Capacitive Behavior Research Articles

Renewable symmetric supercapacitors assembled with lignin nanoparticles-based thin film electrolyte and carbon aerogel electrodes

Lignin as a natural biopolymer is becoming increasingly in demand due to its eco-friendly properties, while lignin-based electrolyte with high conductivity and reliable durability for applications in supercapacitors is still challenging. Herein, a facile method to prepare lignin nanoparticles (LNPs)-based solid electrolyte thin film (LF) was proposed through chemical cross-linking reaction. The fabricated LF exhibited a distinctive spongy porous structure with the ionic conductivity of 3.26 mS cm−1, demonstrating the exceptional flexibility and favorable mechanical properties. Moreover, the assembly of all-LNPs-based symmetric supercapacitor (SSC) devices was achieved using LF electrolyte and LCA electrodes for the first time, confirming the LF3 electrolyte superior to commercial cellulose separator in capacitive behaviour. This SSC device exhibited a specific capacitance of 122.7 F g−1 at 0.5 A g−1 and the maximum energy density of 17.04 W h kg−1. Furthermore, the incorporation of sodium alginate (SA) significantly enhanced the ionic conductivity of SA/LF3 electrolyte, and the resulting SSC device delivered a higher specific capacitance of 174.5 F g−1 at 0.5 A g−1 and the maximum energy and power densities of 24.24 W h kg−1 and 5023 W kg−1, respectively. This study proposes a promising approach for sustainable utilization of lignin in energy storage applications.

Pulsed laser-modified zinc anode with improved dendrite and corrosion resistance for sustainable high performance zinc ion hybrid supercapacitors

This research explores the development and evaluation of zinc ion hybrid supercapacitors (ZIHSCs) with a focus on the enhanced performance and low corrosion attributes of pulsed laser-modified zinc anodes compared to their non-modified counterparts. These anodes, paired with cathodes crafted from activated carbon derived from jute sticks on graphite foil, were immersed in a 2 M zinc sulfate electrolyte. A pivotal aspect of the study is improving the electrochemical properties and corrosion resistance of zinc anodes achieved through precise pulsed laser modification. Extensive electrochemical testing was conducted to assess the capacitive behavior, energy storage capabilities, and durability of the supercapacitors during prolonged cycling. Hence, using the laser modified anode, we attain remarkable stability in Zn||Zn symmetric cells for 1000 h at high current density of 10 mA cm−2 with a capacity of 1 mAh cm−2, and ZIHSCs achieving specific capicitance up to 287 F/g at a current density of 0.1 A/g, and reaching an energy density of 102 Wh/kg while sustaining a power density of 80 W/kg. After 10,000 galvanostatic charge-discharge cycles, these supercapacitors maintained high capacitance values, underscoring their resilience. Notably, charge transfer resistance reduction, improved ion diffusion and enhanced corrosion resistance contributes to the supercapacitors' longevity and efficiency, which can be attributed to these anodes laser-induced surface alterations. This study highlights the crucial role of pulsed laser-modified zinc anodes in advancing ZIHSCs performance, marking a significant step towards achieving efficient and sustainable energy storage solutions.

Effect of surface functionalization on the quantum capacitance of M2CF2 (M = Ti, V, Cr, Zr, Nb, Mo) as supercapacitor electrodes

The surface charge storage capacity, atomic structures, and quantum capacitance of M2CF2 (M=Ti, V, Cr, Zr, Nb, Mo) are investigated using density functional theory (DFT). The influence of different surface functionalization methods on the capacitance performance of M2CF2 is also examined, including the introduction of vacancy defects (C-, F-, M-vacancy) and nonmetal doping (N, O, and S). The findings show that both defects and doping reduce the quantum capacitance of V2CF2, Cr2CF2, and Mo2CF2, but they have a negligible impact on the capacitance behavior of Ti2CF2, Zr2CF2 and Nb2CF2. Furthermore, the pristine Cr2CF2 system exhibits relatively high quantum capacitance and surface charge storage capacity under both positive and negative bias. However, the presence of vacancies and dopants significantly decreases its capacitance. Among the structures studied, pristine and nonmetal-doped V2CF2 demonstrate the highest quantum capacitance values (1302.02–1517.56 μF/cm2), suggesting its potential as an effective positive electrode material. Overall, the findings of this study are expected to boost the development of high-capacitance electrodes in the future.

