Evaluating lithium diffusion mechanisms in the complex spinel Li2NiGe3O8.

Lithium-ion diffusion mechanisms in the complex spinel Li2NiGe3O8 have been investigated using solid-state NMR, impedance, and muon spectroscopies. Partial occupancy of migratory interstitial 12d sites is shown to occur at lower temperatures than previously reported. Bulk activation energies for Li+ ion hopping range from 0.43 ± 0.03 eV for powdered samples to 0.53 ± 0.01 eV for samples sintered at 950 °C for 24 h, due to the loss of Li during sintering at elevated temperatures. A lithium diffusion coefficient of 3.89 × 10-12 cm2 s-1 was calculated from muon spectroscopy data for Li2NiGe3O8 at 300 K.

Nanoscale Mapping of Bromide Segregation on the Cross Sections of Complex Hybrid Perovskite Photovoltaic Films Using Secondary Electron Hyperspectral Imaging in a Scanning Electron Microscope.

Mixed halide (I/Br) complex organic/inorganic hybrid perovskite materials have attracted much attention recently because of their excellent photovoltaic properties. Although it has been proposed that their stability is linked to the chemical inhomogeneity of I/Br, no direct proof has been offered to date. Here, we report a new method, secondary electron hyperspectral imaging (SEHI), which allows direct imaging of the local variation in Br concentration in mixed halide (I/Br) organic/inorganic hybrid perovskites on a nanometric scale. We confirm the presence of a nonuniform Br distribution with variation in concentration within the grain interiors and boundaries and demonstrate how SEHI in conjunction with low-voltage scanning electron microscopy can enhance the understanding of the fundamental physics and materials science of organic/inorganic hybrid photovoltaics, illustrating its potential for research and development in "real-world" applications.

New layered compounds with honeycomb ordering: Li3Ni2BiO6, Li3NiM'BiO6 (M' = Mg, Cu, Zn), and the delafossite Ag3Ni2BiO6.

The new layered compound Li(3)Ni(2)BiO(6) has been prepared by a solid-state reaction. It crystallizes in the monoclinic C2/m space group; its lamellar structure is characterized by a honeycomb ordering between Ni(2+) and Bi(5+) within the slabs, while Li(+) ions occupy octahedral sites in the interslab space. Stacking defects weakly alter the XRD pattern. By substitution of half of the nickel ions, the new phases Li(3)NiM'BiO(6) (M' = Mg, Cu, Zn) isostructural with Li(3)Ni(2)BiO(6) have been synthesized under similar conditions. All these compounds demonstrate paramagnetic behavior at high temperature, and Li(3)Ni(2)BiO(6) exhibits an antiferromagnetic ordering at 5.5 K. By topotactic molten salt ionic exchange, the new delafossite compound Ag(3)Ni(2)BiO(6) has been also obtained and characterized.

Surface complexation of catechol to metal oxides: an ATR-FTIR, adsorption, and dissolution study.

The interaction of catechol with chromium(III) oxide (Cr(2)O(3)), manganese dioxide (MnO(2)), iron(III) oxide (Fe(2)O(3)), and titanium dioxide (TiO(2)) was evaluated as a function of pH conditions (pH 3-10) and ionic strength using a combined approach of bulk adsorption, attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), and dissolution analysis. Adsorption of catechol showed a strong pH-dependent behavior with the metal oxides, remaining constant under acidic-neutral pH (3-7) and increasing under more basic conditions. In situ ATR-FTIR measurements indicate that catechol binds predominately as an outer-sphere complex on MnO(2) and as an inner-sphere complex on Fe(2)O(3), TiO(2), and Cr(2)O(3) substrates. Catechol complexation on Fe(2)O(3), TiO(2), and Cr(2)O(3) promotes dissolution at pH >5, whereas MnO(2) dissolution occurs under acidic and basic conditions (pH 3-10).