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OPEN Impact of ultrasonic treatment

duration on the microstructure and
electrochemical performance of
NiZnCo2O4 electrode materials for
supercapacitors
Yu Zhang1, Huaxing Li2, Qiang Zhang2, Xue Guo2 & Zhaoge Zhu2
This work investigates the impact of different ultrasonic treatment durations on the synthesis and
electrochemical performance of NiZnCo2O4 (NZC) supercapacitor electrodes. Optimizing treatment to
20 min resulted in a uniform, compact NiZnCo2O4 layer with improved nanostructures, which increased
the surface area and active sites for electrochemical reactions. X-ray diffraction (XRD) confirmed
successful NiZnCo2O4 synthesis, revealing distinct crystalline phases of NiO, ZnCo2O4, and Co3O4, with
improved crystallinity. Electrochemical tests, conducted using a 1.0 M KOH electrolyte, demonstrated
that the NZC-2 electrode treated for 20 min achieved the highest 5.678 F/cm3 volumetric capacitance
at 0.5 mA/cm2 current density along with 70.5 Wh/kg an energy density at 260 W/kg power density.
The galvanostatic charge-discharge and cyclic voltammetry tests revealed that NZC-2 maintained
superior charge-discharge efficiency, showing the longest discharge time at 1 mA/cm². Electrochemical
impedance spectroscopy (EIS) measurements demonstrated that NZC-2 exhibited the lowest total
impedance, thereby enhancing ion transport efficiency. The NZC-2/AC asymmetric supercapacitor
showed excellent long-term stability, retaining 64.2% of its capacity after 20,000 charge-discharge
cycles. It successfully powered a 1.2 V small fan, demonstrating its practical applicability. The
results highlight the crucial importance of ultrasonic treatment in greatly improving the structural
and electrochemical characteristics of NiZnCo2O4 electrodes, which opens up possibilities for the
advancement of high-performance supercapacitors.

The increasing environmental issues linked with fossil fuel combustion, including coal, natural gas, and oil, have
highlighted the urgent need for sustainable and efficient energy storage systems1–4. The combustion of fossil fuels
not only releases hazardous pollutants that affect air quality and public health but also experiences inefficiencies
in energy conversion. Hence, it is essential to develop eco-friendly and very effective alternative energy storage
systems to tackle these challenges.
Supercapacitors (SC) are considered highly promising energy storage devices. They serve as a bridge between
batteries and conventional capacitors5–7. They have multiple benefits compared to conventional capacitors, such
as increased power density (Pd), longer cycle life, broader working temperature ranges, and improved safety
profiles. This makes SC an excellent choice for various applications, such as large-scale energy storage systems
and portable electronics. The properties of the electrode materials employed greatly influence the efficacy of
SC8,9.
Conventional carbon materials, such as graphite and activated carbon (AC), have been extensively
employed as electrode materials in SC. However, these materials are constrained by drawbacks such as reduced
conductivity, restricted specific surface area, high internal resistance, and inefficient ion transport10–12. To
address these challenges, transition metal oxides, notably cobalt-based compounds, have emerged as promising
alternatives for electrode materials. Among these, ZnCo2O4, characterized by its spinel structure, has garnered
considerable interest owing to its wide electrochemical window, high specific capacity (Cs), stable cycling
performance, and structural adaptability. Kun et al.13. synthesized ZnCo2O4 nanosheets with oxygen vacancies
using a simple hydrothermal method followed by NaBH4 reduction. As an SC electrode material, it demonstrates

1School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China. 2College
of Mechanical Science and Engineering, Northeast Petroleum University, Daqing 163318, China. email:
[email protected]; [email protected]; [email protected]

