Electrochemical Deposition for Cultivating Nano- and Microstructured Electroactive Materials for Supercapacitors: Recent Developments and Future Perspectives.

The globe is currently dealing with serious issues related to the world economy and population expansion, which has led to a significant increase in the need for energy. One of the most promising energy devices for the next generation of energy technology is the supercapacitor (SC). Among the numerous nanostructured materials examined for SC electrodes, inorganic nanosheets are considered to be the most favorable electrode materials because of their excellent electrochemical performance due to their large surface area, very low layer thickness, and tunable diverse composition. Various inorganic nanosheets (NS) such as metal oxides, metal chalcogenides, metal hydroxides, and MXenes show substantial electrochemical activity. Herein, a comprehensive survey of inorganic NS arrays synthesized through the electrodeposition method is reported with the discussion on detailed growth mechanism and their application in the fabrication of SC electrodes/devices for powering flexible and wearable electronics appliances. To begin with, the first section will feature the various types of electrodeposition working mechanism, SC types and their working mechanisms, importance of nanosheet structure for SCs. This review gives a profound interpretation of supercapacitor electrode materials and their performances in different domains. Finally, a perspective on NS array through electrodeposition method applications in diverse fields is extensively examined.

Construction of Nickel Molybdenum Sulfide/Black Phosphorous 3D Hierarchical Structure Toward High Performance Supercapacitor Electrodes.

Supercapacitors (SCs) with outstanding versatility have a lot of potential applications in next-generation electronics. However, their practical uses are limited by their short working potential window and ultralow-specific capacity. Herein, the facile one-step in-situ hydrothermal synthesis is employed for the construction of a NiMo3S4/BP (black phosphorous) hybrid with a 3D hierarchical structure. After optimization, the NiMo3S4/BP hybrid displays a high specific capacitance of 830 F/g at 1 A/g compared to the pristine NiMo3S4 electrode. The fabricated NiMo3S4/BP//NiCo2S4/Ti3C2Tx asymmetric supercapacitor exhibits a better specific capacitance of 120 F/g at 0.5 A/g, which also demonstrates a high energy density of 54 Wh/kg at 1148.53 W/kg and good cycle stability with capacity retention of 86% and 97% of Coulombic efficiency after 6000 cycles. Further from the DFT simulations, the hybrid NiMo3S4/BP structure shows higher conductivity and quantum capacitance, which demonstrate greater charge storage capability, due to enhanced electronic states near the Fermi level. The lower diffusion energy barrier for the electrolyte K+ ions in the hybrid structure is facilitated by improved charge transfer performance for the hybrid NiMo3S4/BP. This work highlights the potential significance of hybrid nanoarchitectonics and compositional tunability as an emerging method for improving the charge storage capabilities of active electrodes.

Effect of cobalt doping on the enhanced energy storage performance of 2D vanadium diselenide: experimental and theoretical investigations.

Vanadium Diselenide (VSe2) is a prominent candidate in the 2D transition metal dichalcogenides family for energy storage applications. Herein, we report the experimental and theoretical investigations on the effect of cobalt doping in 1T-VSe2. The energy storage performance in terms of specific capacitance, stability and energy and power density is studied. It is observed that 3% Co doped VSe2exhibits better energy storage performance as compared to other concentrations, with a specific capacitance of âˆ¼193 F g-1in a two-electrode symmetric configuration. First-principles Density Functional Theory based simulations support the experimental findings by suggesting an enhanced quantum capacitance value after the Co doping in the 1T-VSe2. By making use of the advantages of the specific electrode materials, a solid state asymmetric supercapacitor (SASC) is also assembled with MoS2as the negative electrode. The assembled Co-VSe2//MoS2SASC device shows excellent energy storage performance with a maximum energy density of 33.36 Wh kg-1and a maximum power density of 5148 W kg-1with a cyclic stability of 90% after 5000 galvano static charge discharge cycles.

