Comparative Investigation of Water-Based CMC and LA133 Binders for CuO Anodes in High-Performance Lithium-Ion Batteries.

Transition metal oxides are considered to be highly promising anode materials for high-energy lithium-ion batteries. While carbon matrices have demonstrated effectiveness in enhancing the electrical conductivity and accommodating the volume expansion of transition metal oxide-based anode materials in lithium-ion batteries (LIBs), achieving an optimized utilization ratio remains a challenging obstacle. In this investigation, we have devised a straightforward synthesis approach to fabricate CuO nano powder integrated with carbon matrix. We found that with the use of a sodium carboxymethyl cellulose (CMC) based binder and fluoroethylene carbonate additives, this anode exhibits enhanced performance compared to acrylonitrile multi-copolymer binder (LA133) based electrodes. CuO@CMC electrodes reveal a notable capacity ~1100 mA h g-1 at 100 mA g-1 following 170 cycles, and exhibit prolonged cycling stability, with a capacity of 450 mA h g-1 at current density 300 mA g-1 over 500 cycles. Furthermore, they demonstrated outstanding rate performance and reduced charge transfer resistance. This study offers a viable approach for fabricating electrode materials for next-generation, high energy storage devices.

Enhancing Electrochemical Performance of Si@CNT Anode by Integrating SrTiO3 Material for High-Capacity Lithium-Ion Batteries.

Silicon (Si) has attracted worldwide attention for its ultrahigh theoretical storage capacity (4200 mA h g-1), low mass density (2.33 g cm-3), low operating potential (0.4 V vs. Li/Li+), abundant reserves, environmentally benign nature, and low cost. It is a promising high-energy-density anode material for next-generation lithium-ion batteries (LIBs), offering a replacement for graphite anodes owing to the escalating energy demands in booming automobile and energy storage applications. Unfortunately, the commercialization of silicon anodes is stringently hindered by large volume expansion during lithiation-delithiation, the unstable and detrimental growth of electrode/electrolyte interface layers, sluggish Li-ion diffusion, poor rate performance, and inherently low ion/electron conductivity. These present major safety challenges lead to quick capacity degradation in LIBs. Herein, we present the synergistic effects of nanostructured silicon and SrTiO3 (STO) for use as anodes in Li-ion batteries. Si and STO nanoparticles were incorporated into a multiwalled carbon nanotube (CNT) matrix using a planetary ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the STO. We discovered that the introduction of STO can improve the electrochemical performance of Si/CNT nanocomposite anodes. Experimental measurements and electrochemical impedance spectroscopy provide evidence for the enhanced mobility of Li-ions facilitated by STO. Hence, incorporating STO into the Si@CNT anode yields promising results, exhibiting a high initial Coulombic efficiency of approximately 85%, a reversible specific capacity of ~800 mA h g-1 after 100 cycles at 100 mA g-1, and a high-rate capability of 1400 mA g-1 with a capacity of 800 mA h g-1. Interestingly, it exhibits a capacity of 350 mAh g-1 after 1000 lithiation and delithiation cycles at a high rate of 600 mA hg-1. This result unveils and sheds light on the design of a scalable method for manufacturing Si anodes for next-generation LIBs.

A Low-Acidity Chloride Electrolyte Enables Exceptional Reversibility and Stability in Aqueous Tin Metal Batteries.

Tin (Sn) metal has emerged as a promising anode for aqueous batteries, due to its high capacity, non-toxicity, and cost-effectiveness. However, Sn metal has often been coupled with strong and corrosive sulfuric acids (2-3 M), leading to severe electrode corrosion and hydrogen evolution issues. Although high efficiency and long cycling were reported, the results were achieved using high currents to kinetically mask electrode-electrolyte side reactions. Herein, we introduce a low-acidity tin chloride electrolyte (pH=1.09) as a more viable option, which eliminates the need of strong acids and enables a reversible dendrite-free Sn plating chemistry. Remarkably, the plating efficiency approaches unity (99.97 %) under standard testing conditions (1 mA cm-2 for 1 mAh cm-2), which maintains high at 99.23-99.93 % across various aggressive conditions, including low current (0.1-0.25 mA cm-2), high capacity (5-10 mAh cm-2), and extended resting time (24-72 hours). The battery calendar life is further prolonged to 3064 hours, significantly surpassing literature reports. Additionally, we presented an effective method to mitigate the potential Sn2+ oxidization issue on the cathode, demonstrating long-cycling Sn||LiMn2O4 hybrid batteries. This work offers critical insights for developing highly reversible Sn metal batteries.

