Redox additive electrolyte assisted promising pseudocapacitance from strictly 1D and 2D blended structures of MnO2/rGO

https://doi.org/10.1016/j.matchar.2022.111991Get rights and content

Highlights

  • 1D MnO2 is easily blended with fine nanosheets of rGO as a pseudocapacitor electrode.

  • Promising pseudocapacitance of 216 F/g at 3.75 A/g in a two-electrode system is achieved.

  • Pseudocapacitive behaviour is studied under redox additive electrolyte, K3Fe(CN)6.

Abstract

A promising sustainable energy storage characteristic is achieved in redox additive electrolyte by developing strict blend of one dimensional (1D) and two dimensional (2D) structures. Hydrothermal reaction is followed to obtain the desired morphology. Two dimensional (2D) reduced graphene oxide (rGO) is added into the redox reaction between potassium permanganate and sodium nitrite to obtain nanocomposite comprising 1D and 2D blended structures of MnO2/rGO. Their structures and morphologies are studied by XRD, Raman and HRTEM analyses, respectively. The pseudocapacitive behaviour is studied in a redox additive electrolyte comprising KOH and K3Fe(CN)6. The effect of electrolytic concentration was studied by varying the concentration of K3Fe(CN)6. The specific capacity is considerably enhanced up to 1741 F/g, 8.75 A/g with increase in concentration of K3Fe(CN)6. The role of redox couple [Fe(CN)6]3−/[Fe(CN)6]4− played a key role in adding the charge movement across the electrode which tuned well with the manganese ions to obtain one of the most promising pseudocapacitances from the developed 1D and 2D blended structures of MnO2/rGO. For in-depth analysis of Fe ions movement, a symmetric supercapacitor cell is constructed to achieve a commendable specific capacitance of 216 F/g at 3.75 A/g. Prolong cycling hinted decreasing electrolytic interfacial layers resulting in fast reversible kinetics of Fe(III) ↔ Fe(II) ions to achieve astonishing capacity retention of 127% after 3000 cycles.

Introduction

Human life is now increasingly depended upon machineries which require nonstop energy supply. Dependency on fossil fuels to power these machineries has impacted negatively due to decaying of these fossil fuels [[1], [2], [3], [4], [5], [6], [7]]. Development of electrochemical energy storage devices like supercapacitors can resolve many issues for sustainable energy supply [[8], [9], [10], [11]]. Generally, these supercapacitors found limited applications such as in hybrid vehicles and power stabilizers in contrast to Li-ion batteries due to their low charge storage capability [[12], [13], [14], [15], [16], [17]]. Fortunately, their charge storage capability can be improved utilizing faradaic activity wherein charges can be stored via adsorption on to the electrodes as well as inside the interstitial sites commonly termed as pseudocapacitance [[18], [19], [20]]. Environmental friendliness and redox reaction capabilities of transition metal oxides such as ruthenium oxide (RuO2) [21], nickel oxide (NiO) [[22], [23], [24]], cobalt oxide (Co3O4) [[25], [26], [27]] and manganese dioxide (MnO2) [[28], [29], [30]] make them favorable electrode materials for pseudocapacitors. Easy availability and attainment of one dimensional (1D) tunneled structure of MnO2 offers short diffusion path for ions or charges, facilitating the charge storage capability [[31], [32], [33], [34], [35], [36]]. Hence, it arouses the need to explore the capacitive behaviour of MnO2. Researchers have explored the excellent capacitive behaviour of MnO2 nanorods [37,38]. Anyhow, MnO2 exhibits low conductivity and to compensate this, it should be coated with suitable conducting material especially carbonaceous materials. Graphene oxide is the most preferred one for its confined 2D structures which could offer high surface area with improved conductivity [39,40].

