Degradation Mechanisms of Electrodes Promotes Direct Regeneration of Spent Li-Ion Batteries: A Review.

The rapid growth of electric vehicle use is expected to cause a significant environmental problem in the next few years due to the large number of spent lithium-ion batteries (LIBs). Recycling spent LIBs will not only alleviate the environmental problems but also address the challenge of limited natural resources shortages. While several hydro- and pyrometallurgical processes are developed for recycling different components of spent batteries, direct regeneration presents clear environmental, and economic advantages. The principle of the direct regeneration approach is restoring the electrochemical performance by healing the defective structure of the spent materials. Thus, the development of direct regeneration technology largely depends on the formation mechanism of defects in spent LIBs. This review systematically details the degradation mechanisms and types of defects found in diverse cathode materials, graphite anodes, and current collectors during the battery's lifecycle. Building on this understanding, principles and methodologies for directly rejuvenating materials within spent LIBs are outlined. Also the main challenges and solutions for the large-scale direct regeneration of spent LIBs are proposed. Furthermore, this review aims to pave the way for the direct regeneration of materials in discarded lithium-ion batteries by offering a theoretical foundation and practical guidance.

Stoichiometrically optimized eg orbital occupancy of Ni-Co oxide catalysts for Li-air batteries.

Li-air battery (LAB) technology is making continuous progress toward its theoretical capacity, which is comparable to gasoline. However, the sluggish reaction at the cathode is still a challenge. We propose a simple strategy to optimize the surface eg occupancy by adjusting the stoichiometric ratios of transition metal-based spinel structures through a controlled hydrothermal synthesis. Three distinct stoichiometries of Ni-Co oxides were used to demonstrate the direct correlation between stoichiometry and catalytic performance. The groundsel flower-like structure having a 1 : 1.4 Ni : Co atomic ratio with high surface area, high defect density, and an abundance of Ni3+ at the surface with semi-filled eg orbitals was found to benefit the structure promoting high catalytic activities in aqueous and aprotic media. The assembled LAB cells employing this cathode demonstrate an exceptional lifespan, operating for 3460 hours and completing 173 cycles while achieving the highest discharge capacity of 13 759 mA h g-1 and low charging overpotentials. The key to this prolonged performance lies in the full reversibility of the cell, attributed to its excellent OER performance. A well-surface adsorbed, amorphous LiO2/Li2O2 discharge product is found to possess high diffusivity and ease of decomposition, contributing significantly to the enhanced longevity of the cell.

Transforming Nature's Bath Sponge into Stacking Faults-Enhanced Ag Nanorings-Decorated Catalyst for Hydrogen Evolution Reaction.

The rational design of cost-effective and efficient electrocatalysts for electrochemical water splitting is essential for green hydrogen production. Utilizing nanocatalysts with abundant active sites, high surface area, and deliberate stacking faults is a promising approach for enhancing catalytic efficiency. In this study, we report a simple strategy to synthesize a highly efficient electrocatalyst for the hydrogen evolution reaction (HER) using carbonized luffa cylindrica as a conductive N-doped carbon skeleton decorated with Ag nanorings that are activated by introducing stacking faults. The introduction of stacking faults and the resulting tensile strain into the Ag nanorings results in a significant decrease in the HER overpotential, enabling the use of Ag as an efficient HER electrocatalyst. Our findings demonstrate that manipulating the crystal properties of electrocatalysts, even for materials with intrinsically poor catalytic activity such as Ag, can result in highly efficient catalysts. Further, applying a conductive carbon backbone can lower the quantities of metal needed without compromising the HER activity. This approach opens up new avenues for designing high-performance electrocatalysts with very low metallic content, which could significantly impact the development of sustainable and cost-effective electrochemical water-splitting systems.

Sustainable regeneration of high-performance LiCoO2 from completely failed lithium-ion batteries.

Utilising the solid-state synthesis method is an easy and effective way to recycle spent lithium-ion batteries. However, verifying its direct repair effects on completely exhausting cathode materials is necessary. In this work, the optimal conditions for direct repair of completely failed cathode materials by solid-state synthesis are explored. The discharge capacity of spent LiCoO2 cathode material is recovered from 21.7 mAh g-1 to 138.9 mAh g-1 under the optimal regeneration conditions of 850 °C and n(Li)/n(Co) ratio of 1:1. The regenerated materials show excellent electrochemical performance, even greater than the commercial LiCoO2. In addition, based on the whole closed-loop recycling process, the economic and environmental effects of various recycling techniques and raw materials used in the battery production process are assessed, confirming the superior economic and environmental feasibility of direct regeneration method.