Trivalent Indium Metal as a High-Capacity, High-Efficiency, Low-Polarization, and Long-Cycling Anode for Aqueous Batteries.

Aqueous batteries using multivalent metals hold great promise for energy storage due to their low cost, high energy, and high safety. Presently, divalent metals (zinc, iron, nickel, and manganese) prevail as the leading choice, which, however, suffer from low Coulombic efficiency or dendrite growth. In stark contrast, trivalent metals have received rare attention despite their capability to unlock unique redox reactions. Herein, we investigate trivalent indium as an innovative and high-performance metal anode for aqueous batteries. The three-electron In3+/In redox endows a high capacity of ∼700 mAh g-1, on par with the Zn metal. Besides, indium exhibits a suitable redox potential (-0.34 V vs standard hydrogen electrode) and dendrite-free plating process, which renders an ultrahigh Coulombic efficiency of 99.3-99.8%. More surprisingly, it features an exceedingly low polarization of 1 mV in symmetrical cells, which is 1-2 orders of magnitude lower than any reported metals. The In-MnO2 full cell also delivers impressive performance, with a cell voltage of ∼1.2 V, a high capacity of ∼330 mAh g-1, and a long cycling time of 680 cycles. Our work exemplifies the efficacy of exploiting trivalent metals as an excellent metal anode, which provides an exciting direction for building high-performance aqueous batteries.

Water treatment membranes embedded with a stable and bactericidal nanodiamond material.

Filtration has emerged as a critical technology to reduce waterborne diseases caused by poor water quality. Filtration technology presents key challenges, such as membrane selectivity, permeability and biofouling. Nanomaterials can offer solutions to these challenges by varying the membranes' mechanical and bactericidal properties. This research uses nanodiamond particles with facile surface functionality and biocompatibility properties that are added to membranes used for filtration treatments. Scanning and transmission electron microscopy (SEM and TEM) and Fourier transform infrared spectroscopy (FTIR) were performed to study the membrane surface. FTIR spectra confirms an increase in oxygen functional groups onto the ultradispersed diamond's (UDD) surface following acid treatment. SEM images show particle deagglomeration of functionalized UDD at the membrane surface. Tensile strength tests were done to measure the UDD mechanical properties and Coliscan membrane filtration characterization was performed to determine the filter effectiveness. Polyether sulfone (PES) and polyvinylidene (PVDF) membranes expressed a change in their yield point when UDD was incorporated into the porous matrix. A significant microorganism reduction was obtained and confirmed using t-test analysis at a 95% level of confidence. UDD-embedded membranes exhibit a significant bactericidal reduction compared to commercial membranes suggesting these membranes have the potential to enhance current membrane filtration systems.

Block Copolymer-Assisted Synthesis of Iron Oxide Nanoparticles for Effective Removal of Congo Red.

Iron oxide nanoparticles (IONPs) were synthesized via a block copolymer-assisted hydrothermal method and the phase purity and the crystal structure were investigated by X-ray diffraction. The Rietveld analysis of X-ray diffractometer spectra shows the hexagonal phase symmetry of α-Fe2O3. Further, the vibrational study suggests Raman active modes: 2A1g + 5Eg associated with α-Fe2O3, which corroborates the Rietveld analysis and orbital analysis of 2PFe. The superparamagnetic behavior is confirmed by magnetic measurements performed by the physical properties measurement system. The systematic study of the Congo red (CR) interaction with IONPs using a UV-visible spectrophotometer and a liquid chromatography-tandem mass spectrometry system equipped with a triple quadrupole mass analyzer and an electrospray ionization interface shows effective adsorption. In visible light, the Fe2O3 nanoparticles get easily excited and generate electrons and holes. The photogenerated electrons reduce the Fe3+ ions to Fe2+ ions. The Fe2+/H2O2 oxidizes CR by the Fenton mechanism. The strong adsorption ability of prepared nanoparticles towards dyes attributes the potential candidates for wastewater treatment and other catalytic applications.

