Electrochemical Capacitors Research Articles

High Capacitance Based on Vacancy Defective Porous Carbon in Ionic Liquid

AbstractPorous carbons have been extensively studied in electrochemical capacitors (ECs). However, low capacitance remains a limitation due to the electrical double layer (EDL) storage mechanism when porous carbons are used in ionic liquids (ILs) based ECs. Herein, the nitrogen‐derived vacancy defects in porous carbon nanospheres are found which can boost capacitive charge storage and present reversible high capacitance of 427 F g−1 in pure IL electrolyte, equal to a normalized area capacitance (CA) of 16 µF cm−2, surpassing the theoretical EDL CA (≈11 µF cm−2). When used as capacitive cathode, the assembled Lithium hybrid capacitor express high energy density of 635 Wh kg−1 based on active material under much high‐power density of 14.5 kW kg−1. A combination of control experiments and density functional theory investigation indicate that the EC's performance improvement mostly stems from strong interactions at vacancy defects, triggering extraordinary faradaic capacitance. The results shed light on defect engineering for realizing extra faradaic capacitance of carbon materials, and open up new opportunities for improving EC's energy density.

Advancing supercapacitor performance: a comprehensive review of electrochemical conversion of coconut shells into activated carbon nanofibers

This assessment provides a comprehensive evaluation of the limitations associated with the application of supercapacitors, along with the imperative to enhance their functionality. Following this, the advantages of Electrochemical Double Layer Capacitors (EDLC) are discussed in comparison to other types utilized in supercapacitor contexts. The transformation of coconut shells into carbon nanofibers is extensively investigated through various methodologies, highlighting both their benefits and limitations. It becomes evident that the current utilization of coconut shells has not yet achieved optimal sustainability or viability for energy storage purposes. Nevertheless, coconut shells offer a widely available and sustainable resource that can be converted into Activated Carbon nanofibers for energy storage applications. Diverse techniques have been employed to produce these ACB nanofibers, each targeting specific objectives including improved energy density, adaptable diameter, reduced energy consumption, and faster charging times. Despite these accomplishments, it is evident that numerous significant properties of carbon nanofibers derived from coconut shells remain unexplored, leading to substantial knowledge gaps that must be addressed for each technique. Therefore, further research is warranted to advance the comprehension of key parameters associated with various methods, ultimately facilitating the development of highly desirable carbon nanofibers sourced from coconut shells and catering to the requirements of sustainable energy storage applications.

Sub-millisecond lithiothermal synthesis of graphitic meso–microporous carbon

Porous carbons with concurrently high specific surface area and electronic conductivity are desirable by virtue of their desirable electron and ion transport ability, but conventional preparing methods suffer from either low yield or inferior quality carbons. Here we developed a lithiothermal approach to bottom–up synthesize highly meso–microporous graphitized carbon (MGC). The preparation can be finished in a few milliseconds by the self-propagating reaction between polytetrafluoroethylene powder and molten lithium (Li) metal, during which instant ultra-high temperature (>3000 K) was produced. This instantaneous carbon vaporization and condensation at ultra-high temperatures and in ultra-short duration enable the MGC to show a highly graphitized and continuously cross-coupled open pore structure. MGC displays superior electrochemical capacitor performance of exceptional power capability and ultralong-term cyclability. The processes used to make this carbon are readily scalable to industrial levels.

Optimizing EMIMBF4-based electrolyte with LiBr redox medium for enhanced supercapacitors

The formidable challenge of supercapacitors (SCs) is to achieve both high energy density and high power density simultaneously. Although the utilization of porous carbon materials for physical adsorption in electrochemical double-layer capacitors (EDLCs) applications exhibits promising prospects, attaining exceptional performance necessitates additional methodologies. Here, we propose an effective strategy for formulating redox electrolytes through the incorporation of organic solvents and LiBr into 1-ethyl-3-methylimidazole tetrafluoroborate (EMIMBF4) electrolytes. Within this formulation, LiBr serves as a redox mediator, contributing Br−/Br3− redox pairs to the system. The incorporation of EMIMBF4-LiBr-DMSO in brominated redox EDLCs led to a significant enhancement in specific capacitance, reaching up to 39.72 F g−1, representing a remarkable increase of 159 % compared to EDLCs without any redox media. This configuration achieved a high power density of 496.6 W kg−1 while maintaining an energy density of 34.48 Wh kg−1.