Rational design of selenium inserted 1T/2H mixed-phase molybdenum disulfide for energy storage and pollutant degradation applications.

MoS2based materials are recognized as the promising candidate for multifunctional applications due to its unique physicochemical properties. But presence of lower number of active sites, poor electrical conductivity, and less stability of 2H and 1T MoS2inherits its practical applications. Herein, we synthesized the Se inserted mixed-phase 2H/1T MoS2nanosheets with abundant defects sites to achieve improved overall electrochemical activity. Moreover, the chalcogen insertion induces the recombination of photogenerated excitons and enhances the life of carriers. The bifunctional energy storage and photocatalytic pollutant degradation studies of the prepare materials are carried out. Fabricated symmetric solid-state supercapacitor showed an exceptional capacitance of 178 mF cm-2with an excellent energy density of 8µWh cm-2and power density of 137 mW cm-2, with remarkable capacitance retention of 86.34% after successive 8000 charge-discharge cycles. The photocatalytic dye degradation experiments demonstrate that the prepared Se incorporated 1T/2H MoS2is a promising candidate for dye degradation applications. Further, the DFT studies confirmed that the Se inserted MoS2is a promising electrode material for supercapacitor applications with higherCQdue to a larger density of states near Fermi level as compared to pristine MoS2.

Unveiling and engineering of third-order optical nonlinearities in NiCo2O4 nanoflowers.

In this Letter, we demonstrate for the first time, to the best of our knowledge, NiCo2O4 (NCO) as a novel nonlinear optical material with straightforward potential applications in optical limiting. For the 532 nm nanosecond laser, excited state absorption (ESA) and free-carrier absorption give rise to large ESA coefficient (ßESA) and positive nonlinear n2. On the other hand, when excited with the 800 nm femtosecond laser, two-photon absorption (TPA) takes place, and bound carriers induce strong negative n2. The values of ß and n2 obtained for NCO are found to be higher compared to other conventional transition metal oxides and, therefore, are promising for optics and other photonics applications.

Energy storage performance of 2D MoS2 and carbon nanotube heterojunctions in symmetric and asymmetric configuration.

Excellent cyclic stability and fast charge/discharge capacity demonstrated by supercapacitors foster research interest into new electrode materials with 100% cycle life and high specific capacitance. We report an improvement in the electrochemical performance of MoS2/multiwalled carbon nanotubes (MWCNT) nanohybrid and intensively explored its performance in symmetric and asymmetric supercapacitor (ASC) assembly. The symmetric assembly of MoS2/MWCNT exhibits capacitance of around 274.63 F g-1 at 2 A g-1 with higher specific energy/power outputs (20.70 Wh kg-1/1.49 kW kg-1) as compared to the supercapacitor based on pristine MoS2 (5.82 Wh kg-1/1.07 kW kg-1). On the other hand, a unique all-carbon-based ASC assembled with MoS2/MWCNT and VSe2/MWCNT composite with K2SO4 as electrolyte delivers the highest energy density of 32.18 Wh kg-1 at a power density of 1.121 kW kg-1 with exceptional cycling stability and excellent retention of about 98.43% even after 5000 cycles. These outstanding results demonstrate the excellent electrochemical properties of both symmetric and asymmetric systems with high energy density and performance, which further enable them to be a potential candidate for supercapacitor applications.

Flexible and wearable electrochemical biosensors based on two-dimensional materials: Recent developments.

