Novel porous carbon electrode derived from hypercross-linked polymer of poly(divinylbenzene-co-vinyl benzyl chloride) for supercapacitor applications

doi:10.1016/j.est.2021.103287

Journal of Energy Storage

Volume 43, November 2021, 103287

https://doi.org/10.1016/j.est.2021.103287 Get rights and content

Highlights

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P(DVB:VBC) was used as the starting material to prepare high-performance porous carbon via Friedel-Crafts alkylation followed by carbonization.
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The porous carbon (HCP-800) exhibited high surface area of 1027 m² g⁻¹ with the abundant micropores
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The assembled symmetric supercapacitor made of HCP-800 exhibited highest specific capacitance of 145 F g⁻¹ at 1 A g⁻¹.
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The assembled symmetric supercapacitor retained 94% of its initial capacitance over 5000 GCD cycles at 5 A g⁻¹ current density suggests a good cyclic stability.

Abstract

In the present study, pores enriched high surface area of carbon electrode obtained from hypercross-linked polymer of poly(divinylbenzene-co-vinylbenzyl chloride) [P(DVB:VBC)] for supercapacitor application. First, hypercross-linking reaction was carried out in [P(DVB:VBC)] via. simple Friedel-Crafts alkylation method (HCP) followed by pyrolysis at 800 °C (HCP-800). The surface morphology of the synthesized HCP and HCP-800 materials was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) technique. HCP-800 showed a remarkable surface area of 1027 m² g⁻¹ with the abundance of micropores. In addition, the oxidation state of the porous carbon was assessed by x-ray photo electron spectroscopy (XPS). In a three-electrode and symmetric two-electrode configurations, electrodes exhibited a supreme specific capacitance of 272 and 145 F g⁻¹ in aqueous electrolyte, respectively. Specific energy of 39.47 Wh kg⁻¹ at specific power of 699.96 W kg⁻¹ is yielded from the symmetric supercapacitor device (SSCD). Furthermore, SSCD retains more than 94% of its residual capacitance after 5000 GCD cycles at a current density of 5 A g⁻¹ suggests a good cyclic stability.

Graphical abstract

Introduction

Recently, supercapacitors (SCs) or electrochemical capacitors (ECs) have been gained more interests among the researchers owing to its high specific power, rapid charge-discharge rate and extended durability [1], [2], [3], [4]. In general, SCs can be categorized into two types on their charge storage principal basis, electric double-layer capacitor (EDLC) and pseudocapacitor (PC). In which, EDLC stores charge electrostatically at the electrode/electrolyte interface whereas PC stores charge by reversible faradaic redox reactions [5,6]. Most suitable materials for PCs are manganese oxide (MnO₂) [7], [8], [9] which provides a comparatively high capacitance and high specific energy. However, the main drawback of MnO₂ is the low conductivity, which significantly hinders to attain high theoretical specific capacitance value.

Different types of carbon based materials have been studied thoroughly for EDLC electrodes for supercapacitor applications, such as graphene [10,11], carbon nanotubes (CNTs) [12], activated carbon, porous carbon [13], [14], [15], [16], [17], carbon derived from biomass [18], [19], [20], [21] and carbon nanofibers (CNFs), etc. [22,23]. Due to its high specific surface area, hierarchical pores (micro/mesopores and macropores), excellent electrical conductivity and long cyclic life [24,25]. Though, the above-mentioned carbon-based materials required either chemical activation or physical activation to boost the surface area and porous structure. Recently, hypercross-linked polymers (HCPs) derived porous carbon electrode material has received more attention in supercapacitor applications. However, HCP electrode material exhibits poor capacitance values as compared with the other carbon-based electrode materials. But porous carbon derived from HCPs not required either physical or chemical activation to increase the specific surface area. Because typically HCPs displayed surface area of approximately 500 to 1400 m² g⁻¹. Additionally, HCP has interconnected hierarchical pores in its structure. This is one of the most influential criteria for supercapacitor electrodes [26]. Moreover, the synthesis technique is very simple and facile.