(Sm3+/Eu3+/Tm3+)-TiO2 heterostructures for electrochemical and photovoltaic applications

This study reports on the synthesis of lanthanide oxides triply doped titania, forming a novel hetero-system known as (Sm3+/Eu3+/Tm3+)-TiO2. An environmentally friendly sol gel method was used to synthesize the energy-efficient (Sm3+/Eu3+/Tm3+)-TiO2, and thin films were deposited by spin coating. Electrode and solar cell devices were fabricated under ambient conditions, and rare earth doping enhanced the opto-electronic aspects of the host by narrowing the band gap up to 3.92, 3.85, and 3.56 eV. Particle sizes for the pure and doped materials were 85.15 and 82.72 nm, respectively. With a specific capacitance of 667.34 F g−1, the lanthanide-doped ornamented nickel foam electrode outperformed the pristine electrode, which had a specific capacitance of 169.59 F g−1. Moreover, this electrode exhibited tiny equivalent series resistance (Rs) of 0.13 Ω, indicating quicker response kinetics at the interface, in addition to its electrical double layer capacitance behavior. Electrochemical studies revealed that (Sm3+/Eu3+/Tm3+)-TiO2 semiconductor has a high specific power density of 8157.03 W kg−1, compared to 4079.73 W kg−1 for undoped titania. This improved specific power density demonstrates its suitability for practical scale applications. The produced materials were an excellent HER electro-catalyst with remarkably lower overpotential and Tafel slopes i.e., of 137 mV and 87.6 mV dec−1, in a respective manner, in comparison to the reference TiO2 with 147 mV and 104.5 mV dec−1, respectively. The electro-catalyst's response to the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) was enhanced upon lanthanide doping. Additionally, this substance successfully retrieved electrons from a perovskite solar cell device, achieving efficiency levels of 16.49 and 16.75 % in both forward and reverse bias with fill factor increase.

Bifunctional properties of Ag/α-Fe2O3/rGO nanocomposite for supercapacitor and electrochemical nitrate sensing using tetradodecyl ammonium nitrate as ion-selective membrane.

Noble metal nanoparticles incorporated in hybrid nanocomposites are considered as promising candidates for electrochemical applications owing to their physicochemical properties. In this work, we demonstrated the preparation of Fe2O3/rGO nanocomposite by hydrothermal method, followed by in situ Ag binding synthesis for the fabrication of hybrid nanocomposite (Ag/α-Fe2O3/rGO). The crystallographic structure of the hybrid nanocomposite is examined by X-ray diffraction (XRD) analysis which confirms the characteristics of Ag, Fe2O3, and rGO. The microscopic studies and energy-dispersive X-ray analysis (EDS) spectra confirmed the presence and formation of hybrid nanostructures. Raman analysis results further corroborate the formation of composite with significant D and G bands in Fe2O3/rGO and Ag/α-Fe2O3/rGO samples, which follow XRD results. Cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) studies were carried out to analyze the faradaic capacitor behavior. A specific capacitance of 209.09 F/g was observed by GCD studies for Ag/α-Fe2O3/rGO composites at a current density of 1 A/g, which exhibited good capacitance retention of 94% for 5000 cycles at 7 A/g. Furthermore, the Ag/α-Fe2O3/rGO electrode was used for the electrochemical detection of nitrate ions in soil by utilizing an ion-selective membrane over the surface of the Ag/α-Fe2O3/rGO electrode. The fabricated nanocomposite electrode showed a significant change in the peak current values with the concentration of nitrate in a linear range from 10 to 450μM with the sensitivity to be calculated 1.426 μA μM-1cm-2 and limit of detection (LOD) calculated to be 0.18μM. The reproducibility and interference studies showed a promising result to be utilized for detecting nitrate ions in soil and in real-time applications.

