Original Research
Frontiers in Physics ·
Volume 14 - 2026 | https://doi.org/10.3389/fphy.2026.1875587
Synergistic ZnCo 2 O 4 -PANI heterostructure for high-performance supercapacitor electrodes
- Jagadeep Reddy1
- Neetu Vishwakarma2
- Tim Tim Mashangva1
- Anshika Goel1
- Sangeeta Prasher3
- Ajit Sharma4
- Mukesh Kumar1*corresponding author
- 1Department of Physics, Lovely Professional University, Phagwara, Punjab, India
- 2Department of Physical Science, School of Science, SDGI Global University, Ghaziabad, India
- 3Department of Physics, Kanya Maha Vidyalaya, Jalandhar, Punjab, India
- 4Department of Chemistry, Lovely Professional University, Phagwara, Punjab, India
Abstract
The development of high-performance and cost-effective electrode materials is crucial for the advancement of next-generation energy storage devices. In this study, a zinc cobaltite-polyaniline (ZnCo 2 O 4 -PANI) nanocomposite was successfully synthesized through a simple and economical in-situ polymerization method for supercapacitor applications. The structural and electrochemical properties of the prepared composite were systematically investigated and compared with pristine ZnCo 2 O 4 and pure PANI electrodes. Electrochemical measurements revealed that the ZnCo 2 O 4 -PANI nanocomposite exhibited a high specific capacitance of 660 Fg -1 at a current density of 0.5 Ag -1 , compared to 455 Fg -1 for pristine ZnCo 2 O 4 and 379 Fg -1 for pure PANI under identical conditions. The composite electrode also showed lower charge transfer resistance and improved ion diffusion characteristics, indicating reduced electrochemical impedance. The ZnCo 2 O 4 -PANI nanocomposite demonstrated significantly enhanced electrochemical performance and enhanced charge storage capability due to the synergistic interaction between the excellent redox activity of ZnCo 2 O 4 and the high electrical conductivity of PANI. These results highlight its strong potential as an efficient and durable electrode material for advanced supercapacitor applications.
Keywords
1 Introduction
The combination of increasing global energy consumption and the imperative to mitigate climate change is driving a widespread shift from fossil fuels to sustainable energy alternatives [1]. Compared to other energy storage technologies, supercapacitors are gaining prominence due to their high power density, fast charging capabilities, and impressive durability [2–4]. The primary frontier in supercapacitor research lies in the rational design and engineering of novel electrode materials capable of storing more charge without compromising power or longevity [5, 6].
Transition metal oxides (TMOs), particularly those with a spinel structure (AB2O4), have been identified as exceptional candidates due to their cost-effectiveness, environmental benignity, and high theoretical specific capacitance [7]. Among these, ZnCo2O4, a mixed-metal spinel, is particularly notable. 1t exhibits a high theoretical capacitance (often exceeding 1000 Fg-1) and richer redox chemistry stemming from the synergistic contributions of both zinc and cobalt ions [8].
Conducting polymers have developed as a compelling class of materials for this purpose, with Polyaniline (PANI) standing out as an exemplary candidate [9]. PANI is valued for its high intrinsic electrical conductivity, excellent pseudocapacitive performance arising from its multiple oxidation states, impressive environmental stability, and facile synthesis [10]. The integration of PANI with ZnCo2O4 into a binary composite, therefore, offers a powerful solution where the individual weaknesses of each component are mutually compensated [11]. Priya et al. [12] and Sun et al. [13] successfully synthesized ZnCo2O4 nanoparticles via a hydrothermal method, achieving a specific capacitance of 434 Fg-1 at a scan rate of 5 mVs-1 and 2540 Fg-1 at 1 Ag-1 respectively. The potential of ZnCo2O4 for advanced applications has been demonstrated in the literature [14, 15] and used as the positive electrode in a complex supercapacitor. Their all-solid-state device achieved a good energy density and maintained excellent cycling stability, with above 80% capacitance retention over 5000 cycles, thus validating its potential for practical cell designs [14, 15].
