Jahn-Teller transition in Al doped LiMn2O4 spinel

Al-doped lithium manganese spinels, with starting composition Li_1.02Al_xMn_1.98−xO₄ (0.00<x≤0.06), are investigated to determine the influence of the Al³⁺ doping on the Jahn-Teller (J-T) cooperative transition temperature T_J-T. X-ray powder diffraction (XRPD), nuclear magnetic resonance, electron paramagnetic resonance, conductivity and magnetic susceptibility data are put into relation with the tetrahedral and octahedral occupancy fraction of the spinel sites and with the homogeneous distribution of the Al³⁺ ions in the spinel phase. It is observed that Al³⁺ may distribute between the two cationic sublattices. The J-T distortion, associated with a drop of conductivity near room temperature in the undoped sample, is shifted towards lower temperature by very low substitution. However, for x>0.04 T_J-T it increases with increasing x, as clearly evidenced in low temperature XRPD observations. A charge distribution model in the cationic sublattice, for Al substitution, is proposed to explain this peculiar behavior.     

Electrical and electrochemical properties of molten salt-synthesized Li4Ti5−xSnxO12 (x=0.0, 0.05 and 0.1) as anodes for Li-ion batteries

Submicron-sized polyhedral Li₄Ti_5−xSn_xO₁₂ (x=0.0, 0.05, and 0.1) materials were successfully prepared by a single-step molten salt method. The structural, morphological, transport and electrochemical properties of the Li₄Ti_5−xSn_xO₁₂ were studied. X-ray diffraction patterns showed the formation of a cubic structure with a lattice constant of 8.31 Å, and the addition of dopants follows Vegard's law. Furthermore, FT-IR spectra revealed symmetric stretching vibrations of octahedral groups of MO₆ lattice in Li₄Ti₅O₁₂. The formation of polyhedral submicron Li₄Ti_5−xSn_xO₁₂ particles was inferred from FE-SEM images, and a particle size reduction was observed for Sn-doped Li₄Ti₅O₁₂. The chemical composition of Ti, O and Sn was verified by EDAX. The DC electrical conductivity was found to increase with increasing temperature, and a maximum conductivity of 8.96×10⁻⁶ S cm⁻¹ was observed at 200 °C for Li₄Ti₅O₁₂. The galvanostatic charge–discharge behavior indicates that the Sn-doped Li₄Ti₅O₁₂ could be used as an anode for Li-ion batteries due to its enhanced electrochemical properties.     

Characteristics of spherical-shaped Li4Ti5O12 anode powders prepared by spray pyrolysis

Spherical-shaped Li₄Ti₅O₁₂ anode powders with a mean size of 1.5 μm were prepared by spray pyrolysis. The precursor powders obtained by spray pyrolysis had no peaks of crystal structure of Li₄Ti₅O₁₂. The powders post-treated at temperatures of 800 and 900 °C had the single phase of spinel Li₄Ti₅O₁₂. The powders post-treated at a temperature of 1000 °C had main peaks of the Li₄Ti₅O₁₂ phase and small impurity peaks of Li₂Ti₃O₇. The spherical shape of the precursor powders was maintained after post-treatment at temperatures below 800 °C. The Brunauer-Emmett-Teller (BET) surface areas of the Li₄Ti₅O₁₂ anode powders post-treated at temperatures of 700, 800 and 900 °C were 4.9, 1.6 and 1.5 m²/g, respectively. The initial discharge capacities of Li₄Ti₅O₁₂ powders were changed from 108 to 175 mAh/g when the post-treatment temperatures were changed from 700 to 1000 °C. The maximum initial discharge capacity of the Li₄Ti₅O₁₂ powders was obtained at a post-treatment temperature of 800 °C, which had good cycle properties below current densities of 0.7 C.     