Effects of thermal treatment on the electrical behavior of titanium dioxide thin-films

AbstractElectrochemical biosensors made of titanium dioxide have generated significant interest due to their high sensitivity and selectivity for the detection of a variety of diseases. This study focuses on the impact of thermal treatment in an oxygen environment on the electrical properties of titanium dioxide thin films deposited on silicon substrates using pulsed laser deposition; the films were subjected to temperatures of $$\varvec{100\,\,^{\circ }C}$$ 100 ∘ C , $$\varvec{400\,\,^{\circ }C}$$ 400 ∘ C , and $$\varvec{600\,\,^{\circ }C}$$ 600 ∘ C . The primary objective was to explore how thermal processing influences the electrical characteristics of the thin films, with the goal of enhancing their capacitance and thereby improving the performance of sensors developed by functionalizing these films; X-ray photoelectron spectroscopy revealed the presence of Ti$$^{4+}$$ 4 + , Ti$$^{3+}$$ 3 + and TiO$$_x$$ x species in the untreated thin film and in the heat-treated films, with an increase in TiO$$_x$$ x species observed after oxygen heat treatment. Atomic force microscopy demonstrated a decrease in the surface homogeneity of the films at elevated treatment temperatures, which corresponded to a reduction in capacitive behavior; this was further corroborated by Nyquist plots derived from electrochemical capacitance spectroscopy (ECS). The study found that the electrochemical capacitance at lower frequencies decreased significantly from $$\varvec{1.02\,\, \mu Fcm^{-2}}$$ 1.02 μ F c m - 2 to $$\varvec{0.25\,\, \mu Fcm^{-2}}$$ 0.25 μ F c m - 2 when the treatment temperature was increased to $$\varvec{600\,\,^{\circ }C}$$ 600 ∘ C

Preparation of V2O3 by a short process of ammonium salt reduction and its electrocatalytic properties investigation

Ammonium salt vanadium precipitation is the main method of vanadium metallurgy at home and abroad, but the traditional ammonium precipitation of vanadium can only obtain high valence of V2O5, and the NH3 produced in the calcination process cannot be fully utilized. And the preparation of low-valence vanadium oxide V2O3 is long and costly. Self-reduction of thermal decomposition of nitrogen-containing precipitation products to produce V2O3 is a novel and short process method that can achieve full utilization of ammonia. NaVO3 was used as the vanadium source, choline chloride (C5H14ClNO (ChCl)) was used as the vanadium precipitation reagent, and the vanadium concentration was 30 g/L, n(ChCl)/n(V) = 1.5, the initial pH was 1.5, the temperature was 85°C, the time was 2 h, and the vanadium precipitation efficiency could reach 97.05%. V2O3 with purity of 97.98% can be obtained by calcination at 550°C for 3 h in an argon atmosphere. XRD, FTIR, XPS, SEM-EDS were used to characterize the product, which further proved that the final product was V2O3. The electrocatalytic hydrogen evolution reaction (HER) of V2O3 in acidic media showed high stability after 1000 cyclic voltammetry (CV) cycles, with a low Tafel slope of 88.5 mVdec−1. The electrochemical double layer capacitance (EDLC) was measured by CV at different scan rates, and the EDLC of V2O3 was 1.104 mFcm−2. This study provides a short-flow preparation method for V2O3 and can provide predictions for the application of V2O3 in HER and supercapacitors.

AGRICULTURAL WASTE AS A PANACEA FOR HIGH COST OF ELECTROCHEMICAL DOUBLE LAYER SUPER-CAPACITOR AND SUSTAINABLE ENERGY STORAGE SOLUTION: A REVIEW

Supercapacitors, also known as ultracapacitors or electrochemical capacitors, are energy storage devices that store and release energy quickly. They are used in various applications, including renewable energy systems, electric vehicles, and electronics. Using agricultural waste as a source for supercapacitor’s electrode materials is an innovative and sustainable approach that holds promise for addressing the high cost of these materials. Agricultural wastes, such as crop residues, husks, shells, and other byproducts, often presents challenges in terms of disposal and environmental impact but have proven to be a good precursor material for the synthesis of electrochemical super capacitor’s electrode. By repurpose these waste materials for supercapacitor electrodes, the high cost of the electrode will be reduced and hence the overall cost of the supercapacitors.

