ABSTRACT
Scalable and flexible supercapacitors are in high demand from an application point of view. Through our exploration, we have attained promising performance of electrochemical energy storage under the influence of an external magnetic field for future energy-based applications. In this work, a commercial sponge is used as a template for ultra-large graphene oxide (rULGO) functionalization, followed by the incorporation of Co3O4:BN without the inclusion of binders or conductive additives. The fabricated electrodes, namely, SPG-rULGO and SPG-rULGO-Co3O4:BN, demonstrate superior performance with a potential window of 2.2 V at a magnetic field strength of 13.5 and 28 mT, respectively. A specific capacitance of 218 ± 5% F·g-1 and 312 ± 5% F·g-1, respectively, with retention rates of 80 and 88% over 5000 charge-discharge cycles are achieved. In contrast to the conventional fabrication of the asymmetric device, both electrodes are made using flexible substrates with SPG-rULGO-Co3O4:BN as the positive electrode and SPG-rULGO as the negative electrode eliminating the need to use activated carbon. This configuration yields a specific capacitance of 153 ± 5% F·g-1 at 1 Ag-1, leading to a high energy density of 103 ± 5% W·h·kg-1 at a power density of 1.10 ± 5% kW kg-1 with an 85% retention rate. The charge-discharge mechanism of bare and modified electrodes is probed by the distribution of relaxation time analysis of the coupled electrochemical impedance spectra. The integration of magnetic field with advanced electrode materials opens up other possibilities for optimizing energy storage systems and advancing the field of flexible and mechanically robust supercapacitors.
ABSTRACT
Energy harvesting and energy storage are two critical aspects of supporting the energy transition and sustainability. Many studies have been conducted to achieve excellent performance devices for these two purposes. As energy-storing devices, supercapacitors (SCs) have tremendous potential to be applied in several sectors. Some electrochemical characterizations define the performance of SCs. Electrochemical impedance spectroscopy (EIS) is one of the most powerful analyses to determine the performance of SCs. Some parameters obtained from this analysis include bulk resistance, charge-transfer resistance, total resistance, specific capacitance, response frequency, and response time. This work provides a holistic and comprehensive review of utilizing EIS for SC characterization. Overall, researchers can benefit from this review by gaining a comprehensive understanding of the utilization of electrochemical impedance spectroscopy (EIS) for characterizing supercapacitors (SCs), enabling them to enhance SC performance and contribute to the advancement of energy harvesting and storage technologies.
ABSTRACT
Supercapacitors and water splitting cells have recently played a key role in offering green energy through converting renewable sources into electricity. Perovskite-type electrocatalysts such as BaTiO3, have been well-known for their ability to efficiently split water and serve as supercapacitors due to their high electrocatalytic activity. In this study, BaTiO3, Al-doped BaTiO3, Ce-doped BaTiO3, and Al-Ce co-doped BaTiO3 nanofibers were fabricated via a two-step hydrothermal method, which were then characterized and compared for their electrocatalytic performance. Based on the obtained results, Al-Ce co-doped BaTiO3 electrode exhibited a high capacitance of 224.18 Fg-1 at a scan rate of 10 mVs-1, high durability during over the 1000 CV cycles and 2000 charge-discharge cycles, proving effective energy storage properties. Additionally, the onset potentials for OER and HER processes were 11 and - 174 mV vs. RHE, respectively, demonstrating the high activity of the Al-Ce co-doped BaTiO3 electrode. Moreover, in overall water splitting, the amount of the overpotential was 0.820 mV at 10 mAcm-2, which confirmed the excellent efficiency of the electrode. Hence, the remarkable electrocatalytic performance of the Al-Ce co-doped BaTiO3 electrode make it a promising candidate for renewable energy technologies owing to its high conductivity and fast charge transfer.
