Operando Observation of the De-Evolution/Evolution Process of Hydrated LiOH in Moisture-Assisted Li-O2 Batteries.

All-solid-state Li-O2 batteries that use ceramic electrolytes have been suggested to overcome the limitations posed by the decomposition of organic electrolytes. However, these systems show a low discharge capacity and high overpotential because the discharge product Li2O2 has low electronic conductivity. In this study, all-solid-state planar-type Li-O2 cells were constructed using a lithium anode, a Li1·3Al0·3Ti1·7(PO4) (LATP) inorganic solid electrolyte, and an air electrode composed of a Pt grid pattern. The discharge/charge process was observed in real time in a humidified O2 environment for the first time, which clarified both the hydration process of the discharge products and the charging process of the hydrated discharge products. The discharge product (LiOH) could be easily hydrated in water, which would facilitate ion transport, thereby increasing the discharge capacity and discharge voltage (vs Li/Li+; from 2.96 to 3.4 V). Thus, Li-O2 cells with a high energy density and a capacity of 3600 mAh/gcathode were achieved using a planar Pt-patterned electrode in a humidified O2 environment. This study is the first to demonstrate the hydration of the discharge products of a Li-O2 cell in humidified O2. Based on a thorough understanding of the hydration phenomenon/mechanism, our findings suggest new strategies for developing high-energy-density all-solid-state Li-O2 batteries using a simple, easy-to-manufacture planar Pt-patterned cathode.

Membraneless Ionic Liquid Droplet Nanoprobe for Oxygen Sensing and Gas Phase Scanning Electrochemical Microscopy.

A novel membraneless oxygen sensing nanoprobe was developed based on a hanging drop ionic liquid electrochemical cell. An ultrasmall (<500 nm) working electrode and small volume electrochemical cell allowed for an impressively low detection limit of ∼13 ppm and a response time less than 100 ms, which is unusually fast for an electrochemical gas sensor. The oxygen sensor was stable for hours of operation and, owing to the membraneless design, was easily regenerable when fouled. The pulled capillary form factor of the nanoprobe was found compatible with scanning probe techniques, the demonstration of which was made by application as a tip electrode in gas phase scanning electrochemical microscopy (SECM). In the SECM experiments, the oxygen nanoprobe exhibited micrometer scale spatial resolution with ease. This unique probe design developed here may potentially be engineered into versatile sensors for various volatile molecules other than oxygen, such as those pertinent to hazard analysis and biomedical diagnosis.

Carbon-free high-performance cathode for solid-state Li-O2 battery.

The development of a cathode for solid-state lithium-oxygen batteries has been hindered in practice by a low capacity and limited cycle life despite their potential for high energy density. Here, a previously unexplored strategy is proposed wherein the cathode delivers a specific capacity of 200 milliampere hour per gram over 665 discharge/charge cycles, while existing cathodes achieve only ~50 milliampere hour per gram and ~100 cycles. A highly conductive ruthenium-based composite is designed as a carbon-free cathode by first-principles calculations to avoid the degradation associated with carbonaceous materials, implying an improvement in stability during the electrochemical cycling. In addition, water vapor is added into the main oxygen gas as an additive to change the discharge product from growth-restricted lithium peroxide to easily grown lithium hydroxide, resulting in a notable increase in capacity. Thus, the proposed strategy is effective for developing reversible solid-state lithium-oxygen batteries with high energy density.

High-Energy Density Li-O2 Battery with a Polymer Electrolyte-Coated CNT Electrode via the Layer-by-Layer Method.