This work presents the synthesis of a ZnCo2O4–PANI composite and investigates its properties to understand the interaction between the constituent materials, demonstrating its potential as a high-performance electrode for next-generation energy storage applications.
2 Synthesis of ZnCo2O4-PANI nanocomposite
All chemicals used in this work were of AR grade, procured from Loba Chemie, and their detailed descriptions are provided in the Supplementary Material. Zinc cobaltite (ZnCo2O4) was synthesized by a conventional sol-gel method. Zinc nitrate hexahydrate (1.20 g, 4.03 mmol) and cobalt nitrate hexahydrate (2.40 g, 8.25 mmol) were dissolved in 50 mL of distilled water under continuous magnetic stirring for 30 min until a clear homogeneous solution was obtained. Subsequently, citric acid (7.20 g) was gradually added as a chelating agent while maintaining continuous stirring for an additional 30 min. The precursor solution remained mildly acidic (approximately pH 2–3) because of the presence of citric acid, and no external pH adjustment was carried out. The resulting homogeneous sol was heated on a hot plate at 300 °C until complete evaporation of water and spontaneous combustion produced a brown ash-like precursor. The obtained powder was ground thoroughly and calcined in air at 600 °C for 4 h with a heating rate of 5 °C min-1 to obtain crystalline spinel ZnCo2O4 nanoparticles. Polyaniline (PANI) was prepared through in situ polymerization. Ammonium persulfate (APS) (4 g) solution was prepare by adding it to 30 ml of distilled water. Parallelly, HCL(10 ml) solution was prepared by adding it to 20 ml of distilled water then 3 ml of aniline was added to the solution to obtain HCL/aniline solution. Both solutions were stirred at room temperature until properly mixed. The APS solution was then added drop by drop to the HCL/aniline solution. The resulting solution was bluish green in color and was stirred for 1 h. After stirring, the solution was left for polymerization at room temperature for 48 h. Following this the obtained polymer solution was washed with 500 ml of 0.5:0.5:10 (HCL: ethanol: distilled water) solution and distilled water until a transparent liquid is attained. The filtered material is dried for at least 8 h at 80 °C until completely dry. After drying the material was crushed using a mortar and pastel. For ZnCo2O4–PANI nanocomposite synthesis, ZnCo2O4 powder and PANI precursors were combined in a 3:1 ratio during the in situ polymerization process to form the final composite. The ZnCo2O4: PANI weight (mass) ratio of 3:1 was selected to achieve an optimal balance between the high pseudocapacitive activity of ZnCo2O4 and the excellent electrical conductivity of PANI. A higher ZnCo2O4 content ensures the availability of abundant electroactive sites for redox reactions, while the PANI component enhances charge transport and provides structural connectivity within the composite. This ratio was found to be suitable for obtaining a homogeneous composite with improved electrochemical performance and structural stability.