ABSTRACT
As electronic devices for aviation, space, and satellite applications become more sophisticated, built-in energy storage devices also require a wider temperature spectrum. Herein, an all-climate operational, energy and power-dense, flexible, in-plane symmetric pseudocapacitor is demonstrated with utmost operational safety and long cycle life. The device is constructed with interdigital-patterned laser-scribed carbon-supported electrodeposited V5O12·6H2O as a binder-free electrode and a novel high-voltage anti-freezing water-in-salt-hybrid electrolyte. The anti-freezing electrolyte can operate over a wide temperature range of -40-60 °C while offering a stable potential window of ≈2.5 V. The device undergoes rigorous testing under diverse environmental conditions, including rapid and regular temperature and mechanical transition over multiple cycles. Additionally, detailed theoretical simulation studies are performed to understand the interfacial interactions with the active material as well as the local behavior of the anti-freeze electrolyte at different temperatures. As a result, the all-weather pseudocapacitor at 1 A g-1 shows a high areal capacitance of 234.7 mF cm-2 at room temperature and maintains a high capacitance of 129.8 mF cm-2 even at -40 °C. Besides, the cell operates very reliably for over 80 950 cycles with a capacitance of 25.7 mF cm-2 at 10 A g-1 and exhibits excellent flexibility and bendability under different stress conditions.
ABSTRACT
The advancement of aqueous micro-supercapacitors offers an enticing prospect for a broad spectrum of applications, spanning from wearable electronics to micro-robotics and sensors. Unfortunately, conventional micro-supercapacitors are characterized by low capacity and slopy voltage profiles, limiting their energy density capabilities. To enhance the performance of these devices, the use of 2D MXene-based compounds has recently been proposed. Apart from their capacitive contributions, these structures can be loaded with redox-active nanowires which increase their energy density and stabilize their operation voltage. However, introducing rigid nanowires into MXene films typically leads to a significant decline in their mechanical properties, particularly in terms of flexibility. To overcome this issue, super stretchable micro-pseudocapacitor electrodes composed of MXene nanosheets and in situ reconstructed Ag nanoparticles (Ag-NP-MXene) are herein demonstrated, delivering high energy density, stable operation voltage of ≈1 V, and fast charging capabilities. Careful experimental analysis and theoretical simulations of the charging mechanism of the Ag-NP-MXene electrodes reveal a dual nature charge storage mechanism involving ad(de)sorption of ions and conversion reaction of Ag nanoparticles. The superior mechanical properties of synthesized films obtained through in situ construction of Ag-NP-MXene structure show an ultra stretchability, allowing the devices to provide stable voltage and energy output even at 100% elongation.
ABSTRACT
Revealing the in-depth structure-property relationship and designing specific capacity electrodes are particularly important for supercapacitors. Despite many efforts made to tune the composition and electronic structure of cobalt oxide for pseudocapacitance, insight into the [CoO]6 octahedron from the microstructure is still insufficient. Herein, we present a tunable [CoO]6 octahedron microstructure in LiCoO2 by a chemical delithiation process. The c-strained strain of the [CoO]6 octahedron is induced to form higher valence Co ions, and the (003) crystalline layer spacing increases to allow more rapid participation of OH- in the redox reaction. Interestingly, the specific capacity of L0.75CO2 is nearly four times higher than that of LiCoO2 at 10 mA g-1. The enhanced activity originated from the asymmetric strain [CoO]6 octahedra, resulting in enhanced electronic conductivity and Co-O hybridization for accelerated redox kinetics. This finding provides new insights into the modification strategy for pseudocapacitive transition metal oxides.