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high conductivity and a sufficient number of active sites, leading to a Cs value of 2110.6 F/g at a current density
(Id) equal to 1 A/g. Tiwari et al.14 fabricated ZnCo2O4 materials on stainless steel surfaces using hydrothermal
synthesis and electrodeposition for SC electrodes. They evaluated their electrochemical properties, finding a
Cs value of 430.75 F/g for thermally grown ZnCo2O4 at 5 mV/s scanning rate, compared to 171.03 F/g for
electrodeposited ZnCo2O4 at the same scanning rate. Shang et al.15 synthesized ZnCo2O4 microspheres via the
solvothermal method for SC electrodes. The hollow microsphere structure showed favorable electrochemical
properties, demonstrating a high Cs value equal to 78.89 mAh/g at Id = 1 A/g. Moreover, it maintained excellent
cycle stability, with a load capacity of up to 6 mg/cm 2 after 2000 cycles. Despite the exceptional electrochemical
properties of ZnCo2O4, it is unable to satisfy the high requirements for electrochemical stability and electrical
conductivity in the energy storage field.
Recent research has shifted focus to NiZnCo2O4, building on the promising properties of ZnCo2O4. By
incorporating both nickel and zinc into the spinel structure, the goal is to further enhance its electrochemical
performance. To synthesize and optimize these materials, various techniques have been employed, such as
hydrothermal technique, the sol-gel method, and chemical vapor deposition (CVD). Yewale et al.16 used a facile
hydrothermal technique for fabricating nanostructured CuCo2O4 electrode material and studied how varying
the hydrothermal reaction time affected its properties. They found that after a 7 h reaction period, the CuCo2O4
electrode achieved a capacity equal to 193 F/g (96.5 C/g) at Id = 3 mA/cm2, with an 85.9% capacity retention rate
following 6000 cycles at Id = 15 mA/cm2. Das et al.17. employed the sol-gel method to fabricate rod-like CuBO2
nanostructures, which showed a very high Cs value equal to 142 µF, highlighting their promising electrochemical
performance. Zhang et al.18 used CVD to fabricate 3D graphene (rGo) materials with nickel nanoparticles as a
template. Their findings demonstrate that NiCo2S4 NCAs/3D Gr served as a SC electrode, showing a remarkable
Cs value of 948.9 F/g at 1 A/g. Notably, electrodeposition emerged as particularly noteworthy for its capability
to precisely control the structure and morphology of deposited materials, rendering it highly versatile across
diverse industries, including electronics, energy storage, and material science.
The electrodeposition technique has been enhanced by incorporating ultrasonic technology. Ultrasonic
waves improve ion transport and ensure uniform sediment distribution through cavitation and hydrodynamic
effects. This leads to materials with superior purity, homogeneity, and deposition rates19. Ultrasonic-assisted
electrodeposition holds considerable potential for producing high-performance materials. The growth
mechanism of NiZnCo2O4 during ultrasonic-assisted electrodeposition involves the nucleation and growth
of metal oxide particles on the carbon fiber cloth substrate. Ultrasonic cavitation generates localized high
temperatures and pressures, promoting rapid ion transport and uniform distribution of Ni²⁺, Zn²⁺, and Co²⁺
ions in the electrolyte solution. The extended duration of ultrasonic treatment enhances this effect, leading
to more compact and homogeneous deposition of NiZnCo2O4 particles. As the treatment time increases, the
cavitation bubbles collapse more frequently, providing kinetic energy that facilitates particle formation and
growth, resulting in distinct nanostructures with increased surface area and electrochemical activity.
This explored the impact of ultrasonic treatment duration on the synthesis and electrochemical performance
of NiZnCo2O4 electrode materials. By varying the ultrasonic treatment time during the electrodeposition process,
the aim was to optimize the microstructure and electrochemical properties of the resulting materials. The crystal
structure, morphology, and valence states of the samples were analyzed using advanced characterization tools
such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction
(XRD). Additionally, electrochemical assessments, including galvanostatic charge-discharge (GCD), cyclic
voltammetry (CV), and electrochemical impedance spectroscopy (EIS), were employed to assess the NiZnCo2O4
electrode performance in SC using a 1.0 M KOH electrolyte. This research aimed to offer insights into the
relationship between ultrasonic processing parameters and the performance of NiZnCo2O4-based SCs, thereby
contributing to the advancement of high-efficiency energy storage devices.

Experimental
Synthesis of NiZnCo2O4 electrode materials
The mass loading of the NiZnCo2O4 active material on the carbon fiber cloth substrate was controlled to
approximately 2.5 mg/cm2. NiZnCo2O4 electrode materials were synthesized using an ultrasonic-assisted
electrodeposition technique. A carbon fiber cloth (CFC) with dimensions of 2 cm × 2 cm × 1 cm was selected as
the substrate because of its large surface area and high conductivity. Before deposition, the CFC was pretreated
with acidic and alkaline solutions to remove impurities, followed by rinsing with deionized (DI) water and
drying for 12 h inside a vacuum oven at 70 °C to ensure a clean and dry surface20.
To prepare electroplating solution, Ni(NO3)2·6H2O, Co(NO3)2·6H2O, and Zn(NO3)2·6H2O were dissolved in
DI water to achieve a 1:1:2 molar ratio of Ni: Zn. See Table 1 for the specific formula of electroplating solution.
The solution was stirred until all salts were completely dissolved. The electrodeposition process was carried out
using a 3-electrode system comprising the CFC, a Pt plate, and a saturated calomel, as the working, counter, and
reference electrodes, respectively.
During the electrodeposition process, the electrolyte solution was subjected to ultrasonic irradiation at
200 W for 10, 20, 30, and 60 min to evaluate the influence of ultrasonic treatment time on the efficiency of
NiZnCo2O4 electrodes. The ultrasonic waves induced cavitation in the solution, enhancing the nucleation
and growth of NiZnCo2O4 particles on the substrate. This process resulted in uniform and compact electrode
materials. The experimental parameters involved in the experiment are shown in Table 2. In addition, Fig. 1a
reveals the working principle of ultrasound-assisted electrodeposition and Fig. 1b shows the working process
under different ultrasonic treatments.
After deposition, the samples underwent a rinsing procedure using DI water and were subsequently dried.
Following that, to increase crystallinity, the precursor materials were annealed for 20 h at 450 °C inside a muffle
furnace. The annealing temperature of 450 °C and duration of 20 h were chosen based on the thermal stability

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Chemical reagents Value

Co(NO3)2·6H2O (g/L ) 197.0
Zn(NO3)2·6(H2O) (g/L) 168.0
Ni(NO3)2·6H2O (g/L ) 153.0
NaOH (g/L) 20.0
H3BO3 (g/L) 25.0
C12H25SO4Na (g/L) 0.15
C7H4NNaO3S (g/L) 0.18

Table 1. Electrolytic composition for synthesizing NZCs.

