Hierarchical Mn3O4/NiSe2-MnSe2: A Versatile Electrode Material for High-Performance All-Solid-State Hybrid Pseudocapacitors with Supreme Working Durability.

As highly efficient electrochemical energy storage devices are in indispensable demand for numerous modern-day technologies, herein sluggish precipitation followed by an anion exchange procedure has been developed to synthesize an oxide-selenide mixed phase (Mn3O4/NiSe2-MnSe2) novel electrode material with high surface area and porosity for high-performance all-solid-state hybrid pseudocapacitors (ASSHPC). Mn3O4/NiSe2-MnSe2 shows a rich Tyndall effect (in H2O) and possesses randomly arranged low-dimensional crystallites of nearly similar size and uniform shape. The electrochemical analyses of Mn3O4/NiSe2-MnSe2 corroborate good electrochemical reversibility during charge transfer, superior pseudocapacitive charge-storage efficiency, and very low charge transfer and series resistance, ion-diffusion resistance, and relaxation time, which endorse the quick pseudocapacitive response of the material. The Mn3O4/NiSe2-MnSe2||N-rGO ASSHPC device demonstrates excellent charge-storage physiognomies suggestive of rich electrochemical and electromicrostructural compatibility between the electrode materials in the fabricated assembly. The Mn3O4/NiSe2-MnSe2||N-rGO ASSHPC device delivers high mass and area specific capacitance/capacity, very low charge-transfer resistance (∼0.74 Ω), total series resistance (∼0.76 Ω), diffusion resistance, and a relaxation time constant, which endorse the quick pseudocapacitive response of the device. The device delivers higher energy and power density (∼34 W h kg-1 at ∼2994 W kg-1), rate efficiency (∼17 W h kg-1 at ∼11,995 W kg-1), and cyclic performance (∼97.2% specific capacity/capacitance retention after 9500 continuous GCD cycles). The superior Ragone and cyclic efficiencies of the ASSHPC device are ascribed to the multiple redox-active Ni and Mn ions which lead to the supplemented number of redox reactions; "electroactive-ion buffering pool"-like physiognomics of Mn3O4/NiSe2-MnSe2, which facilitate the electrolyte ion dissemination to the electroactive sites even at high rate redox condition; and ideal electro-microstructural compatibility between the electrode materials, which leads to assisted charge transfer and absolute ion dissemination during the charge-storage process.

Hierarchical and Nanocrystallite-Assembled Ultraporous NiO/MnCo2O4 for All Solid-State Hybrid Supercapacitors with Robust Energy Efficiency and Extended Operational Durability.

To address the growing demand of highly Ragone efficient electrochemical energy storage devices, we have innovated a synthetic design strategy and employed a tartrate-mediated kinetic precipitation process to fabricate an ultraporous ribbon-like hierarchical microstructure of Ni-, Mn-, and Co-based ternary oxide, i.e., NiO/MnCo2O4, and employed it as a battery-type positive electrode material to assemble an ASSHSC (all-solid-state hybrid supercapacitor) device with nitrogen-doped reduced graphene oxide (N-rGO) as the positive electrode material. NiO/MnCo2O4 exhibits distinct crystallographic phase, near-perfect elemental stoichiometry, evident bulk porosity, and rich nanocrystallite assembly in the randomly arranged microstructure of near-uniform size and shape. Thorough electrochemical studies corroborate that the battery-type NiO/MnCo2O4 exhibits remarkable electrochemical reversibility during charge transfer, high efficiency in supercapacitive charge storage, low charge transfer, series and diffusion resistance. The NiO/MnCo2O4||N-rGO ASSHSC device assembled with the PVA-KOH film as the separator electrolyte offers rich charge storage physiognomies, which accentuates excellent electromicrostructural compatibility between the electrode materials in the device. The NiO/MnCo2O4||N-rGO ASSHSC device shows low charge transfer and diffusion resistance, and it also delivers high mass and areal specific capacitance/capacity, energy and power density, Ragone efficiency (∼131 Wh kg-1 at ∼2134 W kg-1 and ∼31 Wh kg-1 at ∼5005 W kg-1), and extended operational durability (98.2% specific capacitance retention after 12,000 successive GCD cycles) under high-rate working conditions. The present optimized approach to design highly efficient multiple transition-metal-based oxides as battery-type electrode materials and fabricate rich Ragone-efficient ASSHSC devices can be widely adopted in the future development of high-performance hybrid supercapacitors, which may be largely integrated in various pioneering technologies.

