Improving the Stability of Ball-Milled Lead Halide Perovskites via Ethanol/Water-Induced Phase Transition.

Recently, lead halide perovskite nanocrystals have been considered as potential light-emitting materials because of their narrow full width at half-maximum (FWHM) and high photoluminescence quantum yield (PLQY). In addition, they have various emission spectra because the bandgap can be easily tuned by changing the size of the nanocrystals and their chemical composition. However, these perovskite materials have poor long-term stability due to their sensitivity to moisture. Thus far, various approaches have been attempted to enhance the stability of the perovskite nanocrystals. However, the required level of stability in the mass production process of perovskite nanocrystals under ambient conditions has not been secured. In this work, we developed a facile two-step ball-milling and ethanol/water-induced phase transition method to synthesize stable CsPbBr3 perovskite materials. We obtained pure CsPbBr3 perovskite solutions with stability retention of 86% for 30 days under ambient conditions. Our materials show a high PLQY of 35% in solid films, and excellent thermal stability up to 80 °C. We believe that our new synthetic method could be applicable for the mass production of light-emitting perovskite materials.

A Redox-Mediator-Integrated Flexible Micro-Supercapacitor with Improved Energy Storage Capability and Suppressed Self-Discharge Rate.

To effectively improve the energy density and reduce the self-discharging rate of micro-supercapacitors, an advanced strategy is required. In this study, we developed a hydroquinone (HQ)-based polymer-gel electrolyte (HQ-gel) for micro-supercapacitors. The introduced HQ redox mediators (HQ-RMs) in the gel electrolyte composites underwent additional Faradaic redox reactions and synergistically increased the overall energy density of the micro-supercapacitors. Moreover, the HQ-RMs in the gel electrolyte weakened the self-discharging behavior by providing a strong binding attachment of charged ions on the porous graphitized carbon electrodes after the redox reactions. The micro-supercapacitors with HQ gel (HQ-MSCs) showed excellent energy storage performance, including a high energy volumetric capacitance of 255 mF cm-3 at a current of 1 µA, which is 2.7 times higher than the micro-supercapacitors based on bare-gel electrolyte composites without HQ-RMs (b-MSCs). The HQ-MSCs showed comparatively low self-discharging behavior with an open circuit potential drop of 37% compared to the b-MSCs with an open circuit potential drop of 60% after 2000 s. The assembled HQ-MSCs exhibited high mechanical flexibility over the applied external tensile and compressive strains. Additionally, the HQ-MSCs show the adequate circuit compatibility within series and parallel connections and the good cycling performance of capacitance retention of 95% after 3000 cycles.

Metal-Organic Frameworks Reinforce the Carbon Nanotube Sponge-Derived Robust Three-Dimensional Sulfur Host for Lithium-Sulfur Batteries.

Sulfur is a prospective material for next-generation batteries with high theoretical capacity, but its drawbacks hinder its commercialization. To overcome the low conductivity of natural sulfur and the shuttle effect of lithium polysulfide, the study proposes a novel sulfur film coated with three-dimensional nitrogen and cobalt-codoped polyhedral carbon wrapped on a multiwalled carbon nanotube sponge (3D-S@NCoCPC sponge) composite as a high-performance cathode material for rechargeable lithium-sulfur batteries. The interconnected conductive carbon network with abundant pores provides more room for the homogeneous distribution of sulfur within the composite and creates a favorable pathway for electrolyte permeability and lithium-ion diffusion. Moreover, the strong interaction between cobalt and lithium polysulfides leads to efficient suppression of the shuttle effect. In addition, the homogeneous distribution of sulfur and cobalt within the composite enhances electronic transfer for the conversion reaction of sulfur. As expected, the cathode with a high sulfur content of 77.5 wt % in the composite achieved a high initial discharge capacity of 1192 mA h g-1 and high Coulombic efficiency of 99.98% after 100 cycles at 100 mA g-1 current density. Stable performance was achieved with 92.9% capacity retention after 200 cycles at 1000 mA/g current density.

Fluorine-Decorated Graphene Nanoribbons for an Anticorrosive Polymer Electrolyte Membrane Fuel Cell.

Pt-supported carbon material-based electrocatalysts are formidably suffering from carbon corrosion when H2O and O2 molecules are present at high voltages in polymer electrolyte membrane fuel cells (PEMFCs). In this study, we discovered that the edge site of a fluorine-doped graphene nanoribbon (F-GNR) was slightly adsorbed with H2O and was thermodynamically unfavorable with O atoms after defining the thermodynamically stable structure of the F-GNR from DFT calculations. Based on computational predictions, the physicochemical and electrochemical properties of F-GNRs with/without Pt nanoparticles derived from a modified Hummer's method and the polyol process were investigated as support materials for electrocatalysts and additives in the cathode of a PEMFC, respectively. The Pt/F-GNR showed the lowest degradation rate in carbon corrosion and was effective in the cathode as additives, resulting from the enhanced carbon corrosion durability owing to the improved structural stability and water management. Notably, the F-GNR with highly stable carbon corrosion contributed to achieving a more durable PEMFC for long-term operation.

