Article

DOI:10.1557/s43578-024-01455-w

Effect of ­Co2+ and ­Mn3+/Mn4+ ratio on high‑performance

supercapattery
Fernando José Soares Barros1,2,a) , Samuel da Silva Eduardo1, Hector A. Vitorino3,
Camila de Lima Ribeiro4, Alysson Martins Almeida Silva4, Elson Longo5, Ivo Mateus Pinatti1,
Auro Atsushi Tanaka1,a)
1
Department of Chemistry, Federal University of Maranhão, Av. dos Portugueses, 1966, São Luís, MA 65080‑805, Brazil
2
Department of Chemical Engineering, Federal University of Ceará, Campus do Pici, 709, Fortaleza, CE 60.455‑760, Brazil
3
Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo, SP 05508‑000, Brazil
4
Department of Mechanical Engineering, University of Brasilia, Campus Universitário Darcy Ribeiro, Asa Norte, Brasília, DF 70910‑900, Brazil
5
Department of Chemistry, CDMF‑UFSCar, Federal University of São Carlos, Rod. Washington Luiz Km 235, São Carlos, SP 13565‑905, Brazil
a)
Address all correspondence to these authors. e-mails: fernando.barros@gpsa.ufc.br; tanaka.auro@ufma.br
Received: 1 July 2024; accepted: 25 September 2024

The growing demand for advanced energy storage highlights supercapacitors for their high power
density and long cycle life. Supercapatteries are hybrid supercapacitors (HSCs) that combine carbon
materials as anode and metal oxides as cathode with a battery-type behavior. Here, electrode materials
of Co-doped ­MnOx nanorods were prepared via incipient wet impregnation. The synthesis induced
morphological modifications in the material and the creation of oxygen vacancies was suggested by their
­Mn3+/Mn4+ ratio. The 4.79 wt.% Co/MnOx electrode delivered a high specific capacitance of 1478.52 F
­g−1 at 1 A g
­ −1 and enhanced stability after 1000 cycles for a symmetric device. Then, the supercapattery
reached 452.19 F ­g−1 at 1 A g
­ −1, energy density of 579 Wh ­kg−1, power density of 2881 W ­kg−1, and good
stability up to 1500 cycles. This study sheds light on the easy and low-cost production of a Co-doped
­MnOx electrode material for enhanced energy storage.

Introduction carbon-based materials as anodes and mixed metal oxides as

The urgent need for renewable and clean energy sources, such cathodes, which exhibit electric double-layer capacitance and
as solar and wind, requires sustainable energy storage technolo- reversible redox processes, respectively [6]. These HSCs leverage
gies to manage the intermittent nature of these sources [1]. The the strengths of both material types, utilizing capacitive EDLC
growing demand for energy storage systems with high power materials such as activated carbon and graphene for the anode
density, rapid charge–discharge rates, and long cycle life has and battery-type or pseudocapacitive materials like Ni(OH)2,
sparked significant research into advanced energy storage tech- ­PbO2, and ­LiMn2O4 for the cathode, thus achieving a balance
nology [2]. Supercapacitors have gathered attention by bridging of high power density, long-life cycles, and high energy density
the gap between conventional capacitors and batteries, with a [7]. The term “supercapattery” refers to a classification of HSC
combination of high power delivery, ideal cycling stability, and frameworks that enables the combination of a battery-type elec-
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efficient energy storage, making them suitable for portable elec- trode (as the energy source via Faradaic process) and a EDLC
tronics, electric vehicles, and renewable energy systems [1, 3–5]. electrode (as the power source) [8]. Because of their high energy
These devices are categorized into electrochemical double-layer density, battery-like supercapacitor electrode materials such
capacitors (EDLC) and pseudocapacitors (PC). EDLCs store metal disulfides, metal oxides, metal hydroxides, and layered
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charge electrostatically using carbon-based materials, while metal hydroxides are potential electrode materials [9–12].
pseudocapacitors utilize reversible redox reactions involving Manganese oxide ­(MnOx) is a promising supercapacitor
Journal of Materials Research

metal oxides and conductive polymers [1, 6]. material due to its high electrochemical activity, theoretical
Hybrid supercapacitors (HSCs) represent a promising specific capacitance of 1370 ­Fg−1, and wide potential range.
advancement in energy storage technology by combining Despite this, its practical capacitance often falls short due to

Vol.:(0123456789)