Active power compensation circuit for resonance mitigation and harmonic reduction in microgrid system

The nature and behavior of capacitors, transformers, inductors, active compensators, and non-linear loads can produce power resonance. Unfortunately, the presence of a resonance phenomenon can have a negative impact on system stability and lead to catastrophic power system failures. Therefore, even when using modern or conventional techniques to enhance total harmonic distortion (THD) or improve input power factor (IPF), it is necessary to avoid resonance. An active power compensation circuit (APCC) is proposed and designed to function with two categories of linear/non-linear loads. The APCC has been implemented and regulated using an adjusted pulse width modulation technique. The aim of the suggested APCC is to minimize AC side distortions, improve the IPF, and mitigate harmonics resonance at the same time. The simulation results demonstrate that the proposed APCC investigates the aim function of this study by absorbing harmonics, correcting IPF, and eliminating resonance problems under both transient and steady-state operating conditions. The supply voltage and current THD values for the first power circuit type are reduced by 96.7 % and 96.3 %, respectively, at α=30°. Meanwhile, for the second power circuit, the THD is reduced by 91.92 % and 90.4 %. Also, the IPF changed for the first and second power circuits from 0.72 and 0.86 to almost unity. These results demonstrated the effective performance of the APCC circuit and controller in reducing power harmonics, eliminating power resonance, and modifying power factors.

Structural, Thermal, Optical, Electrical, and Dielectric Properties of Complex Lead-Free Compound: [Bi1∕2Na1∕2][Fe1∕2W1∕2]O3

Some physical properties (structural, dielectric and optical) of a complex lead-free ceramic [[Formula: see text][Formula: see text]][[Formula: see text][Formula: see text]]O3 have been thoroughly examined in different experimental conditions in this study. It was fabricated via a solid-state reaction method. The crystal structure is monoclinic, according to the detailed analysis of the X-ray diffraction pattern. Also, the functional vibrational bands can be observed in the FT-IR and Raman spectra, which support the creation of the molecular structure. Scanning electron microscope (SEM) images of the sample clearly show the effects of [Formula: see text] and [Formula: see text] incorporation in morphology, and energy dispersive X-ray spectroscopy (EDX) indicates the existence of all constituents. The non-overlapping small polaron tunneling (NSPT) and correlated barrier hopping (CBH) model conduction mechanisms are examined through Jonscher’s power law. The contribution of the grain and grain boundary to the capacitive behavior is shown by Nyquist plots. According to a leakage current analysis, the compound exhibits Ohmic and space charge limited conduction (SCLC) conduction mechanisms. Electric field polarization was used to study the ferroelectric nature. The findings of this study show that the inclusion of [Formula: see text] and [Formula: see text] is an efficient technique to improve its dielectric and optical characteristics.

Application of transition metal doped in boron carbide/graphene heterostructures as an electrode for supercapacitors

The density functional theory (DFT) is applied within the current piece of research for exploring the charge storage capacity, quantum or chemical capacitance (QC), electronic structures and the geometry of modified boron carbide (BC3)/graphene (Gr) heterostructure. Also, the impact of doping the Mn atom upon the capacitance behavior of BC3/Gr is explored. Based on the results, doping the Mn atom improved the QC of BC3/Gr. Moreover, doping the Mn atom was more effective than vacancy defect in enhancing the QC of BC3/Gr. The QC of the Mn-doped BC3/Gr was the highest (280.41 F/cm2), which demonstrates its potential application as an encouraging electrode material in supercapacitors (SCs). Based upon the DOS around the Fermi level, doping the Mn atom could be the reason for the increase in the QC. Finally, the results can provide useful insights into designing high-capacitance SCs.

Linear-Organic-Ions In Situ-Intercalated MoS2 for Unveiling Capacitive Energy Storage Relies on the Chain Length.