The research interest in wearable sensors has tremendously increased in recent years. Amid the different biosensors, electrochemical biosensors are unparalleled and ideal for the design and manufacture of such flexible and wearable sensors because of their various benefits, including convenient operation, quick response, portability, and inherent miniaturization. A number of studies on flexible and wearable electrochemical biosensors have been reported in recent years for invasive/non-invasive and real-time monitoring of biologically relevant molecules such as glucose, lactate, dopamine, cortisol, and antigens. To attain this, novel two-dimensional nanomaterials and their hybrids, various substrates, and detection methods have been explored to fabricate flexible conductive platforms that can be used to develop flexible electrochemical biosensors. In particular, there are many advantages associated with the advent of two-dimensional materials, such as light weight, high stretchability, high performance, and excellent biocompatibility, which offer new opportunities to improve the performance of wearable electrochemical sensors. Therefore, it is urgently required to study wearable/flexible electrochemical biosensors based on two-dimensional nanomaterials for health care monitoring and clinical analysis. In this review, we described recently reported flexible electrochemical biosensors based on two-dimensional nanomaterials. We classified them into specific groups, including enzymatic/non-enzymatic biosensors and affinity biosensors (immunosensors), recent developments in flexible electrochemical immunosensors based on polymer and plastic substrates to monitor biologically relevant molecules. This review will discuss perspectives on flexible electrochemical biosensors based on two-dimensional materials for the clinical analysis and wearable biosensing devices, as well as the limitations and prospects of the these electrochemical flexible/wearable biosensors.Graphical abstract.

Two-Dimensional Layered Metallic VSe2 /SWCNTs/rGO Based Ternary Hybrid Materials for High Performance Energy Storage Applications.

In this work, the ternary hybrid structure VSe2 /SWCNTs/rGO is reported for supercapacitor applications. The ternary composite exhibits a high specific capacitance of 450 F g-1 in a symmetric cell configuration, with maximum energy density of 131.4 Wh kg-1 and power density of 27.49 kW kg-1 . The ternary hybrid also shows a cyclic stability of 91 % after 5000 cycles. Extensive density functional theory (DFT) simulations on the structure as well as on the electronic properties of the binary hybrid structure VSe2 /SWCNTs and the ternary hybrid structure VSe2 /SWCNTs/rGO have been carried out. Due to a synergic effect, there are enhanced density of states near the Fermi level and higher quantum capacitance for the hybrid ternary structure compared to VSe2 /SWCNTs, leading to higher energy and power density for VSe2 /SWCNTs/rGO, supporting our experimental observation. Computed diffusion energy barrier of electrolyte ions (K+ ) predicts that ions move faster in the ternary structure, providing higher charge storage performance.

Comparative electrochemical energy storage performance of cobalt sulfide and cobalt oxide nanosheets: experimental and theoretical insights from density functional theory simulations.

In this study, we have carried out studies on supercapacitor performance comparing cobalt oxide (Co3O4) with cobalt sulfide (Co3S4) nanosheets grown using a facile electrodeposition approach. We have investigated the origin of enhanced energy storage performance of Co3S4 as compared to Co3O4 both by supported experiments and density functional theory investigations. Cobalt oxide exhibits a specific capacitance of 200 F g-1 at a current density of 2 A g-1, whereas a high specific capacitance of 558 F g-1 was achieved in the case of the Co3S4 nanosheets. The enhanced supercapacitor performance of Co3S4 is due to the high surface area, better wettability and high conductivity of the nanosheets. The asymmetric device exhibited a maximum energy density of 47.3 W h kg-1 with a power density of 2388.4 W kg-1 for Co3S4//MWCNT. The electrochemical impedance spectroscopic analysis revealed that Co3O4 has a substantially bigger semicircle as compared to Co3S4, confirming inferior charge-transfer characteristics in Co3O4. Density functional theory (DFT) simulations revealed that bulk structures of both Co3S4 and Co3O4 have an anti-ferromagnetic (AFM) configuration with Co atoms at the tetrahedral site having an opposite spin (∼2.55 µB each) and those at the octahedral sites being non-magnetic. Co3S4 nanosheets are found to be more conducting due to the presence of higher density of states near the Fermi level and a smaller bandgap compared to Co3O4 which support the observed experimental data on enhanced energy storage performance of Co3S4.

High performance supercapacitor electrodes based on spinel NiCo2O4@MWCNT composite with insights from density functional theory simulations.

