Abstract: Although Li-rich layered oxides (Li1+xNiyCozMn1−x−y−zO2 > 250 mAh g−1) are attractive electrode materials providing energy densities more than 15% higher than todays commercial Li-ion cells, they suffer from voltage decay on cycling. To elucidate the origin of this phenomenon, we employ chemical substitution in structurally related Li2RuO3 compounds. Li-rich layered Li2Ru1−yTiyO3 phases with capacities of ~240 mAh g−1 exhibit the characteristic voltage decay on cycling. A combination of transmission electron microscopy and X-ray photoelectron spectroscopy studies reveals that the migration of cations between metal layers and Li layers is an intrinsic feature of the chargedischarge process that increases the trapping of metal ions in interstitial tetrahedral sites. A correlation between these trapped ions and the voltage decay is established by expanding the study to both Li2Ru1−ySnyO3 and Li2RuO3; the slowest decay occurs for the cations with the largest ionic radii. This effect is robust, and the finding provides insights into new chemistry to be explored for developing high-capacity layered electrodes that evade voltage decay.

Abstract: Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g(-1). In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a beta-Li2IrO3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e(-) per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (Mn+) and anionic (O-2)(n-) redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, beta-Li2IrO3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir4+ at potentials as low as 3.4 V versus Li+/Li-0, as equivalently observed in the layered alpha-Li2IrO3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

Abstract: Superparamagnetic iron oxide magnetic nanoparticles (MNPs) are successfully used as contrast agents in magnetic-resonance imaging. They can be easily functionalized for drug delivery functions, demonstrating great potential for both imaging and therapeutic applications. Here we developed new pH-responsive theranostic core-shell-corona nanoparticles consisting of superparamagentic Fe3O4 core that displays high T2 relaxivity, bovine serum albumin (BSA) shell that binds anticancer drug, doxorubicin (Dox) and poly(ethylene glycol) (PEG) corona that increases stability and biocompatibility. The nanoparticles were produced by adsorption of the BSA shell onto the Fe3O4 core followed by crosslinking of the protein layer and subsequent grafting of the PEG corona using monoamino-terminated PEG via carbodiimide chemistry. The hydrodynamic diameter, zeta-potential, composition and T2 relaxivity of the resulting nanoparticles were characterized using transmission electron microscopy, dynamic light scattering, thermogravimetric analysis and T2-relaxometry. Nanoparticles were shown to absorb Dox molecules, possibly through a combination of electrostatic and hydrophobic interactions. The loading capacity (LC) of the nanoparticles was 8 wt.%. The Dox loaded nanoparticles release the drug at a higher rate at pH 5.5 compared to pH 7.4 and display similar cytotoxicity against C6 and HEK293 cells as the free Dox. (C) 2015 Elsevier B.V. All rights reserved.

Abstract: We report crystal structure, electronic structure, and magnetism of manganese tetraboride, MnB4, synthesized under high-pressure, high-temperature conditions. In contrast to superconducting FeB4 and metallic CrB4, which are both orthorhombic, MnB4 features a monoclinic crystal structure. Its lower symmetry originates from a Peierls distortion of the Mn chains. This distortion nearly opens the gap at the Fermi level, but despite the strong dimerization and the proximity of MnB4 to the insulating state, we find indications for a sizable paramagnetic effective moment of about 1.7 mu(B)/f.u., ferromagnetic spin correlations, and, even more surprisingly, a prominent electronic contribution to the specific heat. However, no magnetic order has been observed in standard thermodynamic measurements down to 2 K. Altogether, this renders MnB4 a structurally simple but microscopically enigmatic material; we argue that its properties may be influenced by electronic correlations.

