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Faradically Dominant Pseudocapacitive Manganese Cobalt Oxide

Electrode Materials for Hybrid Supercapacitors and Electrochemical
Water Splitting
Muhammad Zahir Iqbal,* Misbah Shaheen, Umair Aftab, Zubair Ahmad,* Muhammad Yameen Solangi,
Muhammad Ishaq Abro, and Saikh Mohammad Wabaidur

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ABSTRACT: Owing to their potential usage and great electro-

chemical performance, transition metal oxides (TMOs) are attracting
enormous interest to be scrutinized for the energy-storage and
conversion domain. Our work describes the electrochemical response
of spinel transition metal oxides (Co3O4 and MnCo2O4) for
electrochemical water splitting (oxidation evolution reaction
(OER)) and hybrid energy-storage devices. After a comprehensive
study of the structure and morphology, the synthesized materials were
initially evaluated for the OER performance. Mn-doped Co3O4
performed better for OER due to the inclusion of Mn ions in the
spinel structure. For the OER activity, the fabricated electrode showed
an overpotential of 311 mV and a Tafel slope of 71 mV/dec upon
obtaining the good performance of Mn-doped Co3O4 for OER; it was
further utilized for energy-storage application by fabricating its hybrid supercapacitor device with activated carbon. The hybrid
supercapacitor showed a better energy (36 W h/kg) and power density (4274 W/kg) relatively. Moreover, the semiempirical
approach was adapted to further elaborate the experimental results obtained. The significant response of the developed electrodes
enhances their potential for future energy-storage and conversion applications.

1. INTRODUCTION performance for both hydrogen and oxygen evolution is back-

Renewable and clean energy sources, namely, solar, tidal, wind, breaking but a primary task.12
and hydrogen energy, are considered to be key components for Apart from electrochemical energy conversion, energy-
the reduction of worldwide energy crises; however, they require storage technology is currently a focus of research, which may
highly efficient energy-storage systems to upgrade their demand allow the storage of clean energy in an effective manner.
for developing a green environment.1−4 Water electrolysis is an Supercapacitors, also termed ultracapacitors, have gained
essential phenomenon that offers the potential solution for enormous attention owing to their fast charging/discharging,
energy conversion and renewable fuel production.5 Electro- high power density, and longer lifespan.13−16 Depending upon
chemical water splitting is regarded as a carbon-free mechanism the charge-storage characteristics of electrochemical capacitors,
for hydrogen generation from renewable sources and its further they are categorized into electric double-layered capacitors
utilization in fuel cells and power plants.6,7 The electrolysis (EDLCs) and pseudocapacitors.17,18 EDLCs utilize carbon-
process is mainly comprised of two half-cell reactions, such as based electrode materials with relatively poor energy density,
the hydrogen evolution reaction (HER) and the oxygen but they suggest a remarkable power density,19 while
evolution reaction (OER), required for energy-conversion pseudocapacitors tend to exhibit better energy density along
mechanisms.8 There is an urgent need to develop optimal with small power density and long-term stability.20,21 Despite
electrocatalysts with noticeable performance, resplendent
stability, and efficacious performance of these technologies.9
The noble transition metals impart a large-scale adoption for Received: September 16, 2023
boosting the overall electrocatalytic potency, i.e., Pt-, Ru-, and Ir- Revised: January 4, 2024
based electrode materials.10 However, high cost and low Accepted: January 4, 2024
abundance hinder their diversified use for water decomposi- Published: January 19, 2024
tion.11 Alarmed by all of these details, optimizing affordable
electrocatalysts with long-term stability and an ameliorating

