A Radical Pathway and Stabilized Li Anode Enabled by Halide Quaternary Ammonium Electrolyte Additives for Lithium-Sulfur Batteries.

Passivation of the sulfur cathode by insulating lithium sulfide restricts the reversibility and sulfur utilization of Li-S batteries. 3D nucleation of Li2 S enabled by radical conversion may significantly boost the redox kinetics. Electrolytes with high donor number (DN) solvents allow for tri-sulfur (S3 ⋅- ) radicals as intermediates, however, the catastrophic reactivity of such solvents with Li anodes pose a great challenge for their practical application. Here, we propose the use of quaternary ammonium salts as electrolyte additives, which can preserve the partial high-DN characteristics that trigger the S3 ⋅- radical pathway, and inhibit the growth of Li dendrites. Li-S batteries with tetrapropylammonium bromide (T3Br) electrolyte additive deliver the outstanding cycling stability (700 cycles at 1 C with a low-capacity decay rate of 0.049 % per cycle), and high capacity under a lean electrolyte of 5 µLelectrolyte mgsulfur -1 . This work opens a new avenue for the development of electrolyte additives for Li-S batteries.

Si, O-Codoped Carbonized Polymer Dots with High Chemiresistive Gas Sensing Performance at Room Temperature.

A new type of carbonized polymer dot was prepared by the one-step hydrothermal method of triethoxylsilane (TEOS) and citric acid (CA). The sensor made from carbonized polymer dots (CPDs) showed superior gas sensing performance toward ammonia at room temperature. The Si, O-codoped CPDs exhibited superior ammonia sensing performance at room temperature, including a low practical limit of detection (pLOD) of 1 ppm (Ra/Rg: 1.10, 1 ppm), short response/recovery time (30/36 s, 1 ppm), high humidity resistance (less than 5% undulation when changing relative humidity to 80 from 30%), high stability (less than 5% initial response undulation after 120 days), reliable repeatability, and high selectivity against other interferential gases. The gas sensing mechanism was investigated through control experiments and in situ FTIR, indicating that Si, O-codoping essentially improves the electron transfer capability of CPDs and synergistically dominates the superior ammonia sensing properties of the CPDs. This work presents a facile strategy for constructing novel high-performance, single-component carbonized polymer dots for gas sensing.

Segmental Motion Adjustment of the Polycarbonate Electrolyte for Lithium-Metal Batteries.

Carbonyl oxygen atoms are the primary active sites to solvate Li salts that provide a migration site for Li ions conducting in a polycarbonate-based polymer electrolyte. We here exploit the conductivity of the polycarbonate electrolyte by tuning the segmental motion of the structural unit with carbonyl oxygen atoms, while its correlation to the mechanical and electrochemical stability of the electrolyte is also discussed. Two linear alkenyl carbonate monomers are designed by molecular engineering to combine methyl acrylate (MA) and the commonly used ethylene carbonate (EC), w/o dimethyl carbonate (DMC) in the structure. The integration of the DMC structural unit in the side chain of the in situ constructed polymer (p-MDE) releases the free motion of the terminal EC units, which leads to a lower glass-transition temperature and higher ionic conductivity. While pure polycarbonates are normally fragile with high Young's modulus, such a prolonged side chain also manipulates the flexibility of the polymer to provide a mechanical stable interface for Li-metal anode. Stable long-term cycling performance is achieved at room temperature for both LiFePO4 and LiCoO2 electrodes based on the p-MDE electrolyte incorporated with a solid plasticizer.

Enabling High-Voltage "Superconcentrated Ionogel-in-Ceramic" Hybrid Electrolyte with Ultrahigh Ionic Conductivity and Single Li+ -Ion Transference Number.

High room-temperature ionic conductivities, large Li+ -ion transference numbers, and good compatibility with both Li-metal anodes and high-voltage cathodes of the solid electrolytes are the essential requirements for practical solid-state lithium-metal batteries. Herein, a unique "superconcentrated ionogel-in-ceramic" (SIC) electrolyte prepared by an in situ thermally initiated radical polymerization is reported. Solid-state static 7 Li NMR and molecular dynamics simulation reveal the roles of ceramic in Li+ local environments and transport in the SIC electrolyte. The SIC electrolyte not only exhibits an ultrahigh ionic conductivity of 1.33 × 10-3 S cm-1 at 25 °C, but also a Li+ -ion transference number as high as 0.89, together with a low electronic conductivity of 3.14 × 10-10 S cm-1 and a wide electrochemical stability window of 5.5 V versus Li/Li+ . Applications of the SIC electrolyte in Li||LiNi0.5 Co0.2 Mn0.3 O2 and Li||LiFePO4 batteries further demonstrate the high rate and long cycle life. This study, therefore, provides a promising hybrid electrolyte for safe and high-energy lithium-metal batteries.

