A High-Entropy Intergrowth Layered-Oxide Cathode with Enhanced Stability for Sodium-Ion Batteries.

Layered transition metal oxides are widely considered as ideal cathode materials for SIBs. However, the existing P2 and O3 structures possess specific issues, which limit their practical applications. To address these issues, this work designed a novel intergrowth layered oxide cathode with P2 and O3 phases by implementing Cu and Ti into the structure with the formation of high-entropy cathode materials with superior performance for SIBs. The electrochemical test results show that the optimized high-entropy cathode with the P2/O3 intergrowth structure possesses a high initial discharge capacity of 157.85 mAh g-1 at 0.1 C, an excellent rate performance of 84.41 mAh g-1 at 10 C, and long-term stability with capacity retention of 83.25 % after 500 cycles at 5 C. Furthermore, the analysis results of ex situ XRD and in situ XRD indicate that the adverse phase transition of P2-O2 under high voltage is effectively suppressed. This work indicates that the integration of high-entropy strategy with the two-phase intergrowth structure can effectively stabilize the layered structure, suppress the slipping of transition metal layers, and improve electrochemical performance, which provides a new approach for designing high-performance and practical layered transition metal oxide cathode materials for advanced SIBs.

Ni0.5Co0.5S nano-chains: a high-performing intercalating pseudocapacitive electrode in asymmetric supercapacitor (ASC) mode for the development of large-scale energy storage devices.

Grid-scale energy storage solutions are necessary for using renewable energy sources efficiently. A supercapattery (supercapacitor + battery) has recently been introduced as a new variety of hybrid devices that engage both capacitive and faradaic charge storage processes. Nano-chain architectures of Ni0.5Co0.5S electrode materials consisting of interconnected nano-spheres are rationally constructed by tailoring the surface structure. Nano-chains of the bimetallic sulfide Ni0.5Co0.5S are presented to have a superior charge storage capacity. The Ni0.5Co0.5S nano-chain electrode presents a capacitance of 2001.6 F g-1 at 1 mV s-1, with a specific capacity of 267 mA h g-1 (1920 F g-1) at 1 A g-1 in 4 M KOH aqueous electrolyte through the galvanostatic charge-discharge (GCD) method. The reason behind the high charge storage capacity of the materials is the predominant redox-mediated diffusion-controlled pseudocapacitive mechanism coupled with surface capacitance (electrosorption), as the surface (outer) and intercalative (inner) charges stored by the Ni0.5Co0.5S electrodes are close to 46.0% and 54.0%, respectively. Additionally, a Ni0.5Co0.5S//AC two electrode full cell operating in asymmetric supercapacitor cell (ASCs) mode in 4 M KOH electrolyte exhibits an impressive energy density equivalent to 257 W h kg-1 and a power density of 0.73 kW kg-1 at a current rate of 1 A g-1.

Framework structured Ce2(C2O4)3·10H2O as a pseudocapacitive electrode of a hybrid (asymmetric) supercapacitor (HSC) for large scale energy storage applications.

The electrochemical kinetics of the electrode material plays a crucial role in the development of various energy storage devices such as batteries, supercapacitors, and hybrid supercapacitors. Battery-type hybrid supercapacitors are envisaged as excellent candidates to bridge the performance gap between supercapacitors and batteries. Due to its open pore framework structure and more structural stability, porous cerium oxalate decahydrate (Ce2(C2O4)3·10H2O) is found here to be a potential energy storage material partly because of the presence of planer oxalate anions (C2O42-). Superior specific capacitance equivalent to 78 mA h g-1 (capacitance: 401 F g-1) at 1 A g-1 in the potential window of -0.3 to 0.5 V was observed in an aqueous 2 M KOH electrolyte. The predominant pseudocapacitance mechanism seems to operate because of the high charge storage capacity of the electrode as intercalative (diffusion control) and surface control charges stored by the porous anhydrous Ce2(C2O4)3·10H2O, which were close to 48% and 52%, respectively, at a 10 mV s-1 scan rate. Further, in the full cell asymmetric supercapacitor (ASC) mode in which porous Ce2(C2O4)3·10H2O is the positive electrode and activated carbon (AC) is the negative electrode, at the operating potential window of 1.5 V, the highest specific energy of 96.5 W h kg-1 and a specific power of ∼750 W kg-1 at 1 A g-1 current rate and a high power density of 1453 W kg-1, the hybrid supercapacitor still attains an energy density of 10.58 W h kg-1 at a 10 A g-1 current rate, which was obtained with a high cyclic stability. The detailed electrochemical studies confirm a high cyclic stability and a superior electrochemical charge storage property of porous Ce2(C2O4)3·10H2O making it a potential pseudocapacitive electrode for use in large energy storage applications.