© 2024 American Chemical Society https://doi.org/10.1021/acs.energyfuels.3c03444

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the promising behavior of supercapacitors, energy density needs oxide in multiple domains of energy technology. By ingeniously
to be further improved in order to promote their extensive harnessing the catalytic ability of cobalt oxide (Co3O4) and the
utilization in various fields for renewable energy storage.22 Thus, synergistic effects of manganese cobalt oxide (MnCo2O4), this
asymmetric/hybrid supercapacitors have the potential to study not only unveils their potential in energy conversion
improve the energy density of supercapacitors without affecting through OER but also showcases their capabilities in efficient
their power density.23 Such hybrid supercapacitors combine the electrochemical energy storage. The multifaceted functionalities
properties of both EDLCs and battery-grade electrode materials, exhibited by these transition metal oxides exemplify their pivotal
resulting in high energy density.23−25 On that account, there is a role in propelling the frontiers of innovative energy technology.
huge demand for developing novel electrode materials for
fabrication of distinguished asymmetric SCs.19 2. EXPERIMENTAL SECTION
Various materials (i.e., oxides, sulfides, phosphates, metal
2.1. Chemicals. The chemicals required for the synthesis of oxides
chalcogenides, metal−organic frameworks, etc.) are explored in and slurry preparation, including cobalt chloride hexahydrate (CoCl2·
the field of energy to utilize them as electrode materials for 6H2O), potassium permanganate (KMnO4), urea (CH4N2O), N-
energy generation, conversion, storage, and utilization.26−31 methyl-2-pyrrolidone (NMP), a polyvinylidene fluoride (PVDF)
Among these materials, transition metal oxides (TMOs) are binder, activated carbon (AC), potassium hydroxide (KOH), and
prevalent for their applications in energy conversion and acetylene black, were brought from Sigma-Aldrich. All of the above
storage.32,33 Hong et al. reported bimetallic oxides as electrode precursors were of prime quality and utilized without further
materials for hybrid supercapacitors, and the device exhibited an purification.
energy density of 11 W h/kg and a maximum power of 800 W/ 2.2. Synthesis of Co3O4 and MnCo2O4. An aqueous chemical
kg.34 Similarly, Ali et al. constructed a hybrid supercapacitor synthesis method was adapted to procure manganese-doped cobalt
oxide. To synthesize the desired material (Co3O4), a 0.1 M solution of
based on cobalt oxide and activated carbon, and they achieved a CoCl2·6H2O and CH4N2O in DI water was prepared and stirred until a
maximum power density of 11 kW/kg at an energy density of 18 homogeneous solution had been obtained. After mixing, the solution
W h/kg.35 Furthermore, Zheng et al. synthesized Pt/LiCoO2 for was placed in an oven for 5 h at 95 C for the materials to react properly.
water splitting application, and the 30% Pt/LiCoO2 composite The obtained sample was washed with DI water many times and
showed a significant response with 61 and 285 mV for 10 mA collected in a china dish through a sedimentation process. The moisture
cm−2 for HER and OER.36 Huang et al. fabricated a hybrid content in the sample was then removed by placing it in an oven at 100
electrode (Pt@Co3O4/Ni foam) that exhibited a low over- C. For phase formation, the material was subjected to calcination
potential as well as better OER (263 mV@10 mA cm−2) along treatment at 500 C for 5 h, which converted the hydroxides into an
oxide phase. The obtained Co3O4 sample was collected for further
with HER (30 mV@10 mA cm−2) activity.36 These spinel-type
characterization.
compounds with AB2X4 (A, B: metal, X: chalcogen)-type A method similar to that was employed to synthesize MnCo2O4. The
structures have become a prime interest for their different only difference was in the solution preparation stage, where an
applications in the electronic industry, such as electrocatalysis, additional precursor (KMnO4) was added to introduce manganese into