ABSTRACT
The true promise of MXene as a practical supercapacitor electrode hinges on the simultaneous advancement of its three-dimensional (3D) assembly and the engineering of its nanoscopic architecture, two critical factors for facilitating mass transport and enhancing an electrode's charge-storage performance. Herein, we present a straightforward strategy to engineer robust 3D freestanding MXene (Ti3C2Tx) hydrogels with hierarchically porous structures. The tetraamminezinc(II) complex cation ([Zn(NH3)4]2+) is selected to electrostatically assemble colloidal MXene nanosheets into a 3D interconnected hydrogel framework, followed by a mild oxidative acid-etching process to create nanoholes on the MXene surface. These hierarchically porous, conductive holey-MXene frameworks facilitate 3D transport of both electrons and electrolyte ions to deliver an excellent specific capacitance of 359.2 F g-1 at 10 mV s-1 and superb capacitance retention of 79% at 5000 mV s-1, representing a 42.2% and 15.3% improvement over pristine MXene hydrogel, respectively. Even at a commercial-standard mass loading of 10.1 mg cm-2, it maintains an impressive capacitance retention of 52% at 1000 mV s-1. This rational design of an electrode by engineering nanoholes on MXene nanosheets within a 3D porous framework dictates a significant step forward toward the practical use of MXene and other 2D materials in electrochemical energy storage systems.
ABSTRACT
Pseudocapacitors promise to fill the gap between traditional capacitors and batteries by delivering reasonable energy densities and power densities. In this work, pseudocapacitive charge storage properties are demonstrated for two isostructural oxides, Sr2 LaFeMnO7 and Sr2 LaCoMnO7 . These materials comprise spatially separated bilayer stacks of corner sharing BO6 units (B=Fe, Co or Mn). The spaces between stacks accommodate the lanthanum and strontium ions, and the remaining empty spaces are available for oxide ion intercalation, leading to pseudocapacitive charge storage. Iodometric titrations indicate that these materials do not have oxygen-vacancies. Therefore, the oxide ion intercalation becomes possible due to their structural features and the availability of interstitial sites between the octahedral stacks. Electrochemical studies reveal that both materials show promising energy density and power density values. Further experiments through fabrication of a symmetric two-electrode cell indicate that these materials retain their pseudocapacitive performance over hundreds of galvanostatic charge-discharge cycles, with little degradation even after 1000 cycles.
ABSTRACT
In the process of radiation therapy (RT), the cytotoxic effects of excited electrons generated from water radiolysis tend to be underestimated due to multiple biochemical factors, particularly the recombination between electrons and hydroxyl radicals (·OH). To take better advantage of radiolytic electrons, we constructed WO3 nanocapacitors that reversibly charge and discharge electrons to regulate electron transportation and utilization. During radiolysis, WO3 nanocapacitors could contain the generated electrons that block electron-·OH recombination and contribute to the yield of ·OH at a high level. These contained electrons could be discharged from WO3 nanocapacitors after radiolysis, resulting in the consumption of cytosolic NAD+ and impairment of NAD+-dependent DNA repair. Overall, this strategy of nanocapacitor-based radiosensitization improves the radiotherapeutic effects by increasing the utilization of radiolytic electrons and ·OH, warranting further validation in multiple tumour models and preclinical experiments.
Subject(s)
Electrons , NAD , Oxides , WaterABSTRACT
Electrochemical energy storage devices are one of the main protagonists in the ongoing technological advances in the energy field, whereby the development of efficient, sustainable, and durable storage systems aroused a great interest in the scientific community. Batteries, electrical double layer capacitors (EDLC), and pseudocapacitors are characterized in depth in the literature as the most powerful energy storage devices for practical applications. Pseudocapacitors bridge the gap between batteries and EDLCs, thus supplying both high energy and power densities, and transition metal oxide (TMO)-based nanostructures are used for their realization. Among them, WO3 nanostructures inspired the scientific community, thanks to WO3's excellent electrochemical stability, low cost, and abundance in nature. This review analyzes the morphological and electrochemical properties of WO3 nanostructures and their most used synthesis techniques. Moreover, a brief description of the electrochemical characterization methods of electrodes for energy storage, such as Cyclic Voltammetry (CV), Galvanostatic Charge-Discharge (GCD), and Electrochemical Impedance Spectroscopy (EIS) are reported, to better understand the recent advances in WO3-based nanostructures, such as pore WO3 nanostructures, WO3/carbon nanocomposites, and metal-doped WO3 nanostructure-based electrodes for pseudocapacitor applications. This analysis is reported in terms of specific capacitance calculated as a function of current density and scan rate. Then we move to the recent progress made for the design and fabrication of WO3-based symmetric and asymmetric supercapacitors (SSCs and ASCs), thus studying a comparative Ragone plot of the state-of-the-art research.