Novel magneto-luminescent effect in LSMO/ZnS:Mn nanocomposites at near-room temperature.

We report the tuning of the internal Mn photoluminescence (PL) transition of magnetically-ordered Sr-doped lanthanum manganite (LSMO)/Mn-doped zinc sulfide (ZnS:Mn) nanocomposites (NCs) by applying a static magnetic field in the range of 0-1 T below the critical temperature of ∼225 K. To do that, we have systematically fabricated LSMO/ZnS:Mn at different concentrations (1:1, 1:3, 1:5 and 1:10 wt%) via a straightforward solid-state reaction. X-ray diffraction and Raman analyses reveal that both phases coexist with a high degree of crystallinity and purity. Electron microscopy indicates that the NCs are almost spherical with an average crystal size of ∼6 nm, and that their surfaces are clean and smooth. The bifunctional character of LSMO/ZnS:Mn was evidenced by vibrating sample magnetometry and PL spectroscopy analyses, which show a marked ferromagnetic behavior and a broad, intense Mn orange emission band at room temperature. Moreover, the LSMO/ZnS:Mn at 1:3 wt% exhibits magneto-luminescent (ML) coupling below 225 K, and reaches the largest suppression of Mn-band PL intensity (up to ∼10%) at 150 K, when a magnetic field of 1.0 T is applied. The ML effect persists at magnetic fields as low as 0.2 T at 8 K, which can be explained by evoking a magnetic-ordering-induced spin-dependent restriction of the energy transfer to Mn states. No ML effect was observed in bare ZnS:Mn nanoparticles under the same experimental parameters. Our findings suggest that this NC can be considered as a new ML compound, similar to FeCo/InGaN-GaN and LSMO/ZnO NCs, useful as q-bits for quantum computation. The results presented here bring forth new avenues to better understand the interaction between semiconductors and perovskites, and exploit their synergistic effects in magneto-optics, spintronics and nanoelectronics.

Geometry and Surface Area Optimization in Iron Oxide Nanoparticles for Enhanced Magnetic Properties.

Iron oxide nanoparticles (IONPs) are recognized for their potential in biomedical applications due to their distinctive physicochemical properties. This study investigates the synthesis of IONPs with various geometric morphologies-cubic, star-like, truncated icosahedron, and spherical-via thermal decomposition to enhance their utility in magnetic resonance imaging (MRI) and targeted drug delivery. X-ray diffraction analysis verified the Fe3O4 phase in all nanoparticles, illustrating the synthesis's efficacy. Particle morphologies were well-defined, with sizes ranging from 10 to 150 nm, as determined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Magnetic evaluations using a vibrating sample magnetometer (VSM-PPMs) demonstrated their superparamagnetic behavior, with larger particles exhibiting greater saturation magnetization. Notably, truncated icosahedron and cubic IONPs showed superior transverse relaxation rates, with r2 values of 56.77 s1 mM1 and 42.67 s1 mM1, respectively. These results highlight the potential of customizing IONP geometries to optimize their magnetic properties and increase surface area available for functionalization, thereby improving their efficacy for biomedical applications.

Building a Rechargeable Voltaic Battery via Reversible Oxide Anion Insertion in Copper Electrodes.

Voltaic pile, the very first battery built by humanity in 1800, plays a seminal role in battery development history. However, the premature design leads to the inevitable copper ion dissolution issue, which dictates its primary battery nature. To address this issue, solid-state electrolytes, ion exchange membranes, and/or sophisticated electrolytes are widely utilized, leading to high costs and complicated cell configuration. Herein, we build a rechargeable zinc-copper voltaic battery from simple and cheap electrolyte/separator materials, thus eliminating the need to use the above components. Notably, our battery leverages the Zn4SO4(OH)6·xH2O precipitation in ZnSO4 electrolytes, a common side reaction in zinc batteries, to provide a "locally alkaline" environment for copper electrodes. Consequently, oxide (O2-) anion insertion takes place and readily transforms copper to copper(I) oxide (Cu2O) without any copper ion dissolution issue. Therefore, this battery realizes a high capacity of ∼370 mA h g-1 and a long cycling of ∼500 cycles. Our work provides an innovative approach to stabilize anion insertion in metal electrodes for energy storage.