Effect of strontium doping on the electrochemical pseudocapacitance of Y1-xSrxMnO3-δ perovskites.

Grid-scale bulk energy storage solutions are needed to utilize the full potential of renewable energy technologies. Pseudocapacitive electrochemical energy storage can play a vital role in developing efficient energy storage solutions. The use of perovskites as anion intercalation-type pseudocapacitor electrodes has received significant attention in recent years. In this study, Sr-doped YMnO3i.e. Y1-xSrxMnO3-δ perovskite was prepared by the solid-state ceramic route and studied for electrochemical pseudocapacitance in aqueous KOH electrolyte. Microstructures, morphologies, and electrochemical properties of these materials were investigated through X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance method. The formation of the mostly cubic phase, with 50% strontium doped YMnO3 (YSMO-50) provides an equivalent three-dimensional network and superior conductivity due to Mn3+-O2--Mn4+ hopping conduction. YSMO-50 exhibited low intrinsic resistance, 1.45 Ω cm-2, and the highest specific capacity, 259.83 F g-1 at a current density of 1 A g-1 in 2 M KOH aqueous electrolyte. Redox-mediated interconversion of oxide to hydroxide (M2+O2- + H2O + e- ↔ M+OH- + OH-) in aqueous media is shown to be the reason behind the high capacitance of YSMO-50. The excellent electrochemical performance of YSMOs was attributed to the reversible interconversion of oxide-ion into hydroxide ion coupled with surface redox reaction of Mn2+/Mn3+ and Mn3+/Mn4+ occurring during the charge-discharge process. The maximum energy density of 65.13 W h kg-1 was achieved at a power density of 0.45 kW kg-1 for an asymmetric mode, in which YSMO serves as a negative electrode and Activated carbon (AC) as a positive electrode in the PVA-KOH gel electrolyte. Our study reveals that the doping of low valence atom (Sr) at the A-site in perovskite manganites (YMnO3) may be an effective tool to enhance the pseudocapacitive performance of perovskite-based electrodes.

Nanocrystalline ß-NiS: a redox-mediated electrode in aqueous electrolyte for pseudocapacitor/supercapacitor applications.

Currently, enhancing the performance of electrochemical supercapacitors is the subject of intense research to fulfill the ever-increasing demand for grid-scale energy storage and delivery solution, thereby utilizing the full potential of renewable energy resources and decreasing our dependence on fossil fuels. Metal sulfides, such as cobalt sulfide (CoS), nickel sulfide (NiS), molybdenum sulfide (MoS), copper sulfide (CuS), and others, have recently emerged as a promising class of active electrode materials, alongside other supercapacitor electrode materials, due to their relatively high specific capacitance values and exceptional reversible redox reaction activities. The synthesis, characterizations, and electrochemical performances of single-phase nanocrystalline ß-NiS are presented here and the electrode based on this material shows a specific capacitance of 1578 F g-1 at 1 A g-1 from the galvanostatic discharge profile, whereas a capacitance of 1611 F g-1 at 1 mV s-1 was obtained through the CV curve in 2 M KOH aqueous electrolyte. Additionally, the electrode also performs well in neutral 0.5 M Na2SO4 electrolytes resulting in specific capacitance equivalent to 403 F g-1 at 1 mV s-1 scan rate. The high charge storage capacity of the material is due to the superior intercalative (inner) charge storage coupled with the surface (outer) charges stored by the ß-NiS electrode and was found to be 72% and 28%, respectively, in aqueous 2 M KOH electrolyte. This intercalative charge storage mechanism is also responsible for its excellent cycling stability. Additionally, we assembled aqueous asymmetric supercapacitors (ASCs) with activated carbon (AC) as the negative electrode and the ß-NiS electrode as the positive electrode. The combination of the ß-NiS electrode and AC with excellent cycling stability resulted in the highest specific energy equivalent to ∼163 W h kg-1 and a specific power of ∼507 W kg-1 at 1 A g-1 current rate.

Perovskite La1-xKxCoO3-δ (0 ≤ x ≤ 0.5): a novel bifunctional OER/ORR electrocatalyst and supercapacitive charge storage electrode in a neutral Na2SO4 electrolyte.

