Experimental Visualization of Interstitialcy Diffusion of Li Ion in β-Li₂TiO₃

Monoclinic lithium metatitanate, β-Li₂TiO₃, is a member of the Li₂TiO₃ (M = Ti, Mn, Sn, Ru, and/or Ir) series and an important cation conductor for various energy applications such as Li-ion batteries and nuclear fusion reactors. Comprehensive knowledge of the crystal structure is vital to understand the Li-ion diffusion mechanism, and several possibilities were proposed previously. However, the exact crystal structure and Li-ion diffusion paths of β-Li₂TiO₃ are still unclear. Here, the results of a neutron diffraction study of high-purity ⁷Li-enriched β-Li₂TiO₃ are reported. The occupancy factor 0.033(3) and the atomic coordinates of the interstitial Li ion in the Li–O layer are successfully refined by Rietveld analysis of the time-of-flight neutron diffraction data. The three-dimensional network of Li-ion diffusion pathways is visualized by a combined technique of high-temperature neutron-diffraction and maximum-entropy methods. An interstitialcy diffusion mechanism, in which a lithium ion migrates through both the interstitial tetrahedral and lattice octahedral sites, is proposed for the Li₂TiO₃ series

Hydride-based antiperovskites with soft anionic sublattices as fast alkali ionic conductors

ソフトな陰イオンをもつ逆ペロブスカイト化合物で高速イオン伝導を達成. 京都大学プレスリリース. 2021-01-08.Most solid-state materials are composed of p-block anions, only in recent years the introduction of hydride anions (1s2) in oxides (e.g., SrVO2H, BaTi(O, H)3) has allowed the discovery of various interesting properties. Here we exploit the large polarizability of hydride anions (H–) together with chalcogenide (Ch2–) anions to construct a family of antiperovskites with soft anionic sublattices. The M3HCh antiperovskites (M = Li, Na) adopt the ideal cubic structure except orthorhombic Na3HS, despite the large variation in sizes of M and Ch. This unconventional robustness of cubic phase mainly originates from the large size-flexibility of the H– anion. Theoretical and experimental studies reveal low migration barriers for Li+/Na+ transport and high ionic conductivity, possibly promoted by a soft phonon mode associated with the rotational motion of HM6 octahedra in their cubic forms. Aliovalent substitution to create vacancies has further enhanced ionic conductivities of this series of antiperovskites, resulting in Na2.9H(Se0.9I0.1) achieving a high conductivity of ~1 × 10–4 S/cm (100 °C)

Mixed alkali-ion transport and storage in atomic-disordered honeycomb layered NaKNi2TeO6

Honeycomb layered oxides constitute an emerging class of materials that show interesting physicochemical and electrochemical properties. However, the development of these materials is still limited. Here, we report the combined use of alkali atoms (Na and K) to produce a mixed-alkali honeycomb layered oxide material, namely, NaKNi2TeO6. Via transmission electron microscopy measurements, we reveal the local atomic structural disorders characterised by aperiodic stacking and incoherency in the alternating arrangement of Na and K atoms. We also investigate the possibility of mixed electrochemical transport and storage of Na+ and K+ ions in NaKNi2TeO6. In particular, we report an average discharge cell voltage of about 4 V and a specific capacity of around 80 mAh g–1 at low specific currents (i.e., < 10 mA g–1) when a NaKNi2TeO6-based positive electrode is combined with a room-temperature NaK liquid alloy negative electrode using an ionic liquid-based electrolyte solution. These results represent a step towards the use of tailored cathode active materials for “dendrite-free” electrochemical energy storage systems exploiting room-temperature liquid alkali metal alloy materials

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides

Using strain to control oxynitride properties. 京都大学プレスリリース. 2020-12-01.原子空孔の配列を制御する新手法の発見. 京都大学プレスリリース. 2020-12-02.Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain

SYNTHESIS OF PEROVSKITE-TYPE MULTICOMPONENT OXIDES BY POLYMERIZED COMPLEX METHOD

Perovskite-type multicomponent oxides such as BaTiO_3 and LaMnO_, have been synthesized by Polymerized Complex Method. Tetragonal BaTiO_3 with a small domain size formed at about 500℃ in air or 400℃ under O_2 flow. Throughout this process segregation of the individual metals was not observed. LaMnO_ powder with high surface area (>20m^2/g) was formed at about 500℃ in air or 350℃ under O2 flow

Electronic structure and magnetic properties of monoclinic β-Cu2V2O7: A GGA+U study

A first-principles study on monoclinic C2/c copper pyrovanadate β-Cu2V2O7 has been performed using the generalized gradient approximation (GGA) and GGA+U method. The optimized unit-cell parameters and atomic coordinates of β-Cu2V2O7 agree well with experimental data. The optimized crystal structure of β-Cu2V2O7 indicates the existence of one-dimensional -Cu-Cu-Cu-Cu- chains. The electronic structure and magnetic properties were evaluated by the GGA+U calculations, which indicate that the β-Cu2V2O7 is a semiconducting antiferromagnetic material with an indirect band gap and local magnetic moment per Cu atom of 0.73μB. The intrachain exchanges for short and long Cu-Cu couples are estimated to be 6.4 and 4.1 meV, respectively, while the calculated interchain exchange (2.1 meV) is smaller, which indicate the one-dimensional character. The top of the valence band is composed of V 3d, O 2p, and Cu 3d electrons while the bottom of the conduction band is primarily composed of Cu 3d electrons. Valence electron-density distribution map indicates the V-O and Cu-O covalent bonds. Calculated partial electronic density of states strongly suggests that the V-O and Cu-O covalent bonds are mainly attributed to the overlaps of V 3d and O 2p atomic orbitals and of Cu 3d and O 2p, respectively