Item Value
Plating bath temperature (°C) 50.0
Plating current density (A/dm 2) 3.0
Mixer speed (r/min) 1600
Duty cycle (%) 15.0
Activation time (min) 30
pH 4.2
Pulse frequency (Hz) 500
Ultrasonic power (W) 200
Ultrasonic irradiation time (min) 10–60

Table 2. The process parameters used for preparing NZCs.

and decomposition temperature of the precursors. Prolonged annealing at this temperature allows sufficient
energy for grain growth and enhances the crystallinity of the NiZnCo2O4 material without causing excessive
grain coarsening or phase changes. This results in an optimal balance between crystallinity and surface area,
which is crucial for improving the electrochemical performance of the electrode material. After the annealing
process, the samples were naturally cooled down to ambient temperature and were designated as NZC-1, NZC-
2, NZC-3, and NZC-4 according to their respective ultrasonic power settings.
The NiZnCo2O4 materials generated under various conditions were employed as the positive electrode in the
assembly of the asymmetric supercapacitors (ASC). The negative electrode was made using AC, acetylene black
as a conductive agent, and polyvinylidene fluoride, or PVDF, as a binder, in an 8:1:1 mass ratio. A slurry was
formed by dispersing this mixture in N-methyl-2-pyrrolidone (NMP), which was then applied to an aluminum
foil substrate and allowed to dry to produce a uniform electrode layer21.

Assembly of ASC supercapacitors

For assembly, NiZnCo2O4 electrode material (12.0 mg) was weighed and utilized as the positive electrode. The
negative electrode was composed of activated carbon (AC), with a mass loading of approximately 8.0 mg. The
reported mass of 12.0 mg corresponds solely to the NiZnCo2O4 active material used for the positive electrode
and does not include the mass of the negative electrode. Additionally, the loading mass of the electrodes refers
only to the active materials and does not include the mass of the binder and conductive additive. The NiZnCo2O4
materials generated under various conditions were employed as the positive electrode in the assembly of the
asymmetric supercapacitors (ASC). For the positive electrode, NiZnCo2O4 (12.0 mg) was mixed with acetylene
black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1. The mixture was dispersed in N-methyl-2-
pyrrolidone (NMP) to form a slurry, which was then coated onto a piece of nickel foam. The coated electrode was
dried at 70 °C for 12 h before use. The mass loading of the positive electrode in the asymmetric supercapacitor
was approximately 3.0 mg/cm2. A cellulose-based separator, soaked in a 1 M KOH electrolyte, facilitated efficient
ion transport while preventing direct electrode contact. Electrodes and separators were carefully stacked in a
clean environment to ensure optimal contact and prevent contamination. The final assembly was securely sealed
in a designated container to prevent leakage and ensure stable operation.
The assembled ASCs underwent a series of electrochemical tests such as CV, GCD, and EIS to assess their
performance. The same 1 M KOH electrolyte used in the 3-electrode system was also employed for testing the
asymmetric supercapacitor (NiZnCo2O4//AC). These tests offered valuable insights into the capacity, cycling
stability, and overall electrochemical behavior of the NiZnCo2O4-based supercapacitors.

Characterization
The microstructure and surface morphology of the NiZnCo2O4 electrodes were studied by employing SEM (JEOL
JSM-7800 F, Japan) and TEM (Tecnai G2F20, USA). XRD analysis (Rigaku SmartLab, Japan) was conducted
to determine crystal structure and lattice parameters. A Thermo Scientific K-Alpha + X-ray photoelectron
spectroscopy (XPS) was used to determine valence states and surface chemical distributions.

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Fig. 1. (a) The working mechanism and method of nucleation for NZC electrodes made via ultrasonic-assisted
electrodeposition, and (b) Working principle of ultrasonic waves at different treatment durations.

Electrochemical characterization was performed using a CHI660E electrochemical workstation (China). The
3-electrode system was tested in a 1 M KOH electrolytic solution, with the NiZnCo2O4 sample, a Pt wire, and
a saturated calomel electrode as the working, counter, and reference electrodes, respectively. CV, GCD, and
EIS measurements were conducted under specified conditions: a voltage range from 0.01 to 4.00 V, scan rate
(v) equal to 0.5 mV/s, frequency range spanning from 0.01 Hz to 100 kHz, and 5 mV an oscillation amplitude.
The value of Cs (F/g) for NiZnCo2O4 was determined using Eq. (1) and the values of energy density (Ed) and
Pd were obtained through Eqs. (2) and (3)22:

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C = Q/(m × DV )(1)
Ed = (1/2) × C × DV 2(2)
Pd = DV 2/4R(3)

where Q represents the total charge (C) and m denotes the active material’s mass (g). ΔV and R represent the
voltage range (V) and the equivalent series resistance (Ω), respectively.
To analyze the electrochemical performance of ASCs with NiZnCo2O4 electrodes in detail, an ASC was
assembled using NiZnCo2O4 and AC as the positive and negative electrodes, respectively. The electrochemical
measurements were conducted in a 1.0 M K2SO4 electrolyte using an electrochemical workstation. The CV
experiments were conducted using v values between 5 and 200 mV/s, covering a 0–1.6 V potential range.
Similarly, GCD measurements were conducted within the same potential window at Id values between 1 and
30 mA/cm2. To examine the influence of the duration of ultrasonic treatment, the electrochemical behavior of
the ASC was evaluated by comparing the GCD and CV plots that were obtained for the NiZnCo2O4/AC ASC
under various conditions.