3 Results and discussions
3.1 X-ray diffraction (XRD)
The formation of ZnCo2O4, PANI, and the ZnCo2O4-PANI nanocomposite was confirmed through X-ray diffraction (XRD), with the resulting patterns shown in Figure 1a. In the XRD spectrum of ZnCo2O4, the peaks at 19.0°, 32°, 36.0°, 38.6°, 45°, 56°, 60°, and 65.8° are attributed to the (1 1 1), (2 2 0), (3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), and (4 4 0) planes of spinel ZnCo2O4 (JCPDS no. 23-1390), respectively. The XRD pattern of pristine PANI exhibits a broad, characteristic amorphous reflecting the typical semi-crystalline polymer chain alignment. The broad peak of PANI in the composite was confirmed by the peak at an angle of 26.02 corresponding to (200) hkl plane. The XRD pattern of the ZnCo2O4-PANI composite clearly displays characteristic peaks of both PANI and ZnCo2O4, confirming successful growth of PANI on ZnCo2O4. The simultaneous presence of both the sharp crystalline reflections of the spinel oxide and the broad baseline feature of the polymer confirms the successful formulation of ZnCo2O4-PANI composite. Analysis of the XRD data matches the JCPDS Card No. 23-1390 [9]. Quantitatively, the crystallite size was estimated using the Debye-Scherer formula and applied to the highest-intensity peak (3 1 1). The FWHM of ZnCo2O4, and ZnCo2O4-PANI composite were determined to be 0.231 and 0.412 respectively for (3 1 1) peak. The calculated crystallite sizes of ZnCo2O4, and ZnCo2O4-PANI composite are 36.1 nm and 20.3 nm, respectively. While the crystallite size of the composite decreased, its micro-strain increased from 0.00302 to 0.005391 which indicates an inverse relationship between crystallite size and lattice strain where smaller crystallites contain a higher density of structural imperfections and interfacial distortion. The growth of ZnCo2O4 crystallites are likely restricted by PANI during the composite formation, resulting in finer domains, broader XRD peaks, and greater residual strain within the oxide lattice. Thus, the incorporation of the flexible PANI matrix results in modifying the ZnCo2O4 structure by preventing crystallite coarsening and increasing the defect related strain, which can help create more active interfaces and open low-resistance atomic pathways for charge carriers.While the crystallite size of the composite decreased, its micro-strain increased from 0.00302 to 0.005391 which indicates an inverse relationship between crystallite size and lattice strain where smaller crystallites contain a higher density of structural imperfections and interfacial distortion. The growth of ZnCo2O4 crystallites are likely restricted by PANI during the composite formation, resulting in finer domains, broader XRD peaks, and greater residual strain within the oxide lattice. Thus, the incorporation of the flexible PANI matrix results in modifying the ZnCo2O4 structure by preventing crystallite coarsening and increasing the defect related strain, which can help create more active interfaces and open low-resistance atomic pathways for charge carriers.

3.2 SEM Analysis
SEM micrographs shown in Figures 1c–e reveal distinct material morphologies. ZnCo2O4 nanoparticles appear as irregular, porous aggregates, while pure PANI forms an interconnected nanorod network. The composite material demonstrates successful integration, with ZnCo2O4 particles effectively embedded within the PANI matrix, indicating a 3D interconnected network structure [16]. This structural alignment prevents nanoparticle agglomeration and the open morphology acts as an efficient ion-transport reservoir, maximizing the electroactive surface area accessible to the electrolyte.
3.3 FTIR Analysis
For confirmation of chemical interaction and the successful formation of the ZnCo2O4–PANI nanocomposite, FTIR analysis was done and the result is shown in Figure 1b. The bands of PANI in the IR spectra at about 1480 cm-1 and 1570 cm-1 are attributed to the stretching vibrations of benzenoid and quinoid rings, respectively, indicating preservation of the polymer backbone. C–N stretching and in-plane bending vibrations of the protonated PANI structure are attributed to the bands at 1300 cm-1 and 1140 cm-1, respectively. Further, the characteristic absorption bands in the range 500–680 cm-1 is assigned to the metal–oxygen (Zn–O and Co–O) stretching vibration of ZnCo2O4, which indicates the presence of spinel oxide phase in the polymer matrix. A slight shift and broadening of some characteristic PANI peaks in composite spectrum as compared to pure PANI indicate the presence of interfacial interactions between the ZnCo2O4 nanoparticles and PANI chain. Such interactions can also promote charge transfer between the inorganic and organic phases, potentially enhancing the electrochemical properties of the composite material [17].
3.4 EDS Spectroscopy Analysis
The elemental composition of the materials ZnCo2O4, PANI and nanocomposite of ZnCo2O4–PANI was analyzed by the Energy Dispersive X-ray Spectroscopy (EDS) technique, which is illustrated in Figure 2. The EDS pattern of ZnCo2O4 shows the presence of Zn, Co, and O elements, which confirms the successful synthesis of zinc cobaltite. Pure PANI shows characteristic peaks of C and N in addition to some S and O peaks, which are due to the dopant and synthesis precursors. The simultaneous presence of all peaks corresponding to C, N, O, Co and Zn indicates the successful incorporation of PANI on the ZnCo2O4 matrix. The absence of any significant impurity peaks further confirmed the high purity of the synthesized materials and thus the successful formation of the ZnCo2O4–PANI nanocomposite.

