Electric Double Layer Capacitors Research Articles

Evaluation of Structural, Thermal, and Electrochemical Properties of PEO/Ionic Liquid Based Quasi‐Solid‐State Electrolytes for Electrical Double Layer Capacitor Devices

Evaluation of Structural, Thermal, and Electrochemical Properties of <scp>PEO</scp>/Ionic Liquid Based Quasi‐Solid‐State Electrolytes for Electrical Double Layer Capacitor Devices

Optimizing protic ionic liquid electrolyte for pre-intercalated Ti3C2Tx MXene supercapacitor electrodes

Electrical double-layer capacitors (EDLCs) are of increasing importance in energy storage from renewable sources. The properties of the electrode and electrolyte materials influence the energy and power densities of EDLCs. We examined the specific capacitance and ion dynamics of a protic ionic liquid confined in pre-intercalated Ti3C2Tx MXene. Our electrochemical measurements demonstrated that the creation of a protic ionic liquid, 1-butyl-3-H-imidazolium bis(trifluoromethanesulfonyl)imide (BuIMH-NTf2), using a mixture of ionic liquid, 1-butyl imidazole (BuIM), and salt, bis(trifluoromethanesulfonyl)imide (HNTf2), in a ratio of 0.8:0.2 led to the optimal capacitance. Remarkably, quasi-elastic neutron scattering measurements revealed increased particle mobility at this composition, attributed to the more efficient accumulation of BuIMH+ on the electrode surface. This deposit of additional ions results in fewer BuIM molecules away from the surface, enhancing their mobility due to reduced crowding. This composition-dependent electrochemical behavior will guide the formulation of more efficient protic ionic liquid systems, enabling faster ion transport in energy storage devices.

Recycling of activated carbons from spent supercapacitors to refabricate improved supercapacitors

The growing market of commercial electric double-layer capacitors (EDLCs) will lead to a vast accumulation of waste as they arrive out of operation. Recycling the spent electrode activated carbon is a closed-loop solution to provide environmental and economic advantages for EDLC use. However, effectively regenerated methods of high-purity activated carbons are still lacked despite their considerable expense. Herein, a simple steam physical activation method is developed to regenerate high-class activated carbons from spent EDLCs. The process is first demonstrated that can effectively eliminate few electrolytes and complex organics as well as regenerate electrode carbon materials. The activation-recycled carbon materials preserve the physicochemical properties of fresh activated carbons and enhance their mesopore ratios, which contributes to improved EDLC performance, obviously surpassing recycled carbon materials by calcination method, including superior specific capacitance of 103.3 F g−1 at 0.5 A g−1, rate performance and cycling stability, equal to fresh activated carbons. Moreover, the assembled activation-recycled carbon material EDLC delivers low self-discharge rate (89 % of initial voltage after 72 h), wide temperature range (−40 to 85 °C), excellent cycling stability (92.2 % capacitance retention after 10,000 cycles) even at elevated voltages (3.0 V) and temperature (65 °C) test. The present work provides an effective and economic method of recycling high-grade activated carbons for sustainable EDLCs.

Porous activated carbon electrodes derived from Eleusine coracana biowaste in electric double layer capacitors: Nanoarchitectonics and performance

The development of high-performance supercapacitors from biowaste is crucial for advancing sustainable and renewable energy storage technologies. In this study, we report the fabrication of electrodes for high-performance supercapacitors using porous carbon derived from red millet (Eleusine coracana) straw. Porous carbon was synthesized via a two-step chemical activation process using KOH, resulting in a hierarchical pore structure comprising macro-, meso-, and micropores. The red millet-based porous carbon electrodes, assembled in a two-electrode symmetrical supercapacitor, exhibited a specific capacitance of 68 Fg⁻1 at a current density of 0.5 Ag⁻1 in a 1 M Na₂SO₄ aqueous electrolyte. At a mass loading of 5 mg per electrode, the system demonstrated a specific capacitance of 300 Fg⁻1 at 1 Ag⁻1, with an energy density of 9.1 Whkg⁻1 and a power density of 1.86 kWkg⁻1, as determined from galvanostatic charge-discharge measurements. Additionally, the supercapacitor showed excellent cyclic stability, retaining 98.78% of its initial capacitance after 5000 cycles at 10 Ag⁻1. These findings highlight the potential of porous carbon derived from agricultural biowaste for scalable applications in electric double-layer capacitors.