Li-O2 batteries have attracted considerable attention for several decades due to their high theoretical energy density (>3400 Wh/kg). However, it has not been clearly demonstrated that their actual volumetric and gravimetric energy densities are higher than those of Li-ion batteries. In previous studies, a considerable quantity of electrolyte was usually employed in preparing Li-O2 cells. In general, the electrolyte was considerably heavier than the carbon materials in the cathode, rendering the practical energy density of the Li-O2 battery lower than that of the Li-ion battery. Therefore, air cathodes with significantly smaller electrolyte quantities need to be developed to achieve a high specific energy density in Li-O2 batteries. In this study, we propose a core-shell-structured cathode material with a gel-polymer electrolyte layer covering the carbon nanotubes (CNTs). The CNTs are synthesized using the floating catalyst chemical vapor deposition method. The polymeric layer corresponding to the shell is prepared by the layer-by-layer (LbL) coating method, utilizing Li-Nafion along with PDDA-Cl [poly(diallyldimethylammonium chloride)]. Several bilayers of Li-Nafion and PDDA, on the CNT surface, are successfully prepared and characterized via X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The porous structure of the CNTs is retained after the LbL process, as confirmed by the nitrogen adsorption-desorption profile and BJH pore-size distribution analysis. This porous structure can function as an oxygen channel for facilitating the transport of oxygen molecules for reacting with the Li ions on the cathode surface. These polymeric bilayers can provide an Li-ion pathway, after absorbing a small quantity of an ionic liquid electrolyte, 0.5 M LiTFSI EMI-TFSI [1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide]. Compared to a typical cathode, where only liquid electrolytes are employed, the total quantity of electrolyte in the cathode can be significantly reduced; thereby, the overall cell energy density can be increased. A Li-O2 battery with this core-shell-structured cathode exhibited a high energy density of approximately 390 Wh/kg, which was assessed by directly weighing all of the cell components together, including the gas diffusion layer, the interlayer [a separator containing a mixture of LiTFSI, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR-14), and PDDA-TFSI], the lithium anode, and the LbL-CNT cathode. The cycle life of the LbL-CNT-based cathode was found to be 31 cycles at a limited capacity of 500 mAh/gcarbon. Although this is not an excellent performance, it is almost 2 times better than that of a CNT cathode without a polymer coating.

Regiodivergent Ring-Opening Cross-Coupling of Vinyl Aziridines with Phosphorus Nucleophiles: Access to Phosphorus-Containing Amino Acid Derivatives.

Catalytic ring-opening phosphonation and phosphatation of vinyl aziridines have been developed in a regiodivergent fashion, giving linear and branched products. Generation of P-centered radicals enables SN2'-type ring-opening reactions of vinyl aziridines to afford δ-amino alkylphosphorus products at room temperature. On the other hand, in situ generated phosphate anions via the Ag-catalyzed aerobic oxidation of phosphonyl reactants underwent SN2 reaction to provide branched phosphorus-containing amine products. Furthermore, this divergent methodology serves as a powerful tool for the stereospecific synthesis of phosphorus-containing amino acid derivatives.

Carrier Transport Properties of MoS2 Asymmetric Gas Sensor Under Charge Transfer-Based Barrier Modulation.

Over the past few years, two-dimensional materials have gained immense attention for next-generation electric sensing devices because of their unique properties. Here, we report the carrier transport properties of MoS2 Schottky diodes under ambient as well as gas exposure conditions. MoS2 field-effect transistors (FETs) were fabricated using Pt and Al electrodes. The work function of Pt is higher than that of MoS2, while that of Al is lower than that of MoS2. The MoS2 device with Al contacts showed much higher current than that with Pt contacts because of its lower Schottky barrier height (SBH). The electrical characteristics and gas responses of the MoS2 Schottky diodes with Al and Pt contacts were measured electrically and were simulated by density functional theory calculations. The theoretically calculated SBH of the diode (under gas absorption) showed that NOx molecules had strong interaction with the diode and induced a negative charge transfer. However, an opposite trend was observed in the case of NH3 molecules. We also investigated the effect of metal contacts on the gas sensing performance of MoS2 FETs both experimentally and theoretically.

Enhanced Electrochemical Stability of Quasi-Solid-State Electrolyte Containing SiO2 Nanoparticles for Li-O2 Battery Applications.

A stable electrolyte is required for use in the open-packing environment of a Li-O2 battery system. Herein, a gelled quasi-solid-state electrolyte containing SiO2 nanoparticles was designed, in order to obtain a solidified electrolyte with a high discharge capacity and long cyclability. We successfully fabricated an organic-inorganic hybrid matrix with a gelled structure, which exhibited high ionic conductivity, thereby enhancing the discharge capacity of the Li-O2 battery. In particular, the improved electrochemical stability of the gelled cathode led to long-term cyclability. The organic-inorganic hybrid matrix with the gelled structure played a beneficial role in improving the ionic conductivity and long-term cyclability and diminished electrolyte evaporation. The experimental and theoretical findings both suggest that the preferential binding between amorphous SiO2 and polyethylene glycol dimethyl ether (PEGDME) solvent led to the formation of the solidified gelled electrolyte and improved electrochemical stability during cycling, while enhancing the stability of the quasi-solid state Li-O2 battery.

Preparation of a microporous organic polymer by the thiol-yne addition reaction and formation of Au nanoparticles inside the polymer.

A microporous polymer with sulfide and thiol groups was synthesized using the thiol-yne reaction. Au nanoparticles were prepared by in situ reduction reaction inside the polymer and were found to be well dispersed. The Au-containing polymer showed catalytic activity in the reduction of 4-nitrophenol.