Results and discussion

Surface structure of NiZnCo2O4(NZC) electrodes
The surface morphology of NiZnCo2O4 electrodes varied significantly with different ultrasonic treatment
durations at 200 W constant power. The microstructures of the electrodes treated for 10, 20, 30, and 60 min,
labeled NZC-1, NZC-2, NZC-3, and NZC-4 respectively, are shown in Fig. 2a–d. The growth mechanism of
NiZnCo2O4 during ultrasonic-assisted electrodeposition involves the nucleation and growth of metal oxide
particles on the carbon fiber cloth substrate. Ultrasonic cavitation generates localized high temperatures and
pressures, promoting rapid ion transport and uniform distribution of Ni²⁺, Zn²⁺, and Co²⁺ ions in the electrolyte
solution. The extended duration of ultrasonic treatment enhances this effect, leading to more compact and
homogeneous deposition of NiZnCo2O4 particles. As the treatment time increases, the cavitation bubbles
collapse more frequently, providing kinetic energy that facilitates particle formation and growth, resulting in
distinct nanostructures with increased surface area and electrochemical activity.
For the NZC-1 sample (10 min), the surface morphology showed a smooth and uniform structure with small,
evenly distributed micropores (Fig. 2a). Some areas had minor irregularities, indicating early stages of particle
nucleation and growth. Increasing the ultrasonic treatment time to 20 min (NZC-2) resulted in a more refined
and uniform surface with a higher density of micropores (Fig. 2b). The cavitation effect from the prolonged
ultrasonic treatment improved ion transport and distribution, leading to a more compact and homogeneous
deposition of NZC particles. At 30 min (NZC-3), the surface morphology became highly uniform and smooth,
with a significantly increased number of micropores (Fig. 2c). The extended treatment promoted the cavitation
effect, producing more local heat and pressure, which removed surface impurities and enhanced material
uniformity. For the NZC-4 sample (60 min), the surface exhibited a slightly rougher texture with a mixture of
fine and larger micropores (Fig. 2d). Figure 2e and f show the side planing and local magnification respectively
under 20 min of ultrasonic treatment time. The prolonged ultrasonic exposure increased agitation and localized
turbulence, causing excessive particle aggregation and larger pore formation in some areas.
The differences in microstructures among the NZC electrodes can be attributed to varying durations of
ultrasonic treatment. Shorter durations (10 min) were insufficient for achieving uniformity and optimal particle
distribution. Moderate durations (20–30 min) effectively used the cavitation effect to form highly uniform and
compact electrode surfaces. However, excessively long durations (60 min) resulted in over-agitation and uneven
material distribution due to prolonged exposure to intense ultrasonic forces. These morphological variations
significantly impact the electrodes’ electrochemical properties23. The increased micropore density and uniform
particle distribution in the NZC-2 and NZC-3 samples are expected to enhance ion transport and overall
electrochemical performance. Conversely, the rougher surface and larger pores observed in the NZC-4 sample
may adversely affect performance due to non-uniform ion diffusion and potential electrical resistance issues.

EDX analysis of NZC-2

Energy-dispersive X-ray spectroscopy (EDX) was utilized to determine the elemental composition and
distribution of NZC-2 samples on CFC. Figure 3a illustrates the microstructure and element distribution.
Figure 3b–e shows the existence of O, Zn, Co, Ni, and C. Oxygen is highlighted in yellow in Fig. 3a, indicating its
predominance in the sample. Cobalt is marked in blue in Fig. 3b, while nickel and zinc are highlighted in green
and red respectively in Fig. 3c and d. Nickel exhibited a relatively higher abundance compared to zinc, consistent
with expected ratios. The observed lower zinc content could be attributed to initial concentration differences
in the precursor solution and variations during the electrodeposition process. Furthermore, the simultaneous
formation of Ni and Zn oxides likely affected the overall elemental distribution, potentially resulting in a lower
Zn ratio than expected. In Fig. 3e, the pink color denotes carbon from the substrate, indicating its presence in
the CFC. The homogeneous distribution of the Zn, O, Ni, and Co elements across the NZC-2 sample confirms
successful NiZnCo2O4 deposition on the CFC using ultrasonic-assisted electrodeposition. Elemental analysis
indicates that ultrasonic treatment promoted homogeneous element distribution, crucial for achieving a uniform
NiZnCo2O4 structure24.
These findings demonstrate the successful fabrication of NiZnCo2O4 electrodes with a well-distributed
elemental composition, as confirmed by EDX mapping. This method reliably verifies uniform deposition
of NiZnCo2O4 materials on the CFC substrate, ensuring consistency and reproducibility in the electrode
preparation process.

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Fig. 2. The acquired SEM images for the NZC electrodes prepared with different ultrasonic treatment
durations: (a) NZC-1 (10 min), (b) NZC-2 (20 min), (c) NZC-3 (30 min), (d) NZC-3 (60 min), (e) sectional
drawing of NZC-2, and (f) Partial enlarged drawing of NZC-2.

