Mass-Scalable Molecular Monolayer for Ni-Rich Cathode Powder: Solution for Microcrack Failure in Lithium-Ion Batteries.

Ni-rich layered oxide with high reversible capacity, low manufacturing cost, and high potential is recognized as the best practical cathode material for high energy density lithium-ion batteries for affordable electric vehicles. However, they suffer from a poor cycle life owing to internal microcracks, which have been perceived to be due to anisotropic volume changes. Herein, the failure mechanism as well as improved cycle life is demonstrated by a self-assembled molecular monolayer (SAM) on Ni-rich layered oxide powder with a gas-phase precursor of octyltrichlorosilane (OTS), enabling mass-scalable manufacturing. The SAM process with a low heating temperature of 130 °C compared to the commonly used coating is also suitable to the chemically fragile Ni-rich layered oxide. Also, a homogeneous angstrom-level OTS coating is beneficial for preserving the energy density of batteries. In particular, OTS, with electrolyte-phobic functionality, is very effective for mitigating the inherent microcrack failure of the particles by reducing the internal electrolyte decomposition by controlling electrolyte wetting into secondary particles. Systematic surface analyses of the cross section of Ni-rich electrode with the OTS coating found greatly improved particle stability after 100 cycles in comparison with pristine material.

Metal-Organic Framework as a Functional Analyte Channel of Organic-Transistor-Based Air Pollution Sensors.

Air pollution sensors based on organic transistors have attracted much interest recently; however, the devices suffer from low responsivity and slow response and recovery rates for gas analytes. These shortcomings are attributed to the low charge-carrier mobility of organic semiconductors and to a structural limitation resulting from the use of a thick and continuous active layer. In the present work, we investigated the material properties of a multiscale porous zeolitic imidazolate framework, [Zn(2-methylimidazole)2]n (ZIF-8), and examined its potential as an analyte channel material inserted at an organic-transistor active layer. A series of carbonized zeolitic imidazolate frameworks (ZIFs) were prepared by thermal conversion of ZIF-8 and also studied for comparison. The microstructures, morphologies, and optical/electrical characteristics of polythiophene/ZIF-8 hybrid films were systematically investigated. Organic-transistor-type nitrogen dioxide sensors based on the polythiophene/ZIF-8 hybrid films showed substantially improved sensing properties, including responsivity, response rate, and recovery rate. The electrical conductivity of the carbonized ZIF-8s enhanced the field-effect mobility of the organic transistors; however, the sensing performance was not improved, because of the closed pore structures resulting from the carbonization. These results provide invaluable information and useful insights into the design of transistor-type gas sensors based on organic semiconductor/metal-organic framework hybrid films.

Tailoring the crystallinity of solution-processed 6,13-bis(triisopropylsilylethynyl)pentacene via controlled solidification.

Solution processing is one of the most important techniques for producing large-area, uniform films for printed electronics via a low-cost process. Herein, we propose a time-controlled spin-coating method to improve the crystallinity of films of the solution-processable organic small-molecule semiconductor 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene). A key factor in this process was to halt spinning before drying had begun. We used microscopic and spectroscopic analyses to systematically investigate the effect of spinning time on the evaporation rate of solvent at different spinning rates. We found that the crystallinity of the TIPS-pentacene thin films was substantially enhanced when the spinning time was limited to a few seconds, without post-treatment. We fabricated field-effect transistors using thin films deposited by this method and found that the field-effect mobility was enhanced ∼100-fold compared with that of a device fabricated using a film deposited by the conventional spin-coating method.