Three-dimensional hierarchical and interconnected honeycomb-like porous carbon derived from pomelo peel for high performance supercapacitors

https://doi.org/10.1016/j.jssc.2017.07.033Get rights and content

Highlights

  • Pomelo peel was utilized to fabricate heteroatom-functionalized porous carbonaceous materials.

  • The as-prepared carbon materials contains 3D hierarchical and interconnected honeycomb-like structure.

  • The obtained carbon material and symmetric device exhibits superior electrochemical performances for supercapacitor.

Abstract

The urgent need for sustainable development of human society has forced material scientists to explore novel materials starting from cheap natural precursors for next-generation energy storage devices by using environmentally friendly strategies. In this work, heteroatom-functionalized porous carbonaceous materials with 3D hierarchical and interconnected honeycomb-like structure have been successfully synthesized by using waste biomass pomelo peel as raw material through the combination of hydrothermal carbonization and followed KOH activation procedure. Benefiting from the unique honeycomb-like structure and high specific surface area, the as-obtained carbon material exhibits satisfactory capacitive behavior: 374 F/g at 0.1 A/g; excellent cycling stability of 92.5% capacitance retention over continuous 5000 cycles. More importantly, the as-assembled symmetric supercapacitors based on as-prepared electrode material can deliver high gravimetric and volumetric energy density of 20 W h/kg and 18.7 W h/L in 6 M KOH, respectively, as well as outstanding cycling stability. The obtained results demonstrate the possibility for taking full advantage of sustainable and large scale advanced carbon materials by choosing waste biomass, particularly the pomelo peel as a raw material.

Graphical abstract

3D hierarchical and interconnected honeycomb-like porous carbonaceous materials (HPGC) from waste biomass (pomelo peels) were successfully prepared through the combination of hydrothermal carbonization and followed KOH activation procedure. The as-obtained carbon material exhibits satisfactory capacitive behavior. The obtained results demonstrate the possibility for taking full advantage of sustainable carbon materials by choosing biomass waste provided by nature as raw materials.

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Introduction

With the increasing depletion of fossil fuels and environmental pollution, the exploration of new energy and high energy utilization efficiency is one of the most important issues faced by national governments in the twenty-first century. Energy storage, which is an intermediate step to the efficient utilization of energy, has attracted large-scale concern and increasing research interest [1]. Supercapacitor is a new concept of environmentally friendly electrochemical energy storage systems. Combined with superior specific capacitance, exceptionally long cycle life and high power density, supercapacitors can bridge the energy/power gap between traditional batteries/fuel cells and capacitors [2], [3], [4]. An ideal supercapacitor, whose cycle life is typically measured in hundreds of thousands to millions of cycles, can deliver high power delivery>10 kW/kg in few seconds. The electrochemical performances can be successfully increased by the excellent combination of the adopted electrode materials with a proper electrolyte [5], [6] In recent years, the main electrode materials — carbon materials have been deeply studied with the widening of the application areas of supercapacitors, because of their high surface area, chemical stability and low cost [7], [8]

As a kind of environmental friendly renewable resource, biomass, can be a qualified raw material for the synthesis of valuable carbon [9]. At present, hydrothermal carbonization (HTC) process has been turned into a powerful and efficient synthetic method for the production of functional carbonaceous materials from biomass [10], [11]. This method could increase the dehydration, decomposition, condensation and polymerization of carbohydrate or cellulose [12]. Generally speaking, the prepared solid hydrochars possess stable physico-chemical properties and abundant oxygen-containing functional groups [13]. As a result, the hydrochar materials can be excellent precursors for synthesizing hierarchical three-dimensional and interconnected porous carbonaceous materials. Currently, 3D hierarchical and interconnected porous carbonaceous nanomaterials have attracted more and more attention due to 3D porous structures of active materials can provide large surface area, well-defined pathways to electrolyte access and mechanical stability for efficient supercapacitor electrodes. Therefore, tremendous effort has been made to synthesize nanoporous carbon materials via a variety of activation procedures. Wu et al. prepared 3D interconnected honeycomb-like porous carbon foam by carbonizing alkali-treated wheat flour under nitrogen atmosphere at 700 °C [14]. Long et al. had synthesized three-dimensional densely porous graphene-like carbon materials through hydrothermal treatment of fungus and subsequent carbonization/activation process under N2 at 800 °C. The as-prepared material shows a high volumetric capacitance of 360 F/cm3 [15]. Moreover, Long et al. also prepared functionalized porous carbons with 3D interconnected pore structure through a facile thermal-treatment of KOH-soaked soybeans [16]. Therefore, the effective combination of HTC and heat-treatment/KOH activation may take full advantage of the unique structure of sustainable biomass and achieve high performance electrode materials. On account of the structural interconnectivities, 3D carbonaceous nanostructures not only possess hierarchical porous channels which provides continuous electron pathway, but also can allow the electrolyte to penetrate the electrode material and maintain better structural mechanical stability.

