Insertion properties of LiFe<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>PO<Subscript>4</Subscript> electrode materials for Li-ion batteries

This paper addresses the synthesis structural and electrochemical properties of LiFe_0.5Mn_0.5PO₄ electrode materials for Li-ion batteries. The charge–discharge reaction of Li/LiPF₆-EC–DEC/LiFe_0.5Mn_0.5PO₄ cell carried out at the 1-C rate shows a capacity retention of 128 mAh/g. The local structure of the delithiated Li _x Fe_0.5Mn_0.5PO₄ phases have been studied by Fourier transform infrared spectroscopy and magnetometry. Spectral features indicate that the structure of the delithiated phase remains in the orthorhombic system. The compositional dependence of the magnetic moment is found to be in quantitative agreement with the theoretical value predicted for oxidation of M ²⁺ ions in the high spin state. Paper presented at the 11th Euro-Conference on Science and Technology of Ionics, Batz-sur-Mer, France, 9–15 Sept. 2007     

Raman spectroscopy of very small Cd1−xCoxS quantum dots grown by a novel protocol: direct observation of acoustic‐optical phonon coupling

Glass‐embedded Cd_1−xCo_xS quantum dots (QDs) with mean radius of R ≈ 1.70 nm were successfully synthesized by a novel protocol on the basis of the melting‐nucleation synthesis route and herein investigated by several experimental techniques. Incorporation of Co²⁺ ions into the QD lattice was evidenced by X‐ray diffraction and magnetic force microscopy results. Optical absorption features with irregular spacing in the ligand field region confirmed that the majority of the incorporated Co²⁺ ions are under influence of a low‐symmetry crystal field located near to the Cd_1−xCo_xS QD surface. Electron paramagnetic resonance data confirmed the presence of Co²⁺ ions in a highly inhomogeneous crystal field environment identified at the interface between the hosting glass matrix (amorphous) and the crystalline QD. The acoustic‐optical phonon coupling in the Cd_1−xCo_xS QDs (x ≠ 0.000) was directly observed by Raman measurements, which have shown a high‐frequency shoulder of the longitudinal optical phonon peak. This effect is tuned by the size‐dependent sp‐d exchange interaction due to the magnetic doping, causing variations in the coupling between electrons and longitudinal optical phonon. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural studies and Raman spectroscopy of forbidden zone boundary phonons in Ni‐doped ZnO ceramics

We present X‐ray diffraction and Raman spectroscopy studies of Ni‐doped ZnO (Zn_1−xNi_xO, x = 0.0, 0.03, 0.06, and 0.10) ceramics prepared by solid‐state reaction technique. The presence of the secondary phase along with the wurtzite phase is observed in Ni‐doped ZnO samples. The E₂(low) optical phonon mode is seen to be shifted to a lower wavenumber with Ni incorporation in ZnO and is explained on the basis of force‐constant variation of ZnO bond with Ni incorporation. A zone boundary phonon is observed in Ni‐doped samples at ∼130 cm⁻¹ which is normally forbidden in the first‐order Raman scattering of ZnO. Antiferromagnetic ordering between Ni atoms via spin‐orbit mechanism at low temperatures (100 K) is held responsible for the observed zone boundary phonon. Copyright © 2008 John Wiley & Sons, Ltd.     

Doping effect on the phase transition temperature in ferroelectric SrBi2−xNdxNb2O9 layer‐structured ceramics: a micro‐Raman scattering study

The temperature dependence of Raman spectra for SrBi_2−xNd_xNb₂O₉ ceramics (x from 0 to 0.2) has been studied in a wide temperature range from 80 to 873 K. It is found that the peak position of the A_1g[Nb] phonon mode at 207 cm^–1, which is directly associated with the distortion of NbO₆ octahedron, decreases with increasing Nd composition, while the A_1g[O] phonon mode at 835 cm^–1 increases. Moreover, both the peak position and intensity of the A_1g[Nb] phonon mode reveal strong anomalies around the ferroelectric to paraelectric phase transition temperature. It indicates that the phase transition temperature decreases from about 710 to 550 K with increasing Nd composition, which is due to the fact that the introduction of Nd ions in the Bi₂O₂ layers reduces the distortion extent of NbO₆ octahedron. Copyright © 2011 John Wiley & Sons, Ltd.     