Abstract: A polycrystalline sample of LuFe2O4 has been investigated by means of powder synchrotron x-ray and neutron diffraction and transmission electron microscopy (TEM), along with Mössbauer spectroscopy and transport and magnetic properties. A monoclinic distortion is unambiguously evidenced, and the crystal structure is refined in the monoclinic C2/m space group [aM = 5.9563(1) Å, bM = 3.4372(1) Å, cM = 8.6431(1) Å, β = 103.24(1)°]. Along with the previously reported modulations distinctive of the charge-ordering (CO) of the iron species, a new type of incommensurate order is observed, characterized by a vector q⃗1 = α1a⃗M* + γ1c⃗M* (with α1 ≅ 0.55, γ1 ≅ 0.13). In situ heating TEM observations from 300 to 773 K confirm that the satellites associated with q⃗1 vanish completely, only at a temperature significantly higher than the CO temperature. This incommensurate modulation has a displacive character and corresponds primarily to a transverse displacive modulation wave of the Lu cations position, as revealed by the high resolution, high angle annular dark field scanning TEM images and in agreement with synchrotron data refinements. Analyses of vacuum-annealed samples converge toward the hypothesis of a new ordering mechanism, associated with a tiny oxygen deviation from the O4 stoichiometry.

Abstract: We apply neutron diffraction, high-resolution synchrotron x-ray diffraction, magnetization measurements, electronic structure calculations, and quantum Monte-Carlo simulations to unravel the structure and magnetism of (CuCl)LaTa2O7. Despite the pseudo-tetragonal crystallographic unit cell, this compound features an orthorhombic superstructure, similar to the Nb-containing (CuX)LaNb2O7 with X = Cl and Br. The spin lattice entails dimers formed by the antiferromagnetic fourth-neighbor coupling J(4), as well as a large number of nonequivalent interdimer couplings quantified by an effective exchange parameter J(eff). In (CuCl)LaTa2O7, the interdimer couplings are sufficiently strong to induce the long-range magnetic order with the Neel temperature T-N similar or equal to 7 K and the ordered magnetic moment of 0.53 mu(B), as measured with neutron diffraction. This magnetic behavior can be accounted for by J(eff)/J(4) similar or equal to 1.6 and J(4) similar or equal to 16 K. We further propose a general magnetic phase diagram for the (CuCl)LaNb2O7-type compounds, and explain the transition from the gapped spin-singlet (dimer) ground state in (CuCl)LaNb2O7 to the long-range antiferromagnetic order in (CuCl)LaTa2O7 and (CuBr)LaNb2O7 by an increase in the magnitude of the interdimer couplings J(eff)/J(4), with the (CuCl)LaM2O7 (M = Nb, Ta) compounds lying on different sides of the quantum critical point that separates the singlet and long-range-ordered magnetic ground states.

Abstract: The spiral magnetic structure and underlying spin lattice of BiMnFe2O6 are investigated by low-temperature neutron powder diffraction and density functional theory band structure calculations. In spite of the random distribution of the Mn3+ and Fe3+ cations, this centrosymmetric compound undergoes a transition into an incommensurate antiferromagnetically ordered state below TN≃220 K. The magnetic structure is characterized by the propagation vector k=[0,β,0] with β≃0.14 and the P221211′(0β0)0s0s magnetic superspace symmetry. It comprises antiferromagnetic helixes propagating along the b axis. The magnetic moments lie in the ac plane and rotate about π(1+β)≃204.8-deg angle between the adjacent magnetic atoms along b. The spiral magnetic structure arises from the peculiar frustrated arrangement of exchange couplings in the ab plane. The antiferromagnetic coupling along the c axis cancels the possible electric polarization and prevents ferroelectricity in BiMnFe2O6.