3.5 Electrochemical analysis
The working electrode was prepared by coating a cleaned nickel foam substrate (1 cm × 1 cm) with a specialized ink, which was then dried at 70 °C. This ink was formulated in NMP solvent and consisted of the active material, PVDF binder, and carbon black in a weight ratio of 80:10:10. The ink was drop casted onto the substrates such that the obtained mass loading of the samples on the substrate were 1 mg. All experiments were run at room temperature using a three-electrode cell, which contained a 3M KOH electrolyte.
3.5.1 Cyclic voltammetry study
Figure 3 represents the CV of (a) ZnCo2O4, (b) PANI, and the nanocomposite of (c) ZnCo2O4-PANI was carried out in the potential window 0–0.45V at a scan rate of 5–150 mVs-1. To determine the specific capacitance of the samples, the following formula as given in Equation 1 was applied
C s = ∫ I d V m × s c a n r a t e × P o t e n t i a l W i n d o w (1)

The specific capacitance was calculated by dividing the area under the cyclic voltammetry (CV) curve (∫ I d V) by the mass of the active material (m), scan rate and potential window. At a scan rate of 5 mVs-1, the values for ZnCo2O4, PANI, and the ZnCo2O4-PANI composite were 455, 379, and 660 Fg-1, respectively. These results indicate that the prepared nanocomposite has a higher specific capacitance compared to its individual components.
At higher scan rates, a decrease in specific capacitance occurs because of limitations in ion diffusion, as ions do not have enough time to fully access the electrode’s surface. The high capacitance of the ZnCo2O4-PANI composite results from effectively incorporating PANI, which increases the electrochemically active surface area, offers more sites for redox reactions, and creates more direct pathways for electron and ion transport [18]. The Charge storage in the inorganic spinel lattice is due to the surface-controlled Faradaic reactions involving OH− ions. While Zn2+ primarily provides structural stability, the cobalt cations (Co2+/Co3+) undergo consecutive oxidation/reduction transitions. Simultaneously, the conductive polyaniline contributes pseudo-reversible capacitive charge storage via proton doping/dedoping transitions between its distinct oxidation states. Table 1 summarizes the synthesis methods, structural characteristics, and electrochemical performance of previously reported ZnCo2O4-based electrode materials along with the present work.
TABLE 1. Comparative electrochemical performance of ZnCo2O4-based supercapacitor electrodes.
| Sr. No. | Electrode material | Structure/morphology | Synthesis route | Electrolyte/setup | Capacitance/capacity | Current/scan rate | Reference |
|---|---|---|---|---|---|---|---|
| 1 | PANI–ZnCo2O4 | ZnCo₂O₄ nanoparticles embedded in tubular PANI matrix | Hydrothermal ZnCo2O4 + oxidative polymerization of aniline | Supercapacitor three-electrode system | 398 Cg−1 | 1 Ag−1 | [19] |
| 2 | ZnCo2O4 microspheres | Sheet-like microspheres | Hydrothermal method | Solid-state asymmetric supercapacitor with activated carbon | 422 Fg−1 | 1 Ag−1 | [20] |
| 3 | ZnCo2O4 nanoparticles | Urea-controlled nanoparticles | Urea-assisted hydrothermal + calcination | Positive electrode for asymmetric supercapacitor | 635 Fg−1 | 7 mA cm−2 | [21] |