Electrochemical properties of plasticized PVA-based electrolyte inserted with alumina nanoparticles for EDLC application with enhanced dielectric constant

In the current study, the role of alumina nanoparticles was examined in the electrochemical and device performance of PVA-based electrolytes. The NaSCN was used as a cation provider for the host electrolyte, and the glycerol plasticizers were used to enhance conductivity and flexibility. The ratio of salt and plasticizer was fixed, while nanoparticles were varied. The results of impedance AC conductivity confirm that 3 wt% of alumina insertion results in high DC conductivity, which is sufficient for electrochemical device application. Electrode polarization region and plateau area are clearly distinguished in AC spectra. The study of the Dielectric constant reveals that charge storage is maximum at 3 wt% of alumina. The dielectric constant values are about twice the dielectric loss value, which is the topic of immense scientific discussion. The contribution of ion fraction was found to be 0.94, which is excellent compared to the negligible contribution of electrons, which is about 0.05. Electrochemical stability is an additional crucial factor and was found to be 2.47 V. To identify any Redox or non-Redox phenomena occurring in the electrical double-layer capacitor (EDLC) cyclic voltammetry (CV) as the simplest analysis method has been carried out on the sample having the highest DC value. A leaf-like form of the CV plot was noticed at high scan rates, while a rectangular shape was identified at low scan rates. The charge-discharge shape is almost close to the ideal triangular pattern. The discharge part was used to calculate critical EDLC device parameters such as ESR, efficiency, specific capacitance power density, and energy density over 2000 cycles. Low ESR (below 60 Ω) and stable efficiency (almost 100 %) of the device results in high capacitance (≈87 F/g), power density (2978 Wh/kg), and energy density (12.86 W kg−1). The results established that nan-fillers alongside plasticizer is crucial to deliver EDLC devices with improved performances.

Cation-Specific interfacial behavior in organic electrolytes for enhanced energy storage

Energy storage systems such as electrical double-layer capacitors have achieved significant attention due to their high power density and cyclability, attained through charge accumulation at the electrode interfaces. Organic electrolytes are widely investigated for energy storage applications owing to their broad potential windows and high specific energy. In this study, we employed constant potential molecular dynamics simulations at various applied potential differences from 0.0 V to 4.0 V to investigate the interfacial structure between organic electrolytes and graphene electrodes. The electrolytes consisted of propylene carbonate (PC) as the solvent, various cations (Li+, Na+, and K+), and bis(trifluoromethanesulfonyl)imide (TFSI−) as the anion. We observed significant structural reorientation of the PC solvent near the electrode surface under high applied potentials, which altered the K+ layer position near the cathode surface and influenced the capacitive behavior of the system. Additionally, K+ ions exhibited a high desolvation rate, lower ion pair interactions, and faster diffusion capabilities compared to Li+ and Na+ ions. These insights are crucial for advancing the understanding and development of organic electrolyte-based metal ion energy storage systems.

Formulation and Recycling of a Novel Electrolyte Based on Bio-Derived γ-Valerolactone and Lithium Bis(trifluoromethanesulfonyl)imide for Lithium-Ion Batteries.

This work introduces a novel electrolyte comprising lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt dissolved in bio-based γ-valerolactone (GVL) for lithium-ion batteries (LIBs). Moreover, a simple and sustainable aqueous-based recycling approach for recovering the imide-based lithium salt is proposed. Beyond the sustainable origin of the GVL solvent, this electrolyte exhibits reduced flammability risk, characterized by a flash point of 136°C, along with favorable transport properties (conductivity of 6.2mScm-1 at 20°C) and good electrochemical stability (5.0V vs Li+/Li). Its good compatibility with graphite and lithium iron phosphate electrodes ensures remarkable cycling stability in LIB full-cells after 200 galvanostatic cycles at 1C. Furthermore, the proposed liquid-liquid phase electrolyte recycling method allows for a nearly complete recovery of the LiTFSI salt (97-99%) and the GVL solvent (78%). The feasibility of the recycling process is validated by the reutilization of the recovered LiTFSI salt in electric double-layer capacitors, achieving performances similar to that of the pristine salt with exceptional long-term stability.

