Phosphorus-Doped Nickel Oxide Micro-Supercapacitor: Unleashing the Power of Energy Storage for Miniaturized Electronic Devices.

For an uninterrupted self-powered network, the requirement of miniaturized energy storage device is of utmost importance. This study explores the potential utilization of phosphorus-doped nickel oxide (P-NiO) to design highly efficient durable micro-supercapacitors. The introduction of P as a dopant serves to enhance the electrical conductivity of bare NiO, leading to 11-fold augmentation in volumetric capacitance to 841.92 Fcm-3 followed by significant enhancement of energy and power density from 6.71 to 42.096 mWhcm-3 and 0.47 to 1.046 Wcm-3, respectively. Theoretical calculations used to determine the adsorption energy of OH- ions, revealing higher in case of bare NiO (1.52 eV) as compared to phosphorus-doped NiO (0.64 eV) leading to high electrochemical energy storage performance. The as-designed micro-supercapacitor (MSC) device demonstrates a facile integration with the photovoltaic system for renewable energy storage and smooth transfer to external loads for enlightening the blue LED for ≈1 min. The choice of P-NiO/Ni not only contributes to cost reduction but also ensures minimal lattice mismatch at the interface facilitating high durability up to 15 K cycles along with capacitive retention of ≈100% and coulombic efficiency of 93%. Thus, the heterostructure unveils the possibilities of exploring miniaturized energy storage devices for portable electronics.

Porous Carbon Template Decorated with MOF-Driven Bimetallic Phosphide: A Suitable Heterostructure for the Production of Uninterrupted Green Hydrogen via Renewable Energy Storage Device.

Water splitting via an uninterrupted electrochemical process through hybrid energy storage devices generating continuous hydrogen is cost-effective and green approach to address the looming energy and environmental crisis toward constant supply of hydrogen fuel in fuel cell driven automobile sector. The high surface area metal-organic framework (MOF) driven bimetallic phosphides (ZnP2 @CoP) on top of CNT-carbon cloth matrix is utilized as positive and negative electrodes in energy storage devices and overall water splitting. The as-prepared positive electrode exhibits excellent specific capacitances/capacity of 1600 F g-1 /800 C g-1 @ 1A g-1 and the corresponding hybrid device reveals an energy density of 83.03 Wh kg-1 at power density of 749.9 W kg-1 . Simultaneously, the electrocatalytic performance of heterostructure shows overpotentials of 90 mV@HER and 204 mV@OER at current density of 10 and 20 mA cm-2 , respectively in alkaline electrocatalyzer. Undoubtedly, it shows overall water splitting with low cell voltage of 1.53 V@10 mA cm-2 having faradic and solar-to-hydrogen conversion efficiency of 98.81% and 9.94%, respectively. In addition, the real phase demonstration of the overall water-splitting is performed where the electrocatalyzer is connected with a series of hybrid supercapacitor devices powered up by the 6 V standard silicon solar panel to produce uninterrupted green H2 .

Linear piezoresistive strain sensor based on graphene/g-C3N4/PDMS heterostructure.

Here we report a novel hybrid material consists of 2D graphitic carbon nitride (g-C3N4) and graphene heterostructure that exhibits piezoresistivity superior to graphene and potentially being used as a strain sensor. The g-C3N4 that contains periodically spaced triangular nanopores is used for improving the piezoresistivity of the sensor imparting change in the polarization upon application of strain. In this work, we have investigated graphene/g-C3N4 interfaced materials and quantified its piezoresistive effects through experimental analysis and density functional theory (DFT) based computational studies provide insights into the electronic structures of the hybrid interfaces. We have observed a linear response in electrical resistance for a wide range of uniaxial strains up to ∼25%. The observed increase in resistance upon application of strain corroborates with our computational finding of strain-dependent band gap opening. Further, it has been realized that band-gap opening occurs exclusively in the graphitic layer of the composite materials under strain. However, the g-C3N4 bands remain intact at the interface. The linearity and a considerably small gauge factor (1.89) make graphene/g-C3N4 a promising heterostructure material unlike conventional metal gauge sensor in wide strain pressure sensor devices.

Study of field emission properties of pure graphene-CNT heterostructures connected via seamless interface.