Intercalating linear-organic-ions into the MoS2 interlayer is beneficial for optimizing electrons/ions' capacitive storage behavior. The chain length, as an important parameter of linear organic ions, can lead to differences in the dispersion, polarity, critical micelle concentration of organic ions, and steric hindrance to the growth of MoS2 nanosheets. Up until now, the relationship between chain length, synthesis of intercalated-MoS2, and capacitive energy storage has not been unveiled. Herein, we have designed an in situ-intercalation route that is simple, efficient, and high yield for inserting four types of linear organic ions into the interlayer of MoS2 to synthesize four types of in situ-intercalated MoS2 samples. After organic-ion intercalation, the expanded interlayer spacing achieved the introduction of intercalation-type pseudocapacitors, as confirmed by ex situ XRD. Improved extra capacitance is verified due to the enlarged ion storage space from a synergistic spatial effect in the broken-shell-hollow ball. Additionally, the generation of high-valent Mo (+5 and +6) and S-vacancies is beneficial for energy storage. More importantly, according to density functional theory (DFT) calculations, as the chain length increases, the number of negative adsorption sites and the total adsorption ability also increase, leading to significantly improved specific capacitance. This work will provide an archetype for the preparation of in situ-intercalated layered materials and unveil capacitive energy storage that relies on the organic-ion chain length.

Electrochemical characterization of passive film and corrosion in Co-rich high entropy alloys in Ringer's solution

This study investigates the corrosion characteristics of Co30Cr20Ni20Fe20Mo10 (Co30HEA), Co40Cr20Ni15Fe15Mo10 (Co40HEA), and Co50Cr20Ni10Fe10Mo10 (Co50HEA), designed as Co-rich high entropy alloys, compared to 316 L stainless steel and L605. Co30HEA has a single FCC phase, whereas the other two alloys exhibit a dual phase of FCC + (Cr, Mo) σ phase. The presence of high Cr and Mo content in the σ phase results in Cr depletion zones. Co30HEA shows the highest corrosion resistance in Ringer's solution, which diminishes with increasing Co content. Its passive film exhibits ideal capacitive behavior at low frequencies, indicating strong passivation. The films, primarily composed of Cr oxides and hydroxides, vary in thickness, with Co30HEA having a film about twice as thick as the others. All three alloys demonstrate pitting corrosion; however, Co30HEA shows the smallest pits mainly at grain boundaries, while the others show pits near the σ phase due to unstable passive films in the Cr and Mo-depleted zones, acting as anodic sites for galvanic corrosion.

Novel three-dimensional architectured ZnMgAl ternary layered double hydroxide@reduced graphene oxide nanocomposites as electrode material for high-performance supercapacitor

Ternary layered double hydroxides (LDH) have recently attracted immense attention owing to their stupendous features, such as fine compositional tuning, multiple valence states, and superior electrochemical activity. Moreover, their intriguing structures and distinctive physiochemical properties delineate them as an exemplary material to serve as electrodes for high-performance supercapacitors (SCs). The present work reports the in-situ synthesis of Zinc Magnesium Aluminium LDH (ZMA) integrated with reduced graphene oxide (rGO) through a single-step hydrothermal approach. The resulting novel ternary ZMA@rGO nanocomposite (ZMAG) possesses a unique architecture incorporating hierarchical 3D nanoflowers of ZMA embedded on graphene nanosheets. The porous morphology of LDH improves interfacial charge transport, which results in more faradaic reactions at the electrochemically active sites. In addition, the conductive graphene nanosheets render a high specific surface area, endowing excellent capacitive behavior. The amalgamated electrochemical properties of ZMA and rGO develop a competent electrode material (ZMAG) for SCs. The ZMAG2 nanocomposite having ZMA and rGO in 1:1, evinces a specific capacitance (Cs) of 656.7 F/g at a current density (Id) of 1 A/g. Furthermore, the asymmetric supercapacitor (ASC) features admirable cycle stability (retains 89% of initial capacitance after 15,000 charge/discharge cycles). Herein, the real-time application of ZMA@rGO//AC ASC has also been demonstrated. Therefore, hierarchical porous nanostructure proclaims new prospects for fabricating proficient electrode materials for energy storage devices.