Concurrently Improving both Mechanical and Electrochemical Performances of Quasi-Solid-State Electrical Double-Layer Capacitors by a Rational Design of Gel Polymer Electrolytes.

Aqueous poly(vinyl alcohol) (PVA) gel electrolyte-based quasi-solid-state electrical double-layer capacitors (QSEDLCs) have been extensively investigated in the past ten years, but challenges remain to fabricate the PVA gel electrolyte possessing both superior mechanical and outstanding electrochemical performances. Herein, we develop a strategy to address this issue by a rational design of PVA gel electrolytes, based on a combination of the freeze-thaw (FT) method and sodium perchlorate (NaClO4)-based water-in-salt (WIS) electrolyte. Our study demonstrates that either the FT method or the NaClO4-based WIS electrolyte can improve both the mechanical performance of the PVA gel electrolyte by increasing the crystallization of PVA chains and the electrochemical performance of the PVA gel electrolyte-based QSEDLC by different mechanisms. In comparison with the conventional solvent evaporation method, this work provides an effective strategy to concurrently improve both the mechanical and electrochemical performances of aqueous QSEDLCs.

Efficient Isolation of Cellulose Nanocrystals from Seaweed Waste via a Radiation Process and Their Conversion to Porous Nanocarbon for Energy Storage System.

This article presents an efficient method for isolating cellulose nanocrystals (CNcs) from seaweed waste using a combination of electron beam (E-beam) irradiation and acid hydrolysis. This approach not only reduces the chemical consumption and processing time, but also improves the crystallinity and yield of the CNcs. The isolated CNcs were then thermally annealed at 800 and 1000 °C to produce porous nanocarbon materials, which were characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy to assess their structural and chemical properties. Electrochemical testing of electrical double-layer capacitors demonstrated that nanocarbon materials derived from seaweed waste-derived CNcs annealed at 1000 exhibited superior capacitance and stability. This performance is attributed to the formation of a highly ordered graphitic structure with a mesoporous architecture, which facilitates efficient ion transport and enhanced electrolyte accessibility. These findings underscore the potential of seaweed waste-derived nanocarbon as a sustainable and high-performance material for energy storage applications, offering a promising alternative to conventional carbon sources.

Cellulose acetate-based polymer electrolyte for energy storage application with the influence of BaTiO3 nanofillers on the electrochemical properties: A progression in biopolymer-EDLC technology

The bio-based solid polymer electrolyte serves as a promising choice for the next generation of energy storage devices to meet the requirement of green chemistry. In the current research, a green plasticized magnesium ion-conducting biopolymer electrolyte was developed using simple solution casting method for Electric Double Layer Capacitors (EDLC) applications. The biopolymer Cellulose Acetate (CA) as the host polymer, with varying concentrations of BaTiO3 as the nanofiller, Mg(CF3SO3)2 as the ionic dopant, and PEG as the plasticizer. A 2 wt% addition of BaTiO3 to the biopolymer electrolyte exhibits maximum conductivity measuring 2.4 × 10−3 S/cm. Linear Sweep Voltammetry (LSV) analysis demonstrates maximum stability voltage of 3.51 V. The ionic transference number (tion) and (tMg2+) were determined to be 0.99 and 0.41 respectively. The fabricated EDLC device with the same electrolyte showed polarisation curve without any noticeable peaks in the Cyclic Voltammetry (CV) plot, indicating no redox reactions occurring at the electrode-electrolyte interface. Galvanostatic Charge Discharge (GCD) results showed excellent coulombic efficiency, stability and Energy Density and Power Density performance over 2000 cycles. The incorporation of BaTiO3 into biopolymer membranes presents a viable approach towards sustainable energy storage solutions by enhancing the energy storage capacity of EDLC devices.