magnetic data storage, energy storage, etc. The slight change in the structure of cobalt oxide. After that, the same conditions for heating,
the composition of Co3O4 can affect its properties as well as its washing, and calcination were employed as those adapted for Co3O4.
performance when utilized for different applications. For 2.3. Fabrication of Co3O4 and MnCo2O4 Electrodes. For being
instance, doping of manganese in Co3O4 can replace the Co employed as a current collector, a 1 × 1.5 cm2 nickel foam (NF)
ions in the structure, which can be easily understood from the underwent a purification process by subjecting it to a 3 M HCl solution
for 10 min in order to eliminate an oxide layer from its surface. The NF
formula MnxCo3−xO437 However, the phase of the spinel was cleansed with acetone and ethanol to ensure its purity before being
structure can vary depending upon the doping concentration, dried in a vacuum oven.
i.e., a low concentration of Mn will form a tetragonal phase; To prepare a slurry of as-prepared active materials (Co3O4 and
however, high content of Mn tends to create a cubic spinel.38 MnCo2O4), a mixture was created by combining NMP (5 wt %), a
These oxide materials show considerable catalytic activity and PVDF binder (5 wt %), acetylene black (10 wt %), and 80% Co3O4. The
capacity with admirable cyclic stability. Among other oxides, slurry was allowed to be stirred for 8 h until we got a uniform suspension
Co3O4 is reported to have better catalytic activity and storage and drop-cast onto the ∼1 × 1 cm2 NF surface, which was then left to be
capability. Also, the environmentally friendly nature and cost- dried at 70 °C for 4 h. An exactly similar technique was implemented to
effectiveness of Co3O4 make it an easily accessible material. The prepare MnCo2O4 and an activated carbon-based electrode.
2.4. Characterizations. The synthesized samples were first tested
spinel structure of Co3O4 allows it to possess large oxidation for structural and morphological studies through XRD, SEM, EDX,
potential and fast charge transfer, which makes it a highly BET, and FTIR. After confirming the formation of the desired material,
favorable material for the oxidation evolution reaction (OER). the electrochemical activities of manufactured electrode materials
Herein, the transition metal oxides named cobalt oxide toward both energy conversion (in a three-cell assembly) and energy
(Co3O4) and cobalt manganese oxide (MnxCo3−xO4) are storage (in both three- and two-cell assemblies) were evaluated in a 1 M
synthesized to be used in two different applications, i.e., energy KOH medium using an active electrode as a working terminal, while a
conversion and storage. Before testing the electrodes for their platinum wire and Hg/HgO as a counter and a reference electrode,
applications, structural and morphological characterizations respectively. Various characterizations, including cyclic voltammetry
(CV), linear sweep voltammetry (LSV), chronoamperometry,
were performed. The electrodes based on Co3O4 and MnCo2O4
galvanostatic charge/discharge (GCD), and electrochemical impe-
were utilized as catalysts for OER, and the best-performing dance spectroscopy (EIS), were performed for two different
electrode was used for energy-storage application. The energy- applications.
storage measurements were done initially in a three-cell Initially, LSV measurement was done at a scan rate of 5 mV/s. The
assembly, and then a real asymmetric device was fabricated chronoamperometry test was done for durability at 20 mA/cm2 for 40
based on the best-obtained sample by simply combining it with h. In this analysis, all of the potentials were transformed into potential vs
activated carbon. The electrochemical characterizations were reversible hydrogen electrode (RHE) by applying eq 1
performed for electrocatalysis and electrochemical energy-
ERHE = E Hg/HgO + 0.118 + 0.059 × pH (1)
storage applications, which proves the significance of cobalt
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Figure 1. (a) XRD spectra, (b) FTIR spectra, and (c-d) SEM images of Co3O4 and MnCo2O4.