The as-prepared La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) showed superior pseudocapacitive charge storage capacity in a neutral 0.5 M Na2SO4 electrolyte and superior electrocatalytic activities for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in a 1 M KOH electrolyte. 30% K doped p-type La0.7K0.3CoO3-δ presents superior OER activity with an overpotential of ∼335 mV at 10 mA cm-2 current rate in a 1 M KOH electrolyte. Additionally, La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) presents an excellent charge-storage capacitance in a neutral 0.5 M Na2SO4 electrolyte resulting in a gravimetric capacitance of the La0.5K0.5CoO3-δ electrode equivalent to 378 F g-1, 282 F g-1, 221 F g-1, 163 F g-1, and 74 F g-1 at a current density of 1 A g-1, 2 A g-1, 3 A g-1, 5 A g-1, and 10 A g-1, respectively. After 2500 continuous cycles of charge/discharge, the La0.5K0.5CoO3-δ//AC cell exhibits higher stability, capacitive retention (94%) and coulombic efficiency (97%). The gravimetric charge storage capacity of ASCs (La0.5K0.5CoO3-δ//AC) in the full cell mode showed capacitance equivalent to 308 F g-1, 287 F g-1, 238 F g-1, 209 F g-1 and 162 F g-1 at current densities of 1 A g-1, 2 A g-1, 3 A g-1, 5 A g-1 and 10 A g-1 in a neutral 0.5 M Na2SO4 electrolyte respectively. Maximum specific power equivalent to ∼6884 W kg-1 was observed at a current density of 10 A g-1 when the specific energy reached ∼57 W h kg-1 for the full cell. The double exchange mechanism coupled with stoichiometric oxygen defects present in the perovskite lattice seems to be operative behind the enhanced electrocatalytic OER properties, and additionally, it improves the charge storage kinetics of the La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) electrode in a neutral Na2SO4 electrolyte for supercapacitor application. This work presents a rational strategy for introducing facile oxygen ion defects into perovskite structured La1-xKxCoO3-δ (0 ≤ x ≤ 0.5) to develop multifunctional electrode materials for a supercapacitor and energy conversion (OER/ORR) electrode of metal-air batteries.

Photocatalytic dye-degradation activity of nano-crystalline Ti1-x M x O2-δ (M =Ag, Pd, Fe, Ni and x = 0, 0.01) for water pollution abatement.

Nanocrystalline metal-ion (M = Fe, Ni, Ag, and Pd) doped and undoped anatase-TiO2 powders were prepared using a solution combustion method. The photocatalytic degradation of different dyes such as methylene blue (MB), rhodamine B (RB), rhodamine B base (RBB), and thionine acetate (TA) was investigated under UV exposure. The degradation rate of the dyes were found to be better in the case of Ag+ and Pd2+ doped TiO2, whereas Fe3+ and Ni2+ doped TiO2 showed lower photocatalytic activity compared to undoped TiO2 nanoparticles. Combustion synthesized catalysts exhibited much better activity compared to the commercial Degussa P25 (75% anatase + 25% rutile) TiO2 photocatalyst. The intermediate states created in the band gap of the TiO2 photocatalyst due to doping of first row transition metal ions (such as Fe3+ and Ni2+) into the TiO2 lattice act as recombination centres and the electrons present in the d-orbital quench the photogenerated holes by indirect recombination, hence increasing e--h+ recombination rates. As a result, a decrease in the photocatalytic activity of TiO2 doped with first row transition metal ions is observed. However, in the case of noble metal ions (such as Ag+ and Pd2+) in TiO2, photoreduction of Ag+ and Pd2+ ions occurs upon UV irradiation, hence the noble metal-ions act as electron scavengers. Consequently, the lifetime of the holes (h+) increases and hence higher photocatalytic oxidation activity of the dyes is observed. A novel strategy of electron scavenging is envisaged here to develop Ag+ and Pd2+ doped TiO2 to increase the photocatalytic oxidation of organic dyes for the development of better water pollution abatement catalysts. Redox-pair stabilization in the TiO2 lattice similar to photo-chromic glasses play a defining role in enhancing the photocatalytic activity of the catalyst and is a key finding for the development of superior photocatalysts. With the help of UV-vis and fluorescence spectroscopy, the mechanisms of the superior oxidation activity of Pd2+ and Ag+ doped TiO2 nanoparticles are explained.

