Quantitative Operando Visualization of Electrochemical Reactions and Li Ions in All-Solid-State Batteries by STEM-EELS with Hyperspectral Image Analyses.

All-solid-state lithium-ion batteries (LIBs) are one of the promising candidates to overcome some issues of conventional LIBs with liquid electrolytes. However, high interfacial resistance of Li-ion transfer at the electrode/solid electrolyte limits their performance. Thus, it is important to clarify interfacial phenomena in a nanometer scale. Here, we present a new method to dynamically observe the Li-ion distribution and Co-ion electronic states in a LiCoO2 cathode of the all-solid-state LIB during charge and discharge reactions using operando scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). By applying a hyperspectral image analysis of non-negative matrix factorization (NMF) to the STEM-EELS, we succeeded in clearly observing the quantitative Li-ion distribution in the operando condition. We found from the operando observation with NMF that the Li ions did not uniformly extract/insert during the charge/discharge reactions, and the activity of the electrochemical reaction depended on the Li-ion concentration in a pristine state. An electrochemically inactive region was formed about 10-20 nm near the LiCoO2/Li2O-Al2O3-TiO2-P2O5-based solid electrolyte interfaces. The STEM-EELS, electron diffraction, and Raman spectroscopy experimentally showed that the inactive region was a mixture of LiCoO2 and Co3O4, leading to the higher interfacial resistance of the Li-ion transfer because Co3O4 does not have pathways of Li-ion diffusion in its crystal.

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries.

Derivatives of tris-fused TTF extended with two ethanediylidenes (5), tris- and pentakis-fused TTFs extended with two thiophene-2,5-diylidenes (6-9) were successfully synthesized. Cyclic voltammograms of the tetrakis(n-hexylthio) derivative of 5 and 7 (5d, 7d) consisted of two pairs of two-electron redox waves and two pairs of one-electron redox waves. On the other hand, four pairs of two-electron redox waves and two pairs of one-electron redox waves were observed for the tetrakis(n-hexylthio) derivative of 9 (9d). Coin-type cells using the bis(ethylenedithio) derivatives of 5 (5b), 6 (6b) and the tetrakis(methylthio) derivatives of 5 (5c) and 8 (8c) as positive electrode materials showed initial discharge capacities of 157-190 mAh g(-1) and initial energy densities of 535-680 mAh g(-1). The discharge capacities after 40 cycles were 64-86% of the initial discharge capacities.

Polymer-bound pyrene-4,5,9,10-tetraone for fast-charge and -discharge lithium-ion batteries with high capacity.

Organic rechargeable batteries have received significant research interest from the viewpoints of structural diversity and sustainability of electrode materials. We designed core structures of organic cathode materials for lithium-ion (Li-ion) batteries based on density functional theory (DFT) calculations, which indicated that six-membered cyclic 1,2-diketones serve as excellent core structures because of the high redox energy change resulting from favorable coordination of the oxygen atoms to Li and the aromaticity of the reduced form. Here, we show that the Li-ion battery composed of pyrene-4,5,9,10-tetraone (PYT), which has two six-membered cyclic 1,2-diketone units, bound to polymethacrylate exhibits remarkable charge-discharge properties with a high specific capacity of 231 mAh/g, excellent rechargeability (83% of the capacity retained after 500 cycles), and charge-discharge ability (90% of the capacity at 30 C as compared to 1 C) in the LiNTf(2)/tetraglyme ionic-liquid system.