© The Author(s), under exclusive licence to The Materials Research Society 2024
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crystallographic and morphological limitations affecting ion wt.% Co/MnOx, 4.79 wt.% Co/MnOx, and 10.19 wt.% Co/MnOx,
intercalation. Strategies to improve ion storage, such as increas- respectively. The discrepancy between the theoretical and meas-
ing mesoporous M ­ nOx pore size and doping with other materi- ured Co content can be attributed to several factors inherent to
als, have been explored. Cobalt (Co) doping, in particular, has the incipient wetness impregnation method. A primary issue
significantly enhanced the pseudocapacitive performance and may involve incomplete incorporation of the cobalt precursor
conductivity of M ­ nOx electrodes, leading to improved capaci- into the M­ nOx support. In manual impregnation, the distribu-
tance and electrode conductivity in Co-doped ­MnOx nanocom- tion of the solution might not be entirely uniform, leading to
posites [13, 14]. cobalt loss during subsequent drying and calcination. Addi-
The high oxidation potential of Cobalt, combined with elec- tionally, the solubility and deposition behavior of CoCl₂·6H₂O
tron mobility of manganese enhances conductivity and revers- within the ­MnOx matrix likely plays a role in the observed vari-
ibility in bimetallic oxides, offering superior electrochemical ation. Issues such as pore blockage or precursor precipitation
performance for supercapacitors compared to using either can prevent the complete uptake of metal into the support. The
oxide alone [15]. Given such advantages, the use of Co-doped complex interactions between the metal precursor and support,
­MnOx has gained significant attention in recent years, through solvent evaporation, and phase transformations during impreg-
various synthesis strategies to optimize their electrochemical nation, drying, and calcination can result in poor dispersion of
performance in energy storage applications. Hong synthesized the active species in the final material [19].
cobalt-doped manganese oxide (Co-doped MnO₂) through a XRD characterized the structure of the bulk, calcined, and
controlled hydrothermal process and specific heat treatment, Co-doped ­MnOx materials [Fig. 1(A)]. The samples exhibited
resulting in a hierarchical micro-flower structure of α-MnO₂ the main characteristic diffraction peaks of β-MnO2 (JCPDS
with a substantial surface area and mesoporous distribution. 72-1984) at 28.98°, 37.16°, 40.94°, 43.25°, 46.29°, 56.9°, 59.55°,
This structure achieved an impressive specific capacitance of 67.16°, and 72.47° corresponding to (110), (101), (200), (111),
527 F g⁻1 [16]. Similarly, Prajapati utilized a Co-MOF precur- (210), (211), (220), (310), and (301) crystal planes [20]. For
sor via ion exchange to synthesize cobalt–manganese layered the bulk ­MnOx, the diffraction peaks match closely with the
double hydroxides (CoMn LDH), which delivered a remarkable standard reference, indicating that the bulk M ­ nOx retains its
specific capacitance of 1305 F g⁻1, and assembled a high-perfor- original crystalline structure. The sharp and well-defined peaks
mance asymmetric supercapacitor device [17]. Mankge adopted suggest a high degree of crystallinity. After calcination, the mate-
a hydrothermal technique to produce a hybrid composite of rial presents some slight broadening of peaks, however, overall
cobalt–nickel oxalate and multi-atom doped electrochemically structure of the ­MnOx appears preserved, as the peak positions
exfoliated graphene (EEG), which exhibited a notable specific remain consistent. The introduction of a small amount of Co
capacity of 139.2 mAh g⁻1 [18]. Thus, Co-doped M ­ nOx presents (1.37 wt.%) does not seem to change the M ­ nOx phase. The peaks
a compelling avenue for advancing supercapacitor technology. remain largely consistent with those of calcined material, indi-
This study aims to investigate the effect of Co doping on the cating that the Co is well dispersed in the matrix without sig-
structural and electrochemical properties of M ­ nOx nanorods, nificantly affecting the crystalline structure [21]. The 4.79 wt.%
focusing on varying C ­ o2⁺ ion concentrations. The primary goal Co/MnOx sample shows slightly more noticeable changes com-
is to identify the optimal doping level to enhance ­MnOx-based pared to the lower Co-doped sample. There are minor shifts and
supercapacitor performance. The impact of the M ­ n3⁺/Mn4⁺ intensity variations, which could suggest the introduction of lat-
ratio on oxygen vacancy formation and electrochemical behav- tice distortions due to the higher Co content. These distortions
ior is also evaluated. Comprehensive material characterization could lead to the creation of oxygen vacancies or changes in
explores morphological changes, synthesis details, and oxygen the Mn oxidation state. At the highest Co content (10.19 wt.%),
vacancy roles, with the aim of developing high-performance the XRD pattern displays the most significant changes. Peak
electrode material. broadening and intensity variations are evident, which might
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indicate increased structural disorder, smaller crystallite sizes,

or a higher degree of cobalt substitution. The presence of Co at
this concentration likely leads to more substantial lattice distor-
Results and discussion tion and possibly even the formation of new Co–Mn–O phases.
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Physicochemical characterizations The lattice parameters are presented in Table S1, the ther-
This study prepared the Co-doped ­MnOx materials via incipi- mal process had a different effect on the cell volume for the
Journal of Materials Research

ent wet impregnation; the doping amounts were incorporated Co-doped samples in comparison to calcined M ­ nOx, where
in the following quantities: 5, 10, and 20 wt.% Co. However, the the a parameter increases significantly, while the c parameter
ICP-OES technique determined the Co content as 1.37, 4.79, decreases. This suggests structural reorganization or phase tran-
and 10.19 wt.%, respectively. Thus, the samples were labeled 1.37 sition induced by heat treatment. The cell volume also increases

© The Author(s), under exclusive licence to The Materials Research Society 2024 2
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Figure 1:  (A) XRD diffractograms for ­MnOx Bulk, M ­ nOx Calcined, 1.37 wt.% Co/MnOx, 4.79 wt.% Co/MnOx, and 10.19 wt.% Co/MnOx; TEM images for (B,
C) bulk M­ nOx, (D, E) calcined M
­ nOx, (F, G) 1.37 wt.% Co/MnOx, (H, I) 4.79 wt.% Co/MnOx, and (J, K) 10.19 wt.% Co/MnOx.