Eldfellite-structured NaCr(SO4)2: a potential anode for rechargeable Na-ion and Li-ion batteries.

Recent global concerns over continuously increasing air pollution and the related health risks due to automobile exhaust have shifted our attention towards green transportation. Recent decades have witnessed a revolution in portable energy-storage systems, mainly lithium-based energy-storage devices. However, the uneven distribution of global lithium reserves and its scarcity lead to huge price differences and geopolitical imbalances, and hence the research in energy-storage materials has shifted towards the development of cost-effective, abundant electrode materials. Here, NaCr(SO4)2, a transition metal-based polyanionic layered material with low cost and high stability during the charge/discharge process vs. Na, operating on the basis of the Cr3+/2+ redox couple, is presented. The test materials were characterized by techniques like XRD, FTIR, SEM, UV, XPS, TGA-DTA, and a detailed electrochemical analysis of the charge/discharge capacity of the materials is presented here. Here, the findings provide insights towards achieving a Cr3+/Cr2+ redox-couple-based sodium-ion battery with a specific capacity of 75 mA h g-1 and 150 mA h g-1 at operating voltages of 0.95 V vs. Na and 1.05 V vs. Li, respectively, with 100% coulombic efficiency. Cr2+ is a very special oxidation of Cr that cannot be obtained easily and CrTa2O6 is the only known oxide where Cr exists in the 2+ state. Here, a shift in the redox energy of the Cr3+/2+ couple was obtained due to its bonding with (SO4)2- polyanions in eldfellite that made the accessibility of Cr3+/2+ possible, resulting in the superior intercalation/deintercalation of Na and Li and the superior energy-storage capacity of the NaCr(SO4)2vs. Na/Li cell.

Gd3+ and Bi3+ co-substituted cubic zirconia; (Zr1-x-y Gd x Bi y O2-δ ): a novel high κ relaxor dielectric and superior oxide-ion conductor.

Solid oxide fuel cells (SOFCs) offer several advantages over lower temperature polymeric membrane fuels cells (PMFCs) due to their multiple fuel flexibility and requirement of low purity hydrogen. In order to decrease the operating temperature of SOFCs and to overcome the high operating cost and materials degradation challenges, the Cubic phase of ZrO2 was stabilized with simultaneous substitution of Bi and Gd and the effect of co-doping on the oxide-ion conductivity of Zr1-x-y Bi x Gd y O2-δ was studied to develop a superior electrolyte separator for SOFCs. Up to 30% Gd and 20% Bi were simultaneously substituted in the cubic ZrO2 lattice (Zr1-x-y Gd x Bi y O2-δ , x + y ≤ 0.4, x ≤ 0.3 and y ≤ 0.2) by employing a solution combustion method followed by multiple calcinations at 900 °C. Phase purity and composition of the material is confirmed by powder XRD and EDX measurements. The formation of an oxygen vacant Gd/Bi co-doped cubic zirconia lattice was also confirmed by Raman spectroscopy study. With the incorporation of Bi3+ and Gd3+ ions, the cubic Zr1-x-y Bi x Gd y O2-δ phase showed relaxor type high κ dielectric behaviour (ε' = 9725 at 600 °C at applied frequency 20 kHz for Zr0.6Bi0.2Gd0.2O1.8) with T m approaching 600 °C. The high polarizability of the Bi3+ ion coupled with synergistic interaction of Bi and Gd in the host ZrO2 lattice seems to create the more labile oxide ion vacancies that enable superior oxide-ion transport resulting in high oxide ion conductivity (σ o > 10-2 S cm-1, T > 500 °C for Zr0.6Bi0.2Gd0.2O1.8) at relatively lower temperatures.

SrFeO3-δ: a novel Fe4+ ↔ Fe2+ redox mediated pseudocapacitive electrode in aqueous electrolyte.