Carbon nanospheres-induced enhanced capacitive dynamics in C/WS2/WO3 nanocomposites for high-performance electrochemical capacitors

This work investigates the impact of carbon nanospheres on the electrochemical performance of C/WS2/WO3 nanocomposites for electrochemical supercapacitors. The nanocomposites have been synthesized and characterized by various techniques like XRD, UV–vis spectroscopy, SEM, TEM and FTIR. The electrochemical properties of the nanocomposites have been analysed in order to study the charge transport, reaction kinetics, impedimetric properties and specific capacitance by using cyclic voltammetry (CV) and potentio electrochemical impedance spectroscopy (PEIS). The capacitive performance of the samples has been investigated by the obtained specific capacitance values and Nyquist plots. The specific capacitance of the samples has been found in a range of 0.8–2.8F/g at 20 mV/s. The sample with the least amount of carbon showed maximum specific capacitance. The electrochemical insights, combined with comprehensive material characterizations, provide valuable knowledge for tailoring the capacitive performance of C/WS2/WO3 nanocomposites through controlled carbon nanospheres and thus the suitability of materials for electrochemical capacitors.

Electrochemical Investigation of Lithium Perchlorate-Doped Polypyrrole Growing on Titanium Substrate

Lithium perchlorate-doped polypyrrole growing on titanium substrate (LiClO4-PPy/Ti) has been fabricated to act as electroactive electrode material for feasible electrochemical energy storage. A theoretical and experimental investigation is adopted to disclose the conductivity, electroactivity properties and interfacial interaction-dependent capacitance of LiClO4-PPy/Ti electrode. The experimental measurement results disclose that LiClO4-PPy/Ti reveals lower ohmic resistance (0.2226 Ω cm−2) and charge transfer resistance (2116 Ω cm−2) to exhibit higher electrochemical conductivity, a more reactive surface, and feasible ion diffusion to present higher double-layer capacitance (0.1930 mF cm−2) rather than LiClO4/Ti (0.3660 Ω cm−2, 65,250 Ω cm−2, 0.0334 mF cm−2). LiClO4-PPy/Ti reveals higher Faradaic capacitance caused by the reversible doping and dedoping process of perchlorate ion on PPy than the electrical double-layer capacitance of LiClO4/Ti caused by the reversible adsorption and desorption process of the LiClO4 electrolyte on Ti. Theoretical simulation calculation results prove that a more intensive electrostatic interaction of pyrrole N···Ti (2.450 Å) in LiClO4-PPy/Ti rather than perchlorate O···Ti (3.537 Å) in LiClO4/Ti. LiClO4-PPy/Ti exhibits higher density of states (57.321 electrons/eV) at Fermi energy and lower HOMO-LUMO molecule orbital energy gap (0.032 eV) than LiClO4/Ti (9.652 electrons/eV, 0.340 eV) to present the enhanced electronic conductivity. LiClO4-PPy/Ti also exhibits a more declined interface energy (−1.461 × 104) than LiClO4/Ti (−5.202 × 103 eV) to present the intensified interfacial interaction. LiClO4-PPy/Ti accordingly exhibits much higher specific capacitances of 0.123~0.0122 mF cm−2 at current densities of 0.01~0.10 mA cm−2 rather than LiClO4/Ti (0.010~0.0095 mF cm−2, presenting superior electroactivity and electrochemical capacitance properties. LiClO4-PPy/Ti could well act as the electroactive supercapacitor electrode for feasible energy storage.

In-situ synthesis of carbon-coated Mo2C: An exceptionally efficient and robust electrocatalyst for hydrogen evolution reaction (HER)

In the present work, the Mo2C electrocatalyst has been synthesized using waste plastic as carbon source. The use of plastic bottle has been chosen to reduce the cost of electrocatalyst as well to address the environmental issues caused due to these wastes. The pure phase sample was synthesized at 800 °C by carburizing MoO3 in an autoclave. The synthesized sample shows high activity towards HER with a lower Tafel slope of 85.7 mVdec−1. One of the exceptional features of the developed electrocatalyst is the long-term stability up to 7 days as determined by chronopotentiometry results. The improved activity and stability have been attributed to the presence of graphene like structures encapsulating the Mo2C particles. The presence of carbon also shows higher storage ability with an electrochemical double layer capacitance (EDLC, Cdl) of 91.0 μF. The synthesized sample shows an efficient and stable electrocatalyst towards HER.