In this work, we demonstrated the supercapacitor performance of pristine and composites of spinel NiCo2O4 with a multi-walled carbon nanotube (MWCNT) assembled in a two-electrode cell configuration. Spinel NiCo2O4 and NiCo2O4@MWCNT composites were synthesized via a facile hydrothermal method. The supercapacitive performance of as-synthesized NiCo2O4 and NiCo2O4@MWCNT fabricated on Ni-foam was studied in a 0.5M K2SO4 electrolyte using electrochemical measurement techniques. The symmetric cell configuration of NiCo2O4@MWCNT delivers high specific capacitance (374 F/g at 2 A/g) with high energy density and power density (95 Wh/kg and 3 964 W/kg, respectively) compared to that of pristine NiCo2O4 electrodes (137 F/g at 0.6 A/g). Furthermore, the energy storage performance of the asymmetric cells of NiCo2O4//MWCNT and NiCo2O4@MWCNT//MWCNT was studied to enhance cycling stability (retention of 74.85% over 3000 cycles). We have also theoretically studied the supercapacitance performance of pristine NiCo2O4 and NiCo2O4@SWCNT hybrid structures through its structural and electronic properties using density functional theory predictions. The higher specific capacitance of the NiCo2O4@SWCNT hybrid system with high power density and energy density is supported by the enhanced density of states near the Fermi level and increased quantum capacitance of the hybrid structure. We have theoretically computed the diffusion energy barrier of K+ ions of the K2SO4 electrolyte in the NiCo2O4 layer and compared it with the diffusion barrier for Na+ ions. The lesser diffusion energy barrier for K+ ions in the NiCo2O4 layer contributes toward higher energy storage capacity. Thus, owing to superior electrochemical performance of NiCo2O4 composites with MWCNTs, it can serve as a high-performance electrode material for supercapacitor applications.

Superior non-enzymatic glucose sensing properties of Ag-/Au-NiCo2O4 nanosheets with insight from electronic structure simulations.

Ag-/Au-NiCo2O4 nanosheets were synthesized by a facile electrodeposition approach on conducting Ni foam, and their non-enzymatic glucose sensing performance was investigated. The hybrid nanosheets of NiCo2O4 and noble-metal nanoparticles supported on conductive Ni foam possessed high active surface area along with intrinsic electrocatalytic and biocatalytic properties and promoted electronic/ionic transport in the electrodes, leading to improved glucose sensing properties. The sensitivity of the bare NiCo2O4 nanosheets for electrochemical non-enzymatic glucose sensing was 20.8 µA µM-1 cm-2, whereas the NiCo2O4-Ag and NiCo2O4-Au nanosheet electrodes exhibited enhanced sensitivities of 29.86 and 44.86 µA µM-1 cm-2, respectively, with lower response times in the same linear range of 5-45 µM. We also performed density functional theory simulations to corroborate our experimental observations by investigating the interactions and charge-transfer mechanism of glucose on Ag- and Au-doped NiCo2O4. As Au is bound more strongly to the NiCo2O4 surface compared to Ag, the binding energy of glucose is greater on the Au-doped NiCo2O4 surface than on the Ag-doped NiCo2O4 surface, and Au doping makes NiCo2O4 more conductive compared to Ag doping. Thus, it can be theoretically inferred that Au-doped NiCo2O4 has better glucose sensing performance, which supports our experimental data.

Highly sensitive and selective electrochemical dopamine sensing properties of multilayer graphene nanobelts.

In the present study, we report the electrochemical sensing property of multi-layer graphene nanobelts (GNBs) towards dopamine (DA). GNBs are synthesized from natural graphite and characterized by using techniques like field-emission scanning electron microscopy, atomic force microscopy and Raman spectroscopy. An electrochemical sensor based on GNBs is developed for the detection of DA. From the cyclic voltammetry and amperometry studies, it is found that GNBs possess excellent electrocatalytic activity towards DA molecules. The developed DA sensor showed a sensitivity value of 0.95 µA µM(-1) cm(-2) with a linear range of 2 µM to 0.2 mM. The interference data exhibited that GNB is highly selective to DA even in the presence of common interfering species like ascorbic acid, uric acid, glucose and lactic acid.