| 4 | SnO2/ZnCo2O4/GO | Ternary oxide/graphene oxide nanocomposite | Hydrothermal + sonochemical + mild hydrothermal route | Hybrid supercapacitor electrode | 645 Fg−1 | 2.5 Ag−1 | [22] |
| 5 | SnO2/ZnCo2O4 | Binary oxide nanostructure | Sonochemical integration after ZnCo2O4 synthesis | Three-electrode supercapacitor | 400 Fg−1 | 2.5 Ag−1 | [22] |
| 6 | ZnCo2O4 | Nanostructured ZnCo2O4 | Hydrothermal precursor route | Three-electrode supercapacitor | 365 Fg−1 | 2.5 Ag−1 | [22] |
| 7 | Hydrothermal ZnCo2O4 on stainless steel | Microspheres made of crumbled nanosheets | Hydrothermal deposition + annealing | Binder-free electrode | 430.75 Fg−1 | 5 mVs−1 | [23] |
| 8 | Electrodeposited ZnCo2O4 on stainless steel | Nanosheets | Electrodeposition + annealing | Binder-free electrode | 171.03Fg−1 | 5 mVs−1 | [23] |
| 9 | ZnCo2O4 electrode | Microspheres / nanosheet-like structure | Hydrothermal route | Three-electrode supercapacitor | 593Fg−1 | 10 mV s−1 | [24] |
| 10 | ZnCo2O4-based asymmetric device | ZnCo2O4 nanorod fiber electrode | Hydrothermal growth on fiber substrate | Flexible spiral-type supercapacitor | 10.9 Fg−1 | 30 mVs−1 | [25] |
| 11 | ZnCo2O4-PANI | nanocomposite | Sol-gel method | Heterostructured super capacitor electrode | 660Fg−1 | 0.5 Ag−1 | This work |
3.5.2 Galvanostatic charge–discharge
The galvanostatic charge-discharge (GCD) profiles for ZnCo2O4, PANI, and the ZnCo2O4-PANI composite are shown in Figure 4. These curves, recorded at current densities from 1 to 10 Ag-1 within a 0–0.4 V potential range, display clear plateaus [13]. The discharge time of the ZnCo2O4-PANI composite is longer compared to pure PANI, indicating a higher charge storage capacity of the electrode material. The formula used to calculate the specific capacitance from GCD is given below in Equation 2
C s = I m × Δ t Δ V (2)

Where Im is the current density, Δ t is the discharge time, and ΔV is the potential window. The specific capacitance of the samples ZnCo2O4, PANI, and the ZnCo2O4-PANI composite was found to be 261, 215, and 375 Fg-1, respectively, at 1 Ag-1, as shown in Table 2, which agrees with the CV study. The galvanostatic charge-discharge (GCD) data show that the composite’s specific capacitance exceeds that of both ZnCo2O4 and PANI. This result is attributed to the composite’s enhanced redox performance and increased surface area. As the current density increases, the specific capacitance decrease. The rate capability of the composite was evaluated by comparing specific capacitances across scan rates from 1 Ag-1 to 5 Ag-1. The ZnCo2O4-PANI composite retained 67% of its initial capacitance, demonstrating good rate capability. This is attributed to the highly conductive PANI network which maintains rapid electron pathways even at elevated kinetic rates.
TABLE 2. Electrochemical parameters from the GCD and CV curve of ZnCo2O4, PANI and ZnCo2O4-PANI nanocomposite.
| Material | Specific capacitance from CV (Fg−1) | Specific capacitance from GCD (Fg−1) |
|---|---|---|
| ZnCo2O4 | 455 | 261 |
| PANI | 379 | 215 |
| ZnCo2O4-PANI | 660 | 375 |
The schematic illustration in Figure 4e depicts the energy storage mechanism of the ZnCo2O4-PANI composite. ZnCo2O4, as the active material, undergoes redox reactions involving potassium ion intercalation and de-intercalation. PANI improves the electrode’s performance by providing high electrical conductivity and a large surface area.