Electrochemical Etching of Nitrogen Ion‐Implanted Gallium Nitride – A Route to 3D Nanoporous Patterning

Dopant‐selective electrochemical etching (ECE) of gallium nitride (GaN) results in well‐defined porous layers with tunable refractive index, which is extremely interesting for integrating photonic components into nitride technology. Herein, the impact of nitrogen implantation with and without subsequent rapid thermal annealing (RTA) on the porosification process of highly n‐doped GaN ([Si] 3 × 1019 cm−3) is investigated. Implantation is expected to compensate the donors of the n‐GaN layer to spatially suppress porosification during ECE. Optical transmission, electrochemical capacitance–voltage, and X‐Ray diffractometry of as‐grown and as‐implanted GaN suggest successful compensation of n‐dopants. Cross‐sectional scanning electron microscopy reveals the presence of mesopores (diameter 2–50 nm) after ECE of the as‐grown n‐GaN. In the case of implanted n‐GaN, it is found that ECE results in macropores (diameter > 50 nm), which can be suppressed by an intermediate RTA step. The implanted and annealed n‐GaN layers solely exhibit mesopores at the top and bottom, while the intermediate region remains unimpaired. Chronoamperometry and gravimetry provide additional insight and confirm the presence of macro‐ and mesopores in samples without and with RTA, respectively. The results demonstrate a successful implementation of etch‐resisting subsurface layers, which are required for 3D refractive index engineering in porous GaN.

Effect of precursor composition and heat-treatment on the morphology and physical properties of Ag nanosponges

Nanoporous silver (np-S) was prepared by free corrosion dealloying of a series of Ag–Al thin films containing between 25 and 73 at.% Al. It was found that precursor composition had an important influence on the nanostructures and morphologies of the np-S. In particular the size of the Ag ligaments systematically decreased from 32 to 13 nm as the Al content was increased over the series. In contrast, there was only a weak effect on pore size, which remained in the range 11–15 nm, with the maximum occurring at about 55 at.% Al. There was however a significant increase in the density of the pores as the Al content of the precursor was increased. The electrical resistivity of the np-S increases with the decrease in ligament size, changing from about 3 × 10−8 Ω m for sponges with ligaments of about 32 nm diameter rising to 30 × 10−8 Ω m for the sponge with the 13 nm ligaments. The surface area of the np-S was estimated by the electrochemical capacitance in KNO3 solutions and was estimated to increase by an order of magnitude compared to a smooth Ag surface. There was a systematic change in the optical properties of the sponges, with a trend towards less metallic behaviour as the ligament size decreased and pore density increased. These changes culminated in the sponge prepared from the 73 at.% Al precursor having non-metallic characteristics with regard to visible and near-infrared light. The volume fraction of metal was estimated to be of the order of 40 ± 5%. Prior annealing of the precursor inhibited dealloying.

Carbon materials derived by crystalline porous materials for capacitive energy storage

Abstract The controlled synthesis of precise carbon nanostructures with high electron conductivity, high reaction activity, and structural stability plays a significant role in practical applications yet largely unmet. Metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and coordination polymers (CPs) as crystalline porous materials (CPMs) have shown extraordinary porosity, tremendous structural diversity, and highly ordered pores, offering a platform for precise controlled carbon materials (CMs) with regular porous structures and high performances. Some recent studies have shown that CMs derived from CPMs with high specific surface area, superior chemical stability, excellent electrical conductivity offer a great opportunity for electrochemical energy storage and conversion. In this review, we summarize recent milestones of CPMs derived CMs in the field of capacitive energy storage. We hope the more precise design and control at the atomic level of CPMs could provide us a constructive view of the structure-activity relationship between CMs and electrochemical capacitors, as well as future trends and prospects.