Exploring Lead Zirconate Titanate, the Potential Advancement as an Anode for Li-Ion Batteries.

Graphite, widely adopted as an anode for lithium-ion batteries (LIBs), faces challenges such as an unsustainable supply chain and sluggish rate capabilities. This emphasizes the urgent need to explore alternative anode materials for LIBs, aiming to resolve these challenges and drive the advancement of more efficient and sustainable battery technologies. The present research investigates the potential of lead zirconate titanate (PZT: PbZr0.53Ti0.47O3) as an anode material for LIBs. Bulk PZT materials were synthesized by using a solid-state reaction, and the electrochemical performance as an anode was examined. A high initial discharge capacity of approximately 686 mAh/g was attained, maintaining a stable capacity of around 161 mAh/g after 200 cycles with diffusion-controlled intercalation as the primary charge storage mechanism in a PZT anode. These findings suggest that PZT exhibits a promising electrochemical performance, positioning it as a potential alternative anode material for LIBs.

Unveiling Potential of Gallium Ferrite (GaFeO3) as an Anode Material for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) serve as the backbone of modern technologies with ongoing efforts to enhance their performance and sustainability driving the exploration of new electrode materials. This study introduces a new type of alloy-conversion-based gallium ferrite (GFO: GaFeO3) as a potential anode material for Li-ion battery applications. The GFO was synthesized by a one-step mechanochemistry-assisted solid-state method. The powder X-ray diffraction analysis confirms the presence of an orthorhombic phase with the Pc21 n space group. The photoelectron spectroscopy studies reveal the presence of Ga3+ and Fe3+ oxidation states of gallium and iron atoms in the GFO structure. The GFO was evaluated as an anode material for Li-ion battery applications, displaying a high discharge capacity of ∼887 mA h g-1 and retaining a stable capacity of ∼200 mA h g-1 over 450 cycles, with a Coulombic efficiency of 99.6 % at a current density of 100 mA g-1. Cyclic voltammetry studies confirm an alloy-conversion-based reaction mechanism in the GFO anode. Furthermore, density functional theory studies reveal the reaction mechanism during cycling and Li-ion diffusion pathways in the GFO anode. These results strongly suggest that the GFO could be an alternative anode material in LIBs.

Synthesis and Characterization of Carbon-Based Quantum Dots and Doped Derivatives for Improved Andrographolide's Hydrophilicity in Drug Delivery Platforms.

Carbon-based quantum dots (CBQDs), sulfur-doped carbon-based quantum dots (S-CBQDs), and nitrogen-doped carbon-based quantum dots (N-CBQDs) have strong potential for drug delivery platforms. They were conjugated with andrographolide, a well-known hydrophobic drug, to study the concomitant changes in hydrophilicity. The interactions between these nanomaterials and the drug were studied by characterizing the optical and structural properties of the nanoparticles before and after coupling with the drug. It was found that the interaction of the drug with these nanomaterials produced noticeable changes in their optical and structural properties. Moreover, the partition coefficient for the nanocomposites was determined by NMR. The results indicate that conjugating the drug with the nanoparticles significantly enhanced its affinity for the aqueous phase, from 2.632 to 0.1117, thereby opening the possibility of using this approach for developing an effective drug delivery platform for this hydrophobic drug.

Luminescent graphene quantum dots fabricated by pulsed laser synthesis.

Graphene has been the subject of intense research in recent years due to its unique electrical, optical and mechanical properties. Furthermore, it is expected that quantum dots of graphene would make their way into devices due to their structure and composition which unify graphene and quantum dots properties. Graphene quantum dots (GQDs) are planar nano flakes with a few atomic layers thick and with a higher surface-to-volume ratio than spherical carbon dots (CDs) of the same size. We have developed a pulsed laser synthesis (PLS) method for the synthesis of GQDs that are soluble in water, measure 2-6 nm across, and are about 1-3 layers thick. They show strong intrinsic fluorescence in the visible region. The source of fluorescence can be attributed to various factors, such as: quantum confinement, zigzag edge structure, and surface defects. Confocal microscopy images of bacteria exposed to GQDs show their suitability as biomarkers and nano-probes in high contrast bioimaging.

