We report inelastic light scattering measurements of lattice dynamics related to the incommensurate orbital order in CaMn7O12. Below the ordering temperature To ≈ 250 K, we observe extra phonon peaks as a result of Brillouin-zone folding, as well as a soft vibrational mode with a powerlaw T -dependent energy, Ω = Ω0(1 − T /To) 1/2 . This temperature dependence demonstrates the second-order nature of the transition at To, and it indicates that the soft mode can be regarded as the amplitude excitation of the composite order parameter. Our result strongly suggests that the lattice degrees of freedom are actively involved in the orbital-ordering mechanism.
Atomic-scale phenomena fundamentally influence materials form and function that makes the ability to locally probe and study these processes critical to advancing our understanding and development of materials. Atomic-scale chemical imaging by scanning transmission electron microscopy (STEM) using energy-dispersive X-ray spectroscopy (EDS) is a powerful approach to investigate solid crystal structures. Inefficient X-ray emission and collection, however, require long acquisition times (typically hundreds of seconds), making the technique incompatible with electron-beam sensitive materials and study of dynamic material phenomena. Here we describe an atomic-scale STEM-EDS chemical imaging technique that decreases the acquisition time to as little as one second, a reduction of more than 100 times. We demonstrate this new approach using LaAlO3 single crystal and study dynamic phase transformation in beam-sensitive Li[Li0.2Ni0.2Mn0.6]O2 (LNMO) lithium ion battery cathode material. By capturing a series of time-lapsed chemical maps, we show for the first time clear atomic-scale evidence of preferred Ni-mobility in LNMO transformation, revealing new kinetic mechanisms. These examples highlight the potential of this approach toward temporal, atomic-scale mapping of crystal structure and chemistry for investigating dynamic material phenomena.
Electrochemical intercalation can enable lithium extraction from dilute water sources. However, during extraction, co-intercalation of lithium and sodium ions occurs, and the response of host materials to this process is not fully understood. This aspect limits the rational materials designs for improving lithium extraction. Here, to address this knowledge gap, we report one-dimensional (1D) olivine iron phosphate (FePO4) as a model host to investigate the co-intercalation behavior and demonstrate the control of lithium selectivity through intercalation kinetic manipulations. Via computational and experimental investigations, we show that lithium and sodium tend to phase separate in the host. Exploiting this mechanism, we increase the sodium-ion intercalation energy barrier by using partially filled 1D lithium channels via non-equilibrium solid-solution lithium seeding or remnant lithium in the solid-solution phases. The lithium selectivity enhancement after seeding shows a strong correlation with the fractions of solid-solution phases with high lithium content (i.e., LixFePO4 with 0.5 ≤ x < 1). Finally, we also demonstrate that the solid-solution formation pathway depends on the host material’s particle morphology, size and defect content.
We report on observation of ferroelastic domain structure in single crystals of multiferroic CaMn 7 O 12 at room temperature. Two types of ferroelastic domain wall are found, consistent with the material's rhombohedral symmetry that is reduced from cubic symmetry at higher temperatures. Using Raman spectroscopy along with other measurements, we develop a systematic method to determine the microscopic domain orientation. Moreover, we find a switching behavior of the domains, which allows us to detwin the crystals conveniently at room temperature using a moderate uniaxial compression. Our result paves the way for further spectroscopic study and domain engineering in CaMn 7 O 12 .
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