Abstract: We report on the crystal structure of the quantum magnet CuClLaNb2O7 that was controversially described with respect to its structural organization and magnetic behavior. Using high-resolution synchrotron powder x-ray diffraction, electron diffraction, transmission electron microscopy, and band-structure calculations, we solve the room-temperature structure of this compound -CuClLaNb2O7 and find two high-temperature polymorphs. The -CuClLaNb2O7 phase, stable above 640 K, is tetragonal with asub=3.889 Å, csub =11.738 Å, and the space group P4/mmm. In the -CuClLaNb2O7 structure, the Cu and Cl atoms are randomly displaced from the special positions along the 100 directions. The phase asub2asubcsub, space group Pbmm and the phase 2asub2asubcsub, space group Pbam are stable between 640 K and 500 K and below 500 K, respectively. The structural changes at 500 and 640 K are identified as order-disorder phase transitions. The displacement of the Cl atoms is frozen upon the → transformation while a cooperative tilting of the NbO6 octahedra in the phase further eliminates the disorder of the Cu atoms. The low-temperature -CuClLaNb2O7 structure thus combines the two types of the atomic displacements that interfere due to the bonding between the Cu atoms and the apical oxygens of the NbO6 octahedra. The precise structural information resolves the controversy between the previous computation-based models and provides the long-sought input for understanding CuClLaNb2O7 and related compounds with unusual magnetic properties.

Abstract: We demonstrate site-specific mapping of the oxygen coordination number for transition metals in complex oxides using atomically resolved electron energy-loss spectroscopy in an aberration-corrected scanning transmission electron microscope. Pb2Sr2Bi2Fe6O16 contains iron with a constant Fe3+ valency in both octahedral and tetragonal pyramidal coordination and is selected to demonstrate the principle of site-specific coordination mapping. Analysis of the site-specific Fe-L2,3 data reveals distinct variations in the fine structure that are attributed to Fe in a six-fold (octahedron) or five-fold (distorted tetragonal pyramid) oxygen coordination. Using these variations, atomic resolution coordination maps are generated that are in excellent agreement with simulations.

Abstract: Lithium-rich oxides are a promising class of positive electrode materials for next generation lithium-ion batteries, and oxygen plays a prominent role during electrochemical cycling either by forming peroxo-like species and/or by irreversibly forming oxygen gas during first charge. Here, we present Li-Fe-Te-O materials which show a tremendous amount of oxygen gas release. This oxygen release accounts for nearly all the capacity during the first charge and results in vacancies as seen by transmission electron microscopy. There is no oxidation of either metal during charge but significant changes in their environments. These changes are particularly extreme for tellurium. XRD and neutron powder diffraction both show limited Changes during cycling and no appreciable change in lattice parameters. A density functional theory study of this material is performed and demonstrates that the holes created on some of the oxygen atoms upon oxidation are partially stabilized through the formation of shorter O-O bonds, i.e. (O-2)(n-) species which on further delithiation show a spontaneous O-2 de-coordination from the cationic network and migration to the now empty lithium layer. The rate limiting step during charge is undoubtedly the diffusion of oxygen either out along the lithium layer or via columns of oxygen atoms. (C) 2015 The Electrochemical Society. All rights reserved.

Abstract: The crystal structure of SrCo0.7Fe0.2Nb0.1O2.72 was determined using a combination of precession electron diffraction (PED), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and spatially resolved electron energy loss spectroscopy (STEM-EELS). The structure has a tetragonal P4/mmm symmetry with cell parameters a = b = a(p), c = 2a(p) (a(p) being the cell parameter of the perovskite parent structure). Octahedral BO2 layers alternate with the anion-deficient BO1.4 layers, the different B cations are randomly distributed over both layers. The specific feature of the SrCo0.7Fe0.2NB0.1O2.72 microstructure is a presence of extensive nanoscale twinning resulting in domains with alignment of the tetragonal c-axis along all three cubic direction of the perovskite subcell.

Abstract: Single crystal antimony-doped SnO2 whiskers have been synthesized by in situ doping process in horizontal flow reactor. The produced whiskers were modified with 0.1, 0.2, 0.5, 1 or 2 wt.% Pd. The processes of Pd particles growth and aggregation are described on the base of AFM and STEM data. Depending on the content of introduced Pd precursor, the various mechanisms (Volmer-Weber or Stranski-Krastanov) of Pd nanoparticles growth realize. The dependence of sensor signal to CO on Pd concentration has non-monotonous character determined by the size of Pd nanoparticles and their aggregation degree. The best sensor signal toward CO was observed for whiskers decorated with 0.1 wt.% Pd. This concentration corresponds to the presence of individual 3-5 nm Pd nanoparticles on the surface of the whiskers. (C) 2013 Elsevier B.V. All rights reserved.

