Theoretical Protocol Based on Long-Range Corrected Density Functional Theory and Tuning of Range-Split Parameter for Two-Electron Two-Proton Reduction of Phenylazocarboxylates.

A theoretical protocol based on long-range corrected density functional theory is suggested for a highly accurate estimation of the two-electron two-proton (2e2p) reduction potential of ethyl 2-phenylazocarboxylate derivatives. Geometry optimization and single-point energy refinement with ωB97X-D are recommended. The impact of polarization and diffusion functions in the basis sets on the 2e2p reduction potential is discussed. Further improvements can be achieved by tuning the range-split parameter based on the linear relationship between the Hammett constant of phenyl substituents and the optimal ω value that most accurately reproduces the experiments. The suggested protocol can accurately predict the 2e2p reduction potential of five ethyl 2-phenylazocarboxylate derivatives. Based on these findings, 22 additional candidates are suggested to enlarge the electrochemical window and to increase the selectivity of 2e2p reactions. This study contributes to the development of a theoretical approach to accurately estimate the 2e2p reduction potential of azo groups.

Interface-Stabilized Layered Lithium Ni-Rich Oxide Cathode via Surface Functionalization with Titanium Silicate.

Nickel-rich lithium metal oxide cathode materials have recently be en highlighted as next-generation cathodes for lithium-ion batteries. Nevertheless, their relatively high surface reactivity must be controlled, as fading of the cycling retention occurs rapidly in the cells. This paper proposes functionalized nickel-rich lithium metal oxide cathode materials by a multipurpose nanosized inorganic material-titanium silicon oxide-via a simple thermal treatment process. We examined the topologies of the nano-titanium silicate-functionalized nickel-rich lithium metal oxide cathodes with scanning electron microscopy and quantitatively analyzed their improved mechanical properties using microindentation. The cell containing nickel-rich lithium metal oxide cathodes suffered from poor cycling behavior as the electrolytes persistently decomposed; however, this behavior was effectively inhibited in the cell by nano-titanium silicate-functionalized nickel-rich lithium metal oxide cathodes. Further ex situ analyses indicated that the particle hardness of the nano-titanium silicate-functionalized nickel-rich lithium metal oxide cathode materials was maintained, and decomposition of the electrolyte by the dissolution of transition metals was thoroughly inhibited even after 100 cycles. Based on these results, we concluded that the use of nano-titanium silicate as a coating material for nickel-rich lithium metal oxide cathode materials is an effective way to enhance the cycling performance of lithium-ion batteries.

Synergistically Improved Thermoelectric Energy Harvesting of Edge-Oxidized-Graphene-Bridged N-Type Bismuth Telluride Thick Films.

Power generation through the thermoelectric (TE) effect in small-sized devices requires a submillimeter-thick film that is beneficial to effectively maintain ΔT compared with a micron-scale thin film. However, most TE thick films, which are fabricated using printing technologies, suffer from low electrical conductivity due to the porous structures formed after sintering of the organic binder-mixed TE ink. In this study, we report an n-type TE thick film fabricated through bar-coating of the edge-oxidized-graphene (EOG)-dispersed Bi2.0Te2.7Se0.3 (BTS) paste with copper dopants. We have found that EOG provides the conducting pathway for carriers through electrical bridging between the separated BTS grains in porous TE thick films. The simultaneous enhancement in electrical conductivity and the Seebeck coefficient of the EOG-bridged TE film result in a maximum power factor of 1.54 mW·m-1·K-2 with the addition of 0.01 wt % EOG. Furthermore, the single element made of an n-type EOG-bridged BTS exhibits a superior output power of 1.65 µW at ΔT = 80 K. These values are 5 times higher than those of bare BTS films. Our results clearly indicate that the utilization of EOG with a metal dopant exerts a synergistic effect for enhancing the electrical output performance of n-type TE thick films for thermal energy harvesters.