(685.53 Å3), reflecting a more expanded structure, likely due to TEM and SEM–EDS elucidated the morphology of the sol-
the removal of adsorbed species and the formation of a more ids (Fig. 1). Figure 1(B), (C) represents bulk M ­ nOx. The image
stable oxide phase. At the higher doping level, 10.19% Co/MnOx, taken at a lower magnification [Fig. 1(B)] reveals the general
both lattice parameters decrease compared to lower doping lev- morphology of the bulk M ­ nOx, showing a nanorods-like struc-
els 1.37 wt.% and 4.79 wt.%. The cell volume is significantly ture [23]. The image at a higher magnification [Fig. 1(C)] pro-
reduced (304.51 Å3), indicating that higher Co content leads to vides a closer look at the crystalline structure of M
­ nOx, indicat-
further contraction of the M ­ nOx lattice, possibly due to cobalt ing the quality of the synthesis. Figure 1(D), (E) depicts calcined
ions significantly altering the ­MnOx lattice or phase. Co has a ­MnOx. Figure 1(D) shows the morphology after the calcination
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smaller covalent radius, 1.26 Å, than Mn, 1.39 Å. The decrease in process; they appear to have thicker nanorods than the bulk
unit-cell volume upon doping confirms the substitutional effect form. Figure 1(E) provides a high-magnification view, corrobo-
of the element [22]. rating this conclusion.
The calculated crystallite sizes (d, Table S1) obtained from Figure 2(F), (G) focuses on ­MnOx with a 1.37 wt.% Co (1.37
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Debye–Scherrer equation were 48.29 nm, 37.20 nm, 36.69 nm, wt.% Co/MnOx). Figure 2(F) shows the overall morphology with
38.04 nm, and 39.36 nm for ­MnOx bulk, ­MnOx calcined, 1.37 a notable presence of thicker particles, suggesting good inter-
Journal of Materials Research

wt.% Co/MnOx, 4.79 wt.% Co/MnOx, and 10.19 wt.% Co/MnO2, actions between Co and ­MnOx. Figure 2(G), at a higher mag-
respectively. The d value decreased with the thermal treat- nification, emphasizes the fine structural details and potential
ment, whereas with the increasing cobalt content, there was an incorporation of Co within the M ­ nOx matrix. Figure 2(H), (I)
increase in crystallite size. examines ­MnOx with a 4.79 wt.% Co (4.79 wt.% Co/MnOx).

© The Author(s), under exclusive licence to The Materials Research Society 2024 3
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Figure 2:  SEM–EDS images of the nanorods. O (red), Mn (green), and Co (blue) for (A) 1.37 wt.% Co/MnOx, (B) 4.79 wt.% Co/MnOx, and (C)10.19 wt.% Co/
MnOx. (D) XPS spectra for Co 2p: 1.37wt.% Co/MnOx, 4.79wt.% Co/MnOx, and 10.19 wt.% Co/MnOx.

Figure 2(H) presents the general morphology, indicating mor- MnOx, 4.79 wt.% Co/MnOx, and 10.19 wt.% Co/MnOx samples
phology changes. Figure 2(I), taken at a higher magnification, is shown in Fig. 1(L), (M), (N). The dispersion of Mn, O and
highlights how the increased Co content influences the ­MnOx Co, Mn, and O is uniform on the surface of the nanorods. This
structure. Finally, Fig. 2(J), (K) investigates ­MnOx with 10.19 is consistent with the results of XRD demonstrating that the
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wt.% Co (10.19 wt.% Co/MnOx). Figure 2(J) displays the overall introduction of Co changed the lattice structure of the catalysts.
morphology, showing a more nanorod-defined structure than Then, the surface of the precursors and the cobalt-doped
the previous material. Figure 2(K), at a higher magnification, ­MnO2 nanorods were analyzed by XPS, identifying their chemi-
provides detailed insights into the structural changes induced by cal composition, binding energy, and the valence state of ele-
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the high cobalt loading. Notably, defects on the edge of the mate- ments (Fig. 2 and Table 1). The high-resolution spectra of Co 2p
rial are observed. Such partitions at the edge of these nanorods represent the existence of ­Co2+ species. Each spectrum can be
Journal of Materials Research

are noticeable in the Co-doped samples in Fig. 2(G), (I), (K). deconvoluted into four peaks: Co 2­ p3/2 is featured in the range
SEM–EDS demonstrated the distribution of the elements of 785.6–785.9, and Co 2­ p1/2 in the 796.2–796.5 eV range. The
in the materials. The images for bulk and calcined ­MnOx are two regions at 802.4–804.6 eV and 785.6–785.9 eV are satel-
featured in Figure S1. The presence of Co in 1.37 wt.% Co/ lite peaks [24, 25]. Regarding the Mn 2p region, Fig. 3(A), the

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TABLE 1:  XPS results for Co 2p, Mn 2p, and O 1s regions for ­MnOx bulk, ­MnOx calcined, 1.37wt.% Co/MnOx, 4.79wt.% Co/MnOx, and 10.19wt.% Co/MnOx.

Co 2p Mn 2p O1s

BE BE BE BE BE BE
Sample BE Sat (eV) Co 2p 1/2 (eV) BE Sat (eV) Co 2p 3/2 (eV) Mn 2p 1/2 (eV) Mn 2p 3/2 (eV) Oa (eV) Ob (eV) Oα/(Oα + Oβ)