ABSTRACT
Three different compositions of NiCo2 S4 (NCS) materials were prepared using three solvents, named NCS HTDI (hydrothermal in DI water), NCS STEG (solvothermal in ethylene glycol), and a novel carbon-encapsulated NCS STFA (solvothermal in formamide). The structural and morphological properties of the prepared NCS HTDI, NCS STEG, and NCS HTDI materials were analyzed using various physical characterization techniques. As prepared, NCS materials were tested as an electrode for supercapacitor (SC) application using a 3-electrode system in a basic electrolyte (3â M KOH). NCS HTDI exhibits a specific capacitance of 2536â F g-1 , NCS STEG shows 1355â F g-1 , and NCS STFA shows 1178â F g-1 at an input current density of 1â A g-1 . The SBN-PSC material is utilized as a counter electrode in the NCS STFA || SBN-PSC-based asymmetric SC device. The device exhibits exceptionally superior electrochemical performance with a specific capacitance of 172â F g-1 at 10â A g-1 input current density and 97% capacity retention after 5000 cycles in a voltage window of 1.6â V. The results confirm the superiority of NCS STFA||SBN-PSC deviceas an excellent high-energy and high-power SC.
ABSTRACT
We report on the synthesis of activated carbon-semi-polycrystalline polyaniline (SPani-AC) composite material using in-situ oxidative polymerization of aniline on the carbon surface in an aqueous HCl medium at an elevated temperature of 60 °C. The electroactive polymeric composite material exhibits a uniformly distributed spindle-shaped morphology in scanning electron microscopy (SEM) and well-defined crystallographic lattices in the high-resolution transmission electron microscopy (TEM) images. The X-ray diffraction (XRD) spectrum reveals sharp peaks characteristic of crystalline polyaniline. The characteristic chemical properties of polyaniline are recorded using laser Raman spectroscopy. The cyclic voltammetry curves exhibit features of surface-redox pseudocapacitance. The specific capacitance calculated for the material is 507 F g-1 at the scan rate of 10 mV s-1. The symmetrical two-electrodes device exhibits a specific capacitance of 45 F g-1 at a current density of 5 A g-1. The capacitive retention calculated was found to be 96% up to 4500 continuous charge-discharge cycles and observed to be gradually declining at the end of 10,000 cycles. On the other hand, Coulombic efficiency was observed to be retained up to 85% until 4500 continuous charge-discharge cycles which declines up to 72% at the end of 10,000 cycles. The article also presents a detailed description of material synthesis, the formation of polyaniline (Pani) chains, and the role of material architecture in the performance as surface redox supercapacitor electrode.
Subject(s)
Aniline Compounds , Charcoal , Microscopy, Electron, Scanning , Microscopy, Electron, Transmission , Aniline Compounds/chemistryABSTRACT
Harnessing new materials for developing high-energy storage devices set off research in the field of organic supercapacitors. Various attractive properties like high energy density, lower device weight, excellent cycling stability, and impressive pseudocapacitive nature make organic supercapacitors suitable candidates for high-end storage device applications. This review highlights the overall progress and future of organic supercapacitors. Sustainable energy production and storage depend on low cost, large supercapacitor packs with high energy density. Organic supercapacitors with high pseudocapacitance, lightweight form factor, and higher device potential are alternatives to other energy storage devices. There are many recent ongoing research works that focus on organic electrolytes along with the material aspect of organic supercapacitors. This review summarizes the current research status and the chemistry behind the storage mechanism in organic supercapacitors to overcome the challenges and achieve superior performance for future opportunities.