Dielectric properties of lanthanum-doped CaCu3Ti4O12 synthesized by semi-wet route

Effect of La³⁺ doping at Ca²⁺ site in CaCu₃Ti₄O₁₂ has been examined. Compositions with x=0.10, 0.20 and 0.30 were synthesized in the system Ca_(1−3x/2)La_xCu₃Ti₄O₁₂ by semi-wet method. Powder X-ray diffraction confirmed the formation of monophasic compounds. The structure remains cubic similar to CaCu₃Ti₄O₁₂. Lattice parameter increases slightly with increasing La³⁺ concentration. Microstructure has been studied using scanning electron microscopy (SEM). Average grain size is in the range 2-4 μm for various compositions. Energy-dispersive spectrometer (EDS) studies confirm the stoichiometry of the synthesized materials. Dielectric constant, dielectric loss and conductivity of the samples decrease with increasing lanthanum concentrations.     

Electrical properties of neodymium doped CaBi4Ti4O15 ceramics

Neodymium doped bismuth layer structure ferroelectrics (BLSFs) ceramics CaBi_4−xNd_xTi₄O₁₅ (x=0, 0.25, 0.50, 0.75) were prepared by solid-state reaction method. X-ray diffraction pattern showed that single phase was formed when x=0-0.75. The refined lattice parameters showed that a (b) axes decrease at x=0.25 and increase with more Nd³⁺ dopant. The effects of Nd³⁺ doping on the dielectric and ferroelectric properties of CaBi₄Ti₄O₁₅ ceramics are studied. Nd³⁺ dopant decreased the Curie temperature linearly, and the dielectric loss, tan δ, as well. The remnant polarization of Nd³⁺ doped CaBi₄Ti₄O₁₅ ceramics was increased by 80% at x=0.25, while more Nd³⁺ dopant decreased the remnant polarization. CaBi_3.75Nd_0.25Ti₄O₁₅ ceramics had the largest piezoelectric constant d₃₃. The structure and properties of CaBi_4−xNd_xTi₄O₁₅ ceramics showed that Nd³⁺ may occupy different crystal locations when Nd³⁺ content x is less than 0.25 and more than 0.50.     

Electrostatic spray deposition of spinel Li4Ti5O12 thin films for rechargeable lithium batteries

Spinel Li₄Ti₅O₁₂ thin films are important for the fabrication of rechargeable lithium microbatteries. Porous thin films of Li₄Ti₅O₁₂ were prepared by electrostatic spray deposition (ESD) technique with lithium acetate and titanium butoxide as the precursors. The structures of these films were analyzed by scanning electron microscopy and X-ray diffraction. Coin-type cells with a liquid electrolyte were made with the Li₄Ti₅O₁₂ films against metallic lithium. Their electrochemical performance was investigated by means of galvanostatic cell cycling, cyclic voltammetry and Ac impedance spectroscopy. It was found that pure spinel phase of Li₄Ti₅O₁₂ was obtained. After annealing at the optimal temperature of 700 °C, the films can deliver a reversible specific capacity of about 150 mAh/g with excellent capacity retention after 70 cycles. Their electrochemical characteristics were quite comparable with those of the Li₄Ti₅O₁₂ laminate electrodes containing carbon black additive.     

Effect of interface states associated with transitional nanophase precipitates in the enhancement of red emission from SrAl12O19:Pr by Ti incorporation

SrAl₁₂O₁₉:Pr³⁺, Ti⁴⁺ phosphor suitable for field emission displays is prepared by the wet chemical gel-carbonate method and the mechanism of enhancement in red photoluminescence (PL) intensity with Ti⁴⁺ therein has been investigated. The PL spectra of Pr³⁺ show both ¹D₂-³H₄ and ³P₀-³H₆ emission in the red region with very weak intensity when excited at 355 nm. The emission intensity has increased by about 100 times at room temperature in the compositional range SrAl_12−xTi_xO_19+x/2:Pr³⁺, with 0.1≤x≤0.3 in comparison to Ti-free SrAl₁₂O₁₉:Pr³⁺. TEM investigations show the presence of exsolved nanophase of SrAl₈Ti₃O₁₉, the precipitation of which is preceded by the presence of defect centers at the interfacial regions between the semicoherent transient phase and the parent SrAl₁₂O₁₉ matrix. The presence of transitional nanophase and the associated defects modify the excitation-emission process by way of formation of electronic sub-levels at lower energy (3.5 eV) than the band gap of SrAl₁₂O₁₉ (∼7 eV) followed by non-resonance energy transfer to Pr³⁺ level, leading to magnetic-dipole related red emission with enhanced intensity. The PL intensity of Pr³⁺ decreases at high Ti⁴⁺ concentrations (x>0.3) due to higher extent of segregation of non-emissive SrAl₈Ti₃O₁₉:Pr³⁺ phase.     