Figure 2. BET results of (a) Co3O4 and (b) MnCo2O4 and EDX results of (c) Co3O4 and (d) MnCo2O4.

Furthermore, the faster kinetics and efficiency of electrocatalysts can be Cyclic voltammetry (CV) was carried out by sweeping potential (υ)
from 3 to 50 mV/s to study the redox behavior of active materials. In
analyzed by determining their Tafel slope values from polarization
addition, the galvanostatic charging−discharging (GCD) test was
curves by employing eq 2 performed at different current densities to obtain information on the
charge-storage capability of working electrodes. For energy-storage
= a + b log j (2) application, a 0−0.7 V window was used for CV and a 0−0.6 V window

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Figure 3. (a) LSV curves for Co3O4 and MnCo2O4, (b) Tafel slope for Co3O4 and MnCo2O4 in comparison with RuO2, (c) stability test for MnCo2O4,
and (d) LSV curves of MnCo2O4 before and after stability to show the stability of the sample.

was optimized for GCD in a three-cell assembly, whereas a 0−1.6 V Table 1. Comparison of Water-Splitting Results of This Work
window was utilized for a hybrid supercapacitor in a two-cell assembly. with the Previously Reported Literature
The EIS measurements were then performed in a frequency range of
0.1−100 kHz for conductivity studies. materials HER OER ref
The following eqs 3 and 4 were utilized to determine specific NiCo2O4 −46.3 mA/cm 2
67.3 mA/cm 2
40
capacities (Qs) in the three- and two-cell assemblies NiCo2O4/NiO/CoF2@mC700 −45.3 mV 1.47 V 41
I dV CeO2−NiCoPx/NCF 39 mV 260 mV 42
Cs = CuCoO-NWs 85 mV 1.48 V 43
mv (3)
this work 311 mV
I× t
Cs = the Co3O4 structure replaced the Co ions, which caused strain to
m (4)
be produced in the structure. Due to the larger atomic radii of
In eq 1, the integral part is the area under the CV curve, m is the active Mn ions than Co ions, the XRD spectrum of MnCo2O4 has been
mass, and v represents the scan rate. In eq 2, Δt is discharging time (s),
I/m signifies current density, and Cs is measured in C/g. Moreover, the
observed to shift slightly toward a lower angle, as demonstrated
energy and power density of the asymmetric supercapacitor was by Bragg’s law. Figure 1b represents the FTIR spectra of pristine
calculated using eqs 5 and 6 cobalt oxide and Mn-doped cobalt oxide. Both the samples
possess the same peaks of C�C, C−O, C�O, C−H, and O−
Qs × V H, corresponding to 877, 1036, 1747, 2926, and 3437 cm−1,
Es =
2 × 3.6 (5) respectively. The presence of organic bonds is attributed to the
Es × 3600 potassium bromide (KBr) used for sample preparation for FTIR.
Ps = The peaks at a lower wavelength present the metal−oxygen
t (6)
bonds. In addition, the SEM images of Co3O4 and MnCo2O4 are
Here, Qs is specific capacity, Δt is the discharging time for a device, and displayed in Figure 1c,d. Co3O4 formed needle-like structures,
ΔV represents the potential window chosen for working of the device. and on the other hand, the incorporation of Mn showed flake-
like morphology within a needle-like shape. Furthermore, BET
3. RESULTS AND DISCUSSIONS was conducted to determine the surface area of Co3O4 and
3.1. Structural and Morphological Characterizations. MnCo2O4, as the surface area and porosity directly affect the
The synthesized oxides were evaluated for their structural and storage properties of the materials. The BET results are
morphological properties before testing for their electro- displayed in Figure 2a,b, and Co3O4 was observed to have a
chemical characteristics. The XRD of Co3O4 and MnCo2O4 is surface area of 35.8 m2/g, whereas MnCo2O4 exhibited a 77 m2/
represented in Figure 1a. The XRD spectrum of Co3O4 matches g surface area. The EDX results in Figure 2c,d show elemental
well with the JCPDS card no. 01-080-1536, which validates the analysis of Co3O4 and MnCo2O4, respectively, showing the
cubic phase formation of the oxide. The inclusion of Mn ions in presence of all related elements.
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Figure 4. (a) CV curves, (b) GCD curves, (c) specific capacity through CV, and (d) specific capacity through GCD for MnCo2O4 in the three-cell
assembly.