ABSTRACT
In this study, a porous Ni-foam support was employed to enhance the capacitance of nickel cobaltite (NiCo2O4) electrodes designed for supercapacitors. The hydrothermal synthesis method was employed to grow NiCo2O4 as an active material on Ni-foam. The NiCo2O4 sample derived from hydrothermal synthesis underwent subsequent post-heat treatment at temperatures of 250 °C, 300 °C, and 350 °C. Thermogravimetric analysis of the NiCo2O4 showed that weight loss due to water evaporation occurs after 100 °C and enters the stabilization phase at temperatures above 400 °C. The XRD pattern indicated that NiCo2O4 grew into a spinel structure, and the TEM results demonstrated that the diffraction spots (DSs) on the (111) plane of the sample annealed at 350 °C were more pronounced than those of other samples. The specific capacitance of the NiCo2O4 electrodes exhibited a decrease with increasing current density across all samples, irrespective of the annealing temperature. The electrode annealed at 350 °C recorded the highest specific capacitance value. However, the capacity retention rate of the NiCo2O4 electrode revealed a deteriorating trend, declining to 88% at 250 °C, 75% at 300 °C, and 63% at 350 °C, as the annealing temperature increased.
ABSTRACT
Poly(ionic liquid)s (PILs) are used in many electrochemical energy storage/conversion devices owing to their favorable physical properties. Therefore, PIL binders have been examined as polymeric binders for electrodes in energy storage systems (ESSs) and have shown superior performance. Several innovative technologies have been developed to improve the properties of polymers, with cross-linking being the most effective and easy strategy to achieve this. In this study, we designed a breakthrough complex cross-linking and composite technique that could successfully develop the physical properties of a polymer in a simple one-step process. Additionally, the technique could improve the thermal stability and mechanical properties of the polymer. The proposed polymeric binder showed better adhesion, higher capacitance, and good energy density with improved cyclic stability compared to that shown by conventional polyvinylidene fluoride (PVDF). This study revealed that cross-linked networks in polymeric binders are long-cycle-life features for electrochemical redox capacitors.
ABSTRACT
Spinel copper manganese oxide nanoparticles combined with acid-treated multi-walled carbon nanotubes (CuMn2O4/MWCNTs) were used in the development of electrodes for pseudocapacitor applications. The CuMn2O4/MWCNTs preparation involved initial synthesis of Mn3O4 and CuMn2O4 precursors followed by an energy efficient reflux growth method for the CuMn2O4/MWCNTs. The CuMn2O4/MWCNTs in a three-electrode cell assembly and in 3 M LiOH aqueous electrolyte exhibited a specific capacitance of 1652.91 F g-1 at 0.5 A g-1 current load. Similar investigation in 3 M KOH aqueous electrolyte delivered a specific capacitance of 653.41 F g-1 at 0.5 A g-1 current load. Stability studies showed that after 6000 cycles, the CuMn2O4/MWCNTs electrode exhibited a higher capacitance retention (88%) in LiOH than in KOH (64%). The higher capacitance retention and cycling stability with a Coulombic efficiency of 99.6% observed in the LiOH is an indication of a better charge storage behaviour in this electrolyte than in the KOH electrolyte with a Coulombic efficiency of 97.3%. This superior performance in the LiOH electrolyte than in the KOH electrolyte is attributed to an intercalation/de-intercalation mechanism which occurs more easily in the LiOH electrolyte than in the KOH electrolyte.
ABSTRACT
Effective incorporation of conductive and energy storage materials into 3D porous textiles plays a pivotal role in developing and designing high-performance energy storage devices. Here, a fibril-type textile pseudocapacitor electrode with outstanding capacity, good rate capability, and excellent mechanical stability through controlled interfacial interaction-induced electroplating is reported. First, tetraoctylammonium bromide-stabilized copper sulfide nanoparticles (TOABr-CuS NPs) are uniformly assembled onto cotton textiles. This approach converts insulating textiles to conductive textiles preserving their intrinsically porous structure with an extremely large surface area. For the preparation of textile current collector with bulk metal-like electrical conductivity, Ni is additionally electroplated onto the CuS NP-assembled textiles (i.e., Ni-EPT). Furthermore, a pseudocapacitive NiCo-layered double hydroxide (LDH) layer is subsequently electroplated onto Ni-EPT for the cathode. The formed NiCo-LDH electroplated textiles (i.e., NiCo-EPT) exhibit a high areal capacitance of 12.2 F cm-2 (at 10 mA cm-2 ), good rate performance, and excellent cycling stability. Particularly, the areal capacity of NiCo-EPT can be further increased through their subsequent stacking. The 3-stack NiCo-EPT delivers an unprecedentedly high areal capacitance of 28.8 F cm-2 (at 30 mA cm-2 ), which outperforms those of textile-based pseudocapacitor electrodes reported to date.