Pseudocapacitors offer both high energy and high power, making them suitable for grid-scale electrochemical energy storage to harness renewable energy produced from sun, wind, and tides. To overcome performance degradation in terms of cycling fading and lower specific capacitance values at high charge/discharge rates of electrochemical pseudocapacitors based on transition-metal oxides, perovskite-structured SrFeO3-δ was envisaged as a negative electrode that harnesses the Fe4+/3+ and Fe3+/2+ redox couple to deliver superior performance. SrFeO3-δ offers high specific capacitances of ca. 733 F g-1 at a scan rate of 1 mV s-1 and ca. 743 F g-1 at a current density of 1 A g-1 and demonstrates excellent cyclic stability over 2500 repeated cycles with capacitance retention of >92%, achieving 94% coulombic efficiency. The good cycling stability is attributed to the inherent metallic electrical conductivity of SrFeO3-δ and the fortuitous tendency of the robust cation framework structure to accommodate flexible oxygen content. The surface capacitive and diffusion-controlled contributions for capacitance are about ∼30% and ∼70%, respectively, at peak current and a scan rate equivalent to 1 mV s-1. The higher capacitance and stable performance make SrFeO3-δ an economical and abundant pseudocapacitive electrode.

NASICON-structured Na3Fe2PO4(SO4)2: a potential cathode material for rechargeable sodium-ion batteries.

The cost-effective and abundant availability of sodium offers an opportunity for rechargeable Na-ion batteries as an ideal replacement for rechargeable Li-ion batteries. However, the larger size and strong Na+-Na+ interaction create multidimensional phase instability and transformation problems, especially in layer-structured NaxMO2 (Mn, Co, Fe, and Ni) that inhibit the direct transformation of rechargeable Li-ion battery technology to Na-ion batteries. However, framework structures offer superior structural stability due to the interconnection of polyanions or polyhedra forming cationic octahedra. Sodium superionic conductor (NASICON)-type structures are well known for their superior Na+ ion transport and are identified as intercalative hosts as electrodes for rechargeable Na-ion batteries. Here, we report the synthesis of Na3Fe2PO4(SO4)2 in a NASICON framework structure and its investigation as a cathode in a Na/Na3Fe2PO4(SO4)2 cell working on the Fe3+/Fe2+ redox couple. The cell provides a single-phase reaction having a capacity approaching 70 mA h g-1 at 0.1 C after 50 cycles in the voltage range of 2 to 4.2 V, with a columbic efficiency approaching 100%. The large availability of Na and Fe with the stable redox and charge/discharge performance of NASICON-type Na3Fe2PO4(SO4)2 make it a possible cathode candidate for next-generation rechargeable sodium-ion batteries.

Synthesis, Characterizations, and Electrochemical Performances of Highly Porous, Anhydrous Co0.5Ni0.5C2O4 for Pseudocapacitive Energy Storage Applications.

Electrochemical energy storage relies essentially on the development of innovative electrode materials with enhanced kinetics of ion transport. Pseudocapacitors are excellent candidates to bridge the performance gap between supercapacitors and batteries. Highly porous, anhydrous Ni0.5Co0.5C2O4 is envisaged here as a potential electrode for pseudocapacitor applications, mainly because of its open pore framework structure, which poses inherent structural stability due to the presence of planar oxalate anions (C2O4 2-), and active participation of Ni2+/3+ and Co2+/3+ results in high intercalative charge storage capacity in the aqueous KOH electrolyte. The Ni0.5Co0.5C2O4 electrode shows specific capacitance equivalent to 2396 F/g at 1 A/g in the potential window of 0.6 V in the aqueous 2 M KOH electrolyte by galvanostatic charge/discharge experiments. Predominant pseudocapacitive mechanism seems to operative behind high charge storage due to active participation of Ni2+/3+ and Co2+/3+ redox couple as intercalative (inner) and surface (outer) charges stored by porous anhydrous Co0.5Ni0.5C2O4 were close to high 38 and 62% respectively. Further, in full cell asymmetric supercapacitors (ASCs) in which porous anhydrous Co0.5Ni0.5C2O4 was used as the positive electrode and activated carbon (AC) was utilized as the negative electrode, in the operating potential window 1.6 V, the highest specific energy of 283 W h/kg and specific power of ∼817 W/kg were achieved at 1 A/g current rates. Even at a very high power density of 7981 W/kg, the hybrid supercapacitor still attains an energy density of ∼75 W h/kg with high cyclic stability at a 10 A/g current rate. The detailed electrochemical studies confirm higher cyclic stability and a superior electrochemical energy storage property of porous anhydrous Co0.5Ni0.5C2O4, making it a potential pseudocapacitive electrode for large energy storage applications.

Synthesis, Characterization, and Ionic Conductivity Studies of Simultaneously Substituted K- and Ga-Doped BaZrO3.

