Designing Advanced In Situ Electrode/Electrolyte Interphases for Wide Temperature Operation of 4.5 V Li||LiCoO2 Batteries

High-energy-density batteries with a LiCoO₂ (LCO) cathode are of significant importance to the energy-storage market, especially for portable electronics. However, their development is greatly limited by the inferior performance under high voltages and challenging temperatures. Here, highly stable lithium (Li) metal batteries with LCO cathode, through the design of in situ formed, stable electrode/electrolyte interphases on both the Li anode and the LCO cathode, with an advanced electrolyte, are reported. The LCO cathode can deliver a high specific capacity of ≈190 mAh g⁻¹ and show greatly improved cell performances under a high charge voltage of 4.5 V (even up to 4.55 V) and a wide temperature range from −30 to 55 °C. This work points out a promising approach for developing Li||LCO batteries for practical applications. This approach can also be used to improve the high-voltage performance of other batteries in a broad temperature range.     

Effects of Fluorinated Diluents in Localized High-Concentration Electrolytes for Lithium–Oxygen Batteries

A stable electrolyte is critical for practical application of lithium–oxygen batteries (LOBs). Although the ionic conductivity and electrochemical stability of the electrolytes have been extensively investigated before, their oxygen solubility, viscosity, volatility, and the stability against singlet oxygen (¹O₂) still need to be comprehensively investigated to provide a full picture of the electrolytes, especially for an open system such as LOBs. Herein, a systematic investigation is reported on the localized high-concentration electrolytes (LHCEs) using different fluorinated diluents in comparison with those of conventional electrolytes. The physical properties and activation energies for reactions with singlet oxygen (¹O₂) of these electrolytes are calculated by density functional theory. The electrochemical performances of LOBs using these electrolytes are compared. This study reveals that the correlation between the stability of the electrolytes and their physical and electrochemical properties depends strongly on the diluents in LHCEs. Therefore, it shines light on the rational design of new electrolytes for LOBs.     

Suppressing Lithium Dendrite Growth by Metallic Coating on a Separator

Lithium (Li) metal is one of the most promising candidates for the anode in high‐energy‐density batteries. However, Li dendrite growth induces a significant safety concerns in these batteries. Here, a multifunctional separator through coating a thin electronic conductive film on one side of the conventional polymer separator facing the Li anode is proposed for the purpose of Li dendrite suppression and cycling stability improvement. The ultrathin Cu film on one side of the polyethylene support serves as an additional conducting agent to facilitate electrochemical stripping/deposition of Li metal with less accumulation of electrically isolated or “dead” Li. Furthermore, its electrically conductive nature guides the backside plating of Li metal and modulates the Li deposition morphology via dendrite merging. In addition, metallic Cu film coating can also improve thermal stability of the separator and enhance the safety of the batteries. Due to its unique beneficial features, this separator enables stable cycling of Li metal anode with enhanced Coulombic efficiency during extended cycles in Li metal batteries and increases the lifetime of Li metal anode by preventing short‐circuit failures even under extensive Li metal deposition.     

Preparation, characterization and anion exchange properties of polypyrrole/carbon nanotube nanocomposites

In this study, polypyrrole (PPy) thin films were electrodeposited on carbon nanotube (CNT) backbones by applying a constant deposition potential in 0.1 M pyrrole solution with different electrolytes, such as NaCl, NaNO3, or NaClO4. The hybrid films were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy, and cyclic voltammetry. SEM images revealed the nanostructrure of PPy films generated on CNT surface. The electrochemical and anion exchange properties of the PPy-CNT composite films have been investigated. Nanostructured composite thin films of PPy-CNTs were studied by cyclic voltammetry between 0.4 and -0.8 V in aqueous solution to evaluate their cycling stability and capacity for electrically switched anion exchange. The presence of the CNT backbone greatly improved the anion exchange capacity and stability of the PPy-CNT composite film, which may be attributed to the high surface area of CNT matrix, nanostructure of the PPy film, and the interaction between CNTs and PPy.     

Characterization of functionalized nanoporous supports for protein confinement

Here we characterize a highly efficient approach for protein confinement and enzyme immobilization in NH(2)-?or HOOC-?functionalized mesoporous silica (FMS) with pore sizes as large as tens of nanometres. We observed a dramatic increase of enzyme loading in both enzyme activity and protein amount when using appropriate FMS in comparison with unfunctionalized mesoporous silica and normal porous silica. With different protein loading density in NH(2)-FMS, the negatively charged glucose oxidase (GOX) displayed an immobilization efficiency (I(e), the ratio of the specific activity of the immobilized enzyme to the specific activity of the free enzyme in stock solution) in a range from 30% to 160%, while the same charged glucose isomerase (GI) showed an I(e) of 100% to 120%, and the positively charged organophosphorus hydrolase (OPH) exhibited I(e) of more than 200% in HOOC-FMS. The enzyme-FMS composite was stained with the charged gold nanoparticles and imaged by transmission electron microscopy (TEM). Fourier transform infrared (FTIR) spectroscopy showed no major secondary structural change for the enzymes entrapped in FMS. Thanks to the large, rigid, open pore structure of FMS, the reaction rate and K(m) of the entrapped enzymes in FMS were comparable to those of the free enzymes in solution. In principle, the general approach described here should be applicable to many enzymes, proteins, and protein complexes since both pore sizes and functional groups of FMS are controllable.     