However, systematic synthesis of nanomaterials of ultra-finesse morphology with high surface energy suitable for charge storage is still ambiguous. To resolve such issues, a novel systematic approach is presented to get strictly 1D structures of MnO2 and 2D structures of reduced graphene oxide (rGO) with ultra-morphological precision by optimizing a redox reaction maintained at hydrothermal condition. The capacitive performance of the synthesized material when tested as a pseudocapacitor electrode could be further complemented with redox additive, potassium ferricyanide (K3Fe(CN)6) into the KOH electrolyte. Notably, recent studies have showcased an improved capacitive performance using (K3Fe(CN)6) as redox additive to the electrolyte [41,42]. Here, a redox additive electrolyte is employed to extract a promising charge storage capability from the unique blend of 1D and 2D structure. The ease of synthesis technique as presented could potentially be utilized for commercialized production of high performing supercapacitor electrodes. Present work is a continuation of the previous reported works on MnO2 nanostructures based promising functionality [[43], [44], [45], [46], [47], [48], [49], [50]].

Section snippets

Chemicals

Graphite fine powder, Sodium Nitrate (NaNO3), Sodium Nitrite (NaNO2), Hydrochloric acid (HCl), Sulphuric acid (H2SO4), Hydrogen peroxide (H2O2) Potassium Hydroxide (KOH), Potassium Permanganate (KMnO4), Potassium Ferricyanide (K3Fe(CN)6), N-Methyl-2-pyrrolidone (NMP), Super P carbon and Polyvinylidene Fluoride (PVDF) with ultra-pure quality were used from Sigma Aldrich.

1D MnO2 and 2D rGO nanocomposite

Hummers technique was followed with little variations to obtain fine graphene oxide (GO) powder [51,52]. At first, graphite

Structure analysis

Fig. 1(a) represents the XRD pattern of the MnO2/rGO nanocomposite. JCPDS card number 44-0141 corresponds peak at 12.77, 18.05, 25.6, 26.5, 28.7, 36.5, 37.5, 38.8, 41.4, 41.9, 49.83, 56.13, 60.15, 65.28, 69.48 and 72.8 (2θ values) revealing the tetragonal α phase of MnO2 for the material prepared at 0.3 M H2SO4. The miller indices (110), (200), (220), (310), (400), (211), (330), (420), (301), (411), (600), (521), (002), (541) and (312) for each increasing 2θ values with presence of no other

Conclusions

Here, a promising hydrothermal route is developed to control the redox reaction between oxidizing and reducing agents in way to create strictly 1D structures of MnO2 with the help of proton admission. The reaction was successfully optimized in such an extent to incorporate fine 2D structure of rGO over 1D MnO2. The synergistic effect prevailed in the nanocomposite as a pseudocapacitor electrode tuned well with the addition of redox content K3Fe(CN)6 to achieve one of the most promising

Declaration of Competing Interest

None.

Acknowledgements

The author R. Rameshbabu thanks the Chilean National Agency for Research and Development (ANID-FONDECYT), Project No: 3190087 for the financial support. Also, the author Niraj Kumar thanks Uttaranchal University, Dehradun, India for providing seed money grant to carry out this research work under its Division of Research & Innovation.

References (74)

  • Z. Song et al.

    A facile template-free synthesis of-MnO2 nanorods for supercapacitor

    J. Alloys Compd.

    (2013)
  • N. Kumar et al.

    Morphological analysis of ultra fine α-MnO2 nanowires under different reaction conditions

    Mater. Lett.

    (2015)
  • N. Kumar et al.

    Enhanced pseudocapacitance from finely ordered pristine α-MnO2 nanorods at favourably high current density using redox additive

    Appl. Surf. Sci.

    (2018)
  • N. Kumar et al.

    Facile synthesis of 2D graphene oxide sheet enveloping ultrafine 1D LiMn2O4 as interconnected framework to enhance cathodic property for Li-ion battery

    Appl. Surf. Sci.

    (2019)
  • M. Hu et al.

    Role of graphene in MnO2/graphene composite for catalytic ozonation of gaseous toluene

    Chem. Eng. J.

    (2014)
  • Y. Chen et al.