TEM analysis of NZC-2

TEM was employed to examine the nanostructure of the NZC-2 electrode material on CFC. Figure 4a shows a
TEM image revealing a dense 2.3 mm thick oxide layer uniformly coating the carbon fiber substrate, confirming
stable development and strong adhesion of the NiZnCo2O4 layer. Selected area electron diffraction (SAED)
analysis (refer to Fig. 4b) investigated the crystalline structure and lattice parameters of the NZC-2 oxide material,
revealing diverse crystal orientations and structures. High-resolution TEM (HRTEM) (Fig. 4c) provided further
insights into the material’s crystalline properties, highlighting specific regions (I, II, and III). Magnified images
in Fig. 4d–f shows distinct lattice fringes corresponding to various crystalline phases.
The lattice spacing measurements revealed distinct values for each phase: approximately 0.240 nm for the
NiO (111) plane, 0.426 nm for the ZnCo2O4 (311) plane, and 0.283 nm for Co3O4 (220) plane within the NZC-
2 electrode material. These findings confirm the coexistence of NiO, ZnCo2O4, and Co3O4 phases within the
NZC-2. The presence of NiO alongside ZnCo2O4, and Co3O4 suggests a synergistic effect that could enhance the
electrode material’s electrochemical performance25. The uniform and refined crystal structure observed in NZC-

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Fig. 3. Elemental mapping images of NZC-2 showing distribution of elements: (a) O (Lα1), (b) Co (Kα1), (c)
Zn (Kα1), (d) Ni (Kα1), and (e) C.

2 indicates the effectiveness of ultrasonic-assisted electrodeposition in forming well-defined nanostructures.

These results support the successful fabrication of a multi-phase NiZnCo2O4 electrode with distinct
nanostructural features critical for enhancing SC electrochemical properties. The TEM analysis highlights the
importance of optimizing ultrasonic treatment parameters to achieve desired nanostructural characteristics in
electrode materials.

Phase structure analysis of NZC

The XRD spectra for the NZC samples (Fig. 5) display distinct peaks corresponding to the crystalline phases
of NiZnCo₂O₄, with major diffraction peaks at (111), (220), (311), (400), (511), and (440) planes. These peaks
match well with the JCPDS data for spinel NiZnCo2O4 (JCPDS No. 74-2199), confirming successful synthesis
via ultrasonic electrodeposition.
The NZC-1 sample (10 min) shows sharp peaks, indicating high crystallinity and large grain size. NZC-
2 (20 min) exhibits slightly broader peaks, suggesting a finer grain size and an optimal balance between

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Fig. 4. (a) The obtained TEM image for the CFC matrix, (b) SAED pattern, and (c-f) TEM images of NZC-2
on the surface of CFC.

crystallinity and surface area, which enhances ion diffusion. This balance supports an increased number of
active sites, enhancing ion exchange capacity and overall electrochemical performance26. NZC-3 (30 min) shows
intermediate peak width and intensity, while NZC-4 (60 min) has broader peaks and lower intensity, indicating
excessive grain refinement. Overall, the optimal ultrasonic treatment times 20 min balance surface area and
crystallinity, enhancing electrochemical performance.

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Fig. 5. The obtained XRD spectra for the NZC electrode materials and NiZnCo2O4.

Fig. 6. N2 absorption isotherms and pore widths (inset) of NZC-2.

BET analysis of NZC-2

Figure 6 presents the nitrogen (N₂) adsorption-desorption isotherms of the NZC-2 electrode material. The
isotherms exhibit a typical type IV behavior with a noticeable hysteresis loop at higher relative pressures (P/
Po > 0.4), indicative of the mesoporous structure of the material27. This type of isotherm is characteristic of
materials containing mesopores (2–50 nm), where capillary condensation occurs in the pores, resulting in the
observed hysteresis. The sharp increase in volume absorbed at higher relative pressures suggests the presence of
large mesopores or macropores that facilitate enhanced electrolyte accessibility, improving the electrochemical
performance of the electrode material. The inset of Figure X shows the corresponding pore size distribution
(PSD) of the NZC-2 material, derived from the desorption branch of the isotherm using the Barrett-Joyner-
Halenda (BJH) method. The distribution reveals a dominant pore width around 20–30 nm, confirming that
the material predominantly consists of mesopores. The relatively narrow distribution of pore sizes further
supports the homogeneous pore structure, which contributes to efficient ion transport within the material. The
combination of mesopores and a well-defined pore distribution ensures a higher surface area for electrochemical
reactions, enhancing the capacitance of the supercapacitor electrode.

XPS analysis of NZC-2

The X-ray photoelectron spectroscopy (XPS) analysis was performed to investigate the elemental composition
and oxidation states of Ni, Zn, and Co in the NZC-2 sample. The survey scan in Fig. 7a shows the presence of the
main elements, including Ni 2p, Zn 2p, Co 2p, O 1s, and C 1s. High-resolution spectra of Zn 2p, Co 2p, and Ni 2p
are provided in Fig. 7b, c, and f, respectively. In Fig. 7b, the Zn 2p region reveals two prominent peaks at binding

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Fig. 7. XPS spectra of NZC-2: (a) Full survey spectrum showing the presence of Ni, Zn, Co, O, and C
elements, (b) Zn, (c) Co, (d) C, (e) O, and (f) Ni.