Graphitic Carbon Nitride-Induced Multifold Enhancement in Electrochemical Charge Storage of CoS-NiCo2S4 for All-Solid-State Hybrid Supercapacitors.

In order to improve the electro-microstructural physiognomics of electrode materials for applications in better efficiency supercapacitors, herein graphitic carbon nitride (GCN)-heterostructurized CoS-NiCo2S4 is designed using a controlled material growth synthesis procedure. The developed CoS-NiCo2S4/GCN possesses ample hydrophilicity, possible charge transfer between GCN and CoS-NiCo2S4, uniform phase distribution, and distinctive microstructural characteristics. The preliminary electrochemical studies in the three-electrode setup show GCN-induced lower charge transfer resistance and very unique Warburg profile corresponding to extremely low diffusion resistance in CoS-NiCo2S4/GCN as compared to pristine CoS-NiCo2S4. Furthermore, GCN is found to significantly induce surface-controlled (capacitive-type) charge storage and frequency-independent specific capacitance up to 10 Hz in CoS-NiCo2S4. Furthermore, the CoS-NiCo2S4||N-rGO and CoS-NiCo2S4/GCN||N-rGO all-solid-state hybrid supercapacitor (ASSHSC) devices were fabricated using N-rGO as the negative electrode material, and the inducing effect of GCN on the supercapacitive charge storage performance of the devices is thoroughly studied. Results demonstrate that the mass specific capacitance and areal capacitance of CoS-NiCo2S4/GCN||N-rGO are ∼2 and ∼4 times more than those of the CoS-NiCo2S4||N-rGO ASSHSC device, respectively. Furthermore, the CoS-NiCo2S4/GCN||N-rGO offers more energy density, rate energy density, and additional charge-discharge durability (over ∼10,000 cycles) than the CoS-NiCo2S4||N-rGO ASSHSC device. The multifold performance improvement of CoS-NiCo2S4 with GCN heterostructurization is ascribed to GCN-induced supplemented porosity and pore widening, ionic nonstoichiometry (Ni2±Î´, Co2±Î´, and Co3±Î´), wettability, integrated enhancement in the conductivity, and electroactive-ion accessibility in the CoS-NiCo2S4/GCN heterocomposite. The present study offers vital physicoelectrochemical insights toward the future development of low cost and high-performance electrode materials, and their implementation in high-rate and operationally stable all-solid-state hybrid supercapacitor devices, for application in the next-generation front-line technologies.

Ribbon-like Nickel Cobaltite with Layer-by-Layer-Assembled Ordered Nanocrystallites for Next-Generation All-Solid-State Hybrid Supercapatteries.