Vertically aligned carbon nanotubes (CNTs) have proven to be one of the best materials for use as an efficient field emitter. To further improve their efficiency as well as long-term use in practical devices, it is necessary to reduce the quantum resistance originating from the interface between electrode and emitters and the entanglement of the CNTs in a bundle texture. Thus, the incorporation of graphene at the bottom of CNT bundles via a seamless carbonaceous interface can easily solve this bottleneck. In this work we have demonstrated for the first time, growth and field emission properties of pure seamless graphene-CNT heterostructures and pure seamless graphene-vertically patterned oriented CNTs heterostructures (SGVCNTs) on Si/SiO2 substrates in contrast to the bare CNT mats and few-layer graphene structures without using any tedious post transfer processes. It was observed that seamless SGVCNTs show better field emission performance in terms of higher current density (236 mA cm-2), lowered turn-on field (0.45 V µm-1) and threshold field (1.931 V µm-1 @100 mA cm-2), and improved field enhancement factor (ߠ∼ 41 315) which is improved ∼4 fold when compared to a bare CNT mat. The significant improvement of the field emission performance of SGVCNTs is mainly attributed to the low resistive seamless C-C covalent carbonaceous interface, the higher number of emitter sites and patterned vertical orientation that leads to long-term stability of the field emitter with minimal loss up to 32 h. This finding could provide an important solution for carbonaceous material based field emitters for real phase device applications.

Super-Hydrophilic Leaflike Sn4P3 on the Porous Seamless Graphene-Carbon Nanotube Heterostructure as an Efficient Electrocatalyst for Solar-Driven Overall Water Splitting.

Water splitting using renewable energy resources is an economic and green approach that is immensely enviable for the production of high-purity hydrogen fuel to resolve the currently alarming energy and environmental crisis. One of the effective routes to produce green fuel with the help of an integrated solar system is to develop a cost-effective, robust, and bifunctional electrocatalyst by complete water splitting. Herein, we report a superhydrophilic layered leaflike Sn4P3 on a graphene-carbon nanotube matrix which shows outstanding electrochemical performance in terms of low overpotential (hydrogen evolution reaction (HER), 62 mV@10 mA/cm2, and oxygen evolution reaction (OER), 169 mV@20 mA/cm2). The outstanding stability of HER at least for 15 days at a high applied current density of 400 mA/cm2 with a minimum loss of potential (1%) in acid medium infers its potential compatibility toward the industrial sector. Theoretical calculations indicate that the decoration of Sn4P3 on carbon nanotubes modulates the electronic structure by creating a higher density of state near Fermi energy. The catalyst also reveals an admirable overall water splitting performance by generating a low cell voltage of 1.482 V@10 mA/cm2 with a stability of at least 65 h without obvious degradation of potential in 1 M KOH. It exhibited unassisted solar energy-driven water splitting when coupled with a silicon solar cell by extracting a high stable photocurrent density of 8.89 mA/cm2 at least for 90 h with 100% retention that demonstrates a high solar-to-hydrogen conversion efficiency of ∼10.82%. The catalyst unveils a footprint for pure renewable fuel production toward carbon-free future green energy innovation.

Bimetallic Phosphides for Hybrid Supercapacitors.

Supercapacitors (SCs) are considered promising energy storage systems because of their high power output and long-term cycling stability; however, they usually exhibit poor energy density. The hybrid supercapacitor (HSC) is an emerging concept in which two dissimilar electrodes with different charge storage mechanisms are paired to deliver high energy without sacrificing power output. This Perspective highlights the features of transition-metal phosphides (TMPs) as the positive electrode in HSCs. In particular, bimetallic nickel cobalt phosphide (NiCoP) with multiple redox sites, excellent electrochemical reversibility, and stability is discussed. We outline how the rational heterostructures, elemental variations, and nanocomposite morphologies tune the electrochemical properties of NiCoP as the positive electrode in HSCs. The Perspective further sheds light on NiCoP-based composites that help in improving the overall performance of HSCs in terms of energy density and cycling stability. The key scientific challenges and perspectives on building efficient and stable HSCs for future applications are discussed.

In-Situ Growth of Urchin Manganese Sulfide Anchored Three-Dimensional Graphene (γ-MnS@3DG) on Carbon Cloth as a Flexible Asymmetric Supercapacitor.