Electrochemical behaviour of nano-sized spinel LiMn2O4 and LiAlxMn2−xO4 (x=Al: 0.00-0.40) synthesized via fumaric acid-assisted sol-gel synthesis for use in lithium rechargeable batteries

Pristine spinel LiMn₂O₄ and LiAl_xMn_2−xO₄ (x=Al: 0.00-0.40) with sub-micron sized particles have been synthesized using fumaric acid as chelating agent by sol-gel method. The synthesized samples were subjected to thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and cyclic voltammetry (CV) and galvanostatic cycling studies. The TGA curve of the gel shows several weight-loss regions stepwise amounting to 55% till 800 °C attributed to the decomposition of the precursors. Calcination to higher temperatures (800 °C) yields pure-phase spinel (LiAl_xMn_2−xO₄), as it is evident from the high-intensity XRD reflections matching to the standard pattern. SEM and TEM studies confirm that the synthesized grains are of uniform regular surface morphology. FT-IR studies show stretching and bending vibration bands of Li-O, Li-Al-Mn-O. LiAl_0.1Mn_1.90O₄ spinel was found to deliver discharge capacity of 139 mA h/g during the first cycle with columbic efficiency of 97%. LiAl_0.1Mn_1.90O₄ spinel exhibits the high cathodic peak current indicating better electrochemical performance. Low doping (x=0.1) of Al is found to be beneficial in stabilizing the spinel structure.     

Effects of vanadium doping on structure and electrical properties of SrBi4Ti4O15 thin films

The effects of vanadium(V) doping into SrBi₄Ti₄O₁₅ (SBTi) thin films on the structure, ferroelectric, leakage current, dielectric, and fatigue properties have been studied. X-ray diffraction result showed that the crystal structure of the SBTi thin films with and without vanadium is the same. Enhanced ferroelectricity was observed in the V-doped SrBi₄Ti₄O₁₅ (SrBi_4−x/3Ti_4−xV_xO₁₅, SBTiV-x (x = 0.03, 0.06, and 0.09)) thin films compared to the pure SrBi₄Ti₄O₁₅ thin film. The values of remnant polarization (2P_r) and coercive field (2E_c) of the SBTiV-0.09 thin film capacitor were 40.9 μC/cm² and 105.6 kV/cm at an applied electric field of 187.5 kV/cm, respectively. The 2P_r value is over five times larger than that of the pure SBTi thin film capacitor. At 100 kHz, the values of dielectric constant and dielectric loss were 449 and 0.04, and 214 and 0.06 for the SBTiV-0.09 and the pure SBTi thin film capacitors, respectively. The leakage current density of the SBTiV-0.09 thin film capacitor measured at 100 kV/cm was 6.8 × 10⁻⁹ A/cm², which is more than two and a half orders of magnitude lower than that of the pure SBTi thin film capacitor. Furthermore, the SBTiV-0.09 thin film exhibited good fatigue endurance up to 10¹⁰ switching cycles. The improved electrical properties may be related to the reduction of internal defects such as bismuth and oxygen vacancies with changes in the grain size by doping of vanadium into SBTi.     

Influence of Al2O3 additions on crystallization mechanism and conductivity of Li2O-Ge2O-P