In this work we demonstrate a simple and economic strategy for the preparation of 3D hierarchical and interconnected honeycomb-like porous graphitic carbonaceous materials (HPGC) from waste biomass (pomelo peels). Cellulose, hemicellulose, polysaccharides and other organic components of pomelo peels could be transformed into hydrochars and carbon spheres by the HTC procedure. Hydrothermal carbonization can solve the problem that the carbonaceous material prepared from biomass contains certain impurities and high ash content. On the other hand, the hydrochar precursors with their networks of uniformly distributed oxygen within the structure can be efficiently turned into hierarchical and interconnected porous carbons with high specific surface area by subsequent simultaneous heat-treatment/KOH activation. Compared with previous work reported in the literature [17], the combination of HTC and heat-treatment/KOH activation can produce interconnected honeycomb-like porous carbon foam with satisfying electrochemical performances. Therefore, this facile route is beneficial for large-scale production of biomass-derived carbon materials for energy storage devices.

Section snippets

Results and discussion

The main process of preparing heteroatom-functionalized hierarchical porous carbon carbonaceous materials derived from pomelo peel is schematically illustrated in Scheme S1. The detailed fabrication processes are explained in detail in the Experimental Section (Supporting information). In the first HTC procedure, organic components (cellulose, hemicellulose, polysaccharides) in the pomelo peel are decomposed, dehydrated, condensed and polymerized to form thermodynamically stable hydrochar with

Conclusion

To sum up, heteroatom-functionalized porous carbonaceous materials with 3D hierarchical and interconnected honeycomb-like structure have been successfully synthesized by using waste biomass pomelo peel as raw material through the combination of hydrothermal carbonization and followed KOH activation procedure. Benefiting from the unique honeycomb-like structure, plenty of stable and pseudocapacitive functionalities doping and interconnected porous structure with high surface area, the

Acknowledgments

This work was supported by National Natural Science Foundation of China (51402065), Heilongjiang Postdoctoral Fund (LBH-Z12004), China Postdoctoral Science Foundation Grant (2013M531006).

References (44)

  • C. Liu et al.

    Advanced materials for energy storage

    Adv. Mater.

    (2010)
  • Z.N. Yu et al.

    Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions

    Energy Environ. Sci.

    (2015)
  • P. Simon et al.

    Materials for electrochemical capacitors

    Nat. Mater.

    (2008)
  • P. Simon et al.

    Capacitive energy storage in nanostructured carbon–electrolyte systems

    Acc. Chem. Res.

    (2013)
  • J.R. Miller et al.

    Electrochemical capacitors: challenges and opportunities for real-world applications

    Electrochem. Soc. Interface

    (2008)
  • G.P. Wang et al.

    A review of electrode materials for electrochemical supercapacitors

    Chem. Soc. Rev.

    (2012)
  • H.P. Li et al.

    Composite of hierarchical interpenetrating 3D hollow carbon skeleton from lotus pollen and hexagonal MnO2 nanosheets for high-performance supercapacitors

    J. Mater. Chem. A

    (2015)
  • C. Falco et al.

    Hydrothermal carbons from hemicellulose-derived aqueous hydrolysis products as electrode materials for supercapacitors

    ChemSusChem

    (2013)
  • R.J. White et al.

    A sustainable synthesis of nitrogen-doped carbon aerogels

    Green Chem.

    (2011)
  • B. Hu et al.

    Engineering carbon materials from the hydrothermal carbonization process of biomass

    Adv. Mater.

    (2010)
  • M. Sevilla et al.

    Chemical and structural properties of carbonaceous products obtained by hydrothermal carbonization of saccharides

    Chem. – Eur. J.

    (2009)
  • C. Peng et al.

    Oxygen-enriched activated carbons from pomelo peel in high energy density supercapacitors

    RSC Adv.

    (2014)
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    Jingyuan Liu and Hongpeng Li contributed equally to this work.

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