MnOx bulk 655.1 653.1 643.4 641.6 531.22 529.01 0.43

MnOx calcined 656.3 653.2 643.9 641.6 531.5 529.2 0.51
1.37%Co/MnOx 802.4 796.2 785.6 780.5 655.1 653.2 643.5 641.6 531.4 529.3 0.52
4.79%Co/MnOx 802.9 796.2 785.9 780.6 654.3 652.9 643.0 641.4 531.4 529.3 0.57
10.19%Co/MnOx 804.6 796.5 785.8 780.7 656.3 653.4 644.4 641.8 531.5 529.6 0.57

peaks exhibited at binding energy ranges of 641.6- 41.9 eV and foam does exhibit some electrochemical activity, its impact
652.9–653.4 eV are related to 2­ p3/2 and 2­ p1/2 peaks, assigned on the measured values of the ­MnOx and Co/MnOx samples
to ­Mn3+. The peaks in the 643.0–644.4 eV and 655.1–656.3 eV was negligible. When examining the CV curves, distinct oxi-
­ n4+ species [14, 26]. The
are assigned to 2­ p3/2 and 2­ p1/2 of M dation peaks were observed in the most positive region and
mismatch in C ­ o2+ and M­ n4+/Mn3+ ratio is expected to create a reduction peaks in the most negative region for all samples,
charge imbalance in the crystal structure. This imbalance can which is the typical behavior of this type of material. The
be mitigated by the formation of oxygen vacancy close to Co presence of these redox signals suggests the occurrence of
atoms [25]. oxidation and reduction processes associated with the forma-
The O 1 s spectra in Fig. 3(B), Table 1, can be deconvo- tion of manganese and cobalt oxyhydroxides (MnO(OH) and
luted into two contributions. The oxygen species are assigned to CoO(OH))[31] These processes involve electronic transitions
surface-adsorbed oxygen (located at the surface oxygen vacan- between the oxidation states M ­ n +3/Mn +4 and C ­ o +2, which
cies of ­MnOx), ­(Oα) in the range of 531.22−531.5 eV and the are fundamental for forming the corresponding oxides of
lattice oxygen (­ Oβ) at 529.0 -529.6 eV [25, 27]. As indicated in these elements. This mechanism consists of the absorption
Table 1, after doping with cobalt, the ­Oα/Oβ ratio increased with and release of electrons during the reaction, leading to the
the higher Co content, suggesting that more oxygen vacancies formation of manganese and cobalt compounds [3].
and adsorbed oxygen species are enriched on the surface [28, Furthermore, an increase in scanning speed resulted in a
29]. The 4.79 wt.% Co/MnOx nanorod contains the highest ratio shift of the oxidation and reduction signals to more positive
of adsorbed oxygen species. XPS analysis provides indirect evi- and negative regions, respectively, in all electrode materials.
dence for the presence of oxygen vacancies, particularly through This phenomenon highlights kinetic limitations associated with
the observed changes in the O ­ α/Oβ ratio after Co doping. These charge transfer, resulting from the diffusion of ions between the
results are suggestive rather than conclusive. Techniques such electrode and the electrolyte [32]. At higher scan speeds, the
as Electron Paramagnetic Resonance (EPR) could provide more time available for ionic diffusion decreases, leading to a lower
definitive insight into the oxygen vacancy distribution. Never- reaction rate and, consequently, a change in the potentials at
theless, the XPS findings strongly indicate an increase in oxygen which redox reactions occur, Table S2. It is evident that the
vacancies near the Co sites, consistent with the previous litera- CV demonstrated a behavior that encompasses characteristics
ture, even though further characterization techniques would be of battery-type electrodes [33–35]. Figure 4(F) illustrates the
required to confirm these vacancies unambiguously. kinetic and diffusion reactions at the electrodes. The linearity
observed in the relationship between the peak current (Ip) and
the square root of the scanning speed (υ) suggests a diffusion-
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controlled process[36]. High R2 values, above 0.99 for the bulk,

Electrochemical studies
calcined and Co-doped ­MnOx support this interpretation,
To investigate the electrochemical properties of the bulk,
Table S3.
calcined, and Co-impregnated ­M nO x samples, cyclic vol-
To further investigate the charge storage capacity and
tammetry (CV) experiments were conducted in a 2 M KOH
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electrochemical stability of the electrode materials, galvano-

electrolyte solution. The potential range of − 0.2 to 0.5 V was
static charge–discharge (GCD) experiments were carried out.
scanned, with scan rates ranging from 5 to 80 mV ­s –1. The
Journal of Materials Research

Charge–discharge measurements of raw and calcined ­MnOx

resulting CV curves are represented in Fig. 4. The nickel foam
and Co/MnO2 samples were carried out in the potential range
has a minimal contribution to the overall electrochemical
of 0 to 0.45 V, varying the current density from 1 to 20 A ­g−1.
behavior of the tested materials [11, 30]. While the nickel
The resulting GCD curves are presented in Fig. 5. The specific

© The Author(s), under exclusive licence to The Materials Research Society 2024 5
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Figure 3:  XPS spectra of ­MnOx Bulk

(A) Mn 2p, and (B) O 1 s, M­ nOx
Calcined (C) Mn 2p, and (D) O 1 s,
1.37wt.% Co/MnOx (E) Mn 2p, and
(F) O 1 s, 4.79wt.% Co/MnOx (G) Mn
2p, and (H) O 1 s.and 10.19wt.%
Co/MnOx for (I) Mn 2p, and (J) O 1 s.

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© The Author(s), under exclusive licence to The Materials Research Society 2024 6
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Figure 4:  CV curves at different scan rates for (A) bulk ­MnOx, (B) calcined MnO(C) 1.37 wt.% Co/MnOx, (D) 4.79 wt.% Co/MnOx, (E) 10.19 wt.% Co/MnOx,
(F) redox peak current vs. square root of scan rates.

© The Author(s), under exclusive licence to The Materials Research Society 2024 7
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Figure 5:  Discharge curves at different current densities for (A) ­MnOx Bulk, (B) ­MnOx Calcined, (C) 1.37wt.% Co/MnOx, (D) 4.79wt.% Co/MnOx, (E)
10.19wt.% Co/MnOx, and (F) Specific capacity vs. current density.