3.5.3 Electrochemical impedance spectroscopy
This analysis examined conductivity and interfacial charge transfer. The ZnCo2O4-PANI composite showed a lower equivalent series resistance (ESR) of 1.02 Ω compared to 1.45 Ω for pure ZnCo2O4 and 2.34 Ω for PANI, indicating reduced internal resistance, electrolyte resistance, and contact resistance at the current collector interface. The highly depressed, near-negligible high-frequency semicircle in the composite’s EIS plot suggests minimal charge transfer resistance due to its improved electrical conductivity. The integration of the highly conductive PANI matrix provides a continuous metallic-like pathway for rapid electron transport, effectively reducing Rct to near-zero values. Additionally, the composite exhibits a significantly steeper, near-vertical Warburg impedance slope compared to its individual counterparts at low frequencies reflecting better capacitive behaviour and a shorter ion diffusion path. This close-to-ideal vertical behavior confirms an enhanced capacitive response.
These results confirm that the ZnCo2O4-PANI nanocomposite has higher capacitance than pure ZnCo2O4 and PANI [26]. Other than the PANI providing a conductive backbone to the composite, the polyaniline (PANI) matrix facilitates an open, network-like architecture that is central to the composite’s enhanced electrochemical performance. This interconnected morphology shortens solid-state ion diffusion pathways—as evidenced by the steeper Warburg slope—and establishes metallic-like electronic conduction channels, which is strongly corroborated by the exceptionally low ESR.
We further analyze the charge storage mechanism of the ZnCo2O4-PANI composite electrode from the CV profile using the power law equation ip = av^b. The plot to determine the value of the slope (b) is as shown in Figure 4e whose value determines the charge storage mechanism contribution. It is known that the charge storage process is controlled by diffusion if the value of b is 0.5 and capacitive process if the value of b is 1. The value of b was determined to be 0.76 for anodic peak and lies in between 0.5 and 1 suggesting that the charge storage process is governed by both diffusion and capacitive mechanism.
4 Conclusion
A ZnCo2O4-PANI nanocomposite was successfully synthesized using a simple and cost-effective in situ polymerization method. The composite exhibited significantly enhanced electrochemical performance compared to pristine ZnCo2O4 and pure PANI due to the combined effect of the high redox activity of ZnCo2O4 and the excellent electrical conductivity of PANI. The ZnCo2O4-PANI electrode delivered a high specific capacitance of 660 Fg-1 from CV and 375 Fg-1 from GCD analysis, along with reduced charge transfer resistance and improved ion diffusion characteristics. These results demonstrate its strong potential as an efficient electrode material for next-generation supercapacitor applications. However, the present study is limited to a three-electrode configuration, and practical device-level evaluation using a two-electrode system and long-term cycling stability analysis could not be performed due to experimental limitations. Future studies will focus on device fabrication and practical applicability for advanced energy storage systems.
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Supplementary material
The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fphy.2026.1875587/full#supplementary-material
Supplementary material Supplementary material at the source
Footnotes
Edited by: A. K. Haghi, University of Coimbra, Portugal
Reviewed by: Rachna Ahlawat, Chaudhary Devi Lal University Vivekananda Library, India
Gita Rani, Chaudhary Devi Lal University Vivekananda Library, India
Thirumurugan Prakasam, New York University Abu Dhabi Research Institute, United Arab Emirates
Statements
- Conflict of interest
The author(s) declared that this work was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
- Funding
The author(s) declared that financial support was not received for this work and/or its publication.
- Data availability
The data supporting the findings of this study has been presented in the figures and tables and no additional data is available to disclose.
- Author contributions
JR: Writing – original draft, Investigation, Formal Analysis, Methodology, Data curation. NV: Validation, Visualization, Writing – review and editing, Resources. TM: Investigation, Writing – original draft, Validation, Data curation, Methodology. AG: Writing – review and editing. SP: Writing – review and editing, Resources. AS: Data curation, Writing – review and editing. MK: Supervision, Writing – review and editing, Conceptualization, Project administration, Validation.
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Citation
Reddy, J., et al. (2026). Synergistic ZnCo 2 O 4 -PANI heterostructure for high-performance supercapacitor electrodes. Frontiers in Physics, Volume 14. https://doi.org/
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Copyright © 2026 Reddy, Vishwakarma, Mashangva, Goel, Prasher, Sharma and Kumar.
License: https://creativecommons.org/licenses/by/4.0/
*Correspondence: Mukesh Kumar
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