Subject(s)
Electroplating , Nanoparticles , Electrodes , TextilesABSTRACT
Energy storage devices based on earth-abundant materials are key steps towards portable and sustainable technologies used in daily life. Pseudocapacitive devices, combining high power and high energy density features, are widely required, and transition metal oxides represent promising building materials owing to their excellent stability, abundance, and ease of synthesis. Here, we report an original ZnO-based nanostructure, named nanostars (NSs), obtained at high yields by chemical bath deposition (CBD) and applied as pseudocapacitors. The ZnO NSs appeared as bundles of crystalline ZnO nanostrips (30 nm thin and up to 12 µm long) with a six-point star shape, self-assembled onto a plane. X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence spectroscopy (PL) were used to confirm the crystal structure, shape, and defect-mediated radiation. The ZnO NSs, dispersed onto graphene paper, were tested for energy storage by cyclic voltammetry (CV) and galvanostatic charge−discharge (GCD) analyses, showing a clear pseudocapacitor behavior. The energy storage mechanism was analyzed and related to oxygen vacancy defects at the surface. A proper evaluation of the charge stored on the ZnO NSs and the substrate allowed us to investigate the storage efficiency, measuring a maximum specific capacitance of 94 F g−1 due to ZnO nanostars alone, with a marked diffusion-limited behavior. The obtained results demonstrate the promising efficacy of ZnO-based NSs as sustainable materials for pseudocapacitors.
ABSTRACT
Rapidly changing demand on energy storage systems makes it essential to redesign the device architecture and materials required to fabricate the devices. It is crucial to introduce capacitive behaviour in a conventional energy storage device (batteries) to improve the lifetime and power efficiency of the hole energy storage system. The charge storing nature of electrode material primarily depends on particle size, grain size, the electrode's chemical structure, and effective diffusion lengths for electrolytes within the electrode. Here V2O5based Li-ion battery electrode is transformed into a Li-ion pseudocapacitive electrode by structural modifications. The modified structures are achieved by optimizing reaction pressure to obtain larger, medium and smaller V2O5particles (namely, V2O5-L, V2O5-M and V2O5-S). As a result, the plateau regions in galvanostatic charge-discharge plots and highly intense redox peaks in the CV plots of V2O5-L get flattened for V2O5-S. Also, the lucrative improvement in rate capabilities and stability for V2O5-S indicates induced pseudocapacitance in V2O5. Some devices are fabricated with the extrinsic pseudocapacitive material (V2O5-S), providing 4.36 mWh cm-3volumetric energy density with 125 mW cm-3volumetric power density. The device retains around 95% of its initial capacitance after 10k cycles and holds up to 63% after 25k stability cycles.
ABSTRACT
Pseudo-capacitors with electrodes based on polyaniline and vertically aligned multiwalled carbon nanotubes (PANI/VA-MWCNT) composite are studied. Fractional differential models of supercapacitors are briefly discussed. The appropriate fractional circuit model for PANI/MWCNT pseudo-capacitors is found to be a linearized version of the recently proposed phase-field diffusion model based on the fractional Cahn-Hilliard equation. The temperature dependencies of the model parameters are determined by means of impedance spectroscopy. The fractional-order α is weakly sensitive to temperature, and the fractional dynamic behavior is related to the pore morphology rather than to thermally activated ion-hopping in PANI/MWCNT composite.