Herein, we reported an HCP-derived porous carbon via a simple two-step method (Scheme 1). First, poly(divinylbenzene-co-vinylbenzyl chloride) [P(DVB:VBC)] precursor was subjected into hypercross-linking reaction by using Friedel-Crafts catalyst, FeCl₃. Then, the prepared HCP was carbonized at 800 °C under an inert atmosphere to yield pyrolyzed HCP (HCP-800). The obtained HCP-800 has a huge surface area and hierarchical porous structure with ample micro/macropores. Benefitting from the porous structure and extraordinary surface area, when employed as electrode material in SCs, the HCP-800 displays an extreme capacitance value of 272 F g⁻¹ at 1 A g⁻¹ in a three-electrode setup. The constructed symmetric supercapacitor device (SSCD) of HCP-800 with a broad voltage range of 1.4 V, delivered the highest capacitance of 145 F g⁻¹ at 1 A g⁻¹. Additionally, specific energy as high as 39.47 Wh kg⁻¹ is attained at a specific power of 699.96 W kg⁻¹ in 3 M KOH. Furthermore, the SSCD had favorable cyclic life with 94.21% capacitance retention over 5000 cycles. These findings suggest that the HCP-800 with a unique porous structure to be a prominent electrode material for supercapacitors.

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Section snippets

Materials

Poly(divinylbenzene-co-vinylbenzyl chloride) [P(DVB:VBC)] beads, Polyvinylidene fluoride (PVDF), N-methyl-2-pyrrolidone (NMP), and acetylene black (AB) were purchased from Sigma Aldrich, USA. Ferric chloride (FeCl₃), 1, 2-dichloroethane (1, 2-DCE), acetone, and concentrated HCl were procured from Samchun chemicals, South Korea. All the experiments were carried out using deionized water.

Synthesis of HCP from poly(divinylbenzene-co-vinylbenzyl chloride)

The hyper-crosslinking reaction was executed using the below methodology. In brief, 1 g of P(DVB:VBC) was

Results and discussions

The FT-IR spectrum of the P(DVB:VBC) (precursor), HCP, and HCP-800 were shown in Fig. 1(a). From the P(DVB:VBC) spectrum, the peak appear in the region of 700–850 cm⁻¹ is due to C-Cl stretching, and 1265 cm⁻¹ is assigned to CH₂Cl wagging. The peak appears at around 1601 cm⁻¹ is due to aromatic C=C stretching. After the hypercross-linked polymerization reaction, the broad peak at 3500 cm⁻¹ is owing to the –OH stretch of methanol adsorbed in the polymer matrix. It is not owing to -OH stretch of

Conclusions

In summary, the HCP-derived porous carbon electrode was successfully prepared from P(DVB:VBC) and evaluated its performance in supercapacitor applications. The obtained HCP-800 showed a high specific surface area of 1027 m² g⁻¹, hierarchical pore architectures, and an appropriate degree of graphitization. The HCP-800 electrode shows a high specific capacitance of 272 F g⁻¹ at 1 A g⁻¹ in a three-electrode configuration. The specific energy of the HCP-800 based SSCD with 3 M KOH as electrolyte

CRediT authorship contribution statement

Insu Kim: Data curation, Writing – original draft. Rajangam Vinodh: Data curation, Writing – original draft. Chandu V. V. Muralee Gopi: Conceptualization, Methodology. Hee-Je Kim: Conceptualization, Methodology. Rajendran Suresh Babu: Software, Validation, Writing – review & editing. Chinnadurai Deviprasath: Software, Validation, Writing – review & editing. Mani Devendiran: Software, Validation, Writing – review & editing. Sungshin Kim: Supervision, Visualization, Investigation.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgment

The authors gratefully acknowledge the financial support from BK21 Plus Creative Human Resource Education and Research Programs for ICT Convergence in the 4th Industrial Revolution, Pusan National University, Busan, South Korea.

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Novel porous carbon electrode derived from hypercross-linked polymer of poly(divinylbenzene-co-vinyl benzyl chloride) for supercapacitor applications

Highlights

Abstract

Graphical abstract

Introduction

Access through your organization

Section snippets

Materials

Synthesis of HCP from poly(divinylbenzene-co-vinylbenzyl chloride)

Results and discussions

Conclusions

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgment

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