energies of approximately 1021.6 eV and 1044.8 eV, corresponding to Zn 2p2/2 and Zn 2p1/2, indicating the
presence of Zn²⁺ oxidation state. Figure 7c shows the Co 2p spectrum, with peaks at approximately 780.6 eV and
795.6 eV, corresponding to Co 2p2/2 and Co 2p1/2, suggesting the presence of Co²⁺ and Co²⁺ species. The high-
resolution C 1s spectrum in Fig. 7d shows three distinct peaks at binding energies of approximately 284.8 eV,
286.4 eV, and 288.8 eV, corresponding to C–C, C–O–C, and O–C=O bonds, respectively. These peaks suggest
the presence of surface carbon-based compounds, possibly due to the introduction of carbon contamination
during sample preparation or handling. Additionally, the oxygenated carbon species, such as C–O–C and O–
C=O, could contribute to surface redox reactions and enhance the electrochemical performance. The Ni 2p
spectrum in Fig. 7f exhibits peaks at 855.6 eV and 873.2 eV, which can be assigned to Ni²⁺, along with satellite
peaks confirming the presence of Ni²⁺ ions. The O 1s spectrum, shown in Fig. 7e, contains three distinct peaks

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at binding energies around 529.9 eV, 531.5 eV, and 533.2 eV, corresponding to lattice oxygen, hydroxyl groups,
and adsorbed oxygen, respectively.
The XPS analysis confirms the successful formation of NiZnCo₂O₄ with the expected oxidation states of the
constituent elements. The presence of Zn²⁺, Co²⁺/Co²⁺, and Ni²⁺ is indicative of the spinel structure, where Ni, Zn,
and Co ions occupy the octahedral and tetrahedral sites of the lattice. The lattice oxygen peak at 529.9 eV in the
O 1s spectrum further supports the formation of metal-oxygen bonds typical of the spinel phase28. The existence
of hydroxyl and adsorbed oxygen species may arise from surface hydroxylation and atmospheric adsorption,
which can contribute to enhanced electrochemical activity by facilitating ion transport and providing additional
active sites for redox reactions.

Electrochemical analysis of NZC-2

The electrochemical efficiency of NZC was assessed using a three-electrode system, with NZC-2 detached from
the substrate and employed as the working electrode. Figure 8a depicts CV curves taken at different voltages
between 0 and 0.7 V in a 1.0 M KOH electrolyte with a saturated Ag/AgCl reference electrode. The CV curves
for all materials, including NiZnCo2O4 and comparison samples, displayed consistent shapes with observed
REDOX peaks in both scanning directions (negative and positive), indicating pseudocapacitive and reversible
electrochemical processes. The curves’ symmetry emphasizes the uniformity of the charging and discharging
operations. Notably, NZC-2 exhibited the highest peak Id value, attributed to its numerous internal pores
facilitating enhanced ion transport and transfer. This is likely a result of the optimal 20-min ultrasonic treatment
duration employed during NZC-2 preparation. Furthermore, the area below the CV curve correlates directly

Fig. 8. Electrochemical characteristics of NZC electrodes at various ultrasonic treatment times: (a) The
obtained CV plots at v = 20 mV/s, and (b) The acquired GCD plots at Id = 1 to 50 mA/cm2.

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with the electrode’s charge storage capacity. Figure 8a clearly shows that NZC-2 had the largest enclosed area,
indicating that the sample treated for 20 min possessed the highest volumetric capacitance.
In electrochemical energy storage devices, the GCD test is crucial for analyzing the electrode materials.
In Fig. 8b, the results show that the NZC-2 electrode had the longest discharge duration, suggesting a higher
volumetric capacitance in comparable charge-discharge conditions. The GCD curve showed a clear voltage
plateau, which is indicative of the behavior of pseudocapacitance involving Faradaic reactions that significantly
enhance overall capacitance.
To evaluate coulombic efficiency, charge and discharge times were compared. The symmetrical shape of the
discharging-charging curves across all electrodes indicates high coulombic efficiency. Specific capacities and
volumetric capacities of the NZC samples were calculated from Eqs. (4) and (5) respectively, at Id = 2.5 mA/cm2.
Specific capacities for the NZC specimens were found as 235.7, 252.4, 276.8, and 261.5 mAh/g, while volumetric
capacities were measured at 3.26, 3.35, 3.62, and 3.44 mAh/cm329.
Csp = I × ∆t/m × ∆V (4)
Cvol = I × ∆t/v × ∆V (5)

where I (A) denotes the applied current during the discharging-charging cycles, m is the active material mass in
the electrode (g), v represents the electrode volume (cm3), ∫ Vdt denotes the area below the discharge curve, and
V indicates the working voltage range (V).

