First-principles study of LiMPO4 compounds (M=Mn,Fe, Co,Ni) as electrode material for lithium batteries

The intercalation voltages of cathode materials for rechargeable lithium-ion batteries are calculated for lithium-orthophosphate oxides LiMPO₄ (M=Mn, Fe, Co and Ni) using density-functional theory within the local-density (LDA) and LDA?+?U approximations. We show that the LDA?+?U approximation is able to reproduce the experimental volumes as well as the experimentally observed magnetic structures of the lithiated and non-lithiated compounds for which LDA qualitatively fail. Moreover, we find that, using the LDA?+?U approach, the experimental evolution of the lithium intercalation voltage along the series can be reproduced accurately.     

Molecular materials derived from MPc (M=Fe, Pb, Co) and 1,8-dihydroxiantraquinone thin films: Formation, electrical and optical properties

Semiconductor-like thin films were grown using metallic phthalocyanines (MPc) (M=Fe, Pb, Co) and 1,8 dihydroxiantraquinone as initial compounds. The morphology of the deposited films was studied by using scanning electron microscopy and atomic force microscopy. The powder and thin-film samples of the synthesized materials, deposited by vacuum thermal evaporation, showed the same intra-molecular bonds as in IR spectroscopy studies, which suggests that the evaporation process does not alter these bonds. The optical band gap values of C₆₀H₂₈N₈O₈Fe, C₆₀H₂₈N₈O₈Pb and C₆₀H₂₈N₈O₈Co calculated from the absorption coefficient were found to be 1.60, 1.89 and 1.75 eV, respectively, arising from non-direct transitions. The effect of temperature on conductivity was also measured in these samples. It was found that the temperature-dependent electric current in all cases showed a semiconductor behavior with conductivities in the order of 10⁻⁶ Ω⁻¹ cm⁻¹ where the highest value corresponded to the cobalt material. The linear dependence observed in the films implies only one type of conduction mechanism in all cases, with mean activation energies of the order of 1.55, 1.77 and 1.50 eV for iron, lead and cobalt-based thin films, respectively.     

新型锂离子电池正极材料LiMPO_4(M=Fe,Mn)的谱学和电化学研究

采用固相反应与液相反应,合成了新型锂离子电池正极材料LiMPO4(M=Fe,Mn)。粉末X光衍射表明材料均为纯相。对材料的显微拉曼光谱和红外光谱进行了研究和指认。循环伏安研究表明,含锂磷酸盐是一类有潜力的锂离子电池正极材料。     

Dielectric relaxation spectroscopy of phlogopite mica

An in-depth investigation of the dielectric characteristics of annealed phlogopite mica has been conducted in the frequency range 0.1 Hz–10 MHz and over the temperature range 653–873 K through the framework of dielectric permittivity, electric modulus and conductivity formalisms. These formalisms show qualitative similarities in relaxation processes. The frequency dependence of the M″ and dc conductivity is found to obey an Arrhenius law and the activation energy of the phlogopite mica calculated both from dc conductivity and the modulus spectrum is similar, indicating that same type of charge carriers are involved in the relaxation phenomena. The electric modulus and conductivity data have been fitted with the Havriliak–Negami function. Scaling of M′, M″, ac conductivity has also been performed in order to obtain insight into the relaxation mechanisms. The scaling behaviour indicates that the relaxation describes the same mechanism at different temperatures. The relaxation mechanism was also examined using the Cole–Cole approach. The study elaborates that the investigation regarding the temperature and frequency dependence of dielectric relaxation in the phlogopite mica will be helpful for various cutting edge applications of this material in electrical engineering.     

Crystal structure,ionic conductivity and dielectric relaxation studies in the (C5H10N)2BiBr5 compound

The synthesis and crystal structure of the bis (3-dimethylammonium-1-propyne) pentabromobismuthate(III) salt are given in the present paper. After an X-ray investigation, it has been shown that the title compound crystallizes at 298 K in a centrosymmetric monoclinic system, in the space group C₂/c with the following lattice parameters a=12.9034(3) Å, b=19.4505(6) Å, c=8.5188(2) Å, β=102.449(2). Not only were the impedance spectroscopy measurements of (C₅H₁₀N)₂BiBr₅ carried out from 209 Hz to 5 MHz over the temperature range of 318 K–373 K, but also its ac conductivity evaluated. Besides, the dielectric relaxation was examined using the modulus formalism. Actually, the near values of activation energies obtained from the impedance and modulus spectra confirms that the transport is of an ion hopping mechanism, dominated by the motion of the H⁺ ions in the structure of the investigated material.     

