A zinc ion hybrid capacitor based on sharpened pencil-like hierarchically porous carbon derived from metal–organic framework

https://doi.org/10.1016/j.cej.2021.131071Get rights and content

Highlights

  • A sharpened pencil-like hierarchically porous carbon (MPC) is prepared by using the MOFs as precursor/template.

  • The unique structural merits endow the hierarchically porous carbon with superior electrochemical performances.

  • A novel ZIHC device is constructed with high energy/power density and excellent cyclic stability.

Abstract

Aqueous zinc ion hybrid capacitors (ZIHCs) are an emerging class of energy storage devices with the merits of high-energy-power density, low cost and high safety. But the energy density still is behind the expectation due to the low voltage output and small specific capacitance. Seeking high performance capacitive-type carbon material are the one choice to capture these challenges. Herein, a high performance ZIHC device in aqueous electrolyte was assembled by using a sharpened pencil-like hierarchically porous carbon rod derived from the metal–organic framework. Thanks to the high specific surface area, fairish pore size distribution and rich oxygen-containing functional groups of carbon cathode, the excellent specific capacitance and high energy density were demonstrated. The assembled ZIHC device could achieve a high energy density of 130.1 W h kg−1 at power output of 180.3 W kg−1 under a relatively wide operation voltage of 0–1.8 V, and remain 59 W h kg−1 even at high power density of 7.8 kW kg−1. Meanwhile, this device also exhibited an excellent cycling life up to 10 000 cycles at 10 A g−1 with capacity retention of 96.7%. This research provides a new idea for the application of MOF-derived carbon materials in zinc ion hybrid capacitors.

Introduction

With the development of portable electronic equipment and electric vehicles, the ever-increasing requirement for both high energy and high power densities has promoted the search of new efficient energy storage technologies and devices [1], [2], [3]. Among of these, lithium-ion batteries (LIBs) are considered to be one of the most promising electrochemical energy storage devices due to their excellent energy density [4], [5], [6]. But the limited power output of LIBs is far behind the practical application demands [7], [8]. Supercapacitors, as another important energy storage device, are famous by its high power density and excellent cycle life span. However, the low energy density still restricts their widespread applications [9], [10]. By contrast, metal-ion hybrid capacitors, which integrate the high energy density of secondary rechargeable batteries and the high power output of supercapacitors, have sprung up and are considered as promising candidates for next-generation energy storage devices [11], [12], [13]. In recent years, lithium-ion hybrid capacitors (LIHCs) [14], [15], sodium ion hybrid capacitors (SIHCs) [16], [13] and potassium ion hybrid capacitors (PIHCs) [11], [17] have been extensively studied and significant advances have been received. However, most metal ion hybrid capacitors are assembled in organic electrolyte, that can cause the environmental impact and safety issues. In terms of these concerns, aqueous energy storage technologies and devices are the promising candidates due to the better safety, high ionic conductivity, lower toxicity and low cost contributed by aqueous electrolyte. Among various systems in aqueous electrolyte, zinc-based energy storage technology has been received extensive attentions due to the distinctive features of metallic zinc [18], [19], [20]. Metallic zinc has high theoretical capacity (820 mA h g−1), relatively low redox potential (-0.76 V vs. the standard hydrogen electrode), low price, non-toxicity, and good compatibility in aqueous [21]. Zinc ion hybrid capacitors (ZIHCs), featuring both the high energy density and the high power output due to integrating the battery-type Zn anode and capacitive-type carbon cathode in one device, are one of the most promising energy storage device. Recently, increasing research efforts have been devoted to developing the electrode materials of ZIHCs [22]. For example, Li et al. [23] used porous carbon derived from pencil sharpening as the electrode material to construct a ZIHC device with high energy density of 140.7 W h kg−1 (136.1 W kg−1). Yin et al. [24] invented a ZIHC with excellent performance based on an oxygen-rich porous carbon cathode, which could provide a maximum energy density of 104.8 W h kg−1 (58 W kg−1). Due to the limited charge storage capacitance of carbon electrode based on physical adsorption/desorption energy storage mechanism, however, the energy density of ZIHCs still has a room to improve. It can be found from these research that in order to improve the performance of ZIHC, an effective method is to develop carbon materials with stable structure, high specific surface area, suitable pore size distribution and heteroatom doping.

Metal-organic frameworks (MOFs) are a new class of porous materials with periodic network structure formed by self-assembly of multidentate organic ligands and metal ions. Due to its unique pore structure, large specific surface area and structural controllability, MOFs and MOFs-derived materials have been widely used in electrochemical energy storage [25], [26]. Specifically, MOF-derived nanoporous carbon materials largely retain the morphological characteristics of the precursor, have a unique hierarchical porous structure, could provide more active sites for ion adsorption, and shorten the diffusion path of electrolyte ions, showing excellent electrochemical performance [27]. Therefore, the application of MOF-derived nanoporous carbon materials for construction of ZIHCs should have a great potential.

