Electrochemical and Structural Investigation of Calcium Substituted Monoclinic Li3V2(PO4)3 Anode Materials for Li‐Ion Batteries

In this work, the effect of Li⁺ substitution in Li₃V₂(PO₄)₃ with a large divalent ion (Ca²⁺) toward lithium insertion is studied. A series of materials, with formula Li_3?2xCa_xV₂(PO₄)₃/C (x = 0, 0.5, 1, and 1.5) is synthesized and studied in the potential region 3–0.01 V versus Li⁺/Li. Synchrotron diffraction demonstrates that Li₃V₂(PO₄)₃/C has a monoclinic structure (space group P2₁/n), while Ca_1.5V₂(PO₄)₃/C possesses a rhombohedral structure (space group R‐3c). The intermediate compounds, Li₂Ca_0.5V₂(PO₄)₃/C and LiCaV₂(PO₄)₃/C, are composed of two main phases, including monoclinic Li₃V₂(PO₄)₃/C and rhombohedral Ca_1.5V₂(PO₄)₃/C. Cyclic voltammetry reveals five reduction and oxidation peaks on Li₃V₂(PO₄)₃/C and Li₂Ca_0.5V₂(PO₄)₃/C electrodes. In contrast, LiCaV₂(PO₄)₃/C and Ca_1.5V₂(PO₄)₃/C have no obvious oxidation and reduction peaks but a box‐type voltammogram. This feature is the signature for capacitive‐like mechanism, which involves fast electron transfer on the surface of the electrode. Li₃V₂(PO₄)₃/C undergoes two solid‐solution and a short two‐phase reaction during lithiation and delithiation processes, whereas Ca_1.5V₂(PO₄)₃/C only goes through capacitive‐like mechanism. In operando X‐ray absorption spectroscopy confirms that, in both Li₃V₂(PO₄)₃/C and Ca_1.5V₂(PO₄)₃/C, V ions are reduced during the insertion of the first three Li ions. This study demonstrates that the electrochemical characteristic of polyanionic phosphates can be easily tuned by replacing Li⁺ with larger divalent cations.     

Study of Thermal Decomposition of Li1‐x(Ni1/3Mn1/3Co1/3)0.9O2 Using In‐Situ High‐Energy X‐Ray Diffraction

Safety has been a major technological concern hindering the deployment of lithium‐ion batteries for automobile applications. We investigated the decomposition mechanism of delithiated cathode materials at thermal abuse conditions using Li_1.1[Ni_1/3Mn_1/3Co_1/3]_0.9O₂ as a model cathode material. An in‐situ high‐energy X‐ray diffraction technique was established as an alternative to conventional thermal analysis techniques like differential scanning calorimetry and accelerating rate calorimetry. The X‐ray diffraction data revealed that the thermal decomposition pathway of delithiated Li_1‐x[Ni_1/3Mn_1/3Co_1/3]_0.9O₂ strongly depended on the exposed chemical environment, like solvents and lithium salts. A phase transformation of dry delithiated Li_1‐x[Ni_1/3Mn_1/3Co_1/3]_0.9O₂ was observed at about 278 °C, and its onset temperature was reduced to about 197°C with the presence of the electrolyte. It is suggested that the reduction in thermal stability is possibly related to proton intercalation into the delithiated material.     

Highly Stable Carbon‐Free Ag/Co3O4‐Cathodes for Lithium‐Air Batteries: Electrochemical and Structural Investigations

Lithium‐air batteries with an aqueous alkaline electrolyte promise a much higher practical energy density and capacity than conventional lithium‐ion batteries. However, high cathode overpotentials are some of the main problems during cycling. In our previous work, a catalyst combination of Ag and Co₃O₄ is found that reduces overpotential significantly, and is highly active and also long‐term stable. In the present investigations, X‐ray diffraction and X‐ray photoelectron spectroscopy are applied to study the structure and composition of the cathode material during oxygen reduction reaction and oxygen evolution reaction. Changes of the oxidation states during cycling are responsible for an enhanced oxygen evolution reaction current density but also for losses due to a lower electronic conductivity of the electrodes. The presence and formation of a mixed oxidation state for silver oxide (Ag^IAg^IIIO₂) at high potentials is identified. In contradiction to literature, time dependent X‐ray diffraction measurements evidence that this phase is not stable under dry conditions and progressively decays to Ag₂O. Electrode mappings show a highly homogeneous oxidation of the electrodes during cycling and quantitative analysis of the observed phases is carried out by Rietveld analysis. Long‐term material behavior completes the investigations.     

Structural characterization of Er3+,Yb3+‐doped Gd2O3 phosphor,synthesized using the solid‐state reaction method,and its luminescence behavior

We report the synthesis and structural characterization of Er³⁺,Yb³⁺‐doped Gd₂O₃ phosphor. The sample was prepared using the conventional solid‐state reaction method, which is the most suitable method for large‐scale production. The prepared phosphor sample was characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermoluminescence (TL), photoluminescence (PL) and CIE techniques. For PL studies, the excitation and emission spectra of Gd₂O₃ phosphor doped with Er³⁺ and Yb³⁺ were recorded. The excitation spectrum was recorded at a wavelength of 551 nm and showed an intense peak at 276 nm. The emission spectrum was recorded at 276 nm excitation and showed peaks in all blue, green and red regions, which indicate that the prepared phosphor may act as a single host for white light‐emitting diode (WLED) applications, as verified by International de I'Eclairage (CIE) techniques. From the XRD data, the calculated average crystallite size of Er³⁺ and Yb³⁺‐doped Gd₂O₃ phosphor is ~ 38 nm. A TL study was carried out for the phosphor using UV irradiation. The TL glow curve was recorded for UV, beta and gamma irradiations, and the kinetic parameters were also calculated. In addition, the trap parameters of the prepared phosphor were also studied using computerized glow curve deconvolution (CGCD). Copyright © 2015 John Wiley & Sons, Ltd.