A novel method to synthesize LiVPO4F/C composite materials and its electrochemical Li-intercalation performances

Triclinic LiVPO₄F/C composite materials were prepared from a sucrose-containing precursor by one-step heat treatment. As-prepared composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurements. XRD studies showed that Li₃PO₄ impurity phase appeared in the sample synthesized at 600 °C and pure LiVPO₄F samples could be obtained when the sintered temperature was higher than 650 °C. The sample synthesized at 650 °C presents the highest initial discharge capacity of 132 mAh g⁻¹ at 0.2 C rate, and exhibited better cycling stability (124 mAh g⁻¹ at 50th cycle at 0.2 C rate) and better rate capability (100 mAh g⁻¹ at 50th cycle under 1 C rate) in the voltage range 3.0-4.4 V.     

Preparation and efficient visible light-induced photocatalytic activity of m-BiVO4 with different morphologies

The monoclinic scheelite BiVO₄ crystals with peanut-like, oval, twin-quadrangle and twin-four-pointed star morphologies were synthesized via a facile one step hydrothermal method by using sodium citrate as the chelating agent. The X-ray diffraction and scanning electron microscopy were employed to elucidate the structures and mophologies of the as-prepared BiVO₄ samples. The results showed that the formation of m-BiVO₄ with different morphologies relied on the pH value of the precursor solution. The band gaps values (E_g) of all the BiVO₄ samples were around 2.37–2.45 eV according to the UV–vis diffuse reflectance spectrum, which indicated that samples could strongly absorb in the visible light region. The photocatalytic activities of BiVO₄ crystals were evaluated by degradation of MB in aqueous solution under artificial solar-light. The BiVO₄ samples obtained at different pH values showed different photocatalytic activities during the sunlight-driven photodegradation of methylene blue (MB). The sample with peanut-like-shape prepared at pH=1 exhibited the highest activity, and the photocatalytic conversion could reach above 90% after 3 h of irradiation. The result suggested that m-BiVO₄ with peanut-like-shape could be used as an effective photocatalyst in practical application for organic pollutants degradation.     

Digital and analog memory devices based on 2D layered MPS_3 (M= Mn,Co, Ni) materials

We demonstrate digital and analog devices with an Ag/MPS_3/Au structure based on layered MPS_3(M=Mn,Co,Ni)2 D materials.All devices show the bipolar behavior of resistive switching.In addition,Ag/MnPS3/Au and Ag/NiPS_3/Au devices show synaptic characteristics of potentiation and depression.The digital and analog characteristics of resistance states enable Ag/MPS_3/Au devices to work as both binary memory and artificial synapse devices.The Ag/MPS_3/Au memory devices are promising for applications of flexible eye-like and brain-like systems on a chip when they are integrated with photodetectors and FETs composed of full MPS_3 materials.     

Frequency dependence of ionic conductivity and dielectric relaxation studies in Na3H(SO4)2 single crystal

Electrical impedance measurements of Na₃H(SO₄)₂ were performed as a function of both temperature and frequency. The electrical conductivity and dielectric relaxation have been evaluated. The temperature dependence of electrical conductivity reveals that the sample crystals transformed to the fast ionic state in the high temperature phase. The dynamical disordering of hydrogen and sodium atoms and the orientation of SO₄ tetrahedra results in fast ionic conductivity. In addition to the proton conduction, the possibility of a Na⁺ contribution to the conductivity in the high temperature phase is proposed. The frequency dependence of AC conductivity is proportional to ω^s. The value of the exponent, s, lies between 0.85 and 0.46 in the room temperature phase, whereas it remains almost constant, 0.6, in the high-temperature phase. The dielectric dispersion is examined using the modulus formalism. An Arrhenius-type behavior is observed when the crystal undergoes the structural phase transition.     

