Search

Correlating the microscopic structural characteristics with the macroscopic electrochemical performance in electrode materials is critical for developing excellent-performance lithium-ion batteries, which however remains largely unexplored. Here, we show that the Zn 2 SnO 4 (ZTO) nanowires (NWs) with smaller diameters ( d < 5 nm) exhibit slower capacity fade rate and better cycling stability, as compared with the NWs with larger diameters ranging from tens to hundreds of nanometers. By applying in situ transmission electron microscopy (TEM), we discover a strong correlation of cracking behavior with the NW diameter. Upon the first lithiation, there exists a critical diameter of ∼80 nm, below which the NWs neither crack nor fracture, and above which the cracks could easily nucleate and propagate along the specific planes, resulting in the deteriorated cycling stability in larger sized electrodes. Further theoretical calculations based on the finite element model and the climbing image nudged elastic band method faithfully predict the size-dependent cracking behaviors, which may result from the synergistic effect of axial stress evolution as well as preferential Li-ion migration directions during the first lithiation. This work provides a real-time tracking of the tempo-spatial structural evolution of a single ZTO NW, which facilitates a fundamental understanding of how the sample size affects the electrochemical behavior and thus offers a reference for future battery design and application strategy.

The synthesis and characterization of platinum(II) and palladium(II) complexes bearing two (dimers Pt(L pc ) 2 Cl 2 and Pd(L pc ) 2 Cl 2 ), one (monomers Pt(L pc )(L ref )Cl 2 and Pd(L pc )(L ref )Cl 2 ), or no (reference compounds Pt(L ref ) 2 Cl 2 and Pd(L ref ) 2 Cl 2 ) pentacene-based pyridyl ligands are presented. Photophysical properties of the dimers are probed by means of steady-state and time-resolved transient absorption measurements in comparison to the monomer and model compounds. Our results document that despite enhanced spin-orbit coupling from the presence of heavy atoms, intramolecular singlet fission (iSF) is not challenged by intersystem crossing. iSF thus yields correlated triplet pairs and even uncorrelated triplet excited states upon decoherence. Importantly, significant separation of the two pentacenyl groups facilitates decoupling of the two chromophores. Furthermore, the mechanism of iSF is altered depending on the respective metal center, that is, Pt(II) versus Pd(II). The dimer based on Pt(II), Pt(L pc ) 2 Cl 2 , exhibits a direct pathway for the iSF and forms a correlated triplet pair with singlet-quintet spin-mixing within 10 ns in variable solvents. On the other hand, the dimer based on Pd(II), Pd(L pc ) 2 Cl 2 , leads to charge transfer mixing during the population of the correlated triplet pair that is dependent on solvent polarity. Moreover, Pd(L pc ) 2 Cl 2 gives rise to a stable equilibrium between singlet and quintet correlated triplet pairs with lifetimes of up to 170 ns. Inherent differences in the size and polarizability, when contrasting platinum(II) with palladium(II), are the most likely rationale for the underlying trends., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Co-published by University of Science and Technology of China and American Chemical Society.)

An indium(0)-metal-mediated efficient synthesis of benzylic hydroperoxides is described. The reaction proceeds efficiently with a broad range of benzyl bromides under aerobic conditions at room temperature to afford benzyl hydroperoxides in good to excellent yields. In addition, the tandem hydroperoxidation-Michael addition of ( E)-1-(bromomethyl)-2-(2-nitrovinyl)benzene was also demonstrated.