Recent Progress in MXene‐Based Electrochemical Actuators and Capacitors

A new family of two‐dimensional (2D) transition metal carbides, carbonitrides, and nitrides (MXenes) has attracted increasing attention owing to their electrical, chemical, and physical properties. Together with various attractive properties of the MXenes, they also exhibit electrochemical induced deformation (i.e., expansion/contraction) via ion intercalation/de‐intercalation in/from MXene layers. In this respect, MXenes offer the possibility of application as the electrode of electrochemical actuators (ECAs). While the MXene‐based ECAs are still in their infancy stage, researchers have made great effort to achieve high‐performance MXene‐based electrochemical capacitors (ECs). As the name suggests, both ECAs and ECs shared common traits in which their operations are based on electrochemical processes. This review provides the recent progress in the MXene‐based ECAs in parallel with that in the MXene‐based ECs to gain insights from the relatively mature developments in EC applications. Finally, based on the findings from previous studies on both electrochemical applications, perspectives on future MXene‐based ECAs in terms of electrode, electrolyte, and cell configuration are provided.

A Highly Robust and Conducting Ultramicroporous 3D Fe(II)-Based Metal-Organic Framework for Efficient Energy Storage.

Exploitation of metal-organic framework (MOF) materials as active electrodes for energy storage or conversion is reasonably challenging owing to their poor robustness against various acidic/basic conditions and conventionally low electric conductivity. Keeping this in perspective, herein, a 3D ultramicroporous triazolate Fe-MOF (abbreviated as Fe-MET) is judiciously employed using cheap and commercially available starting materials. Fe-MET possesses ultra-stability against various chemical environments (pH-1 to pH-14 with varied organic solvents) and is highly electrically conductive (σ=0.19Sm-1) in one fell swoop. By taking advantage of the properties mentioned above, Fe-MET electrodes give prominence to electrochemical capacitor (EC) performance by delivering an astounding gravimetric (304Fg-1) and areal (181mFcm-2) capacitance at 0.5Ag-1 current density with exceptionally high cycling stability. Implementation of Fe-MET as an exclusive (by not using any conductive additives) EC electrode in solid-state energy storage devices outperforms most of the reported MOF-based EC materials and even surpasses certain porous carbon and graphene materials, showcasing superior capabilities and great promise compared to various other alternatives as energy storage materials.

Bimetal Pyrophosphate of CoNiP2O7@polypyrrole Nanocomposite‐ Based Electrode for Hybrid Supercapacitor Applications

A significant challenge in the realm of asynchronous capacitors is the development of innovative electrode materials with improved electrochemical behaviour and increased cycles. In this article, a new method is proposed for the facile synthesis of bi metal pyrophosphate anchored on polypyrrole (CoNiP2O7/NF@PPy) utilizing the hydrothermal and polymerization procedures. Cobalt nickel pyrophosphate nanoarrays are created, and they are successfully used as an electrode material for supercapacitors. The novelty of this work, a novel electrode of binder free mixed metal pyrophosphate (CoNiP2O7) composited to conducting polymer of polypyrrole is developed. Then, the prepared CoNiP2O7/NF CoNiP2O7/NF@PPy electrodes capacitive and diffusive mechanism discussed by using Trassati method. In electrochemical experiments, the CoNiP2O7/NF@PPy composite showed considerably enhanced specific capacity (1202 mAhg−1), which is much greater than that of pure CoNiP2O7/NF (819 mAhg−1). Additionally, the hybrid supercapacitor (CoNiP2O7/NF@PPy//AC) device manufactured had the highest energy density of 94.6 Wh kg−1. These findings indicate that this composite is a promising option for electrochemical capacitors.

Fabrication of high voltage and energy dense supercapacitor with Manilkara zapota seeds derived porous activated carbon in acidic electrolyte

Achieving a high working potential window beyond the water electrolysis limit (> 1.23 V) has always been a big challenge in the fabrication of aqueous supercapacitors (SCs). Since energy density has quadratic dependence on voltage, broadening of cell voltage can remarkably increase the energy density of the capacitor. Unfortunately, most of the aqueous electrochemical capacitors operated in strongly acidic or alkaline electrolytes show poor energy densities owing to their narrow operating voltage limit. To obtain a high voltage range of aqueous symmetric carbon/carbon capacitors and achieve high energy density, the chemistry of electrode materials and the electrochemical kinetics of electrolytes play a critical role. Hence, in the present work, we explore a porous activated carbon produced from the seeds of Manilkara zapota (ACMZ-700) in combination with sulfuric acid electrolyte to obtain an encouraging electrochemical stable working voltage window. Thus, the resulting symmetric SC effectively exhibited an enlarged cell voltage of 1.5 V in an acidic medium. Importantly, due to the positive role of oxygenated surface functional groups of the ACMZ-700 active material, the fabricated symmetric cell delivered an attractive specific capacitance of 334 F g−1 @ 1 A/g. As a result of high capacitance and broader working voltage, the symmetric device delivered an excellent energy density of 26 Wh kg−1 at a power density of 748 W kg−1 and held excellent cycling stability over 10,000 charge/discharge cycles.