Phonon confinement and substitutional disorder in Cd1−xZnxS nanocrystals

1‐longitudinal optical (LO) phonons in free‐standing mixed Cd_1−xZn_xS nanocrystals, synthesized using chemical precipitation, are investigated using Raman spectroscopy. As expected for the nanocrystals, the 1‐LO modes are found to appear at slightly lower wavenumbers than those in the bulk mixed crystals and exhibit one‐mode behavior. On the other hand, the line broadening is found to be much more than that can be accounted on the basis of phonon confinement. From the detailed line‐shape analysis it turns out that the substitutional disorder in the mixed crystals contributes much more to the line broadening than the phonon confinement. The linewidth arising from these mechanisms are also extracted from the analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

LiFexMn1-xPO4固溶体的密度泛函理论与电化学研究

本文用DFT计算方法研究了LiFe_xMn_1-xPO₄的热力学稳定性和嵌/脱锂电位. 结果表明,LiFe_xMn_1-xPO₄固溶体的自由能比相分离的LiFePO₄/LiMnPO₄混合物略高,这两种形式可能在实际LiFe_xMn_1-xPO₄材料中共存. 计算表明,LiFe_xMn_1-xPO₄固溶体的嵌/脱锂电位随锰/铁比以及过渡金属离子的空间排列而变化,并用计算结果解释了放电曲线的形状. 采用固相反应法合成了LiFe_xMn_1-xPO₄材料并研究了其电化学性质,实验中观察到附加的放电平台,其出现可能与LiFe_xMn_1-xPO₄固溶体的存在有关.     

Electrochemical comparison of LiFe<Subscript>0.4</Subscript>Mn<Subscript>0.595</Subscript>Cr<Subscript>0.005</Subscript>PO<Subscript>4</Subscript>/C and LiMnPO<Subscript>4</Subscript>/C cathode materials

A comparison of electrochemical performance between LiFe_0.4Mn_0.595Cr_0.005PO₄/C and LiMnPO₄/C cathode materials was conducted in this paper. The cathode samples were synthesized by a nano-milling-assisted solid-state process using caramel as carbon sources. The prepared samples were investigated by XRD, SEM, TEM, energy-dispersive X-ray spectroscopy (EDAX), powder conductivity test (PCT), carbon-sulfur analysis, electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge cycling. The results showed that LiFe_0.4Mn_0.595Cr_0.005PO₄/C exhibited high specific capacity and high energy density. The initial discharge capacity of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 163.6 mAh g^?1 at 0.1C (1C = 160 mA g^?1), compared to 112.3 mAh g^?1 for LiMnPO₄/C. Moreover, the Fe/Cr-substituted sample showed good cycle stability and rate performance. The capacity retention of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 98.84 % over 100 charge-discharge cycles, while it was only 86.64 % for the pristine LiMnPO₄/C. These results indicated that Fe/Cr substitution enhanced the electronic conductivity for the prepared sample and facilitated the Li⁺ diffusion in the structure. Furthermore, LiFe_0.4Mn_0.595Cr_0.005PO₄/C composite presented high energy density (606 Wh kg^?1) and high power density (574 W kg^?1), thus suggested great potential application in lithium ion batteries (LIBs).     

Hydrothermal synthesis and properties of manganese-doped LiFePO4

A series of carbon-coated LiFe_1???x Mn _x PO₄ compounds are prepared by a hydrothermal method at 170 °C for 12 h. The structure and morphology of the prepared composites are characterized to examine the effects of Mn²⁺ substitution. All LiFe_1???x Mn _x PO₄ compositions are found to have an ordered olivine-type structure with homogeneous Fe²⁺ and Mn²⁺ distributions. The substitution leads to grain refinement from ~500 to ~150 nm, as well as to increased initial capacity and improved electronic conductivity. The amount of carbon coating varies with increased doping amount. The discharge curves of the LiFe_1???x Mn _x PO₄/C materials reveal a high discharge plateau corresponding to Fe^2+/3+ and no obvious plateau assigned to Mn^2+/3+, although a slight contribution of manganese is detected. However, the electrochemical performance, including the discharge capacity and cyclic performance, deteriorates with increased Mn content in the composite.     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