Holey Graphene/Ferroelectric/Sulfur Composite Cathodes for High-Capacity Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have attracted considerable interest as next-generation high-density energy storage devices. However, their practical applications are limited by rapid capacity fading when cycling cells with high mass loading levels. This could be largely attributed to the inferior electron/ion conduction and the severe shuttling effect of soluble polysulfide species. To address these issues, composites of sulfur/ferroelectric nanoparticles/ho ley graphene (S/FNPs/hG) cathodes were fabricated for high-mass-loading S cathodes. The solvent-free and binder-free procedure is enabled using holey graphene as a unique dry-pressable electrode for Li-S batteries. The unique structure of the holey graphene framework ensures fast electron and ion transport within the electrode and affords enough space to mitigate the electrode's volume expansion. Moreover, ferroelectric polarization due to FNPs within S/hG composites induces an internal electric field, which effectively reduces the undesired shuttling effect. With these advantages, the S/FNPs/hG composite cathodes exhibit sustainable and ultrahigh specific capacity up to 1409 mAh/gs for the S/BTO/hG cathode. A capacity retention value of 90% was obtained for the S/BNTFN/hG battery up to cycle 18. The high mass loading of sulfur ranging from 5.72 to 7.01 mgs/cm2 allows maximum high areal capacity up to ∼10 mAh/cm2 for the S/BTO/hG battery and superior rate capability at 0.2 and 0.5 mA/cm2. These results suggest sustainable and high-yielding Li-S batteries can be obtained for potential commercial applications.

Paramagnetism in Microwave-Synthesized Metal-Free Nitrogen-Doped Graphene Quantum Dots.

Nitrogen-doped graphene quantum dots (NGQDs) have gained significant attention due to their various physical and chemical properties; however, there is a gap in the study of NGQDs' magnetic properties. This work adds to the efforts of bridging the gap by demonstrating the room temperature paramagnetism in GQDs doped with Nitrogen up to 3.26 at.%. The focus of this experimental work was to confirm the paramagnetic behavior of metal free NGQDs resulting from the pyridinic N configuration in the GQDs host. Metal-free nitrogen-doped NGQDs were synthesized using glucose and liquid ammonia as precursors by microwave-assisted synthesis. This was followed by dialysis filtration. The morphology, optical, and magnetic properties of the synthesized NGQDs were characterized carefully through atomic force microscopy (AFM), transmission electron microscopy (TEM)), UV-VIS spectroscopy, fluorescence, X-ray photon spectroscopy (XPS), and vibrating sample magnetometer (VSM). The high-resolution TEM analysis of NGQDs showed that the NGQDs have a hexagonal crystalline structure with a lattice fringe of ~0.24 nm of (1120) graphene plane. The N1s peak using XPS was assigned to pyridinic, pyrrolic, graphitic, and oxygenated NGQDs. The magnetic study showed the room-temperature paramagnetic behavior of NGQDs with pyridinic N configuration, which was found to have a magnetization of 20.8 emu/g.

Graphene Film Growth on Silicon Carbide by Hot Filament Chemical Vapor Deposition.

The electrical properties of graphene on dielectric substrates, such as silicon carbide (SiC), have received much attention due to their interesting applications. This work presents a method to grow graphene on a 6H-SiC substrate at a pressure of 35 Torr by using the hot filament chemical vapor deposition (HFCVD) technique. The graphene deposition was conducted in an atmosphere of methane and hydrogen at a temperature of 950 °C. The graphene films were analyzed using Raman spectroscopy, scanning electron microscopy, atomic force microscopy, energy dispersive X-ray, and X-ray photoelectron spectroscopy. Raman mapping and AFM measurements indicated that few-layer and multilayer graphene were deposited from the external carbon source depending on the growth parameter conditions. The compositional analysis confirmed the presence of graphene deposition on SiC substrates and the absence of any metal involved in the growth process.

Atomic and electronic properties of realizable size single-crystal GaN nanotubes by first principles.