Hybrid and Asymmetric Supercapacitors: Achieving Balanced Stored Charge across Electrode Materials.

An electrochemical capacitor configuration extends its operational potential window by leveraging diverse charge storage mechanisms on the positive and negative electrodes. Beyond harnessing capacitive, pseudocapacitive, or Faradaic energy storage mechanisms and enhancing electrochemical performance at high rates, achieving a balance of stored charge across electrodes poses a significant challenge over a wide range of charge-discharge currents or sweep rates. Consequently, fabricating hybrid and asymmetric supercapacitors demands precise electrochemical evaluations of electrode materials and the development of a reliable methodology. This work provides an overview of fundamental aspects related to charge-storage mechanisms and electrochemical methods, aiming to discern the contribution of each process. Subsequently, the electrochemical properties, including the working potential windows, rate capability profiles, and stabilities, of various families of electrode materials are explored. It is then demonstrated, how charge balancing between electrodes falters across a broad range of charge-discharge currents or sweep rates. Finally, a methodology for achieving charge balance in hybrid and asymmetric supercapacitors is proposed, outlining multiple conditions dependent on loaded mass and charge-discharge current. Two step-by-step tutorials and model examples for applying this methodology are also provided. The proposed methodology is anticipated to stimulate continued dialogue among researchers, fostering advancements in achieving stable and high-performance supercapacitor devices.

GO based nanocomposite hydrogel enabled high performance wearable all-solid supercapacitor based on hierarchical structure electrodes derived from ZIF-67

The flexible and wearable supercapacitors have attracted wide interest because of their widespread application in smart electronic devices with rapid charging and discharging. As an important part of supercapacitor, the electrode materials with a hollow structure, especially those with hierarchical structures that provide an array of continuous hollow cages, are considered promising. Because of its porous shell which is rich in redox reaction sites for supercapacitors. In this work, we fabricated a ZIF-67 derived hollow Co3O4 growth on the surface of 1D NiCo2O4 to assemble into a beaded structure. In this case, NiCo precursor acted as a structure-directing agent to grow a ZIF-67, a promising electroactive material of electrochemical capacitors to provide capacitance after calcination. Combined with the grapheneoxide (GO) based high conductivity hydrogel as the solid electrolyte, the capacitance of the flexible supercapacitor exhibited a high specific capacitance of 90F g−1 at 0.5 A/g, and it was sturdy and durable. There was no significant loss of capacitance while suffering from bending and pressing. The outstanding electrochemical properties of the all-solid supercapacitor can be attributed to the unique nanostructure of the electrode that created more reactive active sites, increased the diffusion pathway for electrolyte ions, along with the high conductivity of the hydrogel electrolyte.

A Review on Nano Fluid Production, Mathematical Modelling and Applications

Recently, nano fluids have taken on a significant role in many human endeavours. A fluid called a nanofluid includes nanoparticles, also called nanoparticles. Colloidal suspensions of nanoparticles in a base fluid are what these fluids are made of. The numerous production procedures and mathematical interpretation models for nanofluids are examined in this review study. Marangoni convection’s advantages, which enhance heat transfer and balance temperature distribution, are underlined. The effects of thermophoresis on surface tension as well as surface tension in laminar natural convection are also discussed in this work. The characteristics of carbon nanotubes and their prospective medical uses are covered in the article. The study covers electrochemical double layer capacitors, which offer greater safety, longer cycle stability, and better power densities. The study explores the impact of magnetic fields on entropy formation and natural convection in a hybrid nanofluid enclosure, revealing four distinct models based on thermal conductivity and viscosity correlations. The information review work is relevant. The review information work is relevant to flow tracers, prosthetic heart valves, oil pipelines, chemical industry separation methods, and oil recovery.