© The Author(s), under exclusive licence to The Materials Research Society 2024 8
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capacitance (Cs) of the materials was calculated from the dis- MnOx was evaluated through 1000 cycles of GCD at a current
charge curve using Eq. 3, with corresponding values detailed in density of 20 A g­ −1. It was observed that the sample contain-
Table S4, furthermore, the coulombic efficiency surpassed 87%, ing 4.79 wt.% cobalt retained 61.9% of the initial Cs until the
as depicted in Table S5. end of 1000 GCD cycles [Fig. 6(A)]. These values represent an
Interestingly, the Co/MnO2 sample doped with 4.79 wt.% Co increase of 9.13% and 19.24% concerning the bulk ­MnO2 and
demonstrates an even higher specific capacitance compared to 1.37 wt.% Co/MnOx samples, respectively. This result demon-
10.19 wt.% Co at a current density of 1 A ­g−1. The higher Cs in all strates that the incorporation of Co, along with the associated
Co-doped electrode materials compared with bulk and calcined morphological changes and formation of oxygen vacancies,
­MnOx indicate that Co doping enhanced specific capacitance enhances electronic conductivity. These improvements con-
and electrical conductivity by introducing Co in the Mn oxide tribute to increased electrode material stability and its reten-
framework [9]. In the potential region examined, a transition tion of specific capacitance over extended periods and multiple
of ­Mn4+/Mn3+ involving single-electron transfer is responsible charge–discharge cycles.
for the pseudocapacitive behavior of the Co-doped Mn oxide. The impact of internal resistances and charge transfer was
Although the presence of Co ions contributes to increasing the investigated using electrochemical impedance spectroscopy
specific capacitance, there may be a saturation point or limit at (EIS), represented in the Nyquist plot, Fig. 6(B). This graph
which additional addition of Co may not result in a proportional presents an incomplete semicircle in the high-frequency region
increase in specific capacitance. The decrease in specific capaci- and an oblique line with an angle between 45 and 90º in the low-
tance with the addition of a higher concentration of Co ions frequency region, corresponding to the diffusion process[39].
indicates an optimal cobalt concentration point to maximize the Interpreting this impedance spectrum allows us to understand
performance of Co-impregnated M ­ nO2 [37, 38]. the electrical and kinetic properties of the electrochemical sys-
Moreover, from the XPS for the Os region, Fig. 3(B), it is tem. The incomplete semicircle in the high-frequency region is
possible to correlate the Cs performance and the higher ratio Oα related to the solution or series resistance (Rs) and the charge
in 4.79 wt.% Co/MnOx electrode material. The oxygen vacancies transfer resistances (Rct) at the electrode–electrolyte interface.
substantially boost the reactive active sites toward the electro- Conversely, the oblique line observed in the low-frequency
lyte; this increased accessibility of reactants for the redox process region of the Nyquist graph is related to the ion diffusion pro-
and explains the improved electrical conductivity, resulting in cesses that occur in the electrode material and is also known as
intensive reaction kinetics and reversible redox reactions [26, Warburg resistance (W) [40, 41].
27]. Furthermore, the Cs values calculated for the 4.79 wt.% Co/ The analysis of the equivalent circuit of the system obtained
MnOx sample in this study present values comparable with those from the impedance spectrum revealed an Rs of 573 mΩ and an
reported for Co/Mn-based nanocomposites and other dopants, Rct of 494 mΩ toward the beginning of the study of charge and
as detailed in Table 2. discharge cycles. After carrying out 1000 cycles, the series resist-
Following, the stability of a supercapacitor is an important ance remained at 573 mΩ, while the charge transfer resistance
performance indicator. The specific capacitance of 4.79 wt.% Co/ increased to 2.538 Ω. This variation in circuit parameters reflects

TABLE 2:  Performance of the 4.79 wt.% Co/MnOx battery-type electrode material in comparison with the previous works.

Specific capacitance Current density

Material Metal Precursor (F ­g−1) (A ­g−1) References

Co-doped on M
­ nOx via incipient wetness 4.79 wt.% Co/MnOx CoCl2.6H2O ­MnO2 bulk 1478.52 1 This work
impregnation
Co-doped ­MnO2 microflower by hydrother- Co-doped MnO₂ KMnO4 527 1 16
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mal method MnSO4·H2O

Co(NO3)2.xH2O
MOF-derived CoMn LDH CoMn MnCl2·4H2O 1305 1 17
Co(NO3)2·6H2O
Co-doped MnO nanomaterial by hydrother- (Co, Mn)3O4 Co ­(NO3)2·6H2O, 1050 0.5 14
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mal method MnSO4.H2O

Co Mn oxide via microwave-assisted syn- Co Mn Co(NO3)2·6H2O, 323 0.5 15
thesis MnCl2.4H2O
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Flowerlike 3D nanostructure of ­Co3O4@ Co3O4@MnO2/NGO Co(NO3)2·6H2O, ­C4H6MnO4 347 0.5 53

MnO2/N-dopped graphene oxide (NGO)
ZnO nanorods/MnO2 nanowires ZnO-40% ­MnO2 304 1 54
Zn-doped­MnOx nanowires 2.1 wt.% Zn/MnOx Zn(NO3)2·6H2O, ­MnSO4.H2O 1082.2 1 55

© The Author(s), under exclusive licence to The Materials Research Society 2024 9
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(A)
800

Specific capacitance (F g-1)

