Hybrid nanostructured PAN@NiCu(CO3)(OH)2 composite for flexible high-performance supercapacitors

Lee, Damin; Verma, Anjneya; Lê, Khan; Fischer, Thomas; Kim, Kwang Ho; Mathur, Sanjay

doi:10.1557/s43578-021-00349-5

Hybrid nanostructured PAN@NiCu(CO₃)(OH)₂ composite for flexible high-performance supercapacitors

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Annual Issue: Early Career Scholars in Materials Science 2022
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Published: 22 October 2021

Volume 37, pages 304–318, (2022)
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Hybrid nanostructured PAN@NiCu(CO₃)(OH)₂ composite for flexible high-performance supercapacitors

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Damin Lee^1,2,
Anjneya Verma¹,
Khan Lê¹,
Thomas Fischer¹,
Kwang Ho Kim^2,3 &
…
Sanjay Mathur¹

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Abstract

A binder-free porous NiCu(CO₃)(OH)₂ composite was grown on a polyacrylonitrile (PAN) nanofiber substrate using a hydrothermal method. PAN nanofibers were fabricated by the electrospinning method, thus producing a substrate with a nano-sized diameter and high specific surface area. The composite NiCu(CO₃)(OH)₂ nanowires on PAN nanofibers provided the large specific surface area required for the redox reaction. Transition metal-based nanowires and nano-sized PAN substrates indicate a synergistic effect in electrochemical performance. The NiCu(CO₃)(OH)₂ on PAN composite showed a remarkable maximum specific capacity of 870 mAh g⁻¹ at a current density of 3 A g⁻¹, which indicates that it can be a suitable electrode material. In addition, an asymmetric supercapacitor with NiCu(CO₃)(OH)₂ on PAN composite as the cathode and graphene as the anode showed an ultra-high energy density of 89.2 W h kg⁻¹ at a power density of 835 W kg⁻¹ and a capacitance retention of 90.1% after 5000 cycles.

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Introduction

In recent years, energy consumption has increased worldwide as human well-being has become increasingly reliant on digital tools, and consequently, the need for high-performance energy storage systems has become prominent [1, 2]. The application of decentralized energy resources and storage technologies in the field of portable, flexible, and smart electronics has significant challenges that need to be addressed in the global context of energy transition [3, 4]. In this regard, flexible energy devices such as batteries and supercapacitors are key technologies for powering body-worn consumer electronics, sensors, or low-energy bioelectronics (e.g., on-skin diagnostics). Similarly, supercapacitors (SCs) that can fit into various device structures and installation spaces are key enablers for buffering excess energy. SCs have gained increasing attention owing to their fast charge and discharge rates, high power density, long cycle life, and high reliability [5,6,7]. However, endowing conventional SCs with good flexibility as well as high energy density is challenging because both charge collectors (substrates) and electrode materials can experience fracture and delamination during flexing. These supercapacitors can be classified into two types: electrical double-layer capacitors (EDLCs), which usually use carbon active materials, and faradaic capacitors, which use redox-active materials [8]. EDLC devices store electrochemical energy via electrostatic accumulation of charges in the electric double layer and currently dominate the SC market because of their ability to accumulate large amounts of charge [9]. However, their relatively low specific capacitance is inhibitive for the increasing requirements of SCs with higher electrochemical performance, which also restricts their potential large-scale applications [10, 11]. Recently, researchers have focused on exploring faradaic capacitors owing to their high specific capacitance, which is induced by fast reversible redox reactions [12]. Faradaic capacitors generally use a metal oxide/hydroxide as the cathode for efficient redox reaction on the electrode surface, which requires an electrode material with a large specific surface area and good electrochemical activity. Transition metal oxides and hydroxides [13, 14], such as NiO [15], Ni(OH)₂ [16], Co₃O₄ [17], MnO₂ [18], and RuO₂ [19], and their binary composites have been considered as optimized materials for SCs. The reversible redox reaction in faradaic capacitors occurs on the surface of the electrode, and because the electrical energy is stored on the electrode surface, the storage capacity of faradaic capacitors is significantly influenced by electrode material properties. For this reason, binary NiCu-oxide/hydroxide compounds, which exhibit rich redox reactions due to their multiple oxidation states, have been widely used as faradaic capacitors electrodes. For example, Zhenyuan et al. fabricated NiO/Co₃O₄ ultrathin nanosheets that have a specific capacitance of 1775 F g⁻¹ at 1 A g⁻¹ [20]. Jun et al. fabricated Cu-metal organic frameworks (MOF) electrodes, which showed a specific capacitance of 318 F g⁻¹ at 1 A g⁻¹ in a KOH electrolyte [21]. Heba et al. prepared Ni–Cu binary phosphides, which exhibited a specific capacitance of 1573 F g⁻¹ at 1 A g [22]. However, oxide and hydroxide composites normally suffer from gradually decreasing stability after several charging and discharging cycles [