Ceramic fuel cells possess tremendous advantages over PMFCs due to their fuel flexibility and requirement of low-purity hydrogen. Despite high conversion efficiency, the high cost of ultra high-purity hydrogen required for the operation limits the application of PMFCs. Although ceramic fuel cells operate at elevated temperature, high performance coupled with multifuel flexibility makes ceramic fuel cells a superior option as a static power source to generate electricity compared to thermal coal-fired power plants. BaZr1-x Y x O3-x/2 based protonic conductors get a high degree of interest due to their superior structural stability, but their poor conductivity at higher temperature limits the performance of ceramic fuel cells. To overcome the low ionic conductivity issues of BaZrO3 based materials at elevated temperature, the simultaneous doping of smaller Ga on the Zr site and K on the Ba site was employed here to create higher concentration of oxide-ion vacancies for the realization of superior conductivities. The simultaneous substitution of K and Ga created the oxygen vacancy-type point defects resulting in higher ionic conductivity ∼10-2 S/cm above 650 °C. The conductivity represented here for the Ba0.8K0.2Zr0.8Ga0.2O2.8 sample is superior or equivalent to the conductivity obtained for yttria-stabilized zirconia, a well-known ceramic oxide-ion electrolyte.

La1-x K x FeO3-δ: An Anion Intercalative Pseudocapacitive Electrode for Supercapacitor Application.

The green energy alternative to a fossil fuel-based economy can be provided only by coupling renewable energy solution solutions such as solar or wind energy plants with large-scale electrochemical energy storage devices. Enabling high-energy storage coupled with high-power delivery can be envisaged though high-capacitive pseudocapacitor electrodes. A pseudocapacitor electrode with multiple oxidation state accessibility can enable more than 1e - charge/transfer per molecule to facilitate superior energy storage. K-doped LaFeO3 (La1-x K x FeO3-δ) is presented here as an electrode having a high pseudocapacitance storage, equivalent to 1.32e - charge/transfer per molecule, resulting in a capacity equivalent of 662 F/g at 1 mV/s scan rate by introduction of a layered potential over the Fe-ion octahedral to utilize higher redox state energies (Fe4+→ Fe2+). La/K ordering in orthorhombic perovskite (La1-x K x FeO3-δ) made the Fe4+ oxidation state accessible, and a systematic shift in the redox energies of Fe4+/3+ and Fe3+/2+ redox couples was observed with K+ ion doping in the A site of the LaFeO3 perovskite, which resulted in a high faradic contribution to the capacitance, coupled with anionic intercalation of H2O/OH- in the host perovskite lattice. The surface capacitive and diffusion control contributions for capacitance are about 42 and 58%, respectively, at -0.6 V, with a scan rate of 1  mV/s. A high gravimetric capacitance, equivalent to 619, 347, 188, 121, and 65 F/g, respectively, at 1, 2, 3, 5, and 10 A/g constant current, was observed for the La0.5K0.5FeO3-δ electrode. Up to 88.9% capacitive retention and 97% Coulombic efficacy were obtained for continuous 5000 cycles of charge/discharge for the La0.5K0.5FeO3-δ electrode. The gravimetric capacitance values of ASCs (activated carbon//La0.5K0.5FeO3-δ) are 348, 290, 228, and 147 F/g at current densities of 1, 2, 3, and 5 A/g, respectively. A maximum specific power of ∼3594 W/kg was obtained when the specific energy reached ∼117 Wh/kg at 5 A/g of current density.

High performing flexible optoelectronic devices using thin films of topological insulator.

Topological insulators (TIs) possess exciting nonlinear optical properties due to presence of metallic surface states with the Dirac fermions and are predicted as a promising material for broadspectral phodotection ranging from UV (ultraviolet) to deep IR (infrared) or terahertz range. The recent experimental reports demonstrating nonlinear optical properties are mostly carried out on non-flexible substrates and there is a huge demand for the fabrication of high performing flexible optoelectronic devices using new exotic materials due to their potential applications in wearable devices, communications, sensors, imaging etc. Here first time we integrate the thin films of TIs (Bi2Te3) with the flexible PET (polyethylene terephthalate) substrate and report the strong light absorption properties in these devices. Owing to small band gap material, evolving bulk and gapless surface state conduction, we observe high responsivity and detectivity at NIR (near infrared) wavelengths (39 A/W, 6.1 × 108 Jones for 1064 nm and 58 A/W, 6.1 × 108 Jones for 1550 nm). TIs based flexible devices show that photocurrent is linearly dependent on the incident laser power and applied bias voltage. Devices also show very fast response and decay times. Thus we believe that the superior optoelectronic properties reported here pave the way for making TIs based flexible optoelectronic devices.