Oxidation of H2S by iron oxides in unsaturated conditions

Previous studies have demonstrated that gas-phase H2S can immobilize certain redox-sensitive contaminants (e.g., Cr, U, Tc) in vadose zone environments. A key issue for effective and efficient delivery of H2S in these environments is the reactivity of the gas with indigenous iron oxides. To elucidate the factors that control the transport of H2S in the vadose zone, laboratory column experiments were conducted to identify reaction mechanisms and measure rates of H2S oxidation by iron oxide-coated sands using several carrier gas compositions (N2, air, and O2) and flow rates. Most experiments were conducted using ferrihydrite-coated sand. Additional studies were conducted with goethite- and hematite-coated sand and a natural sediment. Selective extractions were conducted at the end of each column experiment to determine the mass balance of the reaction products. XPS was used to confirm the presence of the reaction products. For column experiments in which ferrihydrite-coated sand was the substrate and N2 was the carrier gas, the major H2S oxidation products were FeS and elemental sulfur (mostly S8(0), represented as S(0) for simplicity) at ratios that were consistent with the stoichiometry of the postulated reactions. When air or O2 were used as the carrier gas, S(0) became the dominant reaction product along with FeS2 and smaller amounts of FeS, sulfate, and thiosulfate. A mathematical model of reactive transport was used to test the hypothesis that S(0) forming on the iron oxide surfaces reduces access of H2S to the reactive surface. Several conceptual models were assessed in the context of the postulated reactions with the final model based on a linear surface poisoning model and fitted reaction rates. These results indicate that carrier gas selection is a critical consideration with significant tradeoffs for remediation objectives.     

Selective sorption of cesium using self-assembled monolayers on mesoporous supports

The synthesis of a novel nanocomposite sorbent material, copper ferrocyanide immobilized within a mesoporous ceramic matrix, and its use as a novel cesium sorbent material is reported in this paper. Complete removal of cesium was achieved in the presence of competing metal ions for solutions containing 2 ppm cesium under a variety conditions. Loading capacity of more than 1.35 mmol Cs per g of sorbent material has been achieved. The exceptionally fast binding kinetics and high loading capacity, resulting from the rigidly open pore structure and extremely high surface area of the sorbent materials, make them potentially very useful for the removal of cesium from nuclear wastes and contaminated groundwater.     

Continuous precipitation of ceria nanoparticles from a continuous flow micromixer

Cerium oxide nanoparticles were continuously precipitated from a solution of cerium(III) nitrate and ammonium hydroxide using a static microchannel T-mixer. T-mixer synthesis results were compared with synthesis results from batch precipitation. Findings show that the method of mixing is important in the ceria precipitation process. Uniform porous film structures and nanorods were produced when the particle chemistry was synthesized using T-mixing followed by spin coating. Batch mixing, when using higher NH₄OH feed concentrations followed by spin coating, was characterized by the heavy agglomeration of nanoparticles. Similar, high aspect ratio nanorods were produced when feed conditions in both batch mixing and T-mixing were identical demonstrating that the momentum effects of continuous microchannel T-mixing did not impact the synthesis process. In addition, it was found that the micromixing approach reduced the exposure of the Ce(OH)₃ precipitates to oxygen, yielding hydroxide precipitates in place of CeO₂ precipitates. The key advantage of the micro-scale T-mixing approach is higher throughput which is important for the scaling of ceria nanoparticle production.     

Fluorescent dye encapsulated ZnO particles with cell-specific toxicity for potential use in biomedical applications

Fluorescein isothiocyanate (FITC)-encapsulated SiO₂ core-shell particles with a nanoscale ZnO finishing layer have been synthesized for the first time as multifunctional “smart” nanostructures. Detailed characterization studies confirmed the formation of an outer ZnO layer on the SiO₂–FITC core. These ~200 nm sized particles showed promise toward cell imaging and cellular uptake studies using the bacterium Escherichia coli and Jurkat cancer cells, respectively. The FITC encapsulated ZnO particles demonstrated excellent selectivity in preferentially killing Jurkat cancer cells with minimal toxicity to normal primary immune cells (18% and 75% viability remaining, respectively, after exposure to 60 μg/ml) and inhibited the growth of both gram-positive and gram-negative bacteria at concentrations ≥250–500 μg/ml (for Staphylococcus aureus and Escherichia coli, respectively). These results indicate that the novel FITC encapsulated multifunctional particles with nanoscale ZnO surface layer can be used as smart nanostructures for particle tracking, cell imaging, antibacterial treatments and cancer therapy.     

Deposition of tellurium films by decomposition of electrochemically-generated H2Te: application to radiative cooling devices

The preparation of homogenous, large area thin layers of tellurium on thin polyethylene foils is described. The tellurium was formed by room temperature decomposition of electrochemically generated H₂Te. Pre-treatment of the polyethylene substrates with KMnO₄ to give a Mn-oxide layer was found to improve the Te adhesion and homogeneity. Optical characterization of the layers was performed using UV/VIS/NIR spectroscopy. Such coatings have favorable characteristics for use as solar radiation shields in radiative cooling devices. The simplicity of generation of the very unstable H₂Te was also exploited to demonstrate formation of size-quantized CdTe nanocrystals.