Herein, a new type of sharpened pencil-like nanoporous carbon (MPC) is achieved by using metal–organic framework (MIL-47) as precursor combing the chemical activation method (Fig. 1). Using this MPC as cathode material, a high performance ZIHC device is assembled benefiting from the merits of its high specific surface area, hierarchically porous structure and rich oxygen-containing functional groups. As expected, the assembled ZIHC device could deliver an impressive specific capacitance of 289.2 F g−1 at a current density of 0.2 A g−1 and exhibit excellent cycle stability with over 96.7% capacitance retention after 10 000 cycles at a current density of 10 A g−1. Impressively, as-built ZIHC could achieve a high energy density up to 130.1 W h kg−1 at a power output of 180.3 W kg−1. At a maximum power density of 7.8 kW kg−1, the high energy density of 56 W h kg−1 is still delivered, suggesting the application potential of as-assembled ZIHC based on the MOF-derived porous carbon material.

Section snippets

Preparation of MIL-47 (V)

The precursor of MIL-47 (V) was prepared by a modified protocol according to the previously reported method [28]. The typical procedure as follows: 0.32 g terephthalic acid (H2BDC) and 0.43 g VOSO4 were added into 25 mL N, N-dimethylformamide (DMF). After stirred for 30 min, the mixture was transferred to a Teflon-lined stainless-steel autoclave and heated in an oven at 160 °C for 48 h. After cooling down to room temperature, the yellow powder was gathered via centrifugation and washed with

Morphology and structural analysis

The precursor of MIL-47 (V) was successfully synthesized, that demonstrated by the XRD patterns (Fig. S1a). The MIL-47 (V) presented a rod-like morphology similar to a sharpened pencil (Fig. S1b). After pyrolysis/etching and activation, the obtained samples inherited the sharpened pencil-like rod morphology of the MIL-47 (V). However, the roughness and the porosity were different with each other for three samples. Obviously, the rod-like structure became more and more porosity with the

Conclusions

In summary, an aqueous ZIHC with excellent performance was built by utilizing a hierarchically porous carbon derived from MOF. Benefiting from the merits including the high specific surface area, hierarchically porous structure and rich oxygen-containing functional groups, the advanced MPC-2 has sufficient space for ion/charge storage with fast ion/electron transportation rate. Consequently, MPC-2 not only exhibited excellent electrochemical performance in KOH aqueous electrolyte, but also

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.

Acknowledgements

This work was supported by the National Nature Science Foundations of China (Grants No: 22065021, 21867015), the Province Nature Science Foundations of Gansu (Grants No: 20JR5RA453) and Hongliu Outstanding Youth Teacher Cultivate project of Lanzhou University of Technology.

References (48)

  • L. Dong et al.

    Extremely safe, high-rate and ultralong-life zinc-ion hybrid supercapacitors

    Energy Storage Mater.

    (2018)
  • J. Shi et al.

    A new flexible zinc-ion capacitor based on δ-MnO2@carbon cloth battery-type cathode and MXene@cotton cloth capacitor-type anode

    J. Power Sources

    (2020)
  • G. Lou et al.

    Combustion conversion of wood to N, O co-doped 2D carbon nanosheets for zinc-ion hybrid supercapacitors

    Chem. Eng. J.

    (2021)
  • P.E. Brockway et al.

    Estimation of global final-stage energy-return-on-investment for fossil fuels with comparison to renewable energy sources

    Nat. Energy

    (2019)
  • S. Chu et al.

    Opportunities and challenges for a sustainable energy future

    Nature

    (2012)
  • N.R. Chodankar et al.

    True meaning of pseudocapacitors and their performance metrics: asymmetric versus hybrid supercapacitors

    Small

    (2020)
  • Z. Deng et al.

    Recent progress on advanced imaging techniques for lithium-ion batteries

    Adv. Energy Mater.

    (2021)
  • Y. Lu et al.

    Cyclohexanehexone with ultrahigh capacity as cathode materials for lithium-ion batteries

    Angew. Chem. Int. Ed.

    (2019)
  • Q. Zhao et al.

    Flexible 3D porous MXene foam for high-performance lithium-ion batteries

    Small

    (2019)
  • A. Masias et al.

    Opportunities and challenges of lithium ion batteries in automotive applications

    ACS Energy Lett.

    (2021)
  • X. Zeng et al.

    Commercialization of lithium battery technologies for electric vehicles

    Adv. Energy Mater.

    (2019)
  • Q. Zhu et al.

    A new view of supercapacitors: integrated supercapacitors

    Adv. Energy Mater.

    (2019)
  • J. Li et al.

    Three-dimensional nitrogen and phosphorus co-doped carbon quantum dots/reduced graphene oxide composite aerogels with a hierarchical porous structure as superior electrode materials for supercapacitors

    J. Mater. Chem. A

    (2019)
  • M. Liu et al.

    Emerging potassium-ion hybrid capacitors

    ChemSusChem

    (2020)
  • Cited by (0)

    View full text