In energy storage-device it is highly crucial to develop durable electrode materials having high specific capacitance and superior energy density without disturbing its inherent flexibility. Herein, we demonstrate three-dimensional graphene oxide decorated monodispersed hollow urchin γ-MnS (γ-MnS@3DG) via proficient one-step solvothermal method. The designed material delivers a remarkable capacitance of 858 F g-1 at 1 A g-1. A flexible solid state asymmetric supercapacitor (ASCs) device assembled using surface activated carbon cloth (CC) decorated with γ-MnS@3DG as positive and three-dimension graphene on carbon cloth (3DG@CC) as negative electrode, (γ-MnS@3DG//3DG). The device delivers 26 Wh kg-1 energy density at power density 500 W kg-1 @ 1A g-1 and retains favorable energy density 17.8 Wh kg-1 at an ultrahigh power density of 1500 W kg-1@3 A g-1. This carbon embedded transition-metal sulfide (TMS) based ASC demonstrates eminent mechanical flexibility under rigorous bending states maintaining invariant performance.

Super-Hydrophilic Hierarchical Ni-Foam-Graphene-Carbon Nanotubes-Ni2P-CuP2 Nano-Architecture as Efficient Electrocatalyst for Overall Water Splitting.

Water splitting via an electrochemical process to generate hydrogen is an economic and green approach to resolve the looming energy and environmental crisis. The rational design of multicomponent materials with seamless interfaces having robust stability, facile scalability, and low-cost electrocatalysts is a grand challenge to produce hydrogen by water electrolysis. Herein, we report a superhydrophilic homogeneous bimetallic phosphide of Ni2P-CuP2 on Ni-foam-graphene-carbon nanotubes (CNTs) heterostructure using facile electrochemical metallization followed by phosphorization without any intervention of metal-oxides/hydroxides. This bimetallic phosphide shows ultralow overpotentials of 12 (HER, hydrogen evolution reaction) and 140 mV (OER, oxygen evolution reaction) at current densities of 10 and 20 mA/cm2 in acidic and alkaline mediums, respectively. The excellent stability lasts for at least for 10 days at a high current density of 500 mA/cm2 without much deviation, inferring the practical utilization of the catalyst toward green fuel production. Undoubtedly, the catalyst is capable enough for overall water splitting at a very low cell voltage of 1.45 V @10 mA/cm2 with an impressive stability of at least 40 h, showing a minimum loss of potential. Theoretical study has been performed to understand the reaction kinetics and d-band shifting among metal atoms in the heterostructure (Ni2P-CuP2) that favor the HER and OER activities, respectively. In addition, the catalyst demonstrates an alternate transformation of solar energy to green H2 production using a standard silicon solar cell. This work unveils a smart design and synthesizes a highly stable electrocatalyst against an attractive paradigm of commercial water electrolysis for renewable electrochemical energy conversion.

Effect of ionic size compensation by Ag+ incorporation in homogeneous Fe-substituted ZnO: studies on structural, mechanical, optical, and magnetic properties.

Substituting an ion of different size from that of the host element introduces lattice strain and defects. However, this mismatch may be significantly reduced by substituting an additional ion with a compensating size relative to the dopant. Such a double substitution might offer better solubility irrespective of the local distortions as well as the formation of defects in the valence states. Fe-substituted ZnO has been widely reported with conflicting results primarily arising from lack of chemical and structural homogeneity originating from preparation techniques, compositional fluctuations, and equivocal comprehension of actual solubility limits of the dopants. In this study, Ag ion has been incorporated in Fe-substituted ZnO to compensate the ionic size of Zn1-x [Fe0.8Ag0.2] x O (0 ≤ x ≤ 0.03125) by determining the solubility limit of the homogeneous material and their corresponding structural, mechanical, optical and magnetic properties have been investigated thoroughly. Co-substitution rearranges the lattice and leads to better crystal structures with tunable properties related to the amount of substitution.

Correction: Effect of ionic size compensation by Ag+ incorporation in homogeneous Fe-substituted ZnO: studies on structural, mechanical, optical, and magnetic properties.

[This corrects the article DOI: 10.1039/C8RA02393J.].