Surface Modification of Transition Metal Dichalcogenide Nanosheets for Intrinsically Self-Healing Hydrogels with Enhanced Mechanical Properties.

Nanocomposites with enhanced mechanical properties and efficient self-healing characteristics can change how the artificially engineered materials' life cycle is perceived. Improved adhesion of nanomaterials with the host matrix can drastically improve the structural properties and confer the material with repeatable bonding/debonding capabilities. In this work, exfoliated 2H-WS2 nanosheets are modified using an organic thiol to impart hydrogen bonding sites on the otherwise inert nanosheets by surface functionalization. These modified nanosheets are incorporated within the PVA hydrogel matrix and analyzed for their contribution to the composite's intrinsic self-healing and mechanical strength. The resulting hydrogel forms a highly flexible macrostructure with an impressive enhancement in mechanical properties and a very high autonomous healing efficiency of 89.92%. Interesting changes in the surface properties after functionalization show that such modification is highly suitable for water-based polymeric systems. Probing into the healing mechanism using advanced spectroscopic techniques reveals the formation of a stable cyclic structure on the surface of nanosheets, mainly responsible for the improved healing response. This work opens an avenue toward the development of self-healing nanocomposites where chemically inert nanoparticles participate in the healing network rather than just mechanically reinforcing the matrix by slender adhesion.

Cobalt doped titania-carbon nanosheets with induced oxygen vacancies for photocatalytic degradation of uranium complexes in radioactive wastes.

The photocatalytic degradation of uranium complexes is considered among the most efficient techniques for the efficient removal of uranium ions/complexes from radioactive wastewater. Described here is a nanostructured photocatalyst based on a cobalt-doped TiO2 composite with induced oxygen vacancies (Co@TiO2-C) for the photocatalytic removal of uranium complexes from contaminated water. The synergy between oxygen vacancies and Co-doping produced a material with a 1.7 eV bandgap, while the carbon network facilitates electron movement and hinders the e-h recombination. As a result, the new photocatalyst enables the decomposition of uranium-arsenazo iii complexes (U-ARZ3), followed by photocatalytic reduction of hexavalent uranium to insoluble tetravalent uranium. Combined with the nanosheet structure's high surface area, the photocatalytic decomposition, reduction efficiency, and kinetics were significantly enhanced, achieving almost complete U(vi) removal in less than 20 minutes from solution with a concentration as high as 1000 mL g-1. Moreover, the designed photocatalyst exhibits excellent stability and reusability without decreasing the photocatalytic performance after 5 cycles.

Polyoxometalate Ionic Sponge Enabled Dendrite-Free and Highly Stable Lithium Metal Anode.

Metallic lithium batteries are holding great promises for revolutionizing the current energy storage technologies. However, the formation of dendrite-like morphology of lithium deposition caused by uneven distribution of Li+ might cause severe safety concerns of batteries. In this study, a polyoxometalate (POM) cluster, H5 PMo10 V2 O40 (PMo10 V2 ), is added to the conventional electrolyte that can construct a lithium-rich layer and inhibit the growth of Li dendrites effectively. The Li-rich layer can fill any lack of lithium ions on the surface of the metal anode, making the electric field strength consistent across the anode surface, thereby inhibiting the formation of lithium dendrites. Consequently, a significantly prolonged cyclic lifespan is obtained for both Li/Li symmetric cells and Li/LiCoO2 (Li/LCO) full cells. The cells with LCO positive maintains a high reversible specific capacity of 108.5 mAh g-1 after 300 cycles when electrolyte with PMo10 V2 additive is used, compared to 31.5 mAh g-1 for the untreated electrolyte. The findings indicate that POMs endowed as "ionic sponge" can be widely deployed in lithium metal batteries.

Cubically cage-shaped mesoporous ordered silica for simultaneous visual detection and removal of uranium ions from contaminated seawater.