Electrochemical sensing of bisphenol using a multilayer graphene nanobelt modified photolithography patterned platinum electrode.

An electrochemical sensor has been developed for the detection of Bisphenol-A (BPA) using photolithographically patterned platinum electrodes modified with multilayer graphene nanobelts (GNB). Compared to bare electrodes, the GNB modified electrode exhibited enhanced BPA oxidation current, due to the high effective surface area and high adsorption capacity of the GNB. The sensor showed a linear response over the concentration range from 0.5 µM-9 µM with a very low limit of detection = 37.33 nM. In addition, the sensor showed very good stability and reproducibility with good specificity, demonstrating that GNB is potentially a new material for the development of a practical BPA electrochemical sensor with application in both industrial and plastic industries.

High Performance Non-enzymatic Glucose Sensor Based on One-Step Electrodeposited Nickel Sulfide.

Nanostructured NiS thin film was prepared by a one-step electrodeposition method and the structural, morphological characteristics of the as-prepared films were analyzed by X-ray diffractometry (XRD), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDAX). The electrocatalytic activity of NiS thin film towards glucose oxidation was investigated by fabricating a non-enzymatic glucose sensor and the sensor performance was studied by cyclic voltammetry (CV) and amperometry. The fabricated sensor showed excellent sensitivity and low detection limit with values of 7.43 µA µM(-1) cm(-2) and 0.32 µM, respectively, and a response time of <8 s.

Electrodeposition of spinel MnCo2O4 nanosheets for supercapacitor applications.

Herein, we report a facile, low-cost and one-step electrodeposition approach for the synthesis MnCo2O4 (MCO) nanosheet arrays on indium doped tin oxide (ITO) coated glass substrates. The crystalline phase and morphology of the materials are studied by x-ray diffraction, energy dispersive x-ray analysis and field-emission scanning electron microscopy. The supercapacitor performance of the MCO nanosheets are studied in a three-electrode configuration in 2 M KOH electrolyte. The as-prepared binder-free electrode shows a high specific capacitance of 290 F g(-1) at 1 mV s(-1) with excellent cyclic stability even after 1000 charge/discharge cycles. The obtained energy density and power density of the MCO nanosheets are 10.04 Wh kg(-1) and 5.2 kW kg(-1) respectively. The superior electrochemical performances are mainly attributed to its nanosheet like structure which provides a large reaction surface area, and fast ion and electron transfer rate.

Correction: Conducting polymers: a comprehensive review on recent advances in synthesis, properties and applications.

[This corrects the article DOI: 10.1039/D0RA07800J.].

Recent Developments and Future Perspectives of Molybdenum Borides and MBenes.

Metal borides have received a lot of attention recently as a potentially useful material for a wide range of applications. In particular, molybdenum-based borides and MBenes are of great significance, due to their remarkable properties like good electronic conductivity, considerable stability, high surface area, and environmental harmlessness. Therefore, in this article, the progress made in molybdenum-based borides and MBenes in recent years is reviewed. The first step in understanding these materials is to begin with an overview of their structural and electronic properties. Then synthetic technologies for the production of molybdenum borides, such as high-temperature/pressure methods, physical vapor deposition (PVD), chemical vapor deposition (CVD), element reaction route, molten salt-assisted, and selective etching methods are surveyed. Then, the critical performance of these materials in numerous applications like energy storage, catalysis, biosensors, biomedical devices, surface-enhanced Raman spectroscopy (SERS), and tribology and lubrication are summarized. The review concludes with an analysis of the current progress of these materials and provides perspectives for future research. Overall, this review will offer an insightful reference for the understanding molybdenum-based borides and their development in the future.