Electrochemical properties

Figure 5a presents the redox curves of the electrodes with a three-electrode cell, which shows the cyclic voltammetry (CV) curves of the PAN@NiCu(CO₃)(OH)₂ composite in the potential window of 0.15–0.6 V at scan rates from 5 to 50 mV⁻¹ in a 1 M KOH electrolyte. The oxidation and reduction peaks in the CV curves shifted toward more positive and negative potentials, respectively, as the scan speed increased because the internal diffusion resistance increased within the electrode surface. The typical CV peaks of the PAN@NiCu(CO₃)(OH)₂ electrodes showed reduction peak at ~ 0.46 V, and an oxidation peak at ~ 0.34 V, respectively, at 10 mV s⁻¹. As the scan rate increased, the redox peak of the PAN@NiCu(CO₃)(OH)₂ electrode shifted to an extent, indicating that there is the internal resistance of the PAN@NiCu(CO₃)(OH)₂ electrode. And the CV of PAN@NiCu(CO₃)(OH)₂ has a large internal area, which is proportional to its capacity value. This result indicates that the PAN@NiCu(CO₃)(OH)₂ electrode has a great electrochemical value. This electrode exhibits symmetric redox peak property, indicating good performance for redox reactions and largely porous morphology. The CV curves obtained for the PAN@NiCu(CO₃)(OH)₂ nanowire electrode were standard for faradaic capacitors. The faradaic redox reactions of the NiCu(CO₃)(OH)₂ composite occurred according to Eqs. (1–3) [44, 45]:

$${\text{NiCu}}\left( {{\text{CO}}_{{3}} } \right)\left( {{\text{OH}}} \right)_{{2}} + {\text{4OH}}^{-} \rightleftharpoons {\text{NiOOH}} + {\text{CuOOH}} + {\text{CO}}_{3}^{2 - } + {\text{2H}}_{{2}} {\text{O}} + {\text{2e}}^{-},$$

(1)

$${\text{NiOOH}} + {\text{OH}}^{-} \rightleftharpoons {\text{NiO}}_{{2}} + {\text{H}}_{{2}} {\text{O}} + {\text{e}}^{-},$$

(2)

$${\text{CuOOH}} + {\text{OH}}^{-} \rightleftharpoons {\text{CuO}}_{{2}} + {\text{H}}_{{2}} {\text{O}} + {\text{e}}^{-}.$$

(3)

According to these equations, the redox reactions involve OH⁻ from the electrolyte in the optimized NiCu(CO₃)(OH)₂ composite. Figure 5b shows the galvanostatic charge–discharge (GCD) measurements of the PAN@NiCu(CO₃)(OH)₂ composite over a potential range of 0–0.45 V. The GCD curves showed a nonlinear slope and triangular symmetry owing to the occurrence of quasi-reversible redox reactions at the electrolyte/electrode interface. As shown in Fig. 5b, the PAN@NiCu(CO₃)(OH)₂ composite had a long discharge time, indicating that it has high electrochemical performance, which is consistent with the trend observed in the CV analysis. The specific capacities of the previously tested Ni-foam@NiCu(CO₃)(OH)₂ and PAN@NiCu(CO₃)(OH)₂ composites were calculated using the following Eq. (4) [46]:

$$Q_{{\text{D}}} = \frac{{I\Delta t}}{m},$$

(4)

where Q_D (mAh g⁻¹) is the specific capacity, I (mA) is the discharging current, Δt (s) is the discharging time that is measured from 0.0 to 0.45 V, and m (g) is the designated mass of the active material. Using this equation, it was found that the PAN@NiCu(CO₃)(OH)₂ nanowire composite possessed high electrochemical values. As shown in Fig. 5c, the PAN@NiCu(CO₃)(OH)₂ electrode exhibited specific capacities of 870, 936, 1025, 960, 899, and 808 mAh g⁻¹, while the specific capacities of the Ni-foam@NiCu(CO₃)(OH)₂ electrode were calculated to be 759, 632, 496, 424, 364, and 348 mAh g⁻¹ at current densities of 3, 4, 5, 8, 10, and 15 A g⁻¹, respectively. This was attributed to the positive effect of the increased surface area of the PAN@NiCu(CO₃)(OH)₂ electrode structure. As a result, PAN@NiCu(CO₃)(OH)₂ had higher specific capacitance values than the NiCu(CO₃)(OH)₂ composite on the Ni-foam substrate, which indicates the synergetic effect of the PAN nanofibers and NiCu(CO₃)(OH)₂ nanowire electrode. The cycling properties were also measured to investigate the stability of the electrodes. Long-term electrical retention is an important factor for electrodes in supercapacitor applications and industrialization [47]. As shown in Fig. 5d, after satisfactory cycles, the Ni-foam@NiCu(CO₃)(OH)₂ and PAN@NiCu(CO₃)(OH)₂ electrodes exhibited retentions of 88.2% and 84.1%, respectively, after 5000 cycles. The stability of the electrodes was evaluated using the discharging time at a constant current density of 10 A g⁻¹. These results suggest that the Ni-foam@NiCu(CO₃)(OH)₂ electrode exhibited better cycling stability than the PAN@NiCu(CO₃)(OH)₂ electrode. The synergistic effects of the PAN substrate and NiCu(CO₃)(OH)₂ composite contributed to enhanced electrochemical performance for a specific capacitance; however, this electrode possessed a lower retention value owing to its weak polymer properties. Nevertheless, these results indicate better electrochemical properties than those previously reported for NiCu-based electrodes (Table 1). As a result, although the electrode was damaged and the capacity decreased with the increasing number of cycles, it had a high retention value because of the positive influence of the transition metal composites.

TABLE 1 Comparison with the capacitance and retention values of the previously studied nickel- and copper-based electrodes.

