Search for: All records

Oxide solid electrolytes (OSEs) have the potential to achieve improved safety and energy density for lithium-ion batteries, but their high grain-boundary (GB) resistance generally is a bottleneck. In the well-studied perovskite oxide solid electrolyte, Li_3xLa_2/3-xTiO₃(LLTO), the ionic conductivity of grain boundaries is about three orders of magnitude lower than that of the bulk. In contrast, the related Li_0.375Sr_0.4375Ta_0.75Zr_0.25O₃(LSTZ0.75) perovskite exhibits low grain boundary resistance for reasons yet unknown. Here, we use aberration-corrected scanning transmission electron microscopy and spectroscopy, along with an active learning moment tensor potential, to reveal the atomic scale structure and composition of LSTZ0.75 grain boundaries. Vibrational electron energy loss spectroscopy is applied for the first time to reveal atomically resolved vibrations at grain boundaries of LSTZ0.75 and to characterize the otherwise unmeasurable Li distribution therein. We find that Li depletion, which is a major reason for the low grain boundary ionic conductivity of LLTO, is absent for the grain boundaries of LSTZ0.75. Instead, the low grain boundary resistivity of LSTZ0.75 is attributed to the formation of a nanoscale defective cubic perovskite interfacial structure that contained abundant vacancies. Our study provides new insights into the atomic scale mechanisms of low grain boundary resistivity.

A solid with larger sound speeds usually exhibits higher lattice thermal conductivity. Here, we report an exception that CuP₂has a quite large mean sound speed of 4155 m s⁻¹, comparable to GaAs, but single crystals show very low lattice thermal conductivity of about 4 W m⁻¹K⁻¹at room temperature, one order of magnitude smaller than GaAs. To understand such a puzzling thermal transport behavior, we have thoroughly investigated the atomic structures and lattice dynamics by combining neutron scattering techniques with first-principles simulations. This compound crystallizes in a layered structure where Cu atoms forming dimers are sandwiched in between P atomic networks. In this work, we reveal that Cu atomic dimers vibrate as a rattling mode with frequency around 11 meV, which is manifested to be remarkably anharmonic and strongly scatters acoustic phonons to achieve the low lattice thermal conductivity.

All‐solid‐state sodium‐ion batteries are highly promising for next generation grid energy storage with improved safety. Among the known sodium superionic conductors, the Na₃PnS₄family and the recently discovered Na₁₁Sn₂PnS₁₂(Pn = P, Sb) have garnered major interest due to their extremely high ionic conductivities. In this work, comprehensive investigation of the Na₃PnS₄‐Na₄TtS₄(Pn = P/As/Sb, Tt = Si/Ge/Sn) phase space of superionic conductors using density functional theory calculations, as well as AIMD simulations on the promising new Na₁₁Sn₂PnS₁₂(Pn=P/As/Sb) structures are presented. Crucial design rules on the effect of cation mixing are extracted on relative phase stability, electrochemical stability, moisture stability, and ionic conductivity. In particular, it is shown that while larger cations can substantially improve the ionic conductivity and moisture stability in these structures, there is an inherent trade‐off in terms of electrochemical stability. Na₁₁Sn₂AsS₁₂is also identified as a hitherto unexplored stable sodium superionic conductor with higher Na⁺conductivity and better moisture stability than the Na₁₁Sn₂PS₁₂and Na₁₁Sn₂SbS₁₂phases already reported experimentally.

The dynamic behavior of a macroscopic adhered hydrogel stabilized through controllable dynamic covalent interactions is reported. These interactions, involving the cross‐linked formation of a hydrogel through reaction of a diacylhydrazine precursor with a tetraformyl partner, increase as a function of time. By using a contact time of 24 h and different compounds with recognized aggregation‐induced emission features (AIEgens), it proves possible to create six laminated acylhydrazone hydrogels displaying different fluorescent colors. Blocks of these hydrogels are then adhered into a structure resembling a Rubik's Cube, a trademark of Rubik's Brand Limited, (RC) and allowed to anneal for 1 h. This produces a 3 × 3 × 3 block (RC) wherein the individual fluorescent gel blocks are loosely adhered to one another. As a consequence, the 1 × 3 × 3 layers making up the RC can be rotated either horizontally or vertically to produce new patterns. Ex situ modification of the RC or application of a chemical stimulus can be used to produce new color arrangements. The present RC structure highlights how the temporal features, strong versus weak adhesion, may be exploited to create smart macroscopic structures.