10.19 wt% Co/MnOx
700 4.79 wt% Co/MnOx
1.37 wt% Co/MnOx
600
MnOx2 Bulk

500

400

300

200

100

0 200 400 600 800 1000

Cycles numbers (n)

(B)

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­ −1, for ­MnOx Bulk, ­MnOx Calcined, 1.37wt.% Co/MnOx, 4.79wt.% Co/MnOx, and
Figure 6:  (A) Specific capacitances vs. number of cycles at 20 A g
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10.19wt.% Co/MnOx. Tests using 2 M KOH solution as electrolyte. (B) EIS analysis for 4.79 wt.% Co/MnOx sample, before and after 500 and 1000 charge–
discharge cycles. Tests using 2.0 M KOH solution as electrolyte.
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the evolution of the system throughout the charging and dis- an increase in Rct may be related to a lower rate of unwanted
charging life cycle. The gradual increase in charge transfer resist- reactions, resulting in a longer system life [42].
ance may indicate greater system stability over time, whereas

© The Author(s), under exclusive licence to The Materials Research Society 2024 10
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Furthermore, before 1000 GCD cycles, the circuit ele- factors, such as ion adsorption at the electrode–electrolyte
ment capacitance (CPE) had a value of 7708 µF. This value interface, alterations in pore structure, or increased surface
indicates the effective capacitance of the system during the roughness.
first stages of the life cycle, reflecting the capacitive response The battery-type electrode material was also tested as an
of the electrode–electrolyte interfaces and possible adsorp- asymmetric supercapacitor (HSC) using activated carbon as
tion or absorption processes of chemical species on the anode to assess the practical application as a supercapattery.
electrode surface [43, 44]. However, after 1000 GCD cycles, The electrochemical performance was investigated using CV
a notable increase in CPE was observed, rising to 3530 µF. and GCD. In CV, variations in scanning speed were explored
This enhancement in capacitance can be attributed to various within a potential range of 0.0 to 1.6 V at scanning speeds of 5

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Journal of Materials Research

Figure 7:  (A) Cyclic voltammetry for activated carbon and 4.79%Co/MnOx electrodes, (B) CV curves at different scan rates for the HSC device, (C)
Discharge profiles at 1, 2, 4, 6, 8, 10, 15, 20, and 30 A g ­ −1. (D) Specific capacitances vs. current densities and (E) Stability of the 4.79 wt.% Co/MnOx //
Activated carbon HSC after 1500 cycles at 25 A g ­ −1. Tests in 2.0 M KOH solution.

© The Author(s), under exclusive licence to The Materials Research Society 2024 11
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to 80 mV ­s−1. Conversely, in GCD, the behavior of the HSC was capacity per unit mass [48, 49]. Comparing these results with
analyzed at different current densities, ranging from 1 to 30 A Co/Mn-based materials and diverse approaches reported in
­g−1, within a potential range of 0.0 to 1.6 V. Figure 7(A) displays the literature, as described in Table 3, it is possible to indicate
the CVs for the activated carbon (AC) and 4.79 wt.% Co sam- the high competitiveness and effectiveness of the Co/MnOx//
ples, with a scan rate of 5 mV ­s−1. Meanwhile, the CV curves for AC supercapattery. The results presented in Table 3 reinforce
AC, illustrated in Fig. 7(B), reveal a distorted rectangular shape that introducing Co into the structure of the ­MnOx nanorods
with subtle hints of oxidation at 1.08 V and reduction at 0.97 V promoted promising results, indicating the effectiveness of the
(at 5 mV ­s−1), highlighting the distinctive behavior of this type doping process via incipient wet impregnation.
of material.
Figure 7(C) illustrates the galvanostatic discharge curves of
the supercapattery, as the current density increases, there is a
decrease in the specific capacitance of the system. Figure 7(D) Conclusions
shows the specific capacitance of the material 4.79 wt.% Co/ This work highlights the potential of electrochemical energy
MnOx//AC at different current densities. This behavior is storage as a promising solution to contemporary environmental
consistent with prior observations in the GCD curves of Co/ and energy challenges. The Co-doped ­MnOx nanorods were
MnOx materials. The observed decline in specific capacitance successfully synthesized via incipient wet impregnation with
is attributed to the restricted access of cations to the active sites Co-doping levels of 1.37, 4.79, and 10.19 wt.%, as determined
responsible for energy storage. At elevated current densities, the by ICP-OES analysis. The discrepancy between the nominal and
inability of cations to effectively engage in the energy storage actual Co content suggests limitations in the uniform incor-
mechanism results in a diminished specific capacitance [36, poration of the cobalt precursor during the synthesis process.
44−46]. Microscopy revealed that cobalt doping induced significant
The values of specific capacitance calculated for the HSC morphological alterations in the nanorods. Structural charac-
were 452.19 F ­g−1 (1 A ­g−1), 394.38 F ­g−1 (2 A ­g−1), 353.75 F ­g−1 terization by XRD confirmed that low Co doping had minimal
(4 A g­ −1), 315 F g­ −1 (8 A g­ −1), 300 F g­ −1 (10 A g­ −1), 281.25 F g­ −1 impact on the ­MnOx crystalline structure, while higher Co con-
(15 A ­g−1), 268.75 F ­g−1 (20 A ­g−1), and 262.5 F ­g−1 (30 A ­g−1). tent induced lattice distortions and oxygen vacancies, influenc-
The energy and power densities, calculated using Eqs. 4 and 5, ing the electrochemical properties of the material.
respectively, were 578.80 Wh k­ g−1 and 2934.78 kW ­kg−1. The 4.79 wt.%Co/MnOx electrode exhibited a high specific
The supercapattery was subjected to 1500 consecutive gal- capacitance of 1478.52 F ­g−1 at 1 A g­ −1 and demonstrated good
vanostatic charge–discharge cycles at a current density of 25 cycling stability after 1000 cycles. The higher number of oxygen
A ­g−1, as illustrated in Fig. 7(E). The 4.79 wt.% Co/MnOx// vacancies in this material can be related to its enhanced electro-
AC asymmetric system retained 156% of the specific capaci- chemical performance. Moreover, a supercapattery constructed
tance at the end of 1500 GCD cycles. This result highlights using 4.79%Co/MnOx as cathode and an activated carbon elec-
the stability and longevity of the supercapacitor, suggesting trode achieved a specific capacitance of 452.19 F ­g−1 at 1 A ­g−1
an improvement in the accessibility of the active sites on the and an outstanding energy density of 579 Wh k­ g−1, with a power
electrode surface to the electrolyte [47]. These values provide density of 2881 W k­ g−1. Furthermore, the device demonstrates
a meaningful measure of the performance of the supercapat- impressive cycling stability in a wide potential window of 1.6 V
tery in terms of its energy storage capacity and energy supply with capacitance retention even after 1500 cycles. These results