Full size table

To further investigate the viability of the electrodes in energy storage devices, an ASC was fabricated using Ni-foam@NiCu(CO₃)(OH)₂ and PAN@NiCu(CO₃)(OH)₂ composites as the cathode and graphene as the anode. A cellulose separator paper and 1 M KOH electrolyte were used for the ASC device. A schematic diagram of the cathode and anode ASC electrodes is shown in Scheme 2. The electrochemical performance of the graphene electrode was measured in the potential range of − 1 to 0 V, as shown in Fig. 6. The CV curves of graphene showed typical rectangular shapes, which represent the ideal faradaic capacitor (Fig. 6a). The GCD curves exhibited linear and symmetric shapes, as shown in Fig. 6b. The specific capacity (Fig. 6c) of the graphene electrode was 122 mAh g⁻¹ at 2 A g⁻¹ and 60 mAh g⁻¹ at 15 A g⁻¹, respectively. EIS analyses were performed to investigate the conductivity behavior and charge-transfer kinetics of the graphene electrode. In the high-frequency region, the graphene electrode showed low R_s and R_ct values of 0.6 Ω and 0.82 Ω, respectively (inset of Fig. 6d). The slope of the linear section of the graphene electrode has a higher incline in the low-frequency region, which represents a low Z_w value, as shown in Fig. 6d. These results confirmed that the graphene electrode could be a suitable negative electrode for ASCs. Figure 7 shows the CV curves of the assembled ASC, which demonstrate electrical double-layer capacitor properties behavior at different scan rates in the voltage range of 0.0–1.5 V. This phenomenon indicates that PAN@NiCu(CO₃)(OH)₂ electrode//graphene ASCs were significantly influenced by graphene, which is a negative electrode material. As shown in Fig. 7a, the PAN@NiCu(CO₃)(OH)₂ composite shows excellent rectangular CV curves, which represent the ideal behavior of SCs. and this ASC device does not have the redox peaks at all scan rates. Figure 7b represents the specific capacity values of the Ni-foam@NiCu(CO₃)(OH)₂//graphene ASC and PAN@NiCu(CO₃)(OH)₂ electrode//graphene ASC from the discharge times, which are calculated to be 64 mAh g⁻¹ and 126 mAh g⁻¹ at 2 A g⁻¹, respectively. This improvement in electrical performance is achieved by the electrical conductivity of the active materials and electrolyte penetration provided by the PAN nanofiber substrate to undergo a redox reaction. Therefore, high-speed performance is achieved of the development for high-performance faradaic capacitors. The retention values of the ASCs were measured with respect to the discharge time at a current density of 5 A g⁻¹ in Fig. 7c. The assembled ASC of the Ni-foam@NiCu(CO₃)(OH)₂ and PAN@NiCu(CO₃)(OH)₂ electrodes retained 91.3 and 90.1% of their capacities, respectively, after 5000 cycles. The retention values of the ASC were similar after 5000 cycles, regardless of the substrate type. These properties indicate that the PAN@NiCu (CO₃)(OH)₂ electrode can facilitate a more stable cycle reaction when measuring the electrochemical value with the ASC than with the half-cell electrode. In addition, the energy density and power density were calculated using Eqs. (5) and (6) [64, 65]:

$$E = \frac{I\int V\mathrm{d}t}{M 3.6},$$

(5)

$$P = E/\Delta t,$$

(6)

where E (Wh kg⁻¹) is the energy density, $I$(A) is the applied current, $\int V\mathrm{d}t$ is the galvanostatic discharge current area, $M$ (g) is the active mass, P (W kg⁻¹) is the power density, and $\Delta t$ (s) is the discharge time. Figure 7d presents the ragone plot of the fabricated ASC devices. The PAN@NiCu(CO₃)(OH)₂ electrode ASC shows that the highest energy density with 90 W h kg⁻¹ at a power density of 835 W kg⁻¹ and current density of 2 A g⁻¹. As the current density changes to 15 A g⁻¹, the energy density decreases to 36 W h kg⁻¹ at a power density of 9268 W kg⁻¹. The PAN@NiCu(CO₃)(OH)₂ electrode achieved better energy and power densities than that of the Ni-foam@NiCu(CO₃)(OH)₂ electrode ACS, NiO//carbon [66], Ni(OH)₂//carbon [67], and MnO₂//carbon [68]. These results can aid the development of flexible and wearable faradaic capacitors with enhanced electrochemical performance by synthesizing PAN nanomeshes and modifying their surface through the growth of binary metal hydroxy-carbonates. Thus, PAN@NiCu(CO₃)(OH)₂ nanowires are promising materials of the positive electrode for high-performance supercapacitors.