required for oxygen evolution. It is evident that the Mn-doped

samples show better catalytic activity as they possess a low
overpotential value. Moreover, the Tafel slopes for each active
material are evaluated through a linear fit of their linear sweep
voltammograms (Figure 3b). The Tafel value of Co3O4 is 103
mV/dec, which is greater than that of MnCo2O4 (71 mV/dec),
suggesting its efficient reaction kinetics. Thus, the required
oxides, especially MnCo2O4, show faster OER kinetics, which
can be influenced by their composition, number of active sites,
surface structure, and electrocatalyst loading.
The Tafel slope calculated in our work is 71 mV/dec, which
represents a better performance of the material. To analyze the
stability of the electrocatalyst, a chronopotentiometry test was
performed at a constant current density of 20 mA/cm2. The
potential has no drop even after 40 h at all current densities,
revealing the long-term stability of this fabricated electrode over
time (Figure 3c). After the stability test, LSV measurement was
Figure 5. Schematic demonstration of the fabricated hybrid super- again taken and plotted with the LSV curve before stability, as
capacitor with MnCo2O4 as a positive electrode and AC as a negative
electrode. shown in Figure 3d. The LSV curves before and after stability
exactly matched with each other, with no change after stability.
Thus, oxides proved to be the potential catalysts for OER
3.2. Electrochemical Analysis. 3.2.1. OER Analysis in a activity because of their distinctive redox-active properties.
Three-Cell Assembly. All of the required samples (Co3O4 and Table 1 presents the results obtained in this work with a
MnCo2O4) are investigated for O2 evolution at a scanning comparison of already reported data.
voltage of 10 mV/s in a three-cell assembly. The response of 3.2.2. Energy-Storage Analysis in a Three-Cell Assembly.
these electrodes toward the OER can be observed in Figure 2. From the OER analysis, it is evident that MnCo2O4 performed
The small overpotential and onset potential values represent the better; therefore, it was also utilized for energy-storage
exceptional behavior of the electrocatalyst toward OER. As applications. To investigate the inherent electrochemical
illustrated in Figure 3a, the overpotential of MnCo2O4 is 311 characteristics of MnCo2O4, electrochemical measurements
mV, which is negligibly smaller as compared to Co3O4 (428 were performed in a three-cell assembly initially. The CV tests
mV), hinting at the better catalytic behavior of MnCo2O4. The were executed at various potential sweeps ranging from 3 to 50
results confirm that the synergistic influence of manganese and mV/s. The voltammograms for the active material are listed in
cobalt metal ions can significantly decrease the overpotential Figure 4a. The deviation from pure capacitive behavior and the
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Figure 6. (a) CV results at various scan rates, (b) GCD results at various current densities, (c) calculated specific capacity at all current densities, (d)
energy and power density at all current densities, (e) Ragone plot of energy and power density, (f) and stability test results conducted for 1000 GCD
cycles.

Figure 7. Semiempirical method of fitting using Dunn’s model showing capacitive and diffusive contributions at three different scan rates: (a) 3 mV/s,
(b) 50 mV/s, and (c) 100 mV/s. (d) Trend of capacitive and diffusive contributions at all scan rates describing the increase in the capacitive part and
the decline in the diffusive part with the increase in the scan rate.