In the context to develop ultra-efficient electrode materials with good physicoelectrochemical and electrostructural properties, for their application in high-performance supercapatteries, herein, a facile tartrate-mediated inhibited crystal growth method is reported to engineer thoroughly uniform ribbon-like nickel cobaltite (NiCo2O4) microstructure with unique layer-by-layer-assembled nanocrystallites. This material demonstrates significant kinetic reversibility, good rate efficiency and bulk diffusibility of the electroactive ions, and a predominant semi-infinite diffusion mechanism during the redox-based charge storage process. This material also shows bias-potential-independent equivalent series resistance, very low charge-transfer resistance, and diagonal Warburg profile, corresponding to the ion diffusion occurring during the electrochemical processes in supercapacitors and batteries. Further, the fabricated NiCo2O4-based all-solid-state supercapattery (NiCo2O4||N-rGO) delivers excellent rate-specific capacity, very low internal resistance, good electrochemical and electrostructural stability (∼94% capacity retention after 10,000 charge-discharge cycles), energy density (31 W h kg-1) of a typical rechargeable battery, and power density (13,003 W kg-1) of an ultra-supercapacitor. The ultimate performance of the supercapattery is ascribed to low-dimensional crystallites, ordered inter-crystallite and channel-type bulk and boundary porosity, multiple reactive equivalents, enhanced electronic conductivity, and "ion buffering pool" like behavior of ribbon-like NiCo2O4, supplemented with enhanced electronic and ionic conductivities of N-doped rGO (negative electrode) and PVA/KOH gel (electrolyte separator), respectively.

Archetypal sandwich-structured CuO for high performance non-enzymatic sensing of glucose.

In the quest to enhance the selectivity and sensitivity of novel structured metal oxides for electrochemical non-enzymatic sensing of glucose, we report here a green synthesis of unique sandwich-structured CuO on a large scale under microwave mediated homogeneous precipitation conditions. The physicochemical studies carried out by XRD and BET methods show that the monoclinic CuO formed via thermal decomposition of Cu(2)(OH)(2)CO(3) possesses monomodal channel-type pores with largely improved surface area (~43 m(2) g(-1)) and pore volume (0.163 cm(3) g(-1)). The fascinating surface morphology and pore structure of CuO is formulated due to homogeneous crystallization and microwave induced self assembly during synthesis. The cyclic voltammetry and chronoamperometry studies show diffusion controlled glucose oxidation at ~0.6 V (vs. Ag/AgCl) with extremely high sensitivity of 5342.8 µA mM(-1) cm(-2) and respective detection limit and response time of ~1 µM and ~0.7 s, under a wide dynamic concentration range of glucose. The chronoamperometry measurements demonstrate that the sensitivity of CuO to glucose is unaffected by the absence of dissolved oxygen and presence of poisoning chloride ions in the reaction medium, which essentially implies high poison resistance activity of the sandwich-structured CuO. The sandwich-structured CuO also shows insignificant interference/significant selectivity to glucose, even in the presence of high concentrations of other sugars as well as reducing species. In addition, the sandwich-structured CuO shows excellent reproducibility (relative standard deviation of ~2.4% over ten identically fabricated electrodes) and outstanding long term stability (only ~1.3% loss in sensitivity over a period of one month) during non-enzymatic electrochemical sensing of glucose. The unique microstructure and suitable channel-type pore architecture provide structural stability and maximum accessible electroactive surface for unimpeded mobility of glucose as well as the product molecules, which result in the excellent sensitivity and selectivity of sandwich-structured CuO for glucose under non-enzymatic milieu.

Tuning, via counter anions, the morphology and catalytic activity of CeO2 prepared under mild conditions.

Advanced synthetic methods under mild and controlled conditions for the synthesis of nanocrystals with specific shapes and exposed surfaces are very important for understanding the surface related properties and to explore their structure-property relationship for various potential applications. Here, we report the synthesis of highly uniform CeO(2) nanorods and nanoflowers in large scale using non-hydrothermal homogeneous precipitation method with urea as a precipitating agent and CTAB as a shape directing agent. Uniform microstructures of CeO(2) samples were selectively synthesized using chloride and nitrate as the counter anions. The samples were characterized by thermal analysis, X-ray diffraction, N(2) adsorption-desorption isotherms, SEM, TEM, UV-Vis-DRS, and Raman spectroscopy, and temperature programmed reduction as well as desorption methods. The results show that the physicochemical and optical properties of CeO(2) samples significantly differ with their surface microstructure and morphology. They also strongly influence the redox property, oxygen storage capacity, and surface acidity of the CeO(2) samples. The CeO(2) samples with different morphologies were tested for their soot oxidation activity. The CeO(2) sample with nanorod morphology was found to be more active due to larger CeO(2)/soot interface than the CeO(2) sample with nanoflower morphology.