Conclusions

Faradaic capacitors require a large specific surface area for redox reactions. To provide this large surface area, mesoporous NiCu(CO₃)(OH)₂ composites were grown on PAN nanofiber substrates using a hydrothermal method. PAN nanofibers were fabricated via the electrospinning method, giving a substrate with a nano-sized diameter and high specific surface area. Thus, the beneficial properties of high-performance SCs can arise from the structure as well as the material. The composite of NiCu(CO₃)(OH)₂ on PAN nanofibers provided a highly porous structure and a large surface area, which significantly improved the electrolyte penetration and electrical conductivity of the active materials, while providing a convenient electron diffusion path. The optimized PAN@NiCu(CO₃)(OH)₂ electrode showed an excellent maximum specific capacity of 870 mAh g⁻¹ at 3 A g⁻¹ and superior cycling stability with capacitance retention of 84.1% after 5000 cycles. An asymmetric supercapacitor was fabricated using the PAN@NiCu(CO₃)(OH)₂ composite as the cathode and commercial graphene as the anode. The ASC delivered a high energy density of 90 W h kg⁻¹ at a power density of 835 W kg⁻¹ at 2 A g⁻¹ and maintained 36 W h kg⁻¹ at a high power density of 9268 W kg⁻¹ at 15 A g⁻¹ with satisfactory cycling stability, retaining 90.1% of its capacitance after 5000 cycles. On the other hand, the previously studied NiCu(CO₃)(OH)₂//graphene ASC of Ni-foam substrate showed a relatively low energy density value with the energy density of 27 W h kg⁻¹ at 2 A g⁻¹. These results suggest that the optimized unique NiCu(CO₃)(OH)₂ composite on the PAN nanofiber substrate electrode is a potential material for use in wearable devices demanding flexibility. In conclusion, polymer and transition metal composite electrodes will potentially lead to further research and development of electrode industrialization and high-performance supercapacitors.

Experiment

Materials

The materials used in this study were Ni foam (110 PPI pore density, 320 g m⁻² mass density), polyacrylonitrile (PAN), dimethylformamide (DMF), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O), copper nitrate trihydrate (Cu(NO₃)₂·3H₂O), CO(NH₂)₂ (urea), and KOH (potassium hydroxide). All chemical reagents were used without further purification.

Electrode preparation

Ni foam as substrate: Two pieces of Ni foam (2 × 4 cm) were cleaned for 10 min by rinsing with 2.0 mol L⁻¹ of HCl, washing with DI water and ethanol for 10 min each, and then drying at 50 °C in an oven for 12 h.

PAN nanofibers as substrates: PAN nanofibers were fabricated using the electrospinning method. The experimental conditions were set to PAN (0.72 g) and DMF (9 mL). As demonstrated in our previous experiments, this condition allows for the creation of an optimal nanofiber material. The applied voltage was approximately 15 kV, and the current was adjusted to a constant value. The PAN solution was poured into a syringe attached to a capillary tip with a 0.5 mm diameter, and the flow rate was uniform (20 mL h⁻¹). The capillary tip and deposition position were kept constant at 15 cm. The substrate for PAN was not used separately, and the fabricated PAN nanofibers were directly used as the electrode substrate.

Fabrication of the Ni−Cu electrode: Optimized quantities of 6 mmol of Ni, 3 mmol of Cu, and 13 mmol of urea were placed in 50 mL of DI water and this solution was stirred for 10 min. This solution was moved to a 50 mL autoclave vessel. The Ni foam and PAN-nanofiber substrates were immersed in the aqueous solution separately and heated at 160 °C for 12 h via the hydrothermal method to synthesize NiCu(CO₃)(OH)₂. To remove surface impurities, the electrodes were washed several times with DI water and ethanol. And then, to remove adsorbed solvents, the samples were dried at 50 °C for 12 h. In the synthesis, urea is the source of both carbonate and hydroxyl anions, as indicated in Eqs. (7–9). The synthesis of NiCu(CO₃)(OH)₂ is as follows (7–9) [10, 27].

$${\text{CO}}\left( {{\text{NH}}_{{2}} } \right)_{{2}} + {\text{3H}}_{{2}} {\text{O}} \to {\text{2NH}}_{{4}}^{ + } + {\text{CO}}_{{2}} + {\text{2OH}}^{ - } ,$$

(7)

$${\text{CO}}_{{2}} + {\text{2OH}}^{ - } \to {\text{CO}}_{3}^{2 - } + {\text{H}}_{{2}} {\text{O}},$$

(8)

$${\text{Ni}}^{{{2} + }} + {\text{Cu}}^{{{2} + }} + {\text{CO}}_{3}^{2 - } + {\text{2OH}}^{ - } \to {\text{NiCu}}\left( {{\text{CO}}_{{3}} } \right)\left( {{\text{OH}}} \right)_{{2}}.$$

(9)

Material characterization

The phases of the samples were characterized using X-ray diffraction (XRD; STOE STADI MP), which were measured over a range of 5–60° (2θ). X-ray photoelectron spectroscopy (XPS; ESCALAB250, VG Scientifics) was examined to analyze the valence states of the NiCu(CO₃)(OH)₂ composite powder. The morphology analysis of the PAN@NiCu(CO₃)(OH)₂ nanowire electrodes was performed through scanning electron microscopy (SEM; FEI Strata Dual Beam 235). Transmission electron microscopy was measured using (TEM; JEOL JEM-2200 FS) with energy-dispersive X-ray spectroscopy.

Electrochemical measurements

All electrochemical tests were performed on an electrochemical workstation (VersaSTAT, Princeton Applied Research) using a three-electrode configuration using a 1 M KOH aqueous solution as the electrolyte at room temperature. NiCu(CO₃)(OH)₂ nanowire composites on PAN nanofibers were directly used as the cathode electrode, and Pt and Hg/HgO were used as the counter and reference electrodes, respectively. The cyclic voltammetry (CV) curves were plotted in a potential range between 0.15 and 0.6 V at different scan rates from 5 to 50 mV s⁻¹. The galvanostatic charge–discharge (GCD) processes were evaluated by cycling the potential from 0 to 0.45 V at current densities of 3, 4, 5, 8, 10, and 15 A g⁻¹.

