Versatile electrochemical cell for Li/Na-ion batteries and high-throughput setup for combined operando X-ray diffraction and absorption spectroscopy

A fully operational setup (electrochemical cells, sample changer and interfacing software) that enables combined quasi-simultaneous operando X-ray diffraction (XRD) and absorption (XANES and EXAFS) measurements coupled with electrochemical characterization has been realized for synchrotron based studies. Combined XRD, XANES and EXAFS analysis provides a deep insight into the working mechanisms of electrode materials

Water‐Stable DMASnBr3 Lead‐Free Perovskite for Effective Solar‐Driven Photocatalysis

Water-stable metal halide perovskites could foster tremendous progresses in several research fields where their superior optical properties can make differences. In this work we report clear evidence of water stability in a lead-free metal halide perovskite, namely DMASnBr3, obtained by means of diffraction, optical and x-ray photoelectron spectroscopy. Such unprecedented water-stability has been applied to promote photocatalysis in aqueous medium, in particular by devising a novel composite material by coupling DMASnBr3 to g-C3N4, taking advantage from the combination of their optimal photophysical properties. The prepared composites provide an impressive hydrogen evolution rate >1700 μmol g-1 h-1 generated by the synergistic activity of the two composite costituents. DFT calculations provide insight into this enhancement deriving it from the favorable alignment of interfacial energy levels of DMASnBr3 and g-C3N4. The demonstration of an efficient photocatalytic activity for a composite based on lead-free metal halide perovskite in water paves the way to a new class of light-driven catalysts working in aqueous environments

In operando Synchrotron XRD/XAS Investigation of Sodium Insertion into the Prussian Blue Analogue Cathode Material Na 1.32 Mn[Fe(CN) 6 ] 0.83 · z H 2 O

Prussian Blue Analogues (PBAs) with general formula NaxMA[MB(CN)6]y·z H2O (MA, MB = transition metal) are promising low cost, high rate and high capacity cathodes for sodium ion battery (SIB) technology. Here, we have studied the PBA Na1.32Mn[Fe(CN)6]0.83·z H2O (z = 3.0 and 2.2) with varying structural modifications (monoclinic and cubic) using in operando quasi-simultaneous X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). We observed a series of reversible structural phase transitions which accompany Na insertion/extraction during electrochemical cycling. The samples show pronounced differences in their galvanostatic charge and discharge profiles which could be linked to structural and electronic response. Different desodiation and sodiation mechanisms were identified. The influence of [Fe(CN)6] vacancies and water content on the electrochemical performance was investigated

An Alternative Route to Pentavalent Postperovskite

A novel and advantageous synthetic route to post-perovskite (ppv) has produced the second-only known pentavalent CaIrO3-type structure in a compound where commonly used indicators, such as pseudocubic tilt or tolerance factor, suggest that ppv should not form. In addition to demonstrating that ppv-NaOsO3 can be made from perovskite-type NaOsO3 at 16 GPa and 1135 K, ppv NaOsO3 has also been produced, and recovered, from a cubic KSbO3-containing assemblage, at 6 GPa and 1100 K, from an initial mixed-phase precursor of hexavalent Na2OsO4 and nominally pentavalent KSbO3-like phases. It The latter offers a new lower pressure route to the post-perovskite form – one which completely foregoes any perovskite precursor or intermediate. This work suggests that ppv can be obtained in other KSbO3-like compounds, which lend themselves to technological and synthetic application through their advantageous flexibility towards oxygen content, and cation valences and deficiencies, as well as in otherand chemistries where generalized rules based on the pv structure may not apply, or where no perovskite is known. One more obvious consequence of our second route is that perovskite formation may even mask and hinder other less extreme chemical pathways to post-perovskite phases

Improving In-Situ Sodium Metal Plating on Copper Foil Through Optimization of Mechanical Pressure: Towards High-Performance Anode-Free Sodium Ion Batteries

Herein we report key developments on the scale-up of sodium ion anode free batteries through investigation of the effects of applied external pressure cell performance. Sodium ion anode free puts extra emphasis on high plating and stripping efficiency of sodium metal at the anode surface, due to the lack of an excess of the transporting ion. We demonstrate excellent Na||Cu half-cell results in coin cell configuration, and the scalability of the anode-free concept is further demonstrated, by plating and stripping of sodium metal on copper foils 10-fold larger (>10 cm 2) than in other studies in coin cells (∼1 cm2). It is discovered that pressure is paramount in establishing dendrite free sodium deposition at this scale through investigating the half-cell cycling at 56–743 kPa. Achieving a low hysteresis in these large-area cells is found to only require moderate pressures (∼185 kPa). However, achieving a high cycle life required increasing the pressure to 743 kPa. It is only at these high pressures that non-dendritic sodium deposition is demonstrated due to a homogeneous plating distribution enabled by proper contact between electrodes, as confirmed by impedance measurements and optical imaging of the deposited sodium