Electrical and magnetic features in the perovskite-type system Y(Co, Mn)O3

Electrical and magnetic properties of the perovskite-type solid solution YCo_xMn_1−xO₃ (x=0.20-0.60) have been studied at different temperatures and magnetic fields. Electrical conductivity measurements show a semi-conducting behaviour throughout the solid solution. The room-temperature conductivity increases with the Co content up to 33 at.%, and then decreases. The effective moment in the paramagnetic state shows a non-monotonic decrease, when the Co content increases. In the ordered state, the behaviour at low or null magnetic fields corresponds to a spin-glass or antiferromagnetic system, with a transition temperature, which raises with the Co content (up to 50 at.% Co), and then decreases. At high fields, all the solid solutions show a ferromagnetic behaviour, although there is a marked difference in their ferromagnetic cycles, at a threshold value of 33 at.% Co.     

Synthesis and characterization of spinel type high-power cathode materials Li MxMn2−x O4 (M=Ni,Co, Cr)

The transition metal-doped spinel cathode materials, LiM_0.5Mn_1.5O₄ (M=Ni. Co, Cr) were prepared by solid-state reaction. The structure and morphology of the samples were investigated by X-ray diffraction, Rietveld refinement and scanning electron microscopy (SEM). The diffraction peaks of all the samples corresponded to a single phase of cubic spinel structure with a space group Fd3m. Field-emission SEM shows octahedron like shapes and the primary particles size was between 500 nm and 2 μm. Oxidation states of Ni, Co and Cr were found to be 2+, 2+ and 3+ as revealed by X-ray photoelectron spectroscopy. During discharging, LiNi_0.5Mn_1.5O₄ and LiCo_0.5Mn_1.5O₄ sample shows more than 130 mAh/g between 3.5 and 5.2 V at a current density of 0.65 mA/cm² and well developed plateau around 5 V, respectively.     

Tin-doped spinel-related oxides of composition M3O4 (M = Mn, Fe, Co)

Tin-doped compounds of spinel-related M₃O₄ (M = Fe, Mn, Co) have been studied by ¹¹⁹Sn and ⁵⁷Fe Mössbauer spectroscopy in the temperature range of 20–600 K. The ¹¹⁹Sn Mössbauer spectra recorded down to 20 K from the non-iron-containing compounds of Co₃O₄ and Mn₃O₄ contained only doublets showing no transfer of magnetic properties from cobalt or manganese to the dopant tin ions. In contrast, the tin-doped-(FeCo)₃O₄ and (FeMn)₃O₄ gave ¹¹⁹Sn and ⁵⁷Fe Mössbauer spectra, which showed magnetic hyperfine interactions. The Curie temperature has been estimated for the former sample.     

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Nano-structured LiVPO₄F/Ag composite cathode material has been successfully synthesized via a sol–gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO₄F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO₄F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO₄F material exhibits high discharge capacity, good cycle performance (108.5 mAh g⁻¹ after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g⁻¹ for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (R_ct) of LiVPO₄F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO₄F for lithium-ion batteries cathode material.     

On the power-law behavior of the AC conductivity of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

A power law used to describe the AC conductivity from 299 to 393 K of the mixed crystal (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 led to fractional exponent values ranging from 1.08 to 0.91, depending on structural changes induced on temperature variation [B. Louati, M. Gargouri, K. Guidara and T. Mhiri, J. Phys. Chem. Solids 66 (2005) 762]. In the present note, we suggest that the fractional law exhibits features of lattice relaxation. Despite the structural changes, the parameters of the power law are mutually interconnected to yield a temperature independent phenomenon. Such behavior is probably of general validity and characterizes the universal fractional dispersion of the AC conductivity, as it was also observed in glasses of different composition.     