Improving supercapacitor performance with novel potato starch-PVA solid polymer electrolyte blend modified by sodium perchlorate-glycerol additives

The synthesis and analysis of Solid Polymer Electrolytes (SPEs) derived from a blend of Potato Starch and Poly Vinyl Alcohol (PS-PVA), enhanced with Sodium perchlorate salt (NaClO4) and Glycerol (GCL) are explored in this work. Our focus is on their suitability for Electrical Double-Layer Capacitor (EDLC) devices. GCL, a non-toxic substance, served as the plasticizer, and sodium perchlorate was incorporated to enhance the ionic conductivity of the SPE film. The conductivity at room temperature for pure PS-PVA blend, in the absence of salt and GCL, was found to be 4.16 × 10−8 S cm−1. Upon adding an optimized quantity of NaClO4 salt, the conductivity increased to 1.02 × 10−5 S cm−1. Subsequent plasticization of the salt-polymer blend with GCL induced NaClO4 dissociation, further augmenting the conductivity by one order of magnitude. A conductivity value of 10.35 × 10−5 S cm−1 was achieved for the film with 30 wt% GCL. Morphological, electrical, and structural analyses revealed that synthesized polymer films exhibited favorable characteristics. The suitability of these electrolytes for Electric Double-Layer Capacitors (EDLC) was studied using electrochemical characterizations and cycling tests for 2000 cycles. The findings demonstrate their potential for use in energy storage devices, showcasing excellent performance in specific capacitance, energy, and power densities.

Bio-derived gel polymer electrolytes from zein and honey blends integrated with ammonium nitrate for electrical double layer capacitors

Although electrical double layer capacitors (EDLCs) are known to exhibit impressive power density, rapid charging/discharging, and long cycle life, their energy density remains a hurdle for broader use. Gel polymer electrolytes (GPEs) offer an interesting approach to improve the energy density of EDLCs while maintaining their other desirable characteristics. This study investigates the development of novel GPEs based on zein, honey, and ammonium nitrate (NH4NO3) for EDLC applications. The GPEs are prepared by incorporating zein, honey, and NH4NO3 in a dimethyl sulfoxide (DMSO) solvent system through a solution casting method. The degree of crystallinity of zein successfully reduced from 33.0 % to 15.71 % with the addition of 20 wt% NH4NO3. The interaction between zein, honey and NH4NO3 is confirmed by observing the shifting of the hydroxyl band. The ambient ionic conductivity of zein-honey increases from (4.86 ± 0.36) × 10−4 S cm−1 to (4.19 ± 0.40) × 10−3 S cm−1 with the incorporation of 20 wt% NH4NO3 (ZH20), exhibiting the significantly lowest Tg value (77.53 °C). Linear sweep voltammetry (LSV) demonstrates high electrochemical stability up to 2.6 V of ZH20. Additionally, the transference number (tion) of 0.989 indicates a dominant role of ionic charge carriers in this work. Finally, the ZH20-based GPE is used as both an electrolyte and separator to fabricate EDLC. Its electrochemical behavior has demonstrated stable results in terms of specific capacitance, energy, and power density, with fast rate performance observed through cyclic voltammetry and galvanostatic charge-discharge techniques.

Supercapacitor electrodes derived from ultra-high surface area activated carbon spheres synthesized by fluidized activation

This study thoroughly investigated the effects of activation conditions on pore structure development using response surface methodology with a central composite design. The activated carbon sphere (ACS) derived from phenolic formaldehyde resins by carbonization and fluidized activation was examined and characterized. The pore size distribution of ACS samples was all in the microporous and mesoporous scales. ACS with an ultra-high specific surface area of 3142 m2 g−1 and total pore volume of 1.513 cm3 g−1 was successfully obtained at 900 °C for 4 h. Electric double-layer capacitor (EDLC) electrodes derived from ACS with different activation conditions were examined by using cyclic voltammetry and galvanostatic charge/discharge to comprehend the influence of surface area, pore volumes, and the amount of binder on the electrochemical performance. The optimal EDLC electrode was obtained using ACS with the largest specific surface area and pore volume with 5 wt% of binder addition. The specific capacitance was 143.7 F g−1 in a 1 M H2SO4 solution. The cyclical stability of the carbon electrode was also examined under 5000 cycles, and the charge/discharge efficiency remained nearly 100 % without deterioration. This study provides insights into fabricating ultra-high surface area ACS and their potential application as supercapacitors.