References

P. Kumar, K.-H. Kim, V. Bansal, P. Kumar, Nanostructured materials: A progressive assessment and future direction for energy device applications. Coordin. Chem. Rev 353, 113 (2017)
Article CAS Google Scholar
L.B. Huang, W. Xu, J. Hao, Energy device applications of synthesized 1D polymer nanomaterials. Small 13, 1701820 (2017)
Article Google Scholar
P. Dong, M.-T.F. Rodrigues, J. Zhang, R.S. Borges, K. Kalaga, A.L. Reddy, G.G. Silva, P.M. Ajayan, J. Lou, A flexible solar cell/supercapacitor integrated energy device. Nano Energy 42, 181 (2017)
Article CAS Google Scholar
H. Li, Z. Tang, Z. Liu, C. Zhi, Evaluating flexibility and wearability of flexible energy storage devices. Joule 3, 613 (2019)
Article Google Scholar
J. Wang, X. Zhang, Z. Li, Y. Ma, L. Ma, Recent progress of biomass-derived carbon materials for supercapacitors. J. Power Sources 451, 227794 (2020)
Article CAS Google Scholar
R. Liu, A. Zhou, X. Zhang, J. Mu, H. Che, Y. Wang, T. Wang, Z. Zhang, Z. Kou, Fundamentals, advances and challenges of transition metal compounds-based supercapacitors. Chem. Eng. J. 412, 128611 (2021)
Article CAS Google Scholar
T.-F. Yi, H. Chang, T.-T. Wei, S.-Y. Qi, Y. Li, Y.-R. Zhu, Approaching high-performance electrode materials of ZnCo₂S₄ nanoparticle wrapped carbon nanotubes for supercapacitors. J. Materiomics 7, 563 (2021)
Article Google Scholar
S. Biswas, V. Sharma, T. Singh, A. Chandra, External vibrations can destroy the specific capacitance of supercapacitors–from experimental proof to theoretical explanations. J. Mater. Chem. A 9, 6460 (2021)
Article CAS Google Scholar
S.I. Wong, H. Lin, J. Sunarso, B.T. Wong, B. Jia, Optimization of ionic-liquid based electrolyte concentration for high-energy density graphene supercapacitors. Appl. Mater. Today 18, 100522 (2020)
Article Google Scholar
D. Lee, H.W. Lee, N.M. Shinde, J.M. Yun, S. Mathur, K.H. Kim, Synthesis of nickel–copper composite with controllable nanostructure through facile solvent control as positive electrode for high-performance supercapacitors. Dalton Trans 49, 13123 (2020)
Article CAS Google Scholar
T. Wang, M. Liu, H. Ma, Facile synthesis of flower-like copper-cobalt sulfide as binder-free faradaic electrodes for supercapacitors with improved electrochemical properties. Nanomaterials 7, 140 (2017)
Article Google Scholar
Y. Li, Z. Kang, X. Yan, S. Cao, M. Li, Y. Guo, Y. Huan, X. Wen, Y. Zhang, A three-dimensional reticulate CNT-aerogel for a high mechanical flexibility fiber supercapacitor. Nanoscale 10, 9360 (2018)
Article CAS Google Scholar
X. Zhang, X. Liu, Y. Zeng, Y. Tong, X. Lu, Oxygen defects in promoting the electrochemical performance of metal oxides for supercapacitors: Recent advances and challenges. Small Methods 4, 1900823 (2020)
Article CAS Google Scholar
J. Chen, J. Xu, S. Zhou, N. Zhao, C.-P. Wong, Amorphous nanostructured FeOOH and Co–Ni double hydroxides for high-performance aqueous asymmetric supercapacitors. Nano Energy 21, 145 (2016)
Article CAS Google Scholar
V.S. Kumbhar, H. Lee, J. Lee, N.R. Chodankar, K. Lee, Mesoporous design of ultrathin NiO nanosheet-coated vertically aligned hexagonal CoS nanoplate core–shell array for flexible all-solid-state supercapacitors. J. Alloys Compd. 863, 158064 (2021)
Article CAS Google Scholar
Y. Zhao, Y. Zhang, Y. Cheng, W. Zhao, W. Chen, C. Meng, C. Huang, Synthesis of Co₂SiO₄/Ni(OH)₂ core–shell structure as the supercapacitor electrode material with enhanced electrochemical properties. Mater. Lett. 282, 128774 (2021)
Article CAS Google Scholar
K. Karuppasamy, D. Vikraman, J.-H. Jeon, S. Ramesh, H.M. Yadav, V.R. Jothi, R. Bose, H.S. Kim, A. Alfantazi, H.-S. Kim, Highly porous, hierarchical microglobules of Co₃O₄ embedded N-doped carbon matrix for high performance asymmetric supercapacitors. Appl. Surf. Sci. 529, 147147 (2020)
Article CAS Google Scholar
Z. Song, W. Liu, Q. Zhou, L. Zhang, Z. Zhang, H. Liu, J. Du, J. Chen, G. Liu, Z. Zhao, Cobalt hexacyanoferrate/MnO₂ nanocomposite for asymmetrical supercapacitors with enhanced electrochemical performance and its charge storage mechanism. J. Power Sources 465, 228266 (2020)
Article CAS Google Scholar
M. Chamakh, A.I. Ayesh, Production and investigation of flexible nanofibers of sPEEK/PVP loaded with RuO₂ nanoparticles. Mater. Design 204, 109678 (2021)
Article CAS Google Scholar
S. Vijayakumar, S. Nagamuthu, G. Muralidharan, Supercapacitor studies on NiO nanoflakes synthesized through a microwave route. ACS appl. Mater. inter 5, 2188 (2013)
Article CAS Google Scholar
W. Lv, L. Li, Q. Meng, X. Zhang, Molybdenum-doped CuO nanosheets on Ni foams with extraordinary specific capacitance for advanced hybrid supercapacitors. J. Mater. Sci. 55, 2492 (2020)
Article CAS Google Scholar
V.T. Chebrolu, B. Balakrishnan, V. Raman, I. Cho, J.-S. Bak, K. Prabakar, H.-J. Kim, Co-electrodeposition of NiCu(OH)₂@Ni-Cu-Se hierarchical nanoparticle structure for supercapacitor application with enhanced performance. Appl. Surf. Sci. 506, 145015 (2020)
Article CAS Google Scholar
D. Lee, Q.X. **a, R.S. Mane, J.M. Yun, K.H. Kim, Direct successive ionic layer adsorption and reaction (SILAR) synthesis of nickel and cobalt hydroxide composites for supercapacitor applications. J. Alloys. Compd 722, 809 (2017)