High-Performance All-Solid-State on-Chip Planar Micro-Supercapacitors Based on Aminated Graphene Quantum Dots by Photolithography

Rapid development of portable miniaturized electronic devices has put forward higher requirements for microenergy. Functionalized graphene quantum dots combine the properties of both functionalized graphene and quantum dots, and are expected to promote further development of high-performance energy storage devices. Here, all-solid-state on-chip planar micro-supercapacitors (PMSCs) were fabricated based on aminated graphene quantum dots by modified liquid-gas interface self-assembly and photolithography, with the electrode width/gap of 24 μm/8 μm. The electrochemical performance was analyzed by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), electrochemical impedance spectrometry and cycle stability in PVA/H2SO4 gel electrolyte. The results indicated that the fabricated PMSCs showed good capacitive response at the scan rates of 0.01 V s−1 to 10000 V s−1. The CV curves of the PMSCs displayed a typical pseudocapacitive feature at the scan rates of 0.01 V s−1 to 1 V s−1. The PMSCs had ultrahigh rate capability of up to 10000 V s−1, and the GCD curves were near triangle-shaped curves, demonstrating excellent electrochemical reversibility. The PMSCs showed ideal capacitive behavior at the low frequency region of the Nyquist plot. The Nyquist plot of the PMSCs showed a semicircle at the high frequency region. The relaxation time constant of the PMSCs were 3.59 μs, indicating that the PMSCs had fast frequency response. After 10000 charge-discharge cycles at the scan rate of 500 V s−1, the initial capacitance retention rate of the PMSCs were 99.17%, indicating that the PMSCs possessed good long-term electrochemical stability. This study provides an important reference for the application of functional graphene quantum dots in the field of the PMSCs.

Influence of the activation time of magnesium surfaces on the concentration of active hydroxyl groups and corrosion resistance

Magnesium alloys have been extensively studied as degradable biomaterials for clinical applications due to their biocompatibility and mechanical properties. However, their poor corrosion resistance can lead to issues such as osteolysis and the release of gaseous hydrogen. This study investigated the influence of the activation time of magnesium surfaces in a sodium hydroxide (NaOH) solution on the concentration of active hydroxyl groups and corrosion resistance. The results indicated that immersion time significantly influences the formation of a corrosion-resistant film and the distribution of surface hydroxyl groups. Specifically, specimens treated for 7.5 h exhibited the highest concentration of hydroxyl groups and the most uniform oxide film distribution. Electrochemical tests demonstrated capacitive behavior and passive surface formation for all evaluated times, with the 7.5-h immersion in NaOH yielding superior corrosion resistance, lower current density, and a more efficient and thicker protective film. SEM and EDS analyses confirmed increased formation of Mg(OH)₂ for samples treated for 5 and 7.5 h, while a 10-h treatment resulted in a brittle, porous layer prone to degradation. Statistical analysis using ANOVA and Fisher's LSD test corroborated these findings. The optimal 7.5-h alkali treatment enhanced magnesium's corrosion resistance and surface properties, making it a promising candidate for orthopedic implants. However, further studies are necessary to assess biocompatibility and physiological responses before clinical implementation.

Enhancing the electrochemical properties of biopolymer composites using starch‐graphene nanoplatelets

