.H.; Moniruzzaman, M.; Alzahmi, S.; Obaidat, I.M. Hierarchically Developed Ni(OH)2@MgCo2O4 Nanosheet Composites for Boosting Supercapacitor Performance. Nanomaterials 2023, 13, 1414. https://doi.org/10.3390/nano13081414

AMA Style

Arbi HM, Koyyada G, Anil Kumar Y, Kumar Kulurumotlakatla D, Kim JH, Moniruzzaman M, Alzahmi S, Obaidat IM. Hierarchically Developed Ni(OH)2@MgCo2O4 Nanosheet Composites for Boosting Supercapacitor Performance. Nanomaterials. 2023; 13(8):1414. https://doi.org/10.3390/nano13081414

Chicago/Turabian Style

Arbi, Hammad Mueen, Ganesh Koyyada, Yedluri Anil Kumar, Dasha Kumar Kulurumotlakatla, Jae Hong Kim, Md Moniruzzaman, Salem Alzahmi, and Ihab M. Obaidat. 2023. "Hierarchically Developed Ni(OH)2@MgCo2O4 Nanosheet Composites for Boosting Supercapacitor Performance" Nanomaterials 13, no. 8: 1414. https://doi.org/10.3390/nano13081414

APA Style

Arbi, H. M., Koyyada, G., Anil Kumar, Y., Kumar Kulurumotlakatla, D., Kim, J. H., Moniruzzaman, M., Alzahmi, S., & Obaidat, I. M. (2023). Hierarchically Developed Ni(OH)2@MgCo2O4 Nanosheet Composites for Boosting Supercapacitor Performance. Nanomaterials, 13(8), 1414. https://doi.org/10.3390/nano13081414

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop