Boron-oxy-carbide sheets: A wide voltage symmetric supercapacitor electrode with high temperature tolerance
Graphical abstract
Introduction
The clean and renewable energy resources (wind, geothermal, bio-mechanical, solar energy) along with the related energy conversion and storage technologies becomes indispensable to meet the uncontrollable energy demand [1]. In order to maintain the balanced state between power supply and demand, various kinds of electrical energy storage technologies have been invented, such as flywheels (mechanical energy storage), fuel cells (chemical energy storage and conversion), and batteries & supercapacitors (SCs) devices (electrochemical energy storage), respectively [2], [3]. Among them, SCs or electrochemical capacitors probing the energy demanding sectors through its ultra-fast storing ability, simple operation mode, excellent reversibility with huge power density [4], [5]. These unique features enable the SCs to fill the energy/ power void between the high-power capacitors and high energy fuel cells/ batteries [6], [7]. Into the bargain, the SCs liberates minimal thermochemical heat owing to their simplest form of charge storage mechanism [8] which promotes them to have a wider space in industrial power, electric vehicles (EVs), and consumer electronics. More importantly, the high-power density of SCs make them as an ideal primary energy system for capturing regenerative braking energy in EVs and as secondary energy system (in combination with batteries) to drive EVs [9], [10]. Not only limited to EVs, SCs also find applications in uninterrupted power supply (UPS), wind energy, ac line filtering system in the recent years [9], [11]. Herein, it is worth to mention that the performance metrics of the SC device determines their practical applicability[12]. In general, the performance metrics (energy & power density) of a SC is determined by their capacitance, and operating voltage window which in turn relies on the nature of electrode material, configuration (symmetric, asymmetric, hybrid) and the nature of electrolyte [5]. For instance, aqueous electrolyte possesses higher ionic conductivity (>100 mS/cm) and safer to operate [13], [14]. It is well known that the water splitting reactions in acid and basic electrolytes hinders the extension of voltage window above 1.23 V in most of the aqueous SCs [15] and there the emergence of neutral electrolytes (Li2SO4, Na2SO4 etc.) to be the best candidate for higher working voltages begins. The enhanced adsorption of cations (Li+ and Na+) at the electrode–electrolyte interface inhibits the adsorption of H+ ions from the water part of the electrolyte onto the electrode surface and restricts the hydrogen evolution reaction [16]. In case of the configuration, the construction of supercapacitors with asymmetric electrodes (ASC) is the widely used methodology to extend the operating voltage window. However, the different energy storage mechanism of capacitor type and battery type electrodes results in sluggish dynamics and leads to serious damage in the stability of ASCs [17]. Thus, the pioneering works stimulated us to focus on the construction of symmetric SCs with an electrode material that shadows the benefits of asymmetric electrodes. Recently, much light was shed on the structure modification of electrode materials such as carbon based materials (graphene and their derivatives or hybrids), transition metal oxides (TMOs), transition metal dichalcogenides (TMDCs), conducting polymers (CPs), metal organic frameworks (MOF), and MXenes respectively [18], [19]. This area of research brings in the materials with high specific surface area, rich pores in different size, thereby inducing the electron transport and diffusion kinetics of ions [20].Therefore, the development of new or advanced electrode materials with high capacitance, energy/power ratio, rate capability are being considered as prime factors by researchers [21]. But to extend the practical utility of supercapacitor technology, their operation in harsh environment conditions is being neglected in commonly studied supercapacitor materials.
In this scenario, ceramic materials with their corrosion resistant, and high temperature resistant properties still makes them charismatic for the development of supercapacitor electrode[22], [23], [24]. However, their poor surface activity has been overlooked compare to other superior properties. So, it is necessary to focus on improving the surface activity of ceramic materials to make them a viable candidate for SC electrode. Recently, researchers developed hard or glass ceramic materials as electrodes for batteries and SCs via engineering the material properties. For instance, silicon-oxy carbide (SiOC) materials incorporated graphene composite papers are developed and used as anode for lithium-ion batteries and electrodes for SCs [25], [26]. In our recent study, carbothermally converted siloxene sheets into SiOC lamellas are examined as high-performance electrode for SCs that can store charges via electric double layer and intercalation/de-intercalation capacitance [27]. As an alternative to SiOC, boron-based ceramics are of great interest due to the high theoretical capacitance of boron (400F g−1) that is four-fold higher than graphene, the wonder material [28]. Therefore, studies on the supercapacitive properties of elemental boron in different forms such as sheets, wires, were explored in this decade. However, the current limitation in the use of boron electrodes for supercapacitors is their limited operating voltage window (less than1.0 V) due to the occurrence of hydrogen evolution reaction and oxygen evolution reaction [29], [30]. Further, very recent works demonstrated that the inclusion of oxygen defects in boron sheets or hybridization with carbon results in enhanced capacitive performances [31], [32]. Therefore, developing a multicomponent material made of boron, oxygen, and carbon, i.e., the boron-oxy-carbide might produce significant electrochemical performances via synergic effect from the individual components. Till date, there are few works reported the boron based multicomponent electrodes for SC and batteries. Chang et al. recently reported the application of B4C@C core–shell ceramics as an electrode for solid state supercapacitors [33]. In our recent work, we demonstrated the use of BOC nanostructures for supercapacitors applications, however, their energy density is very moderate compared to the state of art devices [34]. This is mainly due to the poor dispersion of boron and their suboxides in the carbon matrix that might result in poor electrical conductivity which restricts the material unable to operate in aqueous configuration (neutral, acidic and basic electrolytes).
Therefore, in this work, we have prepared the BOC nanostructures in a facile two-step synthetic route (hydrothermal followed by annealing process) to modify the morphology into sheets and explored their charge-storage properties in aqueous and ionic electrolytes. Interestingly, the homogeneous dispersion of boron oxide inside the carbon matrix with more free carbon resulted from hydrothermal activation throughout the 2D sheet structure of BOC enables the aqueous electrolyte ions to access the active sites and overcomes the evolution reaction at the both the potentials to work as negative and positive electrode [0.0; 1.0 V] and [-1.0; 0.0 V] vs Ag/AgCl reference electrode in aqueous electrolyte. Accordingly, we designed the symmetric supercapacitor (SSC) with BOC electrodes in Li2SO4 electrolyte that doubles the single component and sweeps over stable voltage window of 2.0 V thereby producing higher energy and power density.
Section snippets
Materials
All the chemical reagents were research grade and used as received without any further purification. Deionized water was used in all the experiments. Borax (Na₂[B₄O₅(OH)₄] ·8H₂O), carbon black, acetonitrile, and N-Methyl-2-pyrrolidone (NMP) were procured from Dae Jung Chemicals, South Korea. Cellulose and Polyvinylidene fluoride (PVDF) were acquired from Sigma Aldrich Ltd., South Korea. Tetraethylammonium tetrafluoroborate (TEABF4) was purchased from Alfa Aesar Chemicals, South Korea.
Preparation of boron-oxy-carbide (BOC) nanostructures
The BOC
Synthesis and structural characterization of BOC nanostructures
Fig. 1 schemes the preparation of BOC nanostructures using hydrothermal reaction followed by high temperature annealing process using cellulose and borax as starting materials. It is worth to mention that the thermal treatment of (i) cellulose (>150 °C) will result in the formation of furfural products [36], and (ii) borax (>130 °C) will decompose into boron oxide (B2O3) powders [37], respectively. Therefore, the hydrothermal reaction between these two materials might result in the formation of
Conclusion
This work highlights the credibility of boron-oxy-carbide nanostructures in energy storage applications. The ability of BOC electrode to operate in both positive and negative regions upto 1 V overcomes the thermodynamic potential and shows excellent energy storage performance operating upto high voltage of 2 V in aqueous Li2SO4 electrolyte. Then the cell voltage was extended upto 3 V when employing organic TEABF4 electrolyte. An excellent device capacitance of 43.36 F g−1 with maximum energy
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.
Acknowledgement
This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (2019R1A2C3009747, 2021R1A4A2000934))
References (67)
- et al.
Plant growth–inspired design of high-performance composite electrode nanostructures for supercapacitors
Mater. Today Phys.
(2020) - et al.
Tactical and operational management of wind energy systems with storage using a probabilistic forecast of the energy resource
Renew. Energy.
(2017) - et al.
Three-dimensional hollow CoS2 nanoframes fabricated by anion replacement and their enhanced pseudocapacitive performances
Electrochim. Acta.
(2017) - et al.
Electrochemical stability of organic electrolytes in supercapacitors: Spectroscopy and gas analysis of decomposition products
J. Power Sources.
(2008) - et al.
Recent advancements in supercapacitor technology
Nano Energy.
(2018) - et al.
Progress and challenges of ceramics for supercapacitors
J. Mater.
(2021) - et al.
Influence of surface oxygen functional group on the electrochemical behavior of porous silicon carbide based supercapacitor electrode
Electrochim. Acta.
(2016) - et al.
Carbothermal conversion of siloxene sheets into silicon-oxy-carbide lamellae for high-performance supercapacitors
Chem. Eng. J.
(2020) - et al.
Engineering oxygen defects in the boron nanosheet for stabilizing complex bonding structure: An approach for high-performance supercapacitor
Chem. Eng. J.
(2021) - et al.
Application of hard ceramic materials B4C in energy storage: Design B4C@C core-shell nanoparticles as electrodes for flexible all-solid-state micro-supercapacitors with ultrahigh cyclability
Nano Energy.
(2020)
The production of carbon materials by hydrothermal carbonization of cellulose
Carbon N. Y.
Shahzad, Ethylene glycol assisted low-temperature synthesis of boron carbide powder from borate citrate precursors
J. Asian Ceram. Soc.
Boron-doped ordered mesoporous carbons for the application of supercapacitors
Electrochim. Acta.
Highly microporous SbPO4 /BCx hybrid anodes for sodium-ion batteries
Mater. Adv.
Wrinkled, rippled and crumpled graphene: an overview of formation mechanism, electronic properties, and applications
Mater. Today.
Synthesis of ordered mesoporous γ-alumina – Effects of calcination conditions and polymeric template concentration
Microporous Mesoporous Mater.
Controlling electric double-layer capacitance and pseudocapacitance in heteroatom-doped carbons derived from hypercrosslinked microporous polymers
Nano Energy.
Ruthenium sulfide nanoparticles as a new pseudocapacitive material for supercapacitor
Electrochim. Acta.
Electrolyte selection for supercapacitive devices: a critical review
Nanoscale Adv.
Diagnostic analyses for mechanisms of self-discharge of electrochemical capacitors and batteries
J. Power Sources.
Solar energy conversion, storage, and release using an integrated solar-driven redox flow battery
J. Mater. Chem. A.
Supercapacitors Performance Evaluation
Adv. Energy Mater.
Carbon-based materials as supercapacitor electrodes
Chem. Soc. Rev.
1D Supercapacitors for Emerging Electronics: Current Status and Future Directions
Adv. Mater.
Two-Dimensional Siloxene-Graphene Heterostructure-Based High-Performance Supercapacitor for Capturing Regenerative Braking Energy in Electric Vehicles
Adv. Funct. Mater.
High-power graphene supercapacitors for the effective storage of regenerative energy during the braking and deceleration process in electric vehicles
Mater. Chem. Front.
Electrospun Polymer-Derived Carbyne Supercapacitor for Alternating Current Line Filtering
Small.
MnOx -decorated carbonized porous silicon nanowire electrodes for high performance supercapacitors
Energy Environ. Sci.
Electrochemical Supercapacitors, Springer, US, Boston
MA
Development of Electrolytes towards Achieving Safe and High-Performance Energy-Storage Devices: A Review
ChemElectroChem.
Electrochemical neutralization energy: from concept to devices
Chem. Soc. Rev.
3D ordered macroporous MoO2 attached on carbonized cloth for high performance free-standing binder-free lithium–sulfur electrodes
J. Mater. Chem. A.
Integration of nickel–cobalt double hydroxide nanosheets and polypyrrole films with functionalized partially exfoliated graphite for asymmetric supercapacitors with improved rate capability
J. Mater. Chem. A.
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These authors contributed equally to this work.