Electric Double Layer Capacitors: A Review

Electric Double Layer Capacitors: A Review

Secondary carbon skeletons constructed in porous carbon for electric double layer capacitors

In this work, a secondary skeleton was constructed by filling the larger spaces of porous carbon derived from passion fruit peels with glucose to created more carbon surface in same volume. The combined use of KOH activation and simultaneous etching of micropores on the carbon skeleton and secondary skeleton resulted in the preparation of porous carbon (PGC1-0.5) containing a large number of micropores. PGC1-0.5 have less total pore volume (0.987 cm3 g-1), but more micropore volume (0.821 cm3 g-1), different with 1.171 cm3 g-1, 0.668 cm3 g-1 of PGC1-0, which without glucose. Symmetric supercapacitor bases on PPGC1-0.5 have an obvious improvement in specific capacity (275.6 F g-1 (175 F cm-3), 0.1 A g-1) in 6M KOH electrolyte compared to PGC1-0 (215.2 F g-1 (121.5 F cm-3), 0.1 A g-1). Additionally, the device exhibits excellent cycling performance and retained 103% of its specific capacity after 10,000 cycles and notable reduction in transfer internal resistance in comparison to the sample without glucose. This study shows that filling space with glucose to reduce macropores is an effective method for adjusting the pore size distribution of porous carbon.

Effect of different activating agents on carbon derived from Tinospora cordifolia for EDLC application

Abstract The effect of two activating agents namely phosphoric acid (H3PO4) and iron (III) chloride (FeCl3) is investigated, in activation of carbon obtained from Tinospora cordifolia. The structural and morphological properties of the synthesized activated carbons were investigated using X-ray diffraction, scanning electron microscopy, Raman spectroscopy, and Brunauer–Emmett–Teller analysis. A notable yield of ∼60 % of the activated carbons was obtained using a simple and cost-effective approach of chemical activation followed by the thermal activation method. The electrochemical properties of the activated carbons were studied for electric double-layer capacitor application. The electrochemical impedance spectroscopy, galvanostatic charge–discharge and cyclic voltammetry studies revealed superior charge transfer properties of the carbon activated with H3PO4. The capacitor comprising carbon activated with H3PO4 electrodes shows higher specific capacity of 58 F g−1 at 1 A g−1 than that of carbon activated with FeCl3 (37.5 F g−1). The optimized capacitor delivers superior power density and energy density of 2 kW kg−1 and 28.33 W h kg−1, respectively.

O-PHTHALALDEHYDE CROSS-LINKED CHITOSAN MEMBRANE AS A QUASI-SOLID-STATE ELECTROLYTE FOR SUPERCAPACITORS

This study reports a stepwise formation method of a chitosan membrane cross-linked with o-phthalaldehyde and its use as a polymer matrix in a quasi-solid-state-electrolytebased supercapacitor. The proposed method of cross-linking in chitosan solution and evaporation of the solvent yielded a homogeneous and durable chitosan-o-phthalaldehyde membrane, which, after dipping in an aqueous 2 M lithium sulfate solution, formed a quasi-solid-state-electrolyte (CS/OPAQSSE). The prepared CS/OPA-QSSE was then used in an electric double layer capacitor (EDLC) cell to study its electrochemical properties. The electrochemical performance of the EDLC cell was determined by using the electrochemical impedance spectroscopy, cyclic voltammetry and galvanostatic charging/discharging techniques. The results showed that the EDLC cell with the CS/OPA-QSSE is a fully functional and efficient device. The specific capacitance values calculated for the CS/OPA-QSSE EDLC (up to 115 F g–1) always surpassed the reference cell based on a commercial glass fibre separator Therefore, the proposed chitosan modification can be considered as a future alternative to produce other polysaccharide-based materials for electrochemical use.