Article CAS Google Scholar
S. Liu, K. Hui, K. Hui, V.V. Jadhav, Q.X. **a, J.M. Yun, Y. Cho, R.S. Mane, K.H. Kim, Facile synthesis of microsphere copper cobalt carbonate hydroxides electrode for asymmetric supercapacitor. Electrochim. Acta 188, 898 (2016)
Article CAS Google Scholar
T.M. Masikhwa, J.K. Dangbegnon, A. Bello, M.J. Madito, D. Momodu, N. Manyala, Preparation and electrochemical investigation of the cobalt hydroxide carbonate/activated carbon nanocomposite for supercapacitor applications. J. Phys. Chem. Solids 88, 60 (2016)
Article CAS Google Scholar
D. Lee, Q.X. **a, J.M. Yun, K.H. Kim, High-performance cobalt carbonate hydroxide nano-dot/NiCo(CO₃)(OH)₂ electrode for asymmetric supercapacitors. Appl. Surf. Sci. 433, 16 (2018)
Article CAS Google Scholar
M. Azad, Z. Hussain, M.M. Baig, MWCNTs/NiS₂ decorated Ni foam based electrode for high-performance supercapacitors. Electrochim. Acta 345, 136196 (2020)
Article CAS Google Scholar
M. Huang, F. Li, J.Y. Ji, Y.X. Zhang, X.L. Zhao, X. Gao, Facile synthesis of single-crystalline NiO nanosheet arrays on Ni foam for high-performance supercapacitors. CrystEngComm 16, 2878 (2014)
Article CAS Google Scholar
D. Lee, J.M. Yun, K.H. Kim, Preparation and electrochemical properties of nickel iron carbonate hydroxide as a cathode electrode material for asymmetric supercapacitors. Nanosci. Nanotech. Lett. 10, 741 (2018)
Article Google Scholar
M. Panapoy, A. Dankeaw, B. Ksapabutr, Electrical conductivity of PAN-based carbon nanofibers prepared by electrospinning method. Thammasat Int J. Sc. Tech. 13, 11 (2008)
Google Scholar
C. Hellert, J.L. Storck, T. Grothe, B. Kaltschmidt, A. Hütten, A. Ehrmann: Positioning and aligning electrospun PAN fibers by conductive and dielectric substrate patterns, in: Macromolecular Symposia, Macromol. Symposia, 395, 2000213 (2021).
S. Temesgen, M. Rennert, T. Tesfaye, M. Nase, Review on spinning of biopolymer fibers from starch. Polymers 13, 1121 (2021)
Article CAS Google Scholar
E. Boyraz, F. Yalcinkaya, Hydrophilic surface-modified PAN nanofibrous membranes for efficient oil-water emulsion separation. Polymers 13, 197 (2021)
Article CAS Google Scholar
T. Yang, H. Yang, S.J. Zhen, C.Z. Huang, Hydrogen-bond-mediated in situ fabrication of AgNPs/Agar/PAN electrospun nanofibers as reproducible SERS substrates. ACS Appl. Mater. Inter. 7, 1586 (2015)
Article CAS Google Scholar
M. Gao, L. Zeng, J. Nie, G. Ma, Polymer–metal–organic framework core–shell framework nanofibers via electrospinning and their gas adsorption activities. RSC Adv 6, 7078 (2016)
Article CAS Google Scholar
D. Potphode, M.S. Sayed, T.L. Tamang, J.-J. Shim, High-performance binder-free flower-like (Ni_{0. 66}Co_0.3Mn_0.04)₂(OH)₂(CO₃) array synthesized using ascorbic acid for supercapacitor applications. Chem. Eng. J 378, 122129 (2019)
Article CAS Google Scholar
G. Zhang, P. Qin, R. Nasser, S. Li, P. Chen, J. Song, Synthesis of Co(CO₃)_0.5(OH)/Ni₂ (CO₃)(OH)₂ nanobelts and their application in flexible all-solid-state asymmetric supercapacitor. Chem. Eng. J 387, 124029 (2020)
Article CAS Google Scholar
G. Yilmaz, C.F. Tan, Y.F. Lim, G.W. Ho, Pseudomorphic transformation of interpenetrated prussian blue analogs into defective nickel iron selenides for enhanced electrochemical and photo-electrochemical water splitting. Adv. Energy Mater. 9, 1802983 (2019)
Article Google Scholar
S. Ding, T. Zhu, J.S. Chen, Z. Wang, C. Yuan, X.W.D. Lou, Controlled synthesis of hierarchical NiO nanosheet hollow spheres with enhanced supercapacitive performance. J. Mater. Chem. 21, 6602 (2011)
Article CAS Google Scholar
A. Mansour, Characterization of β-Ni(OH)₂ by XPS. Surf. Sci. Spectra 3, 239 (1994)
Article CAS Google Scholar
N. Pauly, S. Tougaard, F. Yubero, Determination of the Cu 2p primary excitation spectra for Cu, Cu₂O and CuO. Surf. Sci. 620, 17 (2014)
Article CAS Google Scholar
R. Morent, N. De Geyter, C. Leys, L. Gengembre, E. Payen, Comparison between XPS-and FTIR-analysis of plasma-treated polypropylene film surfaces, Surface and Interface Analysis: An International Journal devoted to the development and application of techniques for the analysis of surfaces. Interfaces. Thin Films 40, 597 (2008)
CAS Google Scholar
L. Fen-rong, L. Wen, G. Hui-qing, L. Bao-qing, B. Zong-qing, H. Rui-sheng, XPS study on the change of carbon-containing groups and sulfur transformation on coal surface. J. Fuel Chem. Technol. 39, 81 (2011)
Article Google Scholar
D. Lee, N. Shinde, J.C. Ding, J. Fu, R.K. Sahoo, H.W. Lee, J.M. Yun, H.-C. Shin, K.H. Kim, Improvement of electrical performance by surface structure of Ni-material as a high-performance asymmetric supercapacitor electrode. Ceram. Inter. 46, 11189 (2020)
Article CAS Google Scholar
Q. Zhou, J. Huang, C. Li, Z. Lv, H. Zhu, G. Hu, Wrap** CuCo₂S₄ arrays on nickel foam with Ni₂(CO₃)(OH)₂ nanosheets as a high-performance faradaic electrode. New J. Chem. 43, 5904 (2019)
Article CAS Google Scholar
H. Yang, Effects of supercapacitor physics on its charge capacity. IEEE Trans. Power Electr. 34, 646 (2018)
Article Google Scholar
A.M. Patil, X. Yue, A. Yoshida, S. Li, X. Hao, A. Abudula, G. Guan, Redox-ambitious route to boost energy and capacity retention of pouch type asymmetric solid-state supercapacitor fabricated with graphene oxide-based battery-type electrodes. Appl. Mater. Today 19, 100563 (2020)