Borocarbonitride-Based Emerging Materials for Supercapacitor Applications: Recent Advances, Challenges, and Future Perspectives.

Supercapacitors have emerged as a promising energy storage technology due to their high-power density, fast charging/discharging capabilities, and long cycle life. Moreover, innovative electrode materials are extensively explored to enhance the performance, mainly the energy density of supercapacitors. Among the two-dimensional (2D) supercapacitor electrodes, borocarbonitride (BCN) has sparked widespread curiosity owing to its exceptional tunable properties concerning the change in concentration of the constituent elements, along with an excellent alternative to graphene-based electrodes. BCN, an advanced nanomaterial, possesses excellent electrical conductivity, chemical stability, and a large specific surface area. These factors contribute to supercapacitors' overall performance and reliability, making them a viable option to address the energy crisis. This review provides a detailed survey of BCN, its structural, electronic, chemical, magnetic, and mechanical properties, advanced synthesis methods, factors affecting the charge storage mechanism, and recent advances in BCN-based supercapacitor electrodes. The review embarks on the scrupulous elaboration of ways to enhance the electrochemical properties of BCN through various innovative strategies followed by critical challenges and future perspectives. BCN, as an eminent electrode material, holds great potential to revolutionize the energy landscape and support the growing energy demands of the future.

Electrostatic co-assembly of FePS3 nanosheets and surface functionalized BCN heterostructures for hydrogen evolution reaction.

Advances in the hydrogen evolution reaction (HER) are intricately connected with addressing the current energy crisis and quest for sustainable energy sources. The necessity of catalysts that are efficient and inexpensive to perform the hydrogen evolution reaction is key to this. Following the ground-breaking discovery of graphene, metal thio/seleno phosphates (MPX3: M - transition metal, P - phosphorus and X - S/Se), two dimensional (2D) materials, exhibit excellent tunable physicochemical, electronic and optical properties, and are expected to be key to the energy industry for years to come. Taking this into account, a facile time-effective electrostatic restacking synthesis procedure has been followed to synthesize a 2D/2D heterostructure (FePS3@BCN) involving FePS3, one of the prominent MPX3 materials, with borocarbonitride (BCN), for hydrogen evolution reaction (HER). The piled up nanosheets of FePS3 and BCN are held together by an electrostatic force, and display extreme robustness under the harsh conditions of HER application. The amalgamated electrocatalyst achieved an overpotential of 187 mV at a current density of 10 mA cm-2 with a shallow Tafel slope of 41 mV dec-1, following the Volmer-Heyrovsky mechanism. The resilience of the electrocatalyst has been examined through chronoamperometric testing for long term stability, and it is stable for more than 14 hours, which shows the excellent electrocatalytic activity for hydrogen evolution reaction owing to the strategic approach to the catalyst design, the use of numerous electrochemically active sites, large surface area and a barrier-free channel for quick ion transfer.

Synthesis and characterization of patronite form of vanadium sulfide on graphitic layer.

With the exploding interest in transition metal chalcogenides, sulfide minerals containing the dianion S2(2-), such as pyrite (FeS2), cattierite (CoS2), and vaesite (NiS2), have recently attracted much attention for potential applications in energy conversion and storage devices. However, the synthesis of the patronite structure (VS4, V(4+)(S2(2-))2) and its applications have not yet been clearly demonstrated because of experimental difficulties and the existence of nonstoichiometric phases. Herein, we report the synthesis of VS4 using a simple, facile hydrothermal method with a graphene oxide (GO) template and the characterization of the resulting material. Tests of various templates such as CNT, pyrene, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), and graphite led us to the conclusion that the graphitic layer plays a role in the nucleation during growth of VS4. Furthermore, the VS4/rGO hybrid was proved to be a promising functional material in energy storage devices.