Far-infrared spectra of Pb1−xMnxTe alloys

Far-infrared reflectivity spectra of Pb_1−xMn_xTe (0.0001x0.1) single crystals were measured in the 10–250 cm⁻¹ range at room temperature. The analysis of the far-infrared spectra was made by a fitting procedure based on the model of coupled oscillators. In spite of the strong plasmon–LO phonon interaction, we found that the long wavelength optical phonon modes of these mixed crystals showed an intermediate one–two mode behavior.     

Low‐temperature synthesis and Raman scattering of Mn‐doped ZnO nanopowders

Nanocrystalline Mn‐doped zinc oxides Zn_1−xMn_xO (x = 0–0.10) were synthesized by the sol–gel technique at low temperature. The calcination temperature of the as‐prepared powder was found at 350 °C using differential thermal analysis. A thermogravimetric analysis showed that there is a mass loss in the as‐prepared powder till 350 °C and an almost constant mass till 800 °C. The X‐ray diffraction patterns of investigated nanopowders calcined at 350 °C correspond to the hexagonal ZnO structure without any foreign impurities. The average grain size of the nanocrystal that was observed around ∼25–40 nm from transmission electron microscopy matched well with the crystallite size calculated from the line shape of X‐ray diffraction. The chemical bonding structure in Zn_1−xMn_xO nanopowders was examined using X‐ray photoelectron spectroscopy techniques, which indicate substitution of Mn²⁺ ions into Zn²⁺ sites in ZnO lattice. Micro Raman spectroscopy confirmed the insertion of Mn ions in the ZnO host matrix, and similar wurtzite structure of Zn_1−xMn_xO (x < 10%) nanocrystals. Temperature‐dependent Raman spectra of the nanocrystals displayed suppression of luminescence and enhancement in full width at half maximum in pure ZnO nanocrystals with increase in temperature, which suggests an enhancement in particle size at elevated temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

The study of the structure and bioactivity of the B2O3 • Na2O • P2O5 system

In this study, we have investigated calcium and silicate‐free samples over a wide compositional range in the xB₂O₃·30 Na₂O·(70−x)P₂O₅ system, with 0 ≤ x ≤ 70 mol%, in order to determine the influence of the chemical composition on their structure and bioactive response in simulated body fluid. Information related to the chemical structures present in the network was obtained by means of Raman and infrared spectroscopy. For samples containing small amounts of P₂O₅, boron structures are preponderant. Upon increasing the phosphorus content, the samples' network is based on phosphate chains linked by boron groups through ‘P–O–B’ bridges. For high concentration of P₂O₅, the Q³ units form three‐dimensional network, whereas Q² units assist the chain formation. Regarding the in vitro assessment of bioactivity, the clear print of PO₄ asymmetric bending vibrations of apatite‐like layer in the 540–680 cm⁻¹ spectral domain, the scanning electron micrographs and energy dispersive x‐ray analysis spectra demonstrate that the studied borophosphate samples exhibit good bioactive response only for certain chemical compositions. More exactly, the highest bioactivity is obtained for 30% and 20% B₂O₃ (mol%) after 3 and 11 days of immersion, respectively. Therefore, the samples with 20–30 mol% boron content are valuable candidates that can be used as materials for tissue engineering applications. Copyright © 2013 John Wiley & Sons, Ltd.     

An electrochemical cell with sapphire windows for operando synchrotron X‐ray powder diffraction and spectroscopy studies of high‐power and high‐voltage electrodes for metal‐ion batteries

A new multi‐purpose operando electrochemical cell was designed, constructed and tested on the Swiss–Norwegian Beamlines BM01 and BM31 at the European Synchrotron Radiation Facility. Single‐crystal sapphire X‐ray windows provide a good signal‐to‐noise ratio, excellent electrochemical contact because of the constant pressure between the electrodes, and perfect electrochemical stability at high potentials due to the inert and non‐conductive nature of sapphire. Examination of the phase transformations in the Li_1–xFe_0.5Mn_0.5PO₄ positive electrode (cathode) material at C/2 and 10C charge and discharge rates, and a study of the valence state of the Ni cations in the Li_1–xNi_0.5Mn_1.5O₄ cathode material for Li‐ion batteries, revealed the applicability of this novel cell design to diffraction and spectroscopic investigations of high‐power/high‐voltage electrodes for metal‐ion batteries.     