High-pressure high-temperature stability of hcp-IrxOs1−x (x = 0.50 and 0.55) alloys

An in situ powder X-ray diffraction has been used for a monitoring a formation of hcp-Ir0.55Os0.45 alloy from (NH4)2[Ir0.55Os0.45Cl6] precursor. A crystalline intermediate compound and nanodimentional metallic particles with a large concentration of defects has been found as key intermediates in the thermal decomposition process in hydrogen flow. High-temperature stability of titled hcp-structured alloys has been investigated upon compression up to 11 GPa using a multi-anvil press and up to 80 GPa using laser-heated diamond-anvil cells to obtain a phase separation into fcc + hcp mixture. Obtained high-pressure high-temperature data allowed us to construct the first model for pressure-dependent Ir─Os phase diagram

Superconductivity in NdFe1-xCoxAsO (0.05 < x < 0.20) and rare-earth magnetic ordering in NdCoAsO

The phase diagram of NdFe1-xCoxAsO for low cobalt substitution consists of a superconducting dome (0.05 < x < 0.20) with a maximum critical temperature of 16.5(2) K for x = 0.12. The x = 1 end member, NdCoAsO, is an itinerant ferromagnet (TC = 85 K) with an ordered moment of 0.30(1) BM at 15 K. Below TN = 9 K, Nd spin-ordering results in the antiferromagnetic coupling of the existing ferromagnetic planes. Rietveld analysis reveals that the electronically important two-fold tetrahedral angle increases from 111.4 to 115.9 deg. in this series. Underdoped samples with x = 0.046(2) and x = 0.065(2) show distortions to the orthorhombic Cmma structure at 72(2) and 64(2) K, respectively. The temperature dependences of the critical fields Hc2(T) near Tc are linear with almost identical slopes of 2.3(1) T K-1 for x = 0.065(2), x = 0.118(2) and x = 0.172(2). The estimated critical field Hc2(0) and correlation length for optimally doped samples are 26(1) T and 36(1) Angstrom. A comparison of the maximum reported critical temperatures of well-characterized cobalt doped 122- and 1111-type superconductors is presented.Comment: accepted to PR

KCrF_3: Electronic Structure, Magnetic and Orbital Ordering from First Principles

The electronic, magnetic and orbital structures of KCrF_3 are determined in all its recently identified crystallographic phases (cubic, tetragonal, and monoclinic) with a set of {\it ab initio} LSDA and LSDA+U calculations. The high-temperature undistorted cubic phase is metallic within the LSDA, but at the LSDA+U level it is a Mott insulator with a gap of 1.72 eV. The tetragonal and monoclinic phases of KCrF_3 exhibit cooperative Jahn-Teller distortions concomitant with staggered 3x^2-r^2/3y^2-r^2 orbital order. We find that the energy gain due to the Jahn-Teller distortion is 82/104 meV per chromium ion in the tetragonal/monoclinic phase, respectively. These phases show A-type magnetic ordering and have a bandgap of 2.48 eV. In this Mott insulating state KCrF_3 has a substantial conduction bandwidth of 2.1 eV, leading to the possibility for the kinetic energy of charge carriers in electron- or hole-doped derivatives of KCrF_3 to overcome the polaron localization at low temperatures, in analogy with the situation encountered in the colossal magnetoresistive manganites.Comment: 7 pages, 11 figure

High-pressure high-temperature tailoring of High Entropy Alloys for extreme environments

The exceptional performance of some High Entropy Alloys (HEAs) under extreme conditions holds out the possibility of new and exciting materials for engineers to exploit in future applications. In this work, instead of focusing solely on the effects of high temperature on HEAs, the effects of combined high temperature and high pressure were observed. Phase transformations occurring in a pristine HEA, the as-cast bcc–Al2CoCrFeNi, are heavily influenced by temperature, pressure, and by scandium additions. As-cast bcc–Al2CoCrFeNi and fcc–Al0.3CoCrFeNi HEAs are structurally stable below 60 GPa and do not undergo phase transitions. Addition of scandium to bcc–Al2CoCrFeNi results in the precipitation of hexagonal AlScM intermetallic (W-phase), which dissolves in the matrix after high-pressure high-temperature treatment. Addition of scandium and high-pressure sintering improve hardness and thermal stability of well-investigated fcc- and bcc- HEAs. The dissolution of the intermetallic in the main phase at high pressure suggests a new strategy in the design and optimization of HEAs