Article Google Scholar
J. Yan, Z. Fan, W. Sun, G. Ning, T. Wei, Q. Zhang, R. Zhang, L. Zhi, F. Wei, Advanced asymmetric supercapacitors based on Ni(OH) ₂/graphene and porous graphene electrodes with high energy density. Adv. Funct. Mater 22, 2632 (2012)
Article CAS Google Scholar
Y. Wang, B. Chang, D. Guan, K. Pei, Z. Chen, M. Yang, X. Dong, Preparation of nanospherical porous NiO by a hard template route and its supercapacitor application. Mater. Lett. 135, 172 (2014)
Article CAS Google Scholar
C. Wang, J. Xu, M.F. Yuen, J. Zhang, Y. Li, X. Chen, W. Zhang, Hierarchical composite electrodes of nickel oxide nanoflake 3D graphene for high-performance pseudocapacitors. Adv. Funct. Mater. 24, 6372 (2014)
Article CAS Google Scholar
G.S. Gund, D.P. Dubal, S.S. Shinde, C.D. Lokhande, Architectured morphologies of chemically prepared NiO/MWCNTs nanohybrid thin films for high performance supercapacitors. ACS Appl. Mater. Inter. 6, 3176 (2014)
Article CAS Google Scholar
Z. Li, M. Shao, L. Zhou, R. Zhang, C. Zhang, J. Han, M. Wei, D.G. Evans, X. Duan, A flexible all-solid-state micro-supercapacitor based on hierarchical CuO@ layered double hydroxide core–shell nanoarrays. Nano Energy 20, 294 (2016)
Article CAS Google Scholar
K. Krishnamoorthy, S.-J. Kim, Growth: Characterization and electrochemical properties of hierarchical CuO nanostructures for supercapacitor applications. Mater. Res. Bull. 48, 3136 (2013)
Article CAS Google Scholar
M.B. Gholivand, H. Heydari, A. Abdolmaleki, H. Hosseini, Nanostructured CuO/PANI composite as supercapacitor electrode material. Mater. Sci. Semicon. Proc. 30, 157 (2015)
Article CAS Google Scholar
S. Shinde, H. Yadav, G. Ghodake, A. Kadam, V. Kumbhar, J. Yang, K. Hwang, A. Jagadale, S. Kumar, D. Kim, Using chemical bath deposition to create nanosheet-like CuO electrodes for supercapacitor applications. Colloid Surf. B 181, 1004 (2019)
Article CAS Google Scholar
Y. Wang, C. Shen, L. Niu, R. Li, H. Guo, Y. Shi, C. Li, X. Liu, Y. Gong, Hydrothermal synthesis of CuCo₂O₄/CuO nanowire arrays and RGO/Fe₂O₃ composites for high-performance aqueous asymmetric supercapacitors. J. Mater. Chem. A 4, 9977 (2016)
Article CAS Google Scholar
Y. Feng, W. Liu, Y. Wang, W. Gao, J. Li, K. Liu, X. Wang, J. Jiang, Oxygen vacancies enhance supercapacitive performance of CuCo₂O₄ in high-energy-density asymmetric supercapacitors. J. Power Sources 458, 228005 (2020)
Article CAS Google Scholar
S.M. Pawar, B.S. Pawar, P.T. Babar, A.T.A. Ahmed, H.S. Chavan, Y. Jo, S. Cho, J. Kim, B. Hou, A.I. Inamdar, Nanoporous CuCo₂O₄ nanosheets as a highly efficient bifunctional electrode for supercapacitors and water oxidation catalysis. Appl. Surf. Sci 470, 360 (2019)
Article CAS Google Scholar
L. Abbasi, M. Arvand, Engineering hierarchical ultrathin CuCo₂O₄ nanosheets array on Ni foam by rapid electrodeposition method toward high-performance binder-free supercapacitors. Appl. Surf. Sci 445, 272 (2018)
Article CAS Google Scholar
A. Bera, A. Maitra, A.K. Das, L. Halder, S. Paria, S.K. Si, A. De, S. Ojha, B.B. Khatua, A quasi-solid-state asymmetric supercapacitor device based on honeycomb-like nickel–copper–carbonate–hydroxide as a positive and iron oxide as a negative electrode with superior electrochemical performances. ACS Appl. Electron. Mater 2, 177 (2020)
Article CAS Google Scholar
Q. Zhou, T. Wei, Z. Liu, L. Zhang, B. Yuan, Z. Fan, Nickel hexacyanoferrate on graphene sheets for high-performance asymmetric supercapacitors in neutral aqueous electrolyte. Electrochim. Acta 303, 40 (2019)
Article CAS Google Scholar
L. Zhang, H. Gong, Unravelling the correlation between nickel to copper ratio of binary oxides and their superior supercapacitor performance. Electrochim. Acta 234, 82 (2017)
Article CAS Google Scholar
S. Song, L. Zhang, H. Shi, Facile synthesis of three-dimensional nanostructured Ni(HCO₃)₂/(Cu_0.2Ni_0.8) O as high-performance pseudo-capacitance electrode. J. Alloy. Compd 763, 791 (2018)
Article CAS Google Scholar
S. Kumar, G. Saeed, L. Zhu, K.N. Hui, N.H. Kim, J.H. Lee, 0D to 3D carbon-based networks combined with pseudocapacitive electrode material for high energy density supercapacitor: A review. Chem. Eng. J 403, 126352 (2020)
Article Google Scholar
H.-G. Jung, N. Venugopal, B. Scrosati, Y.-K. Sun, A high energy and power density hybrid supercapacitor based on an advanced carbon-coated Li₄Ti₅O₁₂ electrode. J. Power Sources 221, 266 (2013)
Article CAS Google Scholar
Q. Qu, P. Zhang, B. Wang, Y. Chen, S. Tian, Y. Wu, R. Holze, Electrochemical performance of MnO₂ nanorods in neutral aqueous electrolytes as a cathode for asymmetric supercapacitors. J. Phys. Chem. C 113, 14020 (2009)
Article CAS Google Scholar
Y.-H. Lee, K.-H. Chang, C.-C. Hu, Differentiate the pseudocapacitance and double-layer capacitance contributions for nitrogen-doped reduced graphene oxide in acidic and alkaline electrolytes. J. Power Sources 227, 300 (2013)
Article CAS Google Scholar
J. Huang, P. Xu, D. Cao, X. Zhou, S. Yang, Y. Li, G. Wang, Asymmetric supercapacitors based on β-Ni(OH)₂ nanosheets and activated carbon with high energy density. J. Power Sources 246, 371 (2014)
Article CAS Google Scholar