Synthesis, characterizations and electrochemical performances of anhydrous CoC2O4 nanorods for pseudocapacitive energy storage applications.

To overcome the environmental challenges caused by utilization of fossil fuel based energy technologies and to utilize the full potential of renewable energy sources such as solar, wind and tidal, high power and high energy density containing large scale electrochemical energy storage devices are a matter of concern and a need of the hour. Pseudocapacitors with accessibility to multiple oxidation states for redox charge transfer can achieve a higher degree of energy storage density compared to electric double layer capacitors (EDLC) and the hybrid supercapacitor is one of the prominent electrochemical capacitors that can resolve the low energy density issues associated with EDLCs. Due to its open pore framework structure with superior structural stability and accessibility of Co2+/3+/4 redox states, porous anhydrous CoC2O4 nanorods are envisaged here as a potential energy storage electrode in a pseudo-capacitive mode. Superior specific capacitance equivalent to 2116 F g-1 at 1 A g-1 in the potential window of 0.3 V was observed for anhydrous CoC2O4 nanorods in aqueous 2 M KOH electrolyte. A predominant pseudo-capacitive mechanism seems to be operative behind the high charge storage at electrodes as intercalative (Inner) and surface (outer) charge storage contributions were found to be 75% and 25% respectively. Further, in full cell asymmetric supercapacitor (ASC) mode in which porous anhydrous CoC2O4 nanorods were used as positive electrodes and activated carbon (AC) was utilised as negative electrodes within an operating potential window of 1.3 V, a highest specific energy of W h kg-1 and specific power of ∼647 W kg-1 at 0.5 A g-1 current density were obtained with superior cycling stability. High cycling stability coupled with superior electrochemical storage properties make anhydrous CoC2O4 nanorods potential pseudo-capacitive electrodes for large scale energy storage applications.

Cu(i) substituted wurtzite ZnO: a novel room temperature lead free ferroelectric and high-κ giant dielectric.

Semiconducting wurtzite ZnO, with the highest incipient piezoelectricity is an attractive alternative choice with doping transition metal ions in the host lattice to develop novel binary ferroelectric materials that can be easily fabricated in any device architecture. Up to 8% Cu+ ion substitution on Zn2+ sites in the ZnO lattice was achieved by careful selection of raw material and adaptation of a low temperature sol-gel synthesis route for the preparation of bulk material. Phase purity and substitution of Cu+ ions in the ZnO lattice along with oxide-ion vacancy formation was confirmed using Powder X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray analysis (EDX), X-ray Photoelectron Spectroscopy (XPS) and Magnetic property measurement system (MPMS) studies. A giant dielectric constant (∼6300) was observed at 600 °C for Zn0.95Cu0.05O1-δ pellets at 100 kHz frequency. Bulk Zn0.95Cu0.05O1-δ also exhibits ferroelectricity at room temperature with remnant polarization P r and V c equal to 9.60 × 10-3 µC cm-2 and 3.83 × 102 V cm-1 respectively.

Ni stabilized rock-salt structured CoO; Co1-x Ni x O: tuning of eg electrons to develop a novel OER catalyst.

The oxygen evolution reaction (OER) is a key half-reaction in hydrogen-oxygen electrolysers that is very important for efficient electrochemical energy generation, storage and fuel production that offers a clean alternative to fissile fuel combustion based energy systems. Several transition metal containing perovskites were recently explored for the development of superior OER catalysts, and their activity was correlated with the applied potentials at a specific current density to eg electron density present in the materials. The rock salt structure is envisaged here as a model host structure similar to perovskite to tune the eg electrons to obtain superior electro-catalytic activity. Incorporation of Ni into CoO lattices helps to stabilize the rock salt structure and modulate the eg electrons to develop superior OER and ORR electrocatalysts. Nickel doped rock salt structured CoO, Ni x Co1-x O (0 ≤ x ≤ 0.5), were synthesized by employing a solid state metathesis synthesis route. The compounds were characterised by powder X-ray diffraction (XRD), TGA, FT-IR and X-ray Photoelectron Spectroscopy (XPS). Ni0.3Co0.7O with 1.3 eg electrons showed superior electrocatalytic activity for the oxygen evolution reaction. The overpotential for the Ni0.3Co0.7O sample was also found to be ∼0.450 V for 1 M and about ∼0.389 V at 5 M concentration of the KOH electrolyte.

