High-performance supercapacitors based on S-doped polyaniline nanotubes decorated with Ni(OH)2 nanosponge and onion-like carbons derived from used car tyres
Introduction
There is growing interest in supercapacitors especially due to their intermediate properties between those of batteries and conventional electrical double-layer capacitors (EDLCs), which store charges at the electrode/electrolyte interface [1]. On the other hand, pseudocapacitors are a subclass of supercapacitors which store charge via Faradaic reactions near the electrode surface, deliver energy and power instantly and possess specific capacitance which exceeds that of carbon-based EDLCs by far [2,3]. They are important for a number of application areas, such as portable, flexible and wearable electronics, power saving units, regenerative braking systems and electrical vehicles (EVs) [[2], [3], [4], [5]]. Recent attempts have focused on increasing cycling stability by combining Faradaic and non-Faradaic processes, which would thus efficiently sustain cycling stability upon long-term charge-discharge processes [6,7]. In this regard, the integration of transition metal oxides and metal hydroxides with carbonaceous materials [8] or conducting polymers [9] has shown promising results. Materials such as Ni(OH)2@Graphite foam [10], Ni(OH)2@MWCNT [11], CuO@GC [12], rGONF/Ni(OH)2 [13], NiCo2O4-PANI-G [14], Ni,Co–OH/rGO [15], MnO2@rGO/PANI [16], and CNT-MnO2-PANI [17] have shown potential as high-performance hybrid supercapacitor electrodes, delivering higher energy and power densities.
The development of durable and efficient hybrid pseudocapacitors has encountered a number of challenges. Volume expansion during cycling leads to undesirable deterioration of the electrodes and low durability [18,19]. Among the conducting polymers, polyaniline (PANI) shows fast redox rate, desirable electrical conductivity, low cost, eco-friendliness and ease of processing into different nanostructures [[20], [21], [22], [23], [24], [25], [26], [27]], but also suffers from large volume changes upon repeated charging, structural damage and poor durability. Promising metal hydroxides with high theoretical capacitance like Ni(OH)2 (∼2082 F g−1) suffer from low electrical conductivity (10−15 S cm−1) [28,29], large volume expansion and poor electronic conductivity, which constraints their performance [7,30]. Incorporating carbon and carbon-related materials has been shown to promote structural stability and long cycling efficiency [13,[31], [32], [33], [34], [35], [36], [37], [38], [39]]. However, the fabrication of these electrodes still remains a challenge due to weak bonding between Ni(OH)2 and graphene during direct growth of Ni(OH)2@graphene, which results in delamination of electrode material upon repeated cycling [33]. Therefore, there is clearly a need to fabricate electrodes with an architecture that facilitates not only high reaction kinetics and conductivity but also mechanical robustness during repeated charge/discharge cycles.
In the present study we designed a rational combination of 1D and 3D nano-architectures consisting of sulfur-integrated PANI nanotubes which are decorated with sponge-like Ni(OH)2. This nano-architectural design was chosen to increase the surface area and mechanical stability of Ni(OH)2@PANI, whilst still enabling rapid electrochemical reaction kinetics through space confinement electron and ion transfer with short diffusion length. Moreover, the heteroatoms anchored on the PANI nanotubes surface simultaneously enhanced both, oxidation stability and conductivity.
Onion-like carbons (OLCs), a carbon structure of concentric graphene shells have emerged as high-performance supercapacitor electrode materials due to distinctive structural features like large accessible surface for electrolyte ion adsorption, high energy density and high rate capability [[40], [41], [42]]. OLCs are commonly made from nanodiamonds, which makes these expensive as they require more than 1700 °C for their production. In the present study, an alternative approach was used to prepare highly electrically-conductive OLCs from waste-tyres by pyrolysis followed by Hummer’s method and lower temperature (∼800 °C), increasing cost-effectiveness of OLCs. As anode material, the waste-tyre derived OLCs outperformed the commonly used graphitic nanostructures.
Section snippets
Chemicals
Reagent grade aniline monomer (ANI, 99%), ammonium persulfate (APS, 98% purity), 2-naphthalene sulfonic acid (70%), NaNO3, 98% H2SO4, KMnO4, N2H4, and NiCl2 were procured form Sigma Aldrich (USA). Aniline monomer was double distilled and preserved at 0–5 °C prior to use. Polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), KOH and NaOH were also acquired form Sigma Aldrich (USA) and used as received.
Synthesis of S-doped PANI nanotubes and Ni(OH)2@PANI nanocomposites
In a typical synthesis of S-doped PANI nanotubes decorated with Ni(OH)2 [43], 0.2 ml of
Results and discussion
Scheme 1 illustrates the schematic representation of the formation of S-doped PANI nanotubes. As reported by Wei et al. [45], an amphiphilic structure of 2-NSA having the intrinsic properties of hydrophilic –SO3H groups and the lipophilic –C10H7 groups are anticipated to produce micelles when reacting with aniline, and acting as template-like materials in forming the nanotubes of PANI-NSA. In our typical synthesis of PANI nanotubes, the molar ratio of [NSA]/[ANI] was maintained at ∼1 which is
Conclusions
The purpose-driven design of a unique architecture of 3D nanosponge-like Ni(OH)2 decorated sulfur-enriched PANI nanotubes resulted in hybrid electrodes possessing high energy and power densities of 23 Wh kg−1 and 292 kW kg−1, respectively, along with excellent electrochemical cycle stability. Further, we have demonstrated an asymmetric hybrid supercapacitor with onion-like carbon derived from waste-tyre as superior anode material, delivering very high energy and power densities of 70 Wh kg−1
CRediT authorship contribution statement
Madhumita Bhaumik: Conceptualization, Investigation, Data curation, Writing - original draft. Kumar Raju: Conceptualization, Investigation, Writing - original draft. Iviwe Arunachellan: Conceptualization, Methodology, Data curation. Tim Ludwig: Visualization, Investigation, Formal analysis. Mkhulu K. Mathe: Supervision, Writing - review & editing. Arjun Maity: Supervision, Writing - review & editing. Sanjay Mathur: Supervision, Writing - review & editing.
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.
The authors declare no conflict of interest.
Acknowledgments
The authors are grateful to University of Johannesburg and CSIR for providing infrastructural facility and financial support. CSIR is a partner in the CREATe-Network project being funded by the European Commission under the Marie Skłodowska-Curie Actions Research and Innovation Staff Exchange (RISE). SM and TL acknowledge the financial and infrastructural support provided by the University of Cologne, Germany.
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Both authors contributed equally.