R.A. Shakoor

Anomalous Manganese Activation of a Pyrophosphate Cathode in Sodium Ion Batteries: A Combined Experimental and Theoretical Study

Sodium ion batteries (SIBs) have many advantages such as the low price and abundance of sodium raw materials that are suitable for large-scale energy storage applications. Herein, we report an Mn-based pyrophosphate, Na(2)MnP(2)O(7), as a new SIB cathode material. Unlike most Mn-based cathode materials, which suffer severely from sluggish kinetics, Na(2)MnP(2)O(7) exhibits good electrochemical activity at ~3.8 V vs Na/Na(+) with a reversible capacity of 90 mAh g(-1) at room temperature. It also shows an excellent cycling and rate performance: 96% capacity retention after 30 cycles and 70% capacity retention at a c-rate increase from 0.05C to 1C. These electrochemical activities of the Mn-containing cathode material even at room temperature with relatively large particle sizes are remarkable considering an almost complete inactivity of the Li counterpart, Li(2)MnP(2)O(7). Using first-principles calculations, we find that the significantly enhanced kinetics of Na(2)MnP(2)O(7) is mainly due to the locally flexible accommodation of Jahn-Teller distortions aided by the corner-sharing crystal structure in triclinic Na(2)MnP(2)O(7). By contrast, in monoclinic Li(2)MnP(2)O(7), the edge-sharing geometry causes multiple bonds to be broken and formed during charging reaction with a large degree of atomic rearrangements. We expect that the similar computational strategy to analyze the atomic rearrangements can be used to predict the kinetics behavior when exploring new cathode candidates.

Site-Specific Transition Metal Occupation in Multicomponent Pyrophosphate for Improved Electrochemical and Thermal Properties in Lithium Battery Cathodes: A Combined Experimental and Theoretical Study

As an attempt to develop lithium ion batteries with excellent performance, which is desirable for a variety of applications including mobile electronics, electrical vehicles, and utility grids, the battery community has continuously pursued cathode materials that function at higher potentials with efficient kinetics for lithium insertion and extraction. By employing both experimental and theoretical tools, herein we report multicomponent pyrophosphate (Li(2)MP(2)O(7), M = Fe(1/3)Mn(1/3)Co(1/3)) cathode materials with novel and advantageous properties as compared to the single-component analogues and other multicomponent polyanions. Li(2)Fe(1/3)Mn(1/3)Co(1/3)P(2)O(7) is formed on the basis of a solid solution among the three individual transition-metal-based pyrophosphates. The unique crystal structure of pyrophosphate and the first principles calculations show that different transition metals have a tendency to preferentially occupy either octahedral or pyramidal sites, and this site-specific transition metal occupation leads to significant improvements in various battery properties: a single-phase mode for Li insertion/extraction, improved cell potentials for Fe(2+)/Fe(3+) (raised by 0.18 eV) and Co(2+)/Co(3+) (lowered by 0.26 eV), and increased activity for Mn(2+)/Mn(3+) with significantly reduced overpotential. We reveal that the favorable energy of transition metal mixing and the sequential redox reaction for each TM element with a sufficient redox gap is the underlying physical reason for the preferential single-phase mode of Li intercalation/deintercalation reaction in pyrophosphate, a general concept that can be applied to other multicomponent systems. Furthermore, an extremely small volume change of ~0.7% between the fully charged and discharged states and the significantly enhanced thermal stability are observed for the present material, the effects unseen in previous multicomponent battery materials.

A mixed iron–manganese based pyrophosphate cathode, Na2Fe0.5Mn0.5P2O7, for rechargeable sodium ion batteries