Posterior Chamber Scleral Fixation of Intraocular Lenses in Post-Vitrectomised Aphakic Eyes.

INTRODUCTION: The best method of aphakia correction is in the bag implantation of Posterior Chamber Intraocular Lens (PCIOL). When this ideal procedure is not possible due to lack of integrity of posterior capsule or zonules, the other alternatives are broadly categorized into two: extraocular and intraocular. Whereas, the former includes contact lenses and aphakic glasses, the latter ones are further divided into anterior and posterior chamber methods. Anterior Chamber Intraocular Lenses (ACIOL) can be with or without iris claw. At the posterior chamber, fixation of the lenses can be with glue or sutures. When there is combined Pars Plana Vitrectomy (PPV) and lensectomy or if the indication of PPV is dropped nucleus or intraocular lens, a modality of aphakia correction should be devised. Posterior Chamber Scleral Fixation of Intraocular Lenses (PCSFIOL) with sutures is a preferred method because of its low complication profile. However, data on correction of aphakia after combined PPV and lensectomy is limited. To fill in this gap in knowledge, we evaluated the secondary PCSFIOL in aphakic eyes after previous PPV and lensectomy. AIM: To assess the outcome and complication profile of a large series of patients who underwent secondary PCSFIOL implantation with sutures after combined PPV and lensectomy. MATERIALS AND METHODS: Records of all patients who had undergone secondary PCSFIOL implantation with sutures after combined PPV and lensectomy from 2010 to 2014 were reviewed retrospectively for visual outcomes and complications. Patients' demographic data, indication for PPV, best corrected preoperative and postoperative visual acuities, complications of surgery, and indications of PCSFIOL and length of follow up were collected and analyzed. RESULTS: A total of 148 eyes of 148 patients (127 males and 21 females) were identified. Mean age at surgery was 32.5±8 years (range 2.5-73 years) with a mean follow up 23±14 months (range 3-114 months). A total of 95.27%, 2.70% and 2.02% of patients had improvement, maintenance and worsening of their final postoperative visual acuities respectively. A total of 32 (21.62%) of 148 eyes had postoperative complications from PCSFIOL with Epiretinal Membrane (ERM) formation being the most common. They all required one form of management or the other. Suture breakage leading to PCSFIOL subluxation or dislocation occurred in four eyes (2.70%). CONCLUSION: PCSFIOL with sutures is a preferred method in the management of post-vitrectomised aphakic eyes when the capsular or zonular support is not adequate for in the bag implantation of posterior chamber intraocular lenses.

Room-Temperature Magneto-dielectric Effect in LaGa0.7Fe0.3O3+γ; Origin and Impact of Excess Oxygen.

We report an observation of room-temperature magneto-dielectric (RTMD) effect in LaGa0.7Fe0.3O3+γ compound. The contribution of intrinsic/resistive sources in the presently observed RTMD effect was analyzed by measuring direct-current (dc) magnetoresistance (MR) in four-probe geometry and frequency-dependent MR via impedance spectroscopy (MRIS). Present MRIS analysis reveals that at frequencies corresponding to grain contribution (≥1 × 106 Hz for present sample), the observed MD phenomenon is MR-free/intrinsic, whereas at lower probing frequencies (<1 × 106 Hz), the observed MD coupling appears to be MR-dominated possibly due to oxygen excess, that is, due to coexistence of Fe3+ and Fe4+. The magnetostriction is anticipated as a mechanism responsible for MR-free/intrinsic MD coupling, whereas the MR-dominated part is attributed to hopping charge transport along with Maxwell-Wagner and space charge polarization. The multivalence of Fe ions in LaGa0.7Fe0.3O3+γ was validated through iodometric titration and Fe K-edge X-ray absorption near-edge structure measurements. The excess of oxygen, that is, coexistence of Fe3+ and Fe4+, was understood in terms of stability of Fe4+ by means of "bond-valence-sum" analysis and density functional theory-based first-principles calculations. The cation vacancies at La/Ga site (or at La and Ga both) were proposed as the possible origin of excess oxygen in presently studied compound. Present investigation suggests that, to justify the intrinsic/resistive origin of MD phenomenon, frequency-dependent MR measurements are more useful than measuring only dc MR or comparing the trends of magnetic-field-dependent change in dielectric constant and tan δ. Presently studied Fe-doped LaGaO3 can be a candidate for RTMD applications.