A dual-function organic-inorganic mesoporous structure is reported for naked-eye detection and removal of uranyl ions from an aqueous environment. The mesoporous sensor/adsorbent is fabricated via direct template synthesis of highly ordered silica monolith (HOM) starting from a quaternary microemulsion liquid crystalline phase. The produced HOM is subjected to further modifications through growing an organic probe, omega chrome black blue G (OCBBG), in the cavities and on the outer surface of the silica structure. The spectral response for [HOM-OCBBG → U(VI)] complex shows a maximum reflectance at λmax = 548 nm within 1 min response time (tR); the LOD is close to 9.1 µg/L while the LOQ approaches 30.4 µg/L, and this corresponds to the range of concentration where the signal is linear against U(VI) concentration (i.e., 5-1000 µg/L) at pH 3.4 with standard deviation (SD) of 0.079 (RSD% = 11.7 at n = 10). Experiments and DFT calculations indicate the existence of strong binding energy between the organic probe and uranyl ions forming a complex with blue color that can be detected by naked eyes even at low uranium concentrations. With regard to the radioactive remediation, the new mesoporous sensor/captor is able to reach a maximum capacity of 95 mg/g within a few minutes of the sorption process. The synthesized material can be regenerated using simple leaching and re-used several times without a significant decrease in capacity.

Iron Selenide Microcapsules as Universal Conversion-Typed Anodes for Alkali Metal-Ion Batteries.

Rechargeable alkali metal-ion batteries (AMIBs) are receiving significant attention owing to their high energy density and low weight. The performance of AMIBs is highly dependent on the electrode materials. It is, therefore, quite crucial to explore suitable electrode materials that can fulfil the future requirements of AMIBs. Herein, a hierarchical hybrid yolk-shell structure of carbon-coated iron selenide microcapsules (FeSe2 @C-3 MCs) is prepared via facile hydrothermal reaction, carbon-coating, HCl solution etching, and then selenization treatment. When used as the conversion-typed anode materials (CTAMs) for AMIBs, the yolk-shell FeSe2 @C-3 MCs show advantages. First, the interconnected external carbon shell improves the mechanical strength of electrodes and accelerates ionic migration and electron transmission. Second, the internal electroactive FeSe2 nanoparticles effectively decrease the extent of volume expansion and avoid pulverization when compared with micro-sized solid FeSe2 . Third, the yolk-shell structure provides sufficient inner void to ensure electrolyte infiltration and mobilize the surface and near-surface reactions of electroactive FeSe2 with alkali metal ions. Consequently, the designed yolk-shell FeSe2 @C-3 MCs demonstrate enhanced electrochemical performance in lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries with high specific capacities, long cyclic stability, and outstanding rate capability, presenting potential application as universal anodes for AMIBs.

Does the scleral encircling band provide a protective effect against the progression of diabetic retinopathy?

AIM: To evaluate the effect of scleral encircling bands on the development and progression of diabetic retinopathy (DR) in diabetic patients. METHODS: The medical records of diabetic patients who underwent unilateral retinal detachment (RD) surgery using scleral buckle and encircling band were reviewed retrospectively. Both eyes of patients were included in the study: one eye in each patient had a scleral buckle with encircling band (the operated eye) and the other one is the non-operated eye. The demographic characters, duration of diabetes and period between surgery and the last recall visit were retrieved from each patient. All the cases underwent fundus photo and fluorescein angiography (when indicated) to confirm the DR staging. RESULTS: Totally 25 patients fulfilled the inclusion and the exclusion criteria were become eligible for the study. A total of 50 eyes of 25 patients were enrolled in this analysis. The mean period of time passed from surgery with encircling band and the last reassessment visit was 12.5±2y. Even though DR could develop in the operated eyes, it was at a less degree of severity compared to the non-operated eyes of same patients (P=0.027). CONCLUSION: Scleral encircling bands have protective effects against the development and progression of DR.

Porous SnO2-Cu x O nanocomposite thin film on carbon nanotubes as electrodes for high performance supercapacitors.

Metal oxides are promising materials for supercapacitors due to their high theoretical capacitance. However, their poor electrical conductivity is a major challenge. Hybridization with conductive nanostructured carbon-based materials such as carbon nanotubes (CNTs) has been proposed to improve the conductivity and increase the surface area. In this work, CNTs are used as a template for synthesizing porous thin films of SnO2-CuO-Cu2O (SnO2-Cu x O) via an electroless deposition technique. Tin, with its high wettability and electrical conductivity, acts as an intermediate layer between copper and the CNTs and provides a strong interaction between them. We also observed that by controlling the interfacial characteristics of CNTs and varying the composition of the electroless bath, the SnO2-Cu x O thin film morphology can be easily manipulated. Electrochemical characterizations show that CNT/SnO2-Cu x O nanocomposite possesses pseudocapacitive behavior that reaches a specific capacitance of 662 F g-1 and the retention is 94% after 5000 cycles, which outperforms any known copper and tin-based supercapacitors in the literature. This excellent performance is mainly attributed to high specific surface area, small particle size, the synergistic effect of Sn, and conductivity improvement by using CNTs. The combination of CNTs and metal oxides holds promise for supercapacitors with improved performance.

Electrochemical exfoliation of graphite in quaternary ammonium-based deep eutectic solvents: a route for the mass production of graphane.

We demonstrate a facile and scalable electrochemical approach to exfoliate graphite, which permits in situ hydrogenation of the resultant graphene via a solvated NR(4+) graphite compound in quaternary ammonium-based deep eutectic solvents. Spectroscopic studies reveal the presence of sp(3) C-H bonds in the hydrogenated graphene. The resulting materials consist of micrometre-sized and predominantly monolayer to few layers thick hydrogenated graphenic flakes. A large band gap (∼4 eV) further establishes the high level of hydrogenation. It is also possible to tune the band gap introduced to the graphene by controlling the level of hydrogenation. The mechanism of the exfoliation and hydrogenation is also discussed.

Few layer graphene-polypropylene nanocomposites: the role of flake diameter.

Graphene shows excellent potential as a structural reinforcement in polymer nanocomposites due to its exceptional mechanical properties. We have shown previously that graphene composites can be analysed using conventional composite theory with the graphene flakes acting as short fillers which have a critical length of ∼3 µm which is required for good reinforcement. Herein, polypropylene (PP) nanocomposites were prepared using electrochemically-exfoliated few layer graphene (FLG) with two different flake diameters (5 µm and 20 µm). The crystallization temperature and degree of crystallinity of the PP were found to increase with the loading of FLG, which suggests that the flakes acted as crystallisation nucleation sites. Mechanical testing showed that the 5 µm flakes behaved as short fillers and reinforced the PP matrix poorly. The modulus of the 20 µm flake composites, however, increased linearly with loading up to 20 wt%, without any of the detrimental aggregation effects seen in other graphene systems. The mechanical data were compared with our previous work on other graphene composite systems and the apparent need to balance the degree of functionalization to improve matrix compatibility whilst not encouraging aggregation is discussed.

Alkali reduction of graphene oxide in molten halide salts: production of corrugated graphene derivatives for high-performance supercapacitors.

Herein we present a green and facile approach to the successful reduction of graphene oxide (GO) materials using molten halide flux at 370 °C. GO materials have been synthesized using a modified Hummers method and subsequently reduced for periods of up to 8 h. Reduced GO (rGO) flakes have been characterized using X-ray-diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR), all indicating a significantly reduced amount of oxygen-containing functionalities on the rGO materials. Furthermore, impressive electrical conductivities and electrochemical capacitances have been measured for the rGO flakes, which, along with the morphology determined from scanning electron microscopy, highlight the role of surface corrugation in these rGO materials.

Continuous electrochemical exfoliation of micrometer-sized graphene using synergistic ion intercalations and organic solvents.

A novel top-down electrochemical method is demonstrated to prepare gram quantities of few-layer graphene in a single-step, one-pot process. Potential-controlled cathodic reduction is used to intercalate graphite electrodes with alkali-substituted, ammonium- and dimethyl sulfoxide-solvated cations. In situ decomposition of the intercalated compounds breaks the π-π stacking of the graphene layers along the c axis of the graphite gallery, producing 1-20-µm-diameter few-layer graphene sheets, without the need for defect-inducing oxidative or sonication treatments. With a slight modification of the electrodes' configuration, the process can run in a continuous manner, presenting a potentially scalable approach for few-layer graphene production.

Supercapacitance from cellulose and carbon nanotube nanocomposite fibers.

Multiwalled carbon nanotube (MWNT)/cellulose composite nanofibers have been prepared by electrospinning a MWNT/cellulose acetate blend solution followed by deacetylation. These composite nanofibers were then used as precursors for carbon nanofibers (CNFs). The effect of nanotubes on the stabilization of the precursor and microstructure of the resultant CNFs were investigated using thermogravimetric analysis, transmission electron microscopy and Raman spectroscopy. It is demonstrated that the incorporated MWNTs reduce the activation energy of the oxidative stabilization of cellulose nanofibers from ∼230 to ∼180 kJ mol(-1). They also increase the crystallite size, structural order, and electrical conductivity of the activated CNFs (ACNFs). The surface area of the ACNFs increased upon addition of nanotubes which protrude from the fiber leading to a rougher surface. The ACNFs were used as the electrodes of a supercapacitor. The electrochemical capacitance of the ACNF derived from pure cellulose nanofibers is demonstrated to be 105 F g(-1) at a current density of 10 A g(-1), which increases to 145 F g(-1) upon the addition of 6% of MWNTs.