Two potassium rare-earth polyphosphates KLn(PO3)4 (Ln=Ce, Eu): Structural, optical, and electronic properties

Two potassium rare-earth polyphosphate single-crystals KLn(PO₃)₄ (Ln=Ce (1), Eu (2)) have been synthesized by the high-temperature solution reaction and characterized by single-crystal X-ray diffraction. The two isostructural compounds crystallize in the monoclinic system with space group P2₁, and all cell parameters shrink with the decrease of Ln³⁺ ion radius. The main structural feature is (PO₃)₄⁴⁻ wavy chains and infinite tunnels delimited by LnO₈ and KO₈ polyhedra. The energy band structures, density of states (DOS), and optical response functions for 1 have been calculated with the density functional theory (DFT) method, and the dielectric functions and refractive indices have been discussed. The measurements of the absorption and emission spectra show that 1 exhibits the ultraviolet emissions, and 2 displays the characteristic yellow-red emissions of Eu³⁺.     

Effect of reaction systems and surfactant additives on the morphology evolution of hydroxyapatite nanorods obtained via a hydrothermal route

Well-dispersed hydroxyapatite (HA) nanorods with different morphologies were synthesized by a hydrothermal method in oleic acid, ethanol and water reaction system, and the surfactant assisted modifications effect was also comparatively studied. The structure and morphology of samples were characterized using X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM), respectively. The effect of reaction systems and surfactant additives on the morphology evolution of HA nanorods were discussed in detail. The results showed that the controlled experimental conditions in the systems, such as the content ratio of oleic acid/ethanol, pH value and the content ratio of Ca/P source had an significant effect on the morphology evolution of as-prepared HA nanorods. Further, the selected surfactant additives, such as cetyltriethylammnonium bromide (CTAB), sodium dodecyl sulfate (K12) also play an important role in the formation of the uniform morphology of HA nanorods. Some possible formation mechanisms of the HA nanorods in the present reaction systems is proposed.     

Superparamagnetic-like behavior and spin-orbit coupling in (Co,Zn)RE4W3O16 tungstates (RE=Nd, Sm, Eu, Gd, Dy and Ho)

Magnetic susceptibility measurements carried out on (Co,Zn)RE₄W₃O₁₆ compounds revealed a disordered state of magnetic moments above 4.2 K for all compounds under study, and a weak response to magnetic field and temperature for ZnSm₄W₃O₁₆ and ZnEu₄W₃O₁₆ samples. The temperature independent component of magnetic susceptibility has a negative value for ZnGd₄W₃O₁₆ and a positive one for the rest of the tungstates, indicating a domination of van Vleck contribution. The magnetization isotherms of majority of the tungstates under study revealed both spontaneous magnetic moments and hysteresis characteristic for the superparamagnetic-like behavior with blocking temperature T_B∼30 K, except for ZnEu₄W₃O₁₆. Fitting procedure of the Landé factor revealed that the stronger the orbital contribution, the weaker the superparamagnetic effect, namely for ZnRE₄W₃O₁₆. In case of CoRE₄W₃O₁₆ a significant participation of the Co²⁺ moment in the spontaneous magnetization was observed.     

Electronic Structure and Quadrupole Interactions in Promising Cathode Materials NaxMy(MoO4)3, M = Mn,Fe, Co,and Ni

Physics of the Solid State - The electronic structure and the magnetic properties of molybdates NaxMy(MoO4)3 (M = Mn, Fe, Co, and Ni) which are promising materials for sodium batteries have been...     

Mössbauer and magnetic studies of MFe2O4(M = Co, Ni) nanoparticles

Nanocrystalline MFe₂O₄ (M?=?Co, Ni) particles are synthesized by citrate precursor technique. Mössbauer and magnetic studies are carried out with the CoFe₂O₄ samples having particle sizes of 9, 14 and 30 nm and the NiFe₂O₄ samples having particle sizes of 9, 21 and 30 nm. The intrinsic magnetic parameters are found to vary with the particle size. The magnetic interactions and cation distribution present in these systems influence the room temperature Mössbauer parameters. Ferrimagnetic sextets are observed for all the different particle sizes. The observed reduction of the magnetic hyperfine field values with the decrease in the size of MFe₂O₄ particles are attributed to the intrinsic size effect and the canted spin structure at the surface of the nanoparticles.