AbstractThe study presents the ideal distribution of graphene nanoplatelets (GNP) within the thermoplastic starch (TPS) matrix significantly elevated the thermal and electrical conductivities, as well as the electrochemical efficiency of the biocomposites. Additionally, the incorporation of GNP resulted in an increased thermal stability for the TPS, as indicated by the elevated temperatures required for maximum degradation. The biocomposites exhibited a self‐aligned layered structure, creating conductive pathways and enhancing electron conduction. An electrical conductivity increased as the concentration of GNP increased, with the highest conductivity observed on the top and bottom surface with the value of 4.23 × 10−7 S/m and 3.92 × 10−6 S/m when 12 wt% of GNP was added. The presence of hydroxyl groups in TPS facilitated the formation of hydrogen bonds with GNP, preventing GNP from stacking and forming a more uniform conductive network within the film. The addition of 15 wt% GNP also improved the capacitive performance of the TPS matrix, as evidenced by higher current responses and larger quasi‐rectangular areas in the cyclic voltammetry curves compared to neat TPS. The Nyquist plots which are illustrated impedance data showed that the TPS film with 12 wt% GNP exhibits the smallest semicircle, indicating the highest conductivity which is suggested that GNP improves charge transfer compared to pure TPS.Highlights Optimal dispersion of GNP enhanced the biocomposite's properties. The electrical conductivity increases with the GNP content until 12 wt%. TPS/GNP self‐aligned layered improved conduction and capacitive behavior. GNP improved thermal stability by restricting polymer chain movement. Electrochemical impedance shows improved properties of TPS/GNP.

Dual crosslinked interpenetrating polymer network-based porous hydrogel membrane for solid-state supercapacitor applications

Hydrogel membranes have emerged as promising candidates for solid-state supercapacitors (SSCs), overcoming limitations associated with traditional liquid electrolytes like leakage, thermal hazards, and flammability. However, single-network hydrogels often suffer from poor mechanical properties, making them inadequate for wearable applications. Herein, solution casting technique is used to develop a novel dual-crosslinked semi-interpenetrating polymer network (semi-IPN) hydrogel membrane through in-situ polymerisation of acrylic acid (AA) in a polyvinyl alcohol (PVA) matrix, followed by doping with KOH solution. By adjusting the composition between PVA and AA, the phase separation pathway is controlled, resulting in a homogeneously distributed porous architecture that enhances ion-conductive pathways. The hydrogel exhibited excellent properties, including high ionic conductivity (174 mS cm−1), considerable tensile strength (5 MPa), and significant elongation at break (460 %). Dielectric studies confirmed its significantly improved capacitive behaviour and low conductivity relaxation characteristics. Additionally, the resulting pseudocapacitor assembled with graphite-silvernanowire-polyaniline based composite electrode demonstrated a high specific capacitance (302 F g−1 at 0.2 A g−1) with outstanding capacity retention (75 % up to 500 cycles). Overall, the incorporation of this novel material provides great potential for high-performance SSC applications.

Low-frequency approximations to the finite-length Warburg diffusion impedance: The reflexive case

A study on the influence of the characteristic parameters of the finite-length diffusion processes on the galvanostatic dynamic response of electrochemical systems described by the reflexive Warburg impedance, is presented. The characteristic frequencies of the reflexive diffusion impedance, originally including those of the purely diffusive behaviour, are identified. The galvanostatic charge/discharge cycle is interpreted from the truncated series obtained from the development into partial fractions of the impedance. The low-frequency behaviour is also compared to the impedance obtained from the development into continued fractions with an only characteristic frequency. Interesting results associated to the transition between the capacitive and diffusive behaviours, emerge from the use of a hybrid methodology dealing with frequency and time domains. A simple electric circuit physically based on the series developments of the reflexive Warburg impedance with an only relaxation time, is used to interpret the galvanostatic charge curve of a commercial supercapacitor and to validate the theoretical study.

Highly porous carbon with selective transformation of nitrogen groups boosts the capacitive performance through boric acid template assisted strategy