Volumetric capacitance of NZC

The experimental findings illustrating the connection between volumetric capacitance and the value of Id for the
NZC samples are shown in Fig. 930. The NZC-2 electrode achieved the highest values of Cs across the Id range
spanning from 2.5 to 45 mA/cm². At 2.5 mA/cm2, the NZC-2 electrode exhibited 1.725 F/cm² capacitance. In
comparison, the capacitance values for NiZnCo2O4 materials synthesized with other ultrasonic treatment times
were 0.487, 1.245, and 1.612 F/cm2, respectively.
The comparison of NZC-2 electrodes with previously described NiZnCo2O4-type electrodes highlights a
significant enhancement in areal capacitance due to ultrasonic-assisted electrodeposition. This improvement
is particularly notable compared to other recent studies. As the value of Id increased, volumetric capacitance
decreased for all samples. This behavior is consistent with results demonstrated by Xu et al.31, where high Id values
limit ion access to active sites, reducing capacitance. NZC-2 showed the maximum volumetric capacitance,
maintaining 69.1% of its initial value as the value of Cs reduced from 1.725 to 1.189 F/cm2 when the value of Id
was raised from 2.5 to 45 mA/cm². In contrast, untreated NiZnCo2O4 and other NZC samples had retention rates
of 45.3%, 53.5%, and 56.4%, respectively. The untreated NiZnCo2O4 exhibited the lowest volumetric capacitance
and the largest decrease with an increase in the value of Id, because of decreased surface area, an increase in
internal defects, and instability in the structure at high values of Id32.
The NZC-2 electrode, treated with 20 min of ultrasonic exposure at 200 W, revealed a finer crystal structure
and a higher number of microstructural defects. These attributes resulted in an increase in active sites, which
enabled the NZC-2 electrode to sustain a higher capacitance at elevated Id values.

Fig. 9. The volumetric capacitance of NiZnCo2O4 and NZC electrodes at varying ultrasonic treatment
durations.

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EIS analysis for NZC

EIS was utilized to assess the electrochemical characteristics of NZC electrodes by measuring impedance across
various frequencies33. Figure 10a shows the Nyquist plot, while Fig. 10b illustrates the equivalent circuit diagram
for the NZC electrodes. In Fig. 10a, the NZC-2 electrode, represented by the cyan square, exhibited the smallest
semicircle diameter at high frequencies, indicating the lowest charge transfer resistance (Rct). This suggests

Fig. 10. EIS test results for the NZC electrodes: (a) The obtained EIS plots for the NZC electrodes, (b)
equivalent circuit model of the NZC electrodes in 3.5 wt% NaCl solution, and (c) the obtained EIS plots for the
NZC electrodes after 10,000 charge-discharge cycles.

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improved electrochemical kinetics and higher electrode activity. The high-frequency intercept on the real
axis (Z’) corresponds to the solution resistance (Rs), which remained consistent across all samples, indicating
minimal variation in solution resistance. At lower frequencies, the slope of the linear region in the Nyquist
plot represents the Warburg impedance, reflecting ion diffusion within the electrode material. NZC-2 showed
the steepest slope, indicating superior ion diffusion capability. A lower Warburg impedance signifies enhanced
ion transport, crucial for high-rate electrochemical performance. After cycling tests, as shown in Fig. 10c, the
Nyquist plots indicate an increase in the charge transfer resistance (Rct) for all samples, which is attributed to
the degradation of the electrode materials after prolonged cycling. However, NZC-2 still maintained the lowest
Rct, highlighting its better long-term stability compared to the other samples.
In this study, NZC-2 showed the lowest total impedance, indicating superior electrochemical performance.
This is due to optimized ultrasonic treatment (20 min at 200 W), which improved the material’s microstructure
by increasing active sites, refining grain structure, and enhancing porosity. These improvements facilitate
efficient charge transfer and lower impedance at the electrode-electrolyte interface. Ultrasonic treatment
benefits are clear in NZC-2, with more active sites and better ion diffusion pathways. It also removed surface
impurities, reducing interfacial resistance and improving conductivity. Similar studies have reported comparable
enhancements. EIS analysis confirms that the NZC-2 electrode, treated under optimal ultrasonic conditions,
has excellent electrochemical properties, making it an excellent choice for a high-performing SC. The reduced
impedance and improved ion transport significantly enhance its electrochemical behavior.