Nanoscale morphology dependent pseudocapacitance of NiO: Influence of intercalating anions during synthesis.

Three nano-porous NiO samples with high specific surface area were prepared by a simple hydrothermal method under homogeneous precipitation conditions using CTAB as a template and urea as the hydrolysis controlling agent. This study was done to determine the effect of different anions (acetate, nitrate and chloride) present in the precursor salts on the morphology and pseudocapacitance behavior of NiO. The samples were characterized by thermogravimetry (TG), differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), Brunauer-Emmet-Teller (BET) isotherm and field emission scanning electron microscopy (FESEM). The final NiO samples showed different hierarchical surface morphologies and their effect on the electrochemical pseudocapacitance behavior was carefully studied by cyclic voltammetry, galvanostatic charge-discharge cycles (chronopotentiometry) and impedance spectroscopic techniques. The specific capacitance of NiO sample synthesized by NO3- ion intercalation showed higher surface area, intermediate porosity and a novel pine-cone morphology with nano-wire surface attachments. This sample exhibits the highest pseudocapacitance of 279 F g(-1) at a scan rate of 5 mV s(-1), calculated from the cyclic voltammetry measurements. The sample synthesized by Cl- intercalation shows a nano-flower morphology with lower surface area, porosity and pseudocapacitance behaviour. The NiO sample prepared in the presence of CH3COO- ions showed a honeycomb type surface morphology with an intermediate pseudocapacitance value but higher reversibility. The galvanostatic charge-discharge and impedance spectroscopic measurements on these NiO electrodes were consistent with CV results. The Coulombic efficiency of all the three NiO samples was found to be high (∼85 to ∼99%) after 100 galvanostatic charge-discharge cycles. This study shows that the surface morphology and porosity of NiO are strongly influenced by the anions in the precursor salts, and in turn affect significantly the pseudocapacitance behavior and the power performance of NiO powders.

Microwave-mediated synthesis for improved morphology and pseudocapacitance performance of nickel oxide.

Synthetic methods greatly control the structural and functional characteristics of the materials. In this article, porous NiO samples were prepared in conventional-reflux and microwave assisted heating method under homogeneous precipitation conditions. The NiO samples synthesized in conventional reflux method showed flakelike morphology, whereas the sample synthesized in microwave methods showed hierarchical porous ball like surface morphology with uniform ripple-shaped pores. The NiO samples characterized using BET method were found to bear characteristic meso- and macroporosity due to differently crystallized Ni(OH)(2) precursors under various heating conditions. Thermogravimety analysis showed morphology dependent decomposition of Ni(OH)(2) precursors. The microwave synthesized porous NiO sample with unique morphology and pore size distribution showed significantly improved charge storage and electrochemical stability than the flaky NiO sample synthesized by employing conventional reflux method. The cyclic voltammetry measurements on microwave synthesized NiO sample showed considerably high capacitance and better electrochemical reversibility. The charge-discharge measurements made at a discharge current of 2 A/g showed higher rate specific capacitance (370 F/g) for the NiO sample synthesized by microwave method than the sample synthesized by reflux method (101 F/g). The impedance study illustrates lower electronic and ionic resistance of rippled-shaped porous NiO due to its superior surface properties for enhanced electrode-electrolyte contact during the Faradaic redox reactions. It has been further established from the Ragone plot that the microwave synthesized NiO sample shows higher energy and power densities than the reflux synthesized NiO sample. Broadly, this study reveals that microwave-mediated synthesis approach is significantly a better strategy for the synthesis of porous NiO suitable to electrochemical supercapacitor applications.