To address the extensive demand for energy storage, the development of unique carbon-based supercapacitors represents a viable solution. We successfully synthesize the unique boron (B), nitrogen (N)-containing porous carbon (denoted as BNPC) from reed biomass through one-step boric acid templated carbonization method, which are used as high-performance carbon electrode for electric double-layer capacitor (EDLC). By the synergistic effects of boric acid template and N-rich melamine, a well-balanced micro‐/meso-porous structure and abundant N and oxygen (O) heteroatoms within BNPC are readily obtained, exhibiting an ultrahigh specific surface area of 2619 m2·g−1. These distinctive natures endow BNPC electrode with the excellent capacitive behaviors, affording an outstanding specific capacitance of 396.8 F·g−1 at a three-electrode (3E) system with KOH electrolyte. Density functional theory (DFT) method is utilized to further clarify the interaction mechanism between K and designed graphene with various N configurations, revealing the significant roles of Pyridinc-N and Graphitic-N. The two-electrode (2E) symmetric supercapacitor assembled by BNPC electrodes in TEABF4 electrolyte demonstrates an extremely high energy density of 51.82 Wh·kg−1 at a power density of 375 W·kg−1 and great capacitance retention of 91 % after 6000 cycles. This reed-derived highly porous carbons display superior electrochemical performance, making it the ideal candidates for large capacity supercapacitors in practice.

Analysis of a film-forming amine response in impedance spectra

In this study, a detailed analysis of the dielectric response of a film-forming amine (1,3 N-oleyl propanediamine (OLDA)) in impedance spectra is presented, addressing both “bulk” OLDA and adsorbed OLDA layer on a carbon steel surface. The dielectric response of the “bulk” OLDA in the absence of electrolyte over an extensive temperature range (-150 °C to 50 °C) was explored by broadband dielectric spectroscopy (BDS). Subsequently, the response of the OLDA adsorbed layer on the steel surface was analysed by electrochemical impedance spectroscopy (EIS), for various immersion times (2 min to100 min) and temperatures (25 °C to 75 °C) in an aqueous NaCl solution.Impedance spectra (BDS and EIS), interpreted through the complex conductivity formalism, showed a resistive behaviour in the mid-frequency range and a capacitive behaviour at higher frequencies. The high frequency capacitive response in EIS spectra was shown to contain contributions from the OLDA layer and from the electrochemical double layer, as well. The temperature dependency of the OLDA conductivity was found to be similar to the temperature dependency of the electrolyte resistance, suggesting that the electrolyte (water and ions) crossed the OLDA layer to reach the steel surface. The presence of gauche defects in the OLDA alkyl chain, revealed by polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) analyses, may be a contributing factor to the disorder in the adsorbed layer, facilitating electrolyte infiltration.

Electric double layer in ionic liquids: A result of interplay between coupling effects and phase demixing

Ionic liquids (ILs) are appealing electrolytes for their favorable physicochemical properties. However, despite their longstanding use, understanding the capacitive behavior of ILs remains challenging. This is largely due to the formation of a nonconventional electric double layer (EDL) at the electrode-electrolyte interface. This study shows that the short-range Yukawa interactions, representing the large anisotropically charged ILs, demix IL to create a spontaneous surface charge separation, which is reinforced by the strongly coupled charge interaction. The properties of the condensed layer, the onset of charge separation, and the rise of overscreening and crowding critically depend on the asymmetry of Yukawa interactions. Published by the American Physical Society 2024

Synergism of carbonaceous additives in engineering of the supercapacitive performance of α-and λ-phases of manganese oxide

Owing to the presence of valence shells for charge transfer, a high theoretical specific capacitance, and variable redox properties, MnO2 appears as a promising agent in the realm of energy storage. Crystallographic structures of manganese oxide (MnO2), a transition metal oxide, play a crucial role in determining its capacitive behavior by controlling the ion intercalation and double-layer formation. In this work, two different phases of MnO2 were synthesized using the facile chemical reduction method and biological method, say α-MnO2 and λ-MnO2. The phases were incorporated with different carbonaceous additives including GO and CNT while maintaining a constant weight ratio of 8:1:1 between active materials (MnO2), additive, and PVDF binder. Among different composites formed, the best electrode performance is demonstrated by λ-MnO2/CNT/PVDF composite with an excellent specific capacitance of 356 F/g at a scan rate of 1 A/g. Moreover, the best-performing electrodes are investigated with a symmetrical two-electrode system yielding a wide potential window of 1.8V with an outstanding power density of 13.5 KW/Kg at 5 A/g and an energy density of 53.78 Wh/Kg at 1A/g having a specific capacitance of 190 F/g.