The development of secondary batteries based on abundant and cheap elements is vital. Among various alternatives to conventional lithium-ion batteries, sodium-ion batteries (SIBs) are promising due to the abundant resources and low cost of sodium. While there are many challenges associated with the SIB system, cathode is an important factor in determining the electrochemical performance of this battery system. Accordingly, ongoing research in the field of SIBs is inclined towards the development of safe, cost effective cathode materials having improved performance. In particular, pyrophosphate cathodes have recently demonstrated decent electrochemical performance and thermal stability. Herein, we report the synthesis, electrochemical properties, and thermal behavior of a novel Na2Fe0.5Mn0.5P2O7 cathode for SIBs. The material was synthesized through a solid state process. The structural analysis reveals that the mixed substitution of manganese and iron has resulted in a triclinic crystal structure (P1[combining macron] space group). Galvanostatic charge/discharge measurements indicate that Na2Fe0.5Mn0.5P2O7 is electrochemically active with a reversible capacity of ∼80 mA h g(-1) at a C/20 rate with an average redox potential of 3.2 V. (vs. Na/Na(+)). It is noticed that 84% of initial capacity is preserved over 90 cycles showing promising cyclability. It is also noticed that the rate capability of Na2Fe0.5Mn0.5P2O7 is better than Na2MnP2O7. Ex situ and CV analyses indicate that Na2Fe0.5Mn0.5P2O7 undergoes a single phase reaction rather than a biphasic reaction due to different Na coordination environment and different Na site occupancy when compared to other pyrophosphate materials (Na2FeP2O7 and Na2MnP2O7). Thermogravimetric analysis (25-550 °C) confirms good thermal stability of Na2Fe0.5Mn0.5P2O7 with only 2% weight loss. Owing to promising electrochemical properties and decent thermal stability, Na2Fe0.5Mn0.5P2O7, can be an attractive cathode for SIBs.

Using B4C Nanoparticles to Enhance Thermal and Mechanical Response of Aluminum

In this work, Al-B4C nanocomposites were produced by microwave sintering and followed by hot extrusion processes. The influence of ceramic reinforcement (B4C) nanoparticles on the physical, microstructural, mechanical, and thermal characteristics of the extruded Al-B4C nanocomposites was investigated. It was observed that the density decreased and porosity increased with an increase in B4C content in aluminum matrix. The porosity of the composites increased whereas density decreased with increasing B4C content. Electron microscopy analysis reveals the uniform distribution of B4C nanoparticles in the Al matrix. Mechanical characterization results revealed that hardness, elastic modulus, compression, and tensile strengths increased whereas ductility decreases with increasing B4C content. Al-1.0 vol. % B4C nanocomposite exhibited best hardness (135.56 Hv), Young’s modulus (88.63 GPa), and compression/tensile strength (524.67/194.41 MPa) among the materials investigated. Further, coefficient of thermal expansion (CTE) of composites gradually decreased with an increase in B4C content.

Improved properties of Al–Si3N4 nanocomposites fabricated through a microwave sintering and hot extrusion process

In this study, nano-sized Si3N4 (0, 0.5, 1.0 and 1.5 vol%)/Al composites were fabricated using a powder metallurgy method involving microwave sintering technique followed by hot extrusion. The influence of Si3N4 content on the structural, mechanical and thermal behaviour of Al–Si3N4 nanocomposites was systematically investigated. Electron microscopy examination reveals the uniform distribution of hard Si3N4 nanoparticles in the soft Al matrix. The compressive and tensile strengths of Al composites increased with the increase of Si3N4 content while the ductility decreased. The thermal expansion coefficient of the Al composite decreased with the progressive addition of hard Si3N4 nanoparticles. Overall, hot extruded Al–1.5 vol% Si3N4 nanocomposites exhibited the best combination of tensile, compressive, hardness, Youngs modulus and thermal properties of 191 ± 4 MPa, 412 ± 3 MPa, 16.3 ± 0.8 GPa, 94 ± 2 GPa and 19.3 μ K−1, respectively. Tensile tests performed at 200 °C revealed that the tensile strength reduced by ∼35% when compared to the strength at room temperature. The strength, however, was still higher compared to that of the pure Al at 200 °C. The major enhancement in the strength of the nanocomposites is primarily attributed to the presence of uniformly distributed nano-sized Si3N4 nanoparticles in the Al matrix.

A novel classification of prostate specific antigen (PSA) biosensors based on transducing elements

During the last few decades, there has been a tremendous rise in the number of research studies dedicated towards the development of diagnostic tools based on bio-sensing technology for the early detection of various diseases like cardiovascular diseases (CVD), many types of cancer, diabetes mellitus (DM) and many infectious diseases. Many breakthroughs have been developed in the areas of improving specificity, selectivity and repeatability of the biosensor devices. Innovations in the interdisciplinary areas like biotechnology, genetics, organic electronics and nanotechnology also had a great positive impact on the growth of bio-sensing technology. As a product of these improvements, fast and consistent sensing policies have been productively created for precise and ultrasensitive biomarker-based disease diagnostics. Prostate-specific antigen (PSA) is widely considered as an important biomarker used for diagnosing prostate cancer. There have been many publications based on various biosensors used for PSA detection, but a limited review was available for the classification of these biosensors used for the detection of PSA. This review highlights the various biosensors used for PSA detection and proposes a novel classification for PSA biosensors based on the transducer type used. We also highlight the advantages, disadvantages and limitations of each technique used for PSA biosensing which will make this article a complete reference tool for the future researches in PSA biosensing.