TABLE 3:  Comparison of the 4.79

Material ED (Wh ­Kg−1) PD (W ­Kg−1) Stabilization (%) References
wt.% Co/ M ­ nOx//AC supercapattery
www.mrs.org/jmr

with the literature.

4.79wt.% Co/MnOx//AC 578.80 2934.78 156 This work
MCP//CP 19.18 9996 94 56
MnO2/CoWO4/NCNO 18.23 42.05 91.8 57
MnCo2O4 PSs//SCF 42.27 400 95.7 58
H-MCO//AC 33.8 318.9 84.8 59
2024

MnCo2O4 nanotubes 3.4 350 91.2 60

ZnO-40% ­MnO2 26 4790 – 54
Journal of Materials Research

Ni/Co-MOF//rGO 66.2 775.13 91.4 61

ZnO//3D-GF 35 270 – 62
Ag/Co3O4@PANI//AC 14.01 165 121.03 63

ED energy density, PD power density

© The Author(s), under exclusive licence to The Materials Research Society 2024 12
 Article

highlight the potential of Co-doped M

­ nOx nanorods as potential The morphology of the solids was observed on JEOL
electrode material for advancing storage technologies. JSM 7100F Field Emission Scanning Electron Microscope,
equipped with an Electron-Dispersive X-ray Spectroscopy
system (SEM-EDS) (EX-37270VUP).
Experimental section Transmission electron microscopy (TEM) was performed
Incipient wetness impregnation using the JEOL JEM-2100 electron microscope. Sample prepa-
The Co-doped M ­ nO2 electrode materials were synthesized ration involved creating a suspension of the nanostructures in
using the incipient wetness impregnation method, adapting the isopropyl alcohol, followed by ultrasonic agitation and deposition
procedure described in [21, 50]. ­MnO2 (92%, Riedel-de Haën) of a droplet onto a TEM Cu grid coated with an amorphous holey
was used as the support material, and varying amounts of cobalt and lacey film.
were incorporated (5%, 10%, and 20% w/w of support). Specifi- X-ray photoelectron spectroscopy (XPS) was performed
cally, for each synthesis, 1 g of M
­ nO2 was placed in a mortar, using a Scienta Omicron ESCA + spectrometer with a high-
and 1 mL of a precursor solution containing C­ oCl2·6H2O (98%, performance hemispheric analyzer (EA 125) with monochro-
Sigma-Aldrich) dissolved in Milli-Q water was added dropwise matic AlKα (hν = 1486.6 eV) radiation as the excitation source.
with the corresponding Co content. The cobalt precursor solu- During analysis, the operating pressure in the ultrahigh vacuum
tion was added gradually, while the mixture was homogenized chamber (UHV) was 2 × ­10–9 mbar. The survey and high-resolu-
manually using a pestle to ensure uniform distribution of the tion XPS spectra used energy steps of 50 and 20 eV, respectively.
solution throughout the M ­ nO2 powder. The impregnation was
done carefully to avoid agglomeration. Electrochemical studies
After homogenization, the material was dried at 180 °C The electrochemical assays were carried out using a potentiostat/
for 1 h in an oven to evaporate the solvent. The dried sam- galvanostat Autolab PGSTAT302N (Metrohm, The Netherlands).
ples were then transferred to a muffle furnace, where they The data were processed using the NOVA 2.1.4 software. The initial
were calcined without air circulation. The calcination process tests were performed in a three-electrodes cell, using Ag/AgCl as
involved heating at a rate of 25 °C/min from room tempera- the reference electrode, a platinum wire was used as the counter
ture to 500 °C, followed by maintaining this temperature for electrode, and the working electrode was a nickel foam coated with
2 h to ensure complete decomposition of the precursor and the active material (A = 1.5 cm2). A 2 M KOH (99%, Isofar) solu-
formation of the Co-doped M ­ nO2. tion was used as the electrolyte. The preparation of the ink on the
working electrode consisted on using an analytical balance (Kern
410) to weight the active material, Super P carbon black (Super
P, > 99%, Alfa Aesar), and a PVDF (average Mw ~ 534.000, Sigma-
Measurements and characterization
Aldrich) /N-methyl-2-pyrrolidone (NMP, 99.5%, Sigma-Aldrich)
The structure of the solids was characterized by X-ray diffrac-
solution in an 8:1:1 ratio. After macerating this mixture in an agate
tion (XRD) using a Rigaku MiniFlex (Japan) diffractometer with
for 10 min, 20 µL of ink was applied to the nickel foam. Next, it
CuKα radiation (λ = 1.5406 Å) in the 2θ range from 10° to 80° at
was dried at 60 °C for 4 hours. The working electrode was pressed
a scanning speed of 2°/min.
to a nickel wire.
The crystallite size of the materials was determined by
Cyclic voltammetry was performed on a potential range of
the Debye−Scherrer equation based on the (110) diffraction
0–0.55 V for the scan rates of 5, 10, 20,40, and 80 m ­ Vs−1. The
plane [51] Eq. 1:
galvanostatic charge–discharge experiments were carried out for
K current densities ranging from 1 to 10 A.g−1. Regarding the sta-
d= , (1) bility of the supercapacitor, 1000-charge/discharge cycles were
βcosθ
www.mrs.org/jmr