    One-pot synthesis of MnO2/graphene/carbon nanotube hybrid by chemical method

    Carbon

    (2011)
  • X. Wang et al.

    Compounding δ-MnO2 with modified graphene nanosheets for highly stable asymmetric supercapacitors

    Colloids Surf. A Physicochem. Eng. Asp.

    (2019)
  • B. Wang et al.

    Preparation of MnO2/carbon nanowires composites for supercapacitors

    Electrochim. Acta

    (2016)
  • X. Ji et al.

    Ni/MnO2 doping pulping lignin-based porous carbon as supercapacitors electrode materials

    J. Alloys Compd.

    (2021)
  • N. Mohammadi et al.

    Defective mesoporous carbon/MnO2 nanocomposite as an advanced electrode material for supercapacitor application

    J. Alloys Compd.

    (2021)
  • V. Mane et al.

    Manganese dioxide thin films deposited by chemical bath and successive ionic layer adsorption and reaction deposition methods and their supercapacitive performance

    Inorg. Chem. Commun.

    (2020)
  • N. Chodankar et al.

    Flexible all-solid-state MnO2 thin films based symmetric supercapacitors

    Electrochim. Acta

    (2015)
  • J. Zhao et al.

    Vulcanizing time controlled synthesis of NiS microflowers and its application in asymmetric supercapacitors

    Electrochim. Acta

    (2017)
  • N. Chodankar et al.

    Low-cost superior symmetric solid-state supercapacitors based on MWCNTs/MnO2 nanocomposite thin film

    J. Taiwan Inst. Chem. Eng.

    (2017)
  • V.J. Mane et al.

    Enhanced specific energy of silver-doped MnO2/graphene oxide electrodes as facile fabrication symmetric supercapacitor device

    Mater. Today Chem.

    (2021)
  • Y.Z. Zhang et al.

    Room temperature synthesis of cobalt-manganese-nickel oxalates micropolyhedrons for high-performance flexible electrochemical energy storage device

    Sci. Rep.

    (2015)
  • X.B. Cheng et al.

    Dual-phase lithium metal anode containing a polysulfide-induced solid electrolyte interphase and nanostructured graphene framework for lithium–sulfur batteries

    ACS Nano

    (2015)
  • J. Yan et al.

    Recent advances in design and fabrication of electrochemical supercapacitors with high energy densities

    Adv. Energy Mater.

    (2014)
  • J. Yan et al.

    Supercapacitors: recent advances in design and fabrication of electrochemical supercapacitors with high energy densities

    Adv. Energy Mater.

    (2014)
  • X. Tian et al.

    Exploration of the active center structure of nitrogen-doped graphene for control over the growth of Co3O4 for a high-performance supercapacitor

    ACS Appl. Energy Mater.

    (2018)
  • H. Tanaya Das et al.

    Performance of solid-state hybrid energy-storage device using reduced graphene-oxide anchored sol-gel derived Ni/NiO nanocomposite

    Sci. Rep.

    (2017)
  • X. Wang et al.

    An aqueous rechargeable lithium battery using coated Li metal as anode

    Sci. Rep.

    (2013)
  • G. Wang et al.

    A review of electrode materials for electrochemical supercapacitors

    Chem. Soc. Rev.

    (2012)
  • C. Liu et al.

    Advanced materials for energy storage

    Adv. Mater.

    (2010)
  • W. Jiang et al.

    Ternary hybrids of amorphous nickel hydroxide–carbon nanotube-conducting polymer for supercapacitors with high energy density, excellent rate capability, and long cycle life

    Adv. Funct. Mater.

    (2015)
  • D. Cai et al.

    High-performance supercapacitor electrode based on the unique ZnO@Co3O4 core/shell heterostructures on nickel foam

    ACS Appl. Mater. Interfaces

    (2014)
  • H.L. Wang et al.

    Advanced asymmetrical supercapacitors based on graphene hybrid materials

    Nano Res.

    (2011)
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