Design and fabrication of hierarchical heterostructure CuCo2O4@PPy based asymmetric device with ultra high capacitance and attractive cycling performance
Graphical abstract
Extremely, the optimized CuCo2O4@PPy//AC ACS cell can be cycled reversibly in a wide voltage region as high as 1.4 V and exhibits a specific capacitance of 91 Fg−1 even at a high current density of 20 Ag-1 with a maximum energy density of 52 Wh kg−1.
Introduction
Increase of global warming and exhaustion of fossil fuels are major driving forces leads to develop novel energy storage devices with enhanced energy transformation abilities at cheaper costs. Amid different energy conversion and storage devices, fuel cells, batteries, and supercapacitors are few gain significance [1]. Electric vehicle is one of such instruments developed in view of protecting the environment by eco-friendly mechanism, designed with the combination of versatile electronic equipment, high performance electrical energy storage devices. Arrival of these fascinating instruments boosts the demand of innovative storage devices such as batteries and supercapacitors, etc. with enhanced performances [2,3]. Nowadays, transition metal oxides such as Co3O4 [4,5], CuO [6], MnO2 [7,8], RuO2 [9,10] have been extensively used for developing with improved electrochemical pseudocapacitance, which is found to be a supplement to the double-layer capacitance. Among them, cobalt-based oxides are noteworthing electrode materials due to their high theoretical specific capacity and outstanding cycling stability [11,12]. Recently, CuCo2O4 has also been widely accepted as possible candidates to become supercapacitors by virtue of its promising capacitive behavior. It is not only inexpensive and eco-friendly, but also electrochemically active. It also broadly investigated and found suitable an anode material in supercapacitors, Li–air batteries and Li–ion batteries displaying excellent storage capabilities, demonstrates their promising capacitive behavior by the redox reaction and cation intercalation/deintercalation [13,14].
Earlier works acknowledged the application potential of CuCo2O4 electrode as a capacitor [15] and reported its nanodimensional enhancement in the magnitude of areal capacitance as nanowires and nanobelts were 338 F g-1 at 1 A g-1 and 0.6 F cm−2 at 2 A g-1 [16]. Recently, CuCo2O4 nanobelts were successfully synthesized and the areal capacitance of 2.42 Fcm−2 was obtained [17]. Pengju Liang et al. [18] have synthesized a novel binary composite consisting of CuCo2O4 and reduced graphene oxide via a self assembly approach. CuCo2O4 in the composite achieves a high specific capacitance of 978 Fg−1 (or 136 mAhg−1) at 3 Ag−1. Xiaowei Xu et al. [19] have reported high performance electrochemical properties of 3D mesoporous flower-like CuCo2S4/CuCo2O4 heterostructure. The prepared electrode showed outstanding electrochemical properties of specific capacity (599.9 Cg−1), excellent cycling stability and high rate capability. It reveals the need of effort still required for pursuing more outstanding electrochemical performance of CuCo2O4. Recent development exhibits the prospect of improvements in electrochemical activity cobalt spinel based metal oxides by incorporating activated carbon. For example, S. Kamari Kaverlavani et. al [20] have fabricated graphene-wrapped CuCo2O4 hollow spheres electrodes with a 3D composite network, a high surface area of 106.2 m2 g-1. This electrode exhibits excellent electrochemical performance with an ultrahigh specific capacitance of 1813 Fg-1 at 2 Ag-1 (3.63 Fcm−2 at 4 mAcm2) and a significant rate capability of 63 % capacitance retention even at an ultrafast rate of 120 mA cm2. Qian Li et. al [21] fabricated asymmetric supercapacitor, which is consists of NiCo2O4/RGO composite and activated carbon as positive electrode and negative electrode, respectively. The device achieves a high energy density of 57 Wh kg−1 at a power density of 375 W kg−1 in a working potential of 0–1.5 V. Tae Hoon Ko et. al [22] synthesized polyprrole (PPy)-decorated hierarchical NiCo2O4 nanoneedles was grown on highly conductive carbon fiber paper (CFP) for high performance asymmetric supercapacitor. The fabricated asymmetric device delivered a specific capacitance of 118.6 Fg-1 at a current density of 1.0 Ag−1 with a maximum energy density of 40.81 WhKg−1 (at a power density of 738.27 WKg−1) and maximum power density of 3746.77 WKg−1 (at an energy density of 13.53 WhKg−1). Polypyrrole (PPy) is a well-known conducting polymer with good conductivity and stability can be prepared easily [[23], [24], [25]]. Thus the capacitance ability of cobaltite can possibly be enhanced by incorporating suitable element such as PPy. In the present work, heterostructure of CuCo2O4 is proposed to device with an assistance of PPy using Ni foam employing hydrothermal method. Furthermore, we fabricated an asymmetric supercapacitor with CuCo2O4/PPy heterostructure as a positive electrode and activated carbon (AC) as a negative electrode in 0.2 M KOH electrolyte. The as fabricated device displayed a high energy density of 52 Wh kg-1 at a power density of 748 Wkg-1, and excellent cycling stability.
Section snippets
Materials
All reagents used in this study were analytical grade used without further purification. Cobalt nitrate [Co(NO3)2], cupric nitrate [Cu(NO3)2], urea (CO(NH2)2) were obtained from Sigma-Aldrich. Monomer and sodium p-Toluenesulfonate (p-TSS, C7H7SO3Na) and ammonium persulfate [(NH4)2S2O8] were purchased from Alfa Aesar.
Synthesis of Urchin like nanorods CuCo2O4/NF
Before synthesis, a piece of Ni foam (1 cm x 3 cm) was vigilantly cleaned with intense HCl solution (∼ 37 wt%) in an ultrasound bath for 2 min in order to remove NiO layer on the
XRD analysis
Fig. 1 b) shows the powder XRD pattern of pure Ni foam, CCN and CCNP samples respectively. In pure Ni foam showed three prominent diffraction peaks, which were established to be associated to nickel foam (JCPDS card No. 04-0850). The prominent peaks of CuCo2O4 is located at 2θ value of 18.67, 31.56, 36.48, 38.21, and 64.52°, this could be indexed as (111), (220), (311), (222), and (440) are typical cubic structure with the space group of Fd3m and the results are matched well with the standard
Conclusions
In summary, we have successfully fabricated heterostructure of CuCo2O4/NF@PPy (CCNP) by hydrothermal route using Ni foam substrate. The prepared heterostructure CuCo2O4/NF@PPy hybrid electrode exhibits excellent electrochemical properties with a huge specific capacitance of 2272 Fg−1 at 2 Ag−1. Furthermore, asymmetric device (CuCo2O4/NF@PPy and AC) also been fabricated. The device exhibits a high energy density of 52 Whkg−1 at a power density of 748 Wkg−1 and still retains 22 Whkg−1 even at a
Declaration of Competing Interest
The authors declare no conflicts of interest.
Acknowledgments
This research was financially supported by the Department of Science and Technology – Science and Engineering Research Board, New Delhi, India (DST-SERB-EMR; File no: EMR/2016/007280). We also acknowledge Chikkaiah Naicker College (Affiliated to Bharathiar University), Erode, Tamilnadu, India for providing necessary facilities and support to carry out the research.
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