tested. Electrochemical impedance spectroscopy (EIS) measure-

where d is the crystallite size, K is the crystallite shape factor, λ
ments were performed in the range of 0.1 to 1000 Hz, before
is the X-ray wavelength, β is the peak width at half maximum
cycling and after 500 and 1000 cycles.
height, and θ is the Bragg angle.
The specific capacitance (Cs) of the material in Fg−1 was
The elemental composition was assessed by inductively
calculated using data from the GCD discharge curves and Eq. 2:
2024

coupled plasma optical emission spectrometry (ICP-OES)

in an equipment from Spectro Arcos (SPECTRO Analytical I × t
Journal of Materials Research

Cs = Fg−1 , (2)
Instruments GmbH, Kleve, Germany), with a Limit of detec- V × m
tion (LD) = 0.01 ppm. The sample was prepared in aqua regia where Cs is the specific capacitance, I is the current, Δt in (s) is
­(HNO3+HCl, 1:3) and its heating was carried out in a digester the discharge time, ΔV is the voltage window, and m is the mass
block at 100 °C, in closed bottles. of the electrode material in mg.

© The Author(s), under exclusive licence to The Materials Research Society 2024 13
 Article

The Coulombic efficiency (η) is another important perfor- Author contributions

mance indicator that can be calculated using Eq. 3 [52]:
FJSB: conceptualization, methodology, validation, investiga-
td tion, data curation, writing—original draft, and writing—review
η= × 100%, (3)
tc & editing. SSE: investigation, formal analysis, and writing—review
& editing. HAV: investigation, formal analysis, and writing—
where ­td is the discharging time and t­ c is the charging time.
review & editing. CLR: investigation, formal analysis, and writ-
The asymmetric capacitor studies (HSC) were performed
ing—review & editing. AMAS: resources and writing—review &
in two electrodes configuration: one working electrode con-
editing. EL: resources and writing—review & editing. IMP: inves-
taining the active material and the other with activated car-
tigation and writing—review & editing. AAT: conceptualization,
bon (AC). All the tests were carried out at room temperature
writing—review & editing, supervision, and funding acquisition.
using KOH 2 M solution as electrolyte. For the fabrication of
the activated carbon electrode, the following ratio was used:
Funding
8 mg of activated carbon (AC), 1 mg of carbon black, and
1 mg of PVDF dissolved in NMP at a concentration of 1.5% The authors are thankful for the financial support of
(w/V). The mixture was deagglomerated using a mortar and Coordenação de Aperfeiçoamento de Pessoal de Nível Supe-
pestle made of agate. Subsequently, 20 µL of this paste was rior-Brazil (CAPES)—Finance Code 001, Conselho Nacional
applied to the nickel foam and dried in an oven at 80 °C for de Desenvolvimento Científico e Tecnológico (CNPq) (No.
12 h. Electrochemical tests, including cyclic voltammetry and 465389/2014-7), and Fundação de Amparo à Pesquisa e ao
chronoamperometry with galvanostatic charge and discharge, Desenvolvimento Científico e Tecnológico do Maranhão
were conducted following the same protocol used for M ­ nOx (FAPEMA) (No. INFRA-02264/21 and BPV-00095/22). We are
and Co/MnOx electrodes. The electrochemical results for Co/ also thankful to Fundação de Amparo à Pesquisa do Estado de
MnOx and carbon black were compared using Eq. 4, which São Paulo (FAPESP; Grant No. 13/07296-2). The authors would
provided the charge/mass ratio of the materials. These data like to acknowledge the company Petronas and the financial sup-
were crucial for the fabrication of the Co/MnOx(4.79 wt.%)// port of the Fundação de Apoio à Pesquisa do Distrito Federal
AC electrode [3]. (FAPDF) (No. 00193.00000919/2021-80).

m+
=
Q+
=
m × Cs × V
, (4) Data availability
m− Q− m × Cs × V
The data are available from the corresponding author of the
+− +−
where m and Q represent the mass/charge balance, m is article on reasonable request.
the mass (in mg), SC is specific capacitance, ΔV is the voltage
window of both the AC and the active material. Declarations
The energy density (ED) is of utmost importance for the
selection of an energy storage device, here it is calculated using Conflict of interest There are no conflicts to declare.
Eq. 5 [26]:
Supplementary Information
1
ED = × Cs(�V )2 , (5) The online version contains supplementary material avail-
2
able at https://​doi.​org/​10.​1557/​s43578-​024-​01455-w.
where Cs is the specific capacitance (F ­g−1) obtained in the GCD
tests for the hybrid supercapacitor, ∆V (V) is the potential range
between the cathode and anode. References
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