Nanoscale C‐Rich SixC1−x Bus/Ring Waveguide Based Cross‐Wavelength Data Converter

The carbon‐rich silicon carbide (C‐rich Si_xC_1?x) micro‐ring channel waveguide with asymmetric core aspect is demonstrated for all‐optical cross‐wavelength pulsed return‐to‐zero on‐off keying (PRZ‐OOK) data conversion. Enhanced nonlinear optical Kerr switching enables 12‐Gbit per second data processing with optimized modulation depth. The inverse tapered waveguide at end‐face further enlarges the edge‐coupling efficiency, and the asymmetric channel waveguide distinguishes the polarization modes. To prevent data shape distortion, the bus/ring gap spacing is adjusted to control the quality factor (Q‐factor) of the micro‐ring. Designing the waveguide cross section at 500 × 350 nm² provides the C‐rich Si_xC_1?x channel waveguide to induce strong transverse electric mode (TE‐mode) confinement with a large Kerr nonlinearity of 2.44 × 10^?12 cm² W^?1. Owing to the trade‐off between the Q‐factor and the on/off extinction ratio, the optimized bus/ring gap spacing of 1400 nm is selected to provide a coupling ratio at 5–6% for compromising the modulation depth and the switching throughput. Such a C‐rich Si_xC_1?x micro‐ring with asymmetric channel waveguide greatly enhances the cross‐wavelength data conversion efficiency to favor its on‐chip all‐optical data processing applications for future optoelectronic interconnect circuits.     

Correlation of structure and spin–phonon coupling in (La,Nd) doped BiFeO3 films

We studied the effect of structural change on the spin–phonon coupling in doped BiFeO₃ (BFO) films (Bi_0.8La_0.1Nd_0.1FeO₃) grown on SrTiO₃ (001) substrate. The temperature‐dependent Raman studies show phonon anomalies in the vicinity of magnetic ordering temperature T_N owing to the spin–phonon coupling. Doped films exhibit strong anomalies in the line widths of Raman bands around T_N revealing the presence of strong spin–lattice coupling. The modification in structure as a result of A‐site doping in BFO films plays an important role in controlling the nature of spin–phonon coupling. Copyright © 2014 John Wiley & Sons, Ltd.     

Resonant Raman scattering in CdSxSe1−x nanocrystals: effects of phonon confinement,composition, and elastic strain

Optical phonon modes, confined in CdS_xSe_1−x nanocrystal (NC) quantum dots (≈2 nm in radius) grown in a glass matrix by the melting‐nucleation method, were studied by resonant Raman scattering (RRS) spectroscopy and theoretical modeling. The formation of nanocrystalline quantum dots (QDs) is evidenced by the observation of absorption peaks and theoretically expected resonance bands in the RRS excitation spectra. This system, a ternary alloy, offers the possibility to investigate the interplay between the effects of phonon localization by disorder and phonon confinement by the NC/matrix interface. Based on the concept of propagating optical phonons, which is accepted for two‐mode pseudo‐binary alloys in their bulk form, we extended the continuous lattice dynamics model, which has successfully been used for nearly spherical NCs of binary materials, to the present case. After determining the alloy composition for NCs (that was evaluated with only 2–3% uncertainty using the bulk longitudinal optical phonon wavenumbers) and the NC size (using atomic force microscopy and optical absorption data), the experimental RRS spectra were described rather well by this theory, including the line shape and polarization dependence of the scattering intensity. Even though the presence of a compressive strain in the NCs (introduced by the matrix) masks the expected downward shift owing to the phonons' spatial quantization, the asymmetric broadening of both Raman peaks is similar to that characteristic of NCs of pure binary materials. Although with some caution, we suggest that both CdSe‐like and CdS‐like optical phonon modes indeed are propagating within the NC size unless the alloy is considerably heterogeneous. Copyright © 2011 John Wiley & Sons, Ltd.     