Asymmetric supercapacitor
In Fig. 11a, the cyclic voltammetry (CV) profiles of the asymmetric supercapacitor using NZC-2 as the cathode
and activated carbon (AC) as the anode are shown. The rectangular-like CV curve of the activated carbon
(AC) anode reflects typical electric double-layer capacitance behavior, characterized by rapid charge/discharge
processes. In contrast, the NZC-2 cathode exhibits clear redox peaks, indicative of faradaic reactions, which are
characteristic of battery-type materials. This is consistent with the behavior observed in Fig. 11a, where NZC-2
shows distinct redox activity due to its reversible faradaic processes, enhancing the overall capacitance of the
supercapacitor. To evaluate the ASC’s electrochemical performance, CV and GCD curves were analyzed under
various conditions. Figure 11b presents the CV profiles at v values between 5 and 200 mV/s. At lower values
of v (5–25 mV/s), the CV curves remain nearly rectangular, suggesting dominant double-layer charge storage
with efficient ionic diffusion. The CV curves’ enclosed area expanded with increasing values of v, indicating
enhanced charge storage due to rapid pseudocapacitive reactions on the electrode surfaces. Figure 11c shows
the GCD plots obtained for the NZC-2/AC ASC at Id values extending from 1 to 50 mA/cm2. As the value of Id
increased, discharge time decreased, demonstrating efficient discharge performance even at high Id values34. The
longest discharge time at Id = 1 mA/cm2 indicates maximum energy storage, ascribed to increased surface area
and better ionic diffusion. At 50 mA/cm2, the discharge slope considerably increased, signifying faster energy
release due to ion diffusion limits at high Id values. Despite high values of Id, the voltage drop remains minimal,
highlighting the NZC-2 electrode’s structural stability and strong electrochemical performance. The volumetric
capacitance and Pd against Ed curves at various values of Id are presented in Fig. 11d and e, respectively. The
NZC-2/AC ASC achieved its highest capacitance of 5.678 F/cm2 at Id = 0.5 mA/cm2. At Id = 50 mA/cm2, it
maintained a 53.5% volumetric capacitance rate. Retention rates declined more quickly at lower values of Id
(5–10 mA/cm2) in comparison to the higher ones (30–50 mA/cm²). The Ed value of the NZC-2/AC ASC reached
70.5 Wh/kg at Pd= 260 W/kg, marking a 25.1% improvement over SC made without ultrasonic assistance.
This demonstrates the advantageous role of ultrasonic technology in the preparation of ASC. There are few
references to NiZnCo2O4 as an electrode material for supercapacitors, Fig. 11f compares the performance of the
ultrasonically prepared NZC-2/AC ASC with flower-like on NiZnCo2O4, highlighting its superior properties35.
Cycle stability is crucial for practical SC applications. As demonstrated in Fig. 11g, the NZC-2/AC ASC retained
64.2% of its capacity following 20,000 cycles of charge and discharge. The exceptional electrochemical efficiency
of the NZC-2/AC ASC is attributed to its porous structure, achieved through ultrasonic electrodeposition,
which enhances ion transport efficiency and reduces diffusion times. The refined and uniform crystal structure
of the NZC-2 electrodes improves reactivity and supports rapid reaction kinetics, making them well-suited for
high-performance energy storage applications. At the conclusion of this study, we compared the energy and
power densities of the NiZnCo2O4//AC asymmetric supercapacitor with other similar materials reported in
the literature, as shown in Fig. 11h. The comparison highlights that the device fabricated in this work achieves
a superior energy density of 70.5 Wh/kg at a power density of 260 W/kg. In comparison, previously reported
systems such asZnCo2O4@LDH//AC36 ZnCo2O4/rGO//AC37, OV-ZnC2O4//AC38, ZnCo2O4-Ni(OH)2//AC39,
and MoS2/ZnCo2O4//AC40 demonstrate lower energy densities under similar power density conditions.

Conclusions
This study investigates the impact of ultrasonic treatment duration on the synthesis and electrochemical
performance of NZC electrodes for SCs. Optimizing the duration to 20 min resulted in a uniform and
compact NiZnCo2O4 layer with well-defined nanostructures, enhancing the surface area and active sites for
electrochemical reactions. XRD analysis confirmed successful synthesis, revealing distinct crystalline phases
including NiO, ZnCo2O4, and Co3O4, with improved crystallinity. Electrochemical tests showed that the NZC-
2 sample (20-min ultrasonic treatment) attained the maximum 5.678 F/cm3 value of Cs equal to 0.5 mA/cm2,
along with an impressive Ed value equal to70.5 Wh/kg at Pd = 260 W/kg. The CV and GCD tests demonstrated
that NZC-2 exhibited superior discharging-charging efficiency and the longest discharge time at low Id
values, highlighting its maximum energy storage capacity. EIS measurements confirmed NZC-2’s excellent
electrochemical behavior, showing the lowest total impedance and highest ion transport efficiency. The NZC-2/

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Fig. 11. Electrochemical efficiency of NZC-2/AC ASC: (a) CV curves at different scanning rates, (b) At
different scanning values of GCD curves, (c) GCD curves at different current densities, (d) Volumetric
capacitance and capacitance retention of NZC-2/AC ASC and NZC/AC ASC, (e) Pd vs. Ed, (f) Compares the
performance of the ultrasonically prepared NZC-2/AC ASC with flower-like on NiZnCo2O4, (g) Cycle stability
of NZC-2/AC ASC, and (h) Comparison of energy density and power density.

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AC ASC showed impressive long-term stability, retaining 64.2% of its capacity after 20,000 charge and discharge
cycles and effectively powering a 1.2 V small-sized fan at maximum voltage, demonstrating its practical
applicability. These findings reveal the significant enhancement of structural and electrochemical properties
in NiZnCo2O4 electrodes through optimized ultrasonic treatment duration, rendering them highly suitable for
high-performance SCs. Future studies should focus on optimizing ultrasonic settings and investigating their
impact on various electrode materials to advance the development of efficient energy storage devices.

Data availability
Data availability statementThe data that support the findings of this study are available on request from the cor-
responding author, Huaxing Li，upon reasonable request.

Received: 20 June 2024; Accepted: 25 October 2024

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Acknowledgements
The research is supported by the National Natural Science Foundation of China (Granted no. 51974089), and the
Daqing Guiding Science and Technology Project (Granted no. zd-2020-25).

Author contributions
Author contributionsYu Zhang: Investigation, Methodology, Validation, Writing - Original Draft, Writing - Re-
view & Editing.Huaxing Li: Investigation, Validation, Methodology.Qiang Zhang: Investigation, Methodology,
Conceptualization.Guo Xue: Project Administration, Supervision, Review & Editing.Zhaoge Zhu: Resources,
Funding Acquisition, Supervision.

Competing interests
The authors declare no competing interests.

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