Microstructure and properties of Ni–Co–TiO2 composite coatings fabricated by electroplating

Ni–Co coatings are widely used due to their unique mechanical properties, high anticorrosion properties, good thermal stability and special magnetic properties. Ni–Co–xTiO2 (x = 0–20 g/L in the electrolyte) composite coatings were fabricated by electrodeposition on mild steel. The effect of TiO2 concentration on the microhardness, surface morphology and tribological behaviour has been studied. The results show that, comparing with pure Ni–Co coating, both microhardness and wear property of the Ni–Co–TiO2 composite coatings were significantly improved. The microstructure and properties for the Ni–Co–TiO2 composite coatings were varied following with the TiO2 concentration. The mechanism of mechanical property improvement was also discussed.

Compositional engineering of VOPcPhO-TiO2 nano-composite to reduce the absolute threshold value of humidity sensors

This research work demonstrates compositional engineering of an organic-inorganic hybrid nano-composites for modifying absolute threshold of humidity sensors. Vanadyl-2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine (VOPcPhO), an organic semiconductor, doped with Titanium-dioxide nanoparticles (TiO2 NPs) has been employed to fabricate humidity sensors. The morphology of the VOPcPhO:TiO2 nano-composite films has been analyzed by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). The sensors have been examined over a wide range of relative humidity i.e. 20-99% RH. The sensor with TiO2 (90nm) shows reduced sensitivity-threshold and improved linearity. The VOPcPhO:TiO2 (90nm) nano-composite film is comprised of uniformly distributed voids which makes the surface more favorable for adsorption of moisture content from environment. The VOPcPhO:TiO2 nano-composite based sensor demonstrates remarkable improvement in the sensing parameter when equated with VOPcPhO sensors.

Advances in osteobiologic materials for bone substitutes

A significant challenge in the current orthopedics is the development of suitable osteobiologic materials that can replace the conventional allografts, autografts, and xenografts and thereby serve as implant materials as bone substitutes for bone repair or remodelling. The complex biology behind the nanostructure and microstructure of bones and their repair mechanisms, which involve various types of chemical and biomechanical signalling amongst different cells, has set strong requirements for biomaterials to be used in bone tissue engineering. This review presents an overview of various types of osteobiologic materials to facilitate the formation of the functional bone tissue and healing of the bone, covering metallic, ceramic, polymeric, and cell‐based graft substitutes, as well as some biomolecular strategies including stem cells, extracellular matrices, growth factors, and gene therapies. Advantages and disadvantages of each type, particularly from the perspective of osteoinductive and osteoconductive capabilities, are discussed. Although the numerous challenges of bone regeneration in tissue engineering and regenerative medicine are yet to be entirely addressed, further advancements in osteobiologic materials will pave the way towards engineering fully functional bone replacement grafts.

Synthesis and characterisation of Ni–B/Ni–P–CeO2 duplex composite coatings

Binary (Ni–B, Ni–P) and duplex coatings (Ni–B/Ni–P, Ni–B/Ni–P–CeO2) with an inner Ni–B layer were electrodeposited on mild steel substrates. A comparison of the structural, surface, mechanical, and electrochemical properties of the coatings is presented to demonstrate the mechanical behaviour and corrosion protection performance. Scanning electron microscope and atomic force microscope images showed that Ni–B/Ni–P–CeO2 duplex coatings had a well-defined nodular structure compared to Ni–P coatings, and fewer surface defects compared to Ni–B and Ni–B/Ni–P duplex coatings. However, these coatings had high surface roughness owing to the presence of CeO2 ceramic particles. X-ray diffraction analysis revealed that Ni–B coatings were crystalline but Ni–P and Ni–B/Ni–P–CeO2 coatings exhibited an amorphous structure. Ni–B/Ni–P–CeO2 coatings exhibited superior hardness (15%) compared to Ni–P and Ni–B/Ni–P duplex coatings. Potentiodynamic polarisation results confirmed that Ni–B/Ni–P–CeO2 duplex coatings had superior corrosion protection efficiency (91%) compared to Ni–B (30%) and duplex Ni–B/Ni–P coatings (77%). The novel Ni–B/Ni–P–CeO2 duplex coatings demonstrated superior mechanical and promising anti-corrosion properties, which render them attractive for various applications.Graphical Abstract