Facile fabrication of 17ß-estradiol electrochemical sensor using polyaniline/carbon dot-coated glassy carbon electrode with synergistically enhanced electrochemical stability.

Previous 17ß-estradiol sensors required expensive reagents or complicated fabrication of sensing probes. In this work, a cheap, simple, and reusable electrochemical sensor based on commercially available polyaniline (PANI) and carbon dots (CDs) synthesized from iota-carrageenan was developed for the sensitive detection of 17ß-estradiol. The sensor was simply prepared by drop-casting CDs/PANI composite on a glassy carbon electrode (GCE) using poly(vinylidene fluoride) as a binder. With synergistic contributions from both CDs and PANI, the CDs-PANI/GCE was much more electrochemically stable than the CDs/GCE or PANI/GCE. The CDs-PANI/GCE was sensitive to 17ß-estradiol across a linear range from 0.001 to 100 µmol L-1 with a detection limit of 43 nmol L-1. The electrochemical measurement can be performed in 2 min and the probe can be reused for several hundred times. The CDs-PANI/GCE was selective towards 17ß-estradiol against several interferences and gave excellent recovery between 94.4 and 103.7 % from real sample analysis. From intensive investigation on electron transfer process and energy levels, the oxidation reaction of 17ß-estradiol occurred on the surface of CDs-PANI/GCE via favorable energy levels and dominantly surface adsorption process through π-π stacking and hydrogen bonding between 17ß-estradiol and CDs/PANI. Such unique interfacial interactions also resulted in the synergistically enhanced electrochemical stability of the modified electrode.

Transient 2D IR spectroscopy of charge injection in dye-sensitized nanocrystalline thin films.

We use nonlinear 2D IR spectroscopy to study TiO(2) nanocrystalline thin films sensitized with a Re dye. We find that the free electron signal, which often obscures the vibrational features in the transient absorption spectrum, is not observed in the 2D IR spectra. Its absence allows the vibrational features of the dye to be much better resolved than with the typical IR absorption probe. We observe multiple absorption bands but no cross peaks in the 2D IR spectra, which indicates that the dyes have at least three conformations. Furthermore, by using a pulse sequence in which we initiate electron transfer in the middle of the infrared pulse train, we are able to assign the excited state features by correlating them to the ground state vibrational modes and determine that the three conformations have different time scales and cross sections for electron injection. 2D IR spectroscopy is proving to be very useful in disentangling overlapping structural distributions in biological and chemical physics processes. These experiments demonstrate that nonlinear infrared probes are also a powerful new tool for studying charge transfer at interfaces.

Multipurpose sensing applications of biocompatible radish-derived carbon dots as Cu2+ and acetic acid vapor sensors.

A recent trend in the preparation of carbon dots, optically unique nanomaterials, revolves around the use of readily-available, low-cost natural resources as precursors and their multipurpose applications. In this work, a hydrothermal method for preparing biocompatible carbon dots from radish was developed. The carbon dots were then tested for sensing of Cu2+ and acetic acid vapor. The carbon dots exhibited blue emission under UV illumination with, a quantum yield of 15%. The fluorescence emission was selectively quenched when Cu2+ ions were added, giving a detection limit of 0.16 µM. A paper-based fluorescent sensor was fabricated and shown to sense Cu2+ with a limit of detection of 6.8 µM. The carbon dots were able to determine the Cu2+ concentration in real water samples, with excellent recovery and reliability. The carbon dots were also used as the sensing material in an optical electronic nose, and tested for real-time detection of acetic acid vapor. Using principal component analysis, different ratios of acetic acid to methanol in solution were successfully identified with a detection limit of 15.5%. The acetic acid concentration in a real vinegar sample was also accurately determined. Our results demonstrated that label-free carbon dots derived from readily available radish can be simply used as versatile probes, giving them potential uses in multipurpose sensing applications.