presence of redox peaks in CV curves indicate toward its electrode and the electrolyte. The two reduction peaks may be
pseudocapacitive nature. The spinel structure of cobalt oxide attributed to the two-electron transfer process where MnCo2O4
delivers enhanced redox activity due to the presence of Mn and is converted into CoOOH and MnOOH. The reaction scheme
Co ions, which are able to transfer electrons between the is as follows39
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Table 2. Comparison of Energy-Storage Results of This Work behavior of MnCo2O4 toward energy storage, the hybrid device
with Previously Reported Result was designed by utilizing prepared Mn-doped cobalt oxide as a
positive electrode and activated carbon (AC) as a negative
materials energy density power density refs
electrode. A schematic illustration of the assembly of the
CNTs@NCDHNs & rGO-Fe2O3 54.6 W h/kg 12.4 k W/kg 44 asymmetric device is shown in Figure 5. To conduct a systematic
Cu−Ni−Ce−Co oxide and GNP 51 W h/kg 581.9 W/kg 45 assessment of fabricated MnCo2O4//AC, electrochemical
Zn−Mn−Co ternary oxide and AC 35.5 W h/kg 7.5 kW/kg 46 examinations were carried out employing a two-electrode
this work 36 W h/kg 4274 W/kg setup without any reference electrode, as depicted in Figure 5.
The operational voltage range for oxide is 0−0.6 V, whereas, for
MnCo2O4 + H 2O + OH AC, it varies from 0 to −1.0 V. Therefore, it can be confirmed
that the voltage range of 0−1.6 V was opted for conducting the
MnOOH + 2CoOOH + e (7)
CV at different potential windows. Initially, CV analysis for the
CoOOH + OH CoO2 + H 2O + e (8)
fabricated device was carried out at the scanning potential
ranging from 3 to 100 mV/s. The required voltammograms are
MnOOH + OH MnO2 + H 2O + e (9)
depicted in Figure 6a. The hybrid supercapacitor device shows
redox peaks as well as a rectangular enclosed area.
Here, the electrolyte provides OH ions, which are stored Furthermore, galvanostatic charging−discharging plots also
through surface redox and intercalation processes. When the confirm the asymmetric characteristics of the designed hybrid
scan rate is at its lowest, the redox peaks show minimal peak device (Figure 6b). The specific capacity of this fabricated device
separation and are nearly symmetrical, indicating a high level of was analyzed and is displayed in Figure 6c, which shows that the
reversibility in the redox reactions. maximum achieved capacity of the fabricated device is 154 C/g.
GCD analysis has been performed to obtain the charge- Both energy (Es) and power densities (Ps) are considered crucial
storage behavior of electrode materials at different current factors for evaluating the overall performance of the hybrid
densities ranging from 0.7 to 6.0 A/g (Figure 4b). In charge/ device and are scrutinized by using eqs 5 and 6. The trend of
discharge measurements, a constant current is applied to the energy and power density at all current densities is presented in
active material, causing it to charge or discharge over time. The Figure 6d, which demonstrates that the device exhibits
redox reactions that were observed in cyclic voltammograms can maximum Es of 36 W/kg along with a Ps yield of 4274 W h/
also be identified in GCD via plateaus in the charge−discharge kg. Also, the Ragone plot (power vs energy) is shown in Figure
curves of the pseudocapacitive sample. As the current density 6e to estimate the position of this hybrid supercapacitor among
increases, the rate of charge−discharge mechanisms in required other energy-storage devices. Overall, 5000 GCD cycles were
samples also increases, resulting in a shorter discharge time. run to estimate the stability of the real device, which presents a
However, the GCD plots demonstrated symmetric discharge 91.1% retention in capacity, as displayed in Figure 6f.
humps at all current densities, indicating that the materials To further justify the hybrid nature of MnCo2O4//AC,
remained stable even at higher current densities. The shorter Dunn’s model was employed to evaluate the capacitive as well as
discharge time observed at increased current densities may be diffusive characteristics of the active material, as illustrated in the
attributed to the inadequate intercalation of hydroxyl ions into following equation.
the electrode, which could be caused by insufficient available
1 /2
time for the ions to occupy the redox sites. i(V ) = k1 + k 2 (10)
Moreover, the Qs of the sample through CV and GCD is
plotted in Figure 4c,4d, respectively. The material exhibits Qs The results accomplished from Dunn’s approach affirm the
values of 241 and 162 C/g from CV and GCD, respectively. hybrid behavior of the fabricated device (Figure 7) as it
Table 1 demonstrates the outcomes of the water-splitting possesses both capacitive and diffusive characteristics. The
experiment with previously reported data. The favorable capacitive and diffusive contributions are plotted at three
pseudocapacitive behavior of MnCo2O4 makes it a promising different scan rates (3, 50, and 100 mV/s), demonstrating the
candidate for energy-storage devices. variation in capacitive and diffusive behavior with changing scan
3.2.3. Electrochemical Analysis of the Hybrid Energy- rates (Figure 7a−c). Also, the determined capacitive and
Storage Device (MnCo2O4//AC). Considering the exceptional diffusive contributions at all scan rates are displayed in the

Figure 8. EIS curves of the best sample MnCo2O4 in(a) three-cell and (b) two-cell assemblies.

