Carbyne-enriched carbon anchored on nickel foam: A novel binder-free electrode for supercapacitor application

https://doi.org/10.1016/j.jcis.2019.08.055Get rights and content

Abstract

Carbon- and carbon derivatives are widely employed as efficient electrode materials for supercapacitor applications. Herein, we demonstrate a cost-effective dip-coating process followed by dehydrohalogenation of PVDF-Ni for the preparation of carbyne enriched carbon anchored on nickel (CEC-Ni) as high-performance electrode material. The removal of halogens in the prepared CEC-Ni were widely characterized using XRD, XPS, Laser Raman, and FT-IR analysis. The occurrence of carbon-carbon vibration in the prepared CEC-Ni foam was confirmed using FT-IR spectroscopy. Laser Raman analysis confirms that the CEC-Ni foam contains both sp and sp2 hybridized carbon. The electrochemical properties of prepared carbyne enriched carbon anchored on nickel foam electrode (CEC-NiE) showed an ideal capacitive properties and delivered a maximum specific capacitance of about 106.12 F g−1 with excellent cyclic retention. Furthermore, the mechanism of charge-storage in the CEC-NiE was analyzed using Dunn’s method. In additon, the asymmetric supercapacitor device was fabricated using CEC-NiE as positive and rGO as negative electrode achieved a remarkable energy density of 33.57 Wh Kg−1 with a maximal power density of 14825.71 W Kg−1. These results suggested that the facile preparation of CEC-NiE could be a promising and effective electrode material for future energy storage application.

Introduction

Evolving technological innovations in the electronic field urge the need for renewable energy sources over fossil fuels to meet energy demand [1]. To overcome this issue, significant interest in novel materials have been put forth. In this regard, carbon and carbon family is a promising candidate due to their peculiar properties in the arena of energy storage and conversion system [2], [3], [4], [5], [6]. Among various electrochemical storage system, supercapacitor (SCs) outnumbers in virtue upon comparing with conventional batteries in terms of long cycle life, comparable energy, and high-power density, environmentally friendly and maintenance-free system [7], [8], [9], [10], [11]. The SCs can be classified into two types based on the charge storage mechanism, i.e., electrical double-layer capacitors (EDLC) and pseudocapacitors (intercalation/deintercalation). The former stores charges via adsorption/desorption of electrolyte ions at the electrode/electrolyte interface, whereas the latter stores charge via fast faradic reactions occur at the surface of the electrode materials [12], [13], [14], [15], [16], [17]. Usually, the carbon material is used for the electric double-layer capacitor while transition metal oxide, transition metal chalcogenides, and conducting polymer are used as redox capacitor [18]. In spite of having fast response time, the carbon-based materials suffer from low intrinsic capacitance [19]. In addition, redox capacitors lack efficient performance due to their insulating behavior, despite possessing high energy and power density [20]. To resolve the aforementioned limitations, the synthesized material should possess both carbon and redox capacitive material. This can be achieved by synthesizing the carbon material by a chemical treatment that will enrich the surface functionalities [21], [22], [23], [24]. The carbon based material is mostly used as electrode material for SCs application owing to their cost-effective, outstanding conductivity, less weight, and eco-friendly in nature. Additional it possess various form of structures (powder, onion, fiber, aerogel, and so on), an amusing variety of dimensionality from 0 to 3D (carbon dot, CNT, Graphene, and graphite), modest processing ability and relatively low cost making the researcher to focus on the carbon and carbon-based derivatives as an attracting electrode material for SCs application [25], [26], [27], [28]. Even though there is lots of carbon-based material as an electrode for SCs application, still researcher is focusing on the new novel kind of stuff for supercapacitor application due to the evolution of technology.

In this work, we reported CEC-Ni as a binder free electrode for SCs application due to its fascinating physio-chemical properties. The valence electron of carbyne possesses sp, and sp2 hybridized atom, which is different from graphene and diamond-like carbon [29]. Generally, carbyne is a linear chain of ‘n’ number of carbon atom composed of either single and triple bond (single bondCtriple bondCsingle bond)n or consecutive double bond (double bondCdouble bondCdouble bond)n over the liner chain [30], [31]. The theoretical study by Liu et al. proposed that carbyne possesses high strength, high flexibility, and chemically stable in nature [32]. Wesley A. Chalifoux et al. experimental result confirms that carbyne possesses the bandgap of ∼2.56 eV [33]. This outstanding property of carbyne opens the gateway towards the various application. Bettini et al. inspected the use of carbyne-rich carbon films (fabricated by low kinetic energy deposition method) as an electrode material for supercapacitors application [34]. The work by Bettini et al. validates that prospective studies are important for improving the electrochemical properties of carbyne which can be attained either by changing the synthesis method, or removing the binder from the electrode, or applying both faradic and nonfaradic mechanism on charge storage and so on. Therefore in this report, we prepared the novel binder free CEC-Ni foam via extracting the halogen in the PVDF-Ni foam using chemical dehydrohalogenation process and examined its use as a potential binder free electrode for SCs application.

Section snippets

Preparation of CEC-Ni foam:

At first 1 g of PVDF is liquified in 10 ml of N-Methyl-2-Pyrrolidone (NMP) solution under constant stirring until homogenous transparent solution is achieved [3], [35]. An inexpensive and more reliable technique of dip and coat process method is employed for the coating of PVDF on the Ni foam. The dip and coat process were continued for 6 cycles and dried in an electric oven at 70 °C for 12 h. Then the PVDF-Ni foam is converted into carbyne-enriched carbon-Ni via one-step extraction of halogen

Results and discussion

In this work, binder-free carbyne-enriched carbon on nickel foam (CEC-Ni) is prepared via extracting the halogen in the PVDF-Ni using chemical dehydrohalogenation process. The mechanism behind the formation of carbyne-enriched carbon on the surface of nickel foam using dehydrohalogenation process is explained in detail in the electronic supplementary information (ESI) [37]. Fig. 1 displays the graphical representation of the preparation of binder free CEC-Ni foam using chemical

Conclusions

In conclusion, we used a simple and cost-effective dip and dry process for the fabrication of high-performance electrode for next generation supercapacitor application. The CEC-Ni were prepared via extraction of halogens from the PVDF-Ni using chemical dehydrohalogenation process. In-depth physio-chemical characterization such as XRD, XPS, Laser Raman spectroscopy, FT-IR, and FE-SEM with elemental mapping was analyzed to confirm the extraction of halogen from the PVDF-Ni foam using

Acknowledgment

This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (2018R1A4A1025998, 2019R1A2C3009747).

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