Mechanistic study on Mo(CO)6‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes

By means of density functional theory, the Mo(CO)₆‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes was investigated. All the intermediates and transition states were optimized completely at B3LYP/6‐311++G(d,p) level (LANL2DZ(f) for Mo). Calculations indicate that the complexation of 5‐allenyl‐1‐ynes with Mo(CO)₆ occurred preferentially at the triple bond to give the complex M1 and then the complexation with the distal double bond of the allenes generates the complex M5 . In this reaction, Mo(CO)₆‐catalyzed intramolecular [2 + 2] cycloaddition is more favorable than [2 + 2 + 1] cycloaddition. The reaction pathway Mo(CO)₆ + R → M5 → T7 → M12 → M13 → T11 → M18 → P4 is the most favorable one, and the most dominant product predicted theoretically is P4 . The solvation effect is remarkable, and it decreases the reaction energy barriers. Copyright © 2011 John Wiley & Sons, Ltd.     

Toward a Raman/FORS discrimination between Art Nouveau and contemporary stained glasses from CdSxSe1 − x nanoparticles signatures

CdS_xSe_{1 − x} quantum dots received considerable attention in academic studies and as cut‐off filters and indirect‐gap semiconductors. These later compounds have also been used for artistic purposes to produce colored glass since the 1920s thanks to their bright colors. Because non‐invasive conditions are now mandatory when considering objects belonging to the cultural heritage, the use of Raman and fiber optics reflectance spectroscopy has been identified as potential ones to obtain information about the nanostructure of six samples of historical glass produced between the late 1920s and modern days. The average elemental composition of the nanocrystals has been deduced processing both optical and vibrational data, and the result arising has been compared taking into account the several factors affecting the experimental results. The diffusion of zinc inside the nanocrystals has also been questioned by the shift caused on the CdS‐ and CdSe‐like phonon band wavenumber and on the absorption edge wavelength. An investigation of the size distribution and crystallinity of CdS_xSe_{1 − x} nanoparticles has been also performed considering those parameters that are mainly influenced by the disorder of the system, such as the extent of the Urbach tail and the Raman bandwidth. Thanks to the results obtained, discrimination between the more recent glass and the older Art Nouveau ones has been verified, leading to the identification of a useful analytical protocol for conservation purposes. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrical and electrochemical behaviour of several LiFe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> solid solutions as cathode materials for lithium ion batteries

Several olivine phosphates were investigated in the last years as cathode materials for secondary lithium ion batteries. Among these compounds, LiFe _x Co_1 − x PO₄ solid solutions might be interesting candidates because they should combine the high potential value of Co³⁺/Co²⁺ (higher than 4.5 V vs Li⁺/Li) with the relatively high charge–discharge rate of LiFePO₄. Solid solutions were prepared by solid-state route and characterised by X-ray powder diffraction, cyclic voltammetry, impedance spectroscopy and the Hebb–Wagner method. The results show that also low amount of iron induces high electronic conductivity in the solid solutions.     

Temperature‐dependent Raman scattering in ferroelectric Bi4−xNdxTi3O12(x = 0, 0.5, 0.85) single crystals

The temperature‐dependent Raman spectra of ferroelectric Bi_4−xNd_xTi₃O₁₂(x = 0, 0.5, 0.85) single crystals were recorded from 100 to 800 K. It was found that there is a critical Nd content x₀ between 0.5 and 0.85. The Nd³⁺ ions prefer to replace Bi³⁺ ions in pseudo‐perovskite layers when x < x₀, while they might begin to incorporate into (Bi₂O₂)²⁺ layers when x ≥ x₀. Nd substitution leads to a decrease in the ferroelectric–paraelectric transition temperature (T_c). A monoclinic distortion of orthorhombic structure occurs in Bi₄Ti₃O₁₂ crystals at temperatures below 200 K. Copyright © 2009 John Wiley & Sons, Ltd.