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form of a bar chart in Figure 7d. The capacitive contribution

increased with an increase in the scan rate, determining the faster
■ AUTHOR INFORMATION
Corresponding Authors
kinetics of ions and less time for redox reactions. Table 2
Muhammad Zahir Iqbal − Renewable Energy Research
demonstrates the outcomes of hybrid supercapacitors with Laboratory, Faculty of Engineering Sciences, Ghulam Ishaq
previously reported data. The impressive results achieved by Khan Institute of Engineering Sciences and Technology, Topi
MnCo2O4 allow it to be employed as advanced active electrodes 23640 Khyber Pakhtunkhwa, Pakistan; orcid.org/0000-
in energy-storage domains. 0003-4985-0981; Email: [email protected]
3.2.4. Electrochemical Impedance Spectroscopy of the Zubair Ahmad − School of Chemical Engineering, Yeungnam
MnCo2O4 Electrode in Three- and Two-Electrode Setups. The University, Gyeongsan, Gyeongbuk 38541, Republic of Korea;
EIS measurement effectively determines the conductivity Email: [email protected]
properties of the whole system, which are crucial for water-
splitting and energy-storage applications. The results of the EIS Authors
spectrum for the fabricated electrode in a three-cell assembly can Misbah Shaheen − Renewable Energy Research Laboratory,
be interpreted by the Nyquist plot, as shown in Figure 8a. It Faculty of Engineering Sciences, Ghulam Ishaq Khan Institute
reveals information about the electrical properties of the of Engineering Sciences and Technology, Topi 23640 Khyber
electrode−electrolyte interface, including ion-transfer kinetics, Pakhtunkhwa, Pakistan; orcid.org/0000-0002-8626-
3113
resistance at the interface, and double-layer capacitance. The
Umair Aftab − Department of Metallurgy and Materials
EIS plot for MnCo2O4 does not exhibit a semicircle that Engineering, Mehran University of Engineering and
expresses its better conductivity. The point of overlapping on Technology, 76080 Jamshoro, Pakistan
the x-scale in the high-frequency domain of the EIS spectrum Muhammad Yameen Solangi − Department of Metallurgy and
indicates the equivalent series resistance (ESR) of required Materials Engineering, Mehran University of Engineering and
samples, which holds information about resistance offered to the Technology, 76080 Jamshoro, Pakistan
ions in the electrolyte. The smaller value (0.8 ohm) of ESR for Muhammad Ishaq Abro − Department of Metallurgy and
MnCo2O4 makes it a suitable material for energy conversion and Materials Engineering, Mehran University of Engineering and
storage as it exhibits faster kinetics and considerable Technology, 76080 Jamshoro, Pakistan
conductivity. Furthermore, the presence of an angled line in Saikh Mohammad Wabaidur − Department of Chemistry,
the low-frequency range is an indication of Warburg impedance, College of Science, King Saud University, Riyadh 11451, Saudi
which arises due to either ion transport or diffusion kinetics in an Arabia
electrolyte. EIS assessments were also performed for the Complete contact information is available at:
fabricated real device (MnCo2O4//AC) in a two-cell assembly https://pubs.acs.org/10.1021/acs.energyfuels.3c03444
to adjudge the electrical conductivity of the device. It can be
observed from Figure 8b that the ESR value for the hybrid Notes
supercapacitor is 0.3 ohm. These attributes of the MnCo2O4 The authors declare no competing financial interest.
material make it a viable and attractive material for numerous
energy-storage and conversion applications. ■ ACKNOWLEDGMENTS
This work was supported by Researchers Supporting Project
4. CONCLUSIONS number (RSP2024R448), King Saud University, Riyadh, Saudi
In this study, we present the dual applications of spinel- Arabia.
structured oxides, including Co3O4 and MnCo2O4, with high
catalytic activity and charge-storage capability for the OER as
well as energy storage, respectively. The morphological and
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