New germanides with composition RE3Pt4Ge13 (RE = Y, Pr, Sm, Gd, Tb, Tm) have been prepared by high-pressure, high-temperature synthesis. Their crystal structures have been refined, and the relationship of this new rhombohedral and monoclinic structure types with the primitive cubic Yb3Rh4Sn13 prototype is discussed. Band structure calculations within density functional theory confirm the distorted rhombohedral and monoclinic structural arrangements to be energetically more favorable than the simple cubic one. X-ray absorption spectroscopy and magnetic susceptibility measurements indicate that the RE-atoms are in the +3 oxidation state in all studied compounds.
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http://dx.doi.org/10.1039/c4dt03155e | DOI Listing |
Materials (Basel)
December 2024
Arrhenius Laboratory, Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden.
The phase evolution of Li-rich Li-Mn-Ni-(Al)-O cathode materials upon heat treatments in the air at 900 °C was studied by X-ray and neutron powder diffraction. In addition, the structures of LiMnAl NiO, x = 0.0, 0.
View Article and Find Full Text PDFLangmuir
December 2024
School of Chemical Engineering and Energy Technology & School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan 523808, PR China.
Sodium manganese hexacyanoferrate, also called Prussian white (PW), has attracted much attention as a promising cathode material for Na-ion batteries due to its high-voltage platform and inexpensive elemental composition. However, their parasitic vacancies and water molecules often deteriorate the electrochemical performance. Proper regulation of such defects in scale-up preparation is still a challenge.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, United Kingdom.
Below its Jahn-Teller transition temperature, , NaNiO has a monoclinic layered structure consisting of alternating layers of edge-sharing NaO and Jahn-Teller-distorted NiO octahedra. Above where NaNiO is rhombohedral, diffraction measurements show the absence of a cooperative Jahn-Teller distortion, accompanied by an increase in the unit cell volume. Using neutron total scattering, solid-state Nuclear Magnetic Resonance (NMR), and extended X-ray absorption fine structure (EXAFS) experiments as local probes of the structure we find direct evidence for a displacive, as opposed to order-disorder, Jahn-Teller transition at .
View Article and Find Full Text PDFSmall
December 2024
Materials Science & Engineering Program and Texas Materials Institute, The University of Texas at Austin, Austin, Texas, 78712, USA.
3D-framework Prussian blue analogues (PBAs) are appealing as a cost-effective, sustainable cathodes for Na-ion batteries. However, the aqueous-based synthesis of PBAs inherently introduces three different forms of water molecules (surface, interstitial and crystal) into the structure. Removal of water molecules causes phase transformation from monoclinic (M) to rhombohedral (R).
View Article and Find Full Text PDFActa Crystallogr B Struct Sci Cryst Eng Mater
October 2024
Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut (PSI), 5232 Villigen PSI, Switzerland.
The magnetic and crystal structures of manganese and nickel monoxides have been studied using high-resolution neutron diffraction. The known 1k-structures based on the single propagation vector [½ ½ ½] for the parent paramagnetic space group Fm3m are forced to have monoclinic magnetic symmetry and are not possible in rhombohedral symmetry. However, the monoclinic distortions from the rhombohedral crystal metric allowed by symmetry are very small, and the explicit monoclinic splittings of the diffraction peaks have not been experimentally observed.
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