Understanding intra-pore electrolyte resistances and distributed capacitances in carbon electrodes used in supercapacitors using a robust modeling process to separate the charge-storage occurring into macro-, meso-, and micro-pore structures

In this study, a Modified Generic Electrochemical (MGE) model is introduced for studying rough/porous carbon-based electrode materials employed in electrical double-layer capacitors (EDLC) which contain different types of surface defects. Instead of adopting the common theoretical approach involving the use of transmission line models or ad hoc equivalent circuits, a rational equivalent circuit model has been devised, which permitted us to derive the different equations for each electrochemical technique. The MGE representing the overall electrochemical behavior of EDLCs obtained using the different techniques (e.g., cyclic voltammetry, chronoamperometry, chronopotentiometry, and impedance) is formally derived based on a simple premise considering that the different inhomogeneous surface defects, which are geometrically arranged under equipotential conditions, are not electrochemically equivalent. In this sense, the presence of hierarchically distributed charge-storage processes with different time constants, accounting for the ionic accumulation at the electrode/solution interface, can be ascertained. We verified that is imperative to avoid the determination of the specific capacitances and resistances in EDLCs using a single electrochemical technique or several techniques whose model equations are based on different theoretical premises. The use of the MGE model unequivocally revealed that isolated measurements of the specific capacitance in the absence of the associated intra-pore resistances are not sufficient to ensure the presence of rapid charge storage allied with high-power characteristics. With the appropriate choice of carbon-based materials with very low intra-pore resistances, substantial progress can be made in ushering in the next generation of EDCLs with very high-power characteristics.

Size polydisperse model ionic liquid under confinement: A molecular dynamics study

The performance of an electric double-layer capacitor is strongly influenced by the choice of electrolyte, and the use of ionic liquid (IL) mixtures as an electrolyte has shown great promise. In this study, a model IL made of a mixture of anions and size-polydisperse cations in equal numbers and confined between two electrodes is investigated by means of molecular dynamics simulations. In particular, using the extent of size-polydispersity (characterized by polydispersity index, δ) as a control parameter, we systematically explore its effect on the local structure, charge profile, ion size distribution in the vicinity of electrode surfaces, and differential capacitance. It is observed that the charge density profiles near cathode, i.e., region comprising both Stern and diffused layers, are significantly affected under the variation of δ in addition to the electrode charge density. Ion population, ordering of different-size cations, and its effective size in the vicinity of electrodes under neutral and applied potential conditions are also quantified. An interesting observation is that the effective cation size in the Stern layer decreases with increasing value of δ in the case of moderate to strong electrode surface charge density. This behaviour can be qualitatively understood from the interplay of enthalpic and entropic forces in the system. Finally, a non-monotomic dependence of capacitance on δ is observed with maximum value of capacitance at a rather small value of δ(≈3%) for the model system.

Stable Efficient Solid-State Supercapacitors and Dye-Sensitized Solar Cells Using Ionic Liquid-Doped Solid Biopolymer Electrolyte.

As synthetic and nonbiodegradable compounds are becoming a great challenge for the environment, developing polymer electrolytes using naturally occurring biodegradable polymers has drawn considerable research interest to replace traditional aqueous electrolytes and synthetic polymer-based polymer electrolytes. This study shows the development of a highly conducting ionic liquid (1-hexyl-3-methylimidazolium iodide)-doped corn starch-based polymer electrolyte. A simple solution cast method is used to prepare biopolymer-based polymer electrolytes and characterized using different electrical, structural, and photoelectrochemical studies. Prepared polymer electrolytes are optimized based on ionic conductivity, which shows an ionic conductivity as high as 1.90 × 10-3 S/cm. Fourier transform infrared spectroscopy (FTIR) confirms the complexation and composite nature, while X-ray diffraction (XRD) and polarized optical microscopy (POM) affirm the reduction of crystallinity in biopolymer electrolytes after doping with ionic liquid (IL). Thermal and photoelectrochemical studies further affirm that synthesized material is well stable above 200 °C and shows a wide electrochemical window of 3.91 V. The ionic transference number measurement (t ion) confirms the predominance of ionic charge carriers in the present system. An electric double-layer capacitor (EDLC) and a dye-sensitized solar cell (DSSC) were fabricated by using the highest conducting corn starch polymer electrolyte. The fabricated EDLC and DSSC delivered an average specific capacitance of 130 F/g and an efficiency of 1.73% in one sun condition, respectively.