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Acknowledgments

This study was supported by the Global Frontier Hybrid Interface Materials (GFHIM) program of the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2013M3A6B1078874). The authors are thankful to the University of Cologne for infrastructural support and for hosting Dr. Damin Lee.

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Department of Chemistry, Inorganic and Materials Chemistry, Cologne University, 50939, Cologne, Germany
Damin Lee, Anjneya Verma, Khan Lê, Thomas Fischer & Sanjay Mathur
Global Frontier R&D Center for Hybrid Interface Materials, Pusan National University, San 30 Jangjeon-dong, Geumjeong-gu, Pusan, 609-735, Republic of Korea
Damin Lee & Kwang Ho Kim
School of Materials Science and Engineering, Pusan National University, San 30 Jangjeon-dong, Geumjeong-gu, Pusan, 609-735, Republic of Korea
Kwang Ho Kim

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Damin Lee
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Anjneya Verma
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Khan Lê
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Thomas Fischer
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Kwang Ho Kim
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Sanjay Mathur
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Lee, D., Verma, A., Lê, K. et al. Hybrid nanostructured PAN@NiCu(CO₃)(OH)₂ composite for flexible high-performance supercapacitors. Journal of Materials Research 37, 304–318 (2022). https://doi.org/10.1557/s43578-021-00349-5

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Received: 02 June 2021
Accepted: 11 August 2021
Published: 22 October 2021
Issue Date: 14 January 2022
DOI: https://doi.org/10.1557/s43578-021-00349-5

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