We studied the diameter and wall thickness dependent atomic and electronic properties of practical size single-crystal GaN nanotubes using first principle calculations. Single-crystal GaN nanotubes are similar to the hexagonal GaN nanowires, grown in the [0001] direction with [10-10] facets, except there is an axial hexagonal void in them. We first demonstrated that the atomic and electronic properties of these tubes are mainly determined by the thickness of their wurtzite walls; and their diameters have negligible effects. Then, considering the individual walls of GaN nanotubes in two-dimensional slab calculations we examine the bond distances, formation energy, band gap, effective electron mass and the evolution of electronic density of the states as a function of thickness for unsaturated and hydrogen-saturated slabs of GaN. Calculations revealed that the unsaturated dangling bonds at the surfaces induce defect states in the band gap region of unsaturated tubes. Therefore, regardless of diameter and wall thickness, their band gaps are always smaller than that of the bulk GaN. However, the band gaps of the hydrogen-saturated tubes are found to be amplified with respect to bulk GaN. The amplification in the band gaps as a function of wall thickness in the range of 5.6-16.9 A and 16.9-28.1 A scales with a factor of 1/d(0.9281) and 1/d(1.769), respectively. Our results show that, regardless of diameter, hydrogen saturated single-crystal GaN tubes with the wall thickness as small as 28.1 A would be stable and they would have a noticeably larger band gap with respect to the band gap of bulk GaN.

Magnetic Control of the Manganese Photoluminescence in Fe3O4/l-Cys ZnS:Mn Nanocomposites.

We investigated the magnetic control of the Mn photoluminescence (PL) in iron oxide/l-cysteine-capped zinc sulfide (Fe3O4/l-cys ZnS:Mn) nanocomposites via temperature- and field-dependent PL intensity studies. Fe3O4/l-cys ZnS:Mn was synthesized following a wet chemical deposition route and then its physicochemical, morphological, and magnetic properties were characterized. X-ray diffraction analysis indicates the formation of a semiconducting composite material with coexisting phases with high crystalline quality and purity. Electron microscopy reveals that the surfaces of the nanoparticles are clean and smooth, sized between 15 and 30 nm, without any sheathed amorphous phase. Vibrating sample magnetometry and UV light excitation show a clear superparamagnetic behavior and an optical response of Fe3O4/l-cys ZnS:Mn, which revealed its bifunctional nature. Magnetoluminescent coupling at 1.0 T is seen in the form of PL suppression in Fe3O4/l-cys ZnS:Mn from low temperature (10 K) to room temperature, with a PL intensity drop of ∼5% at 10 K and a maximum drop of 10% at room temperature. This observation can be explained by restriction of the energy transfer to Mn orbitals through magnetic ordering and Jahn-Teller distortions. Fe3O4/l-cys ZnS:Mn shows promise as a bifunctional biocompatible compound that can be applied as a theranostic agent and a quantum computational element. A deeper understanding behind the magnetic control of the optical response in bifunctional materials brings forth new arenas in diagnostics and drug delivery.

Graphene Growth Directly on SiO2/Si by Hot Filament Chemical Vapor Deposition.

We report the first direct synthesis of graphene on SiO2/Si by hot-filament chemical vapor deposition. Graphene deposition was conducted at low pressures (35 Torr) with a mixture of methane/hydrogen and a substrate temperature of 970 °C followed by spontaneous cooling to room temperature. A thin copper-strip was deposited in the middle of the SiO2/Si substrate as catalytic material. Raman spectroscopy mapping and atomic force microscopy measurements indicate the growth of few-layers of graphene over the entire SiO2/Si substrate, far beyond the thin copper-strip, while X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy showed negligible amounts of copper next to the initially deposited strip. The scale of the graphene nanocrystal was estimated by Raman spectroscopy and scanning electron microscopy.

Fabrication and field emission study of novel rod-shaped diamond-like carbon nanostructures.

Novel sp(3) rich diamond-like carbon nanorod films were fabricated by a hot filament chemical vapour deposition technique. The results are indicative of a bottom-up synthesis process, which results in a hierarchical structure that consists of microscale papillae comprising numerous nanorods. The papillae have diameters ranging from 2 to 4 microm and the nanorods have diameters in the 35-45 nm range. A growth mechanism based on the vapour-liquid-solid mechanism is proposed that accounts for the morphological aspects at the microscale and nanoscale. Investigation of field emission properties of fabricated nanorods reveals a low turn-on field of about 4.9 V microm( - 1) at 1 nA and a high field-enhancement factor.