Electrochemically active hydroquinone-based redox mediator for flexible energy storage system with improved charge storing ability.

Electrochemically active redox mediators have been widely investigated in energy conversion/storage system to improve overall catalytic activities and energy storing ability by inducing favorable surface redox reactions. However, the enhancement of electrochemical activity from the utilization of redox mediators (RMs) is only confirmed through theoretical computation and laboratory-scale experiment. The use of RMs for practical, wearable, and flexible applications has been scarcely researched. Herein, for the first time, a wearable fiber-based flexible energy storage system (f-FESS) with hydroquinone (HQ) composites as a catalytically active RM is introduced to demonstrate its energy-storing roles. The as-prepared f-FESS-HQ shows the superior electrochemical performance, such as the improved energy storage ability (211.16 F L-1 and 29.3 mWh L-1) and long-term cyclability with a capacitance retention of 95.1% over 5000 cycles. Furthermore, the f-FESS-HQ can well maintain its original electrochemical properties under harsh mechanical stress (bending, knotting, and weaving conditions) as well as humid conditions in water and detergent solutions. Thus, the strategical use of electrochemically active RMs can provide the advanced solution for future wearable energy storage system.

Li7La3Zr2O12 Garnet Solid Polymer Electrolyte for Highly Stable All-Solid-State Batteries.

All-solid-state batteries have gained significant attention as promising candidates to replace liquid electrolytes in lithium-ion batteries for high safety, energy storage performance, and stability under elevated temperature conditions. However, the low ionic conductivity and unsuitability of lithium metal in solid polymer electrolytes is a critical problem. To resolve this, we used a cubic garnet oxide electrolyte (Li7La3Zr2O12 - LLZO) and ionic liquid in combination with a polymer electrolyte to produce a composite electrolyte membrane. By applying a solid polymer electrolyte on symmetric stainless steel, the composite electrolyte membrane shows high ionic conductivity at elevated temperatures. The effect of LLZO in suppressing lithium dendrite growth within the composite electrolyte was confirmed through symmetric lithium stripping/plating tests under various current densities showing small polarization voltages. The full cell with lithium iron phosphate as the cathode active material achieved a highest specific capacity of 137.4 mAh g-1 and a high capacity retention of 98.47% after 100 cycles at a current density of 50 mA g-1 and a temperature of 60°C. Moreover, the specific discharge capacities were 137 and 100.8 mAh g-1 at current densities of 100 and 200 mA g-1, respectively. This research highlights the capability of solid polymer electrolytes to suppress the evolution of lithium dendrites and enhance the performance of all-solid-state batteries.

High Lithium Ion Transport Through rGO-Wrapped LiNi0.6Co0.2Mn0.2O2 Cathode Material for High-Rate Capable Lithium Ion Batteries.

In this work, we show an effective ultrasonication-assisted self-assembly method under surfactant solution for a high-rate capable rGO-wrapped LiNi0.6Co0.2Mn0.2O2 (Ni-rich cathode material) composite. Ultrasonication indicates the pulverization of the aggregated bulk material into primary nanoparticles, which is effectively beneficial for synthesizing a homogeneous wrapped composite with rGO. The cathode composite demonstrates a high initial capacity of 196.5 mAh/g and a stable capacity retention of 83% after 100 cycles at a current density of 20 mA/g. The high-rate capability shows 195 and 140 mAh/g at a current density of 50 and 500 mA/g, respectively. The high-rate capable performance is attributed to the rapid lithium ion diffusivity, which is confirmed by calculating the transformation kinetics of the lithium ion by galvanostatic intermittent titration technique (GITT) measurement. The lithium ion diffusion rate (D Li) of the rGO-wrapped LiNi0.6Co0.2Mn0.2O2 composite is ca. 20 times higher than that of lithium metal plating on anode during the charge procedure, and this is demonstrated by the high interconnection of LiNi0.6Co0.2Mn0.2O2 and conductive rGO sheets in the composite. The unique transformation kinetics of the cathode composite presented in this study is an unprecedented verification example of a high-rate capable Ni-rich cathode material wrapped by highly conductive rGO sheets.

Hierarchical Core-Shell Nickel Cobaltite Chestnut-like Structures as Bifunctional Electrocatalyst for Rechargeable Metal-Air Batteries.

Nano-engineered hierarchical core-shell nickel cobaltite chestnut-like structures were successfully synthesized as a bifunctionally active electrocatalyst for rechargeable metal-air battery applications. Both the morphology and composition of the catalyst were optimized by a facile hydrothermal reaction, resulting in a 10 h reacted sample demonstrating significantly enhanced activity toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in 0.1 m KOH. Specifically, the catalyst demonstrated -0.28 and 0.60 V versus SCE (saturated calomel electrode) at the ORR half-wave potential and an OER current density of 10 mA cm-2 , respectively. The resulting ORR/OER potential difference of 0.90 V was the smallest compared to the catalysts synthesized using 2, 6, and 12 h of hydrothermal reaction time. The excellent bifunctional activity of the catalyst is attributed to the nanoscale porous morphology and the spinel nickel cobaltite composition, which improved the active site exposure and transport of reactants and charges during the oxygen reactions.

Self-Assembly of Spinel Nanocrystals into Mesoporous Spheres as Bifunctionally Active Oxygen Reduction and Evolution Electrocatalysts.

The present work introduces spinel oxide nanocrystals self-assembled into mesoporous spheres that are bifunctionally active towards catalyzing both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The electrochemical evaluation reveals that (Ni,Co)3 O4 demonstrates a significantly positive-shifted ORR onset and half-wave potentials [-0.127 and -0.292 V vs. saturated calomel electrode (SCE), respectively], whereas Co3 O4 results in a negative-shifted OER potential (0.65 V vs. SCE) measured at 10 mA cm-2 . Based on the DFT analysis, the potential at which all oxygen intermediate reactions proceed spontaneously is the highest for (Ni,Co)3 O4 (U=0.66 eV) during ORR, whereas it is the lowest for Co3 O4 (U=2.09 eV) during OER. The high ORR activity of (Ni,Co)3 O4 is attributed to the enhanced electrical conductivity of the spinel lattice, and the high OER activity of Co3 O4 is attributed to relatively weak adsorption energy promoting rapid release of evolved oxygen.

Highly Oriented Graphene Sponge Electrode for Ultra High Energy Density Lithium Ion Hybrid Capacitors.

Highly oriented rGO sponge (HOG) can be easily synthesized as an effective anode for application in high-capacity lithium ion hybrid capacitors. X-ray diffraction and morphological analyses show that successfully exfoliated rGO sponge on average consists of 4.2 graphene sheets, maintaining its three-dimensional structure with highly oriented morphology even after the thermal reduction procedure. Lithium-ion hybrid capacitors (LIC) are fabricated in this study based on a unique cell configuration which completely eliminates the predoping process of lithium ions. The full-cell LIC consisting of AC/HOG-Li configuration has resulted in remarkably high energy densities of 231.7 and 131.9 Wh kg(-1) obtained at 57 W kg(-1) and 2.8 kW kg(-1). This excellent performance is attributed to the lithium ion diffusivity related to the intercalation reaction of AC/HOG-Li which is 3.6 times higher that of AC/CG-Li. This unique cell design and configuration of LIC presented in this study using HOG as an effective anode is an unprecedented example of performance enhancement and improved energy density of LIC through successful increase in cell operation voltage window.

Sulfur Nanogranular Film-Coated Three-Dimensional Graphene Sponge-Based High Power Lithium Sulfur Battery.

To meet the requirements of both high energy and power density with cycle durability of modern EVs, we prepared a novel nanosulfur granular assembled film coated on the three-dimensional graphene sponge (3D-GS) composite as a high-performance active material for rechargeable lithium sulfur batteries. Instead of conventional graphene powder, three-dimensional rGO sponge (3D-rGO) is employed for the composite synthesis, resulting in a sulfur film directly in contact with the underlying graphene layer. This significantly improves the overall electrical conductivity, strategically addressing challenges of conventional composites of low sulfur utilization and dissolution of polysulfides. Additionally, the synthesis mechanism of 3D-GS is elucidated by XPS and DFT analyses, where replacement of hydroxyl group of 3D-rGO sponge by sulfur (S8) is found to be thermodynamically favorable. As expected, 3D-GS demonstrates outstanding discharge capacity of 1080 mAh g(-1) at a 0.1C rate, and 86.2% capacity retention even after 500 cycles at a 1.0C rate.

Preparation of a reduced graphene oxide wrapped lithium-rich cathode material by self-assembly.

A lithium-rich cathode material wrapped in sheets of reduced graphene oxide (RGO) and functionalized with polydiallyldimethylammonium chloride (PDDA) was prepared by self-assembly induced from the electrostatic interaction between PDDA-RGO and the Li-rich cathode material. At current densities of 1000 and 2000 mA g(-1), the PDDA-RGO sheet wrapped samples demonstrated increased discharge capacities, increasing from 125 to 155 mA h g(-1) and from 82 to 124 mA h g(-1), respectively. The decreased resistance implied by this result was confirmed from electrochemical impedance spectroscopy results, wherein the charge-transfer resistance of the pristine sample decreased after wrapping with the PDDA-RGO sheets. The PDDA-RGO sheets served as a protective layer sand as a conductive material, which resulted in an improvement in the retention capacity from 56 to 81% after 90 cycles.