Abstract: The Ca0.85-1.5xGdxEu0.1_0.05-0.5xWO4 (0 < x < 0.567) series of cation-deficient scheelites is investigated to unveil the influence of the cation vacancies on the crystal structure and luminescent properties. The concentration of the vacancies is varied by the heterovalent substitution of Gd3+ for Ca2+, keeping the concentration of the Eu3+ luminescent centers constant in all compounds of the series. The crystal structure of the materials is studied using a combination of transmission electron microscopy and synchrotron X-ray powder diffraction. At low vacancy concentration (x = 0.1, 0.2), cations and cation vacancies are randomly distributed in the structure, and the materials preserve the I41/a symmetry of the parent scheelite structure [x = 0.1: a = 5.25151(1) Å, c = 11.39479(2) Å; x = 0.2: a = 5.25042(1) Å, c = 11.41335(2) Å]. At higher concentration, the cation-vacancy ordering gives rise to incommensurately modulated structures. The x = 0.3 structure has a (3 + 2)D tetragonal symmetry [superspace group I41/a(a,b,0)00(-b,a,0)00, a = 5.24700(1) Å, c = 11.45514(3) Å, q1 = 0.51637(14)a* + 0.80761(13)b*, q2 = -0.80761a* + 0.51637b*]. At x = 0.4, the scheelite basic cell undergoes a monoclinic distortion with the formation of the (3 + 1)D structure [superspace group I2/b(a,b,0)00, a = 5.23757(1) Å, b = 5.25035(1) Å, c = 11.45750(2) Å, g = 90.5120(2) o, q = 0.54206(8)a* + 0.79330(8)b*]. In both structures, the antiphase Ca and (Gd,Eu) occupancy modulations indicate that the ordering between the A cations and vacancies also induces partial Ca/(Gd,Eu) cation ordering. Further increase of the Gd3þ content up to x = 0.567 leads to the formation of a monoclinic phase (space group C2/c) with the Eu2/3WO4-type structure. Despite the difference in the cation-vacancy ordering patterns, all materials in the series demonstrate very similar quantum efficiency and luminescence decay lifetimes. However, the difference in the local coordination environment of the A cation species noticeably affects the line width and the multiplet splitting of the 4f6-4f6 transitions.

Abstract: Pr2−xCexCuO4 (x = 0.05; 0.1; 0.15) samples were synthesized and systematically characterized towards application as a cathode material for solid oxide fuel cells (SOFCs). High-temperature electrical conductivity, thermal expansion, and electrocatalytic activity in the oxygen reduction reaction (ORR) were examined. The electrical conductivity of Pr2−xCexCuO4 oxides demonstrates semiconducting behavior up to 900 °C. Small Ce-doping (2.5 at%) allows an increase in electrical conductivity from 100 to 130 S cm−1 in air at 500–800 °C. DFT calculations revealed that the density of states directly below the Fermi level, comprised mainly of Cu 3d and O 2p states, is significantly affected by atoms in rare earth positions, which might give an indication of a correlation between calculated electronic structures and measured conducting properties. Ce-doping in Pr2−xCexCuO4 slightly increases TEC from 11.9 × 10−6 K−1 for x = 0 to 14.2 × 10−6 K−1 for x = 0.15. Substitution of 2.5% of Pr atoms in Pr2CuO4 by Ce is effective to enhance the electrochemical performance of the material as a SOFC cathode in the ORR (ASR of Pr1.95Ce0.05CuO4 electrode applied on Ce0.9Gd0.1O1.95 electrolyte is 0.39 Ω cm2 at 750 °C in air). The peak power density achieved for the electrolyte-supported fuel cell with the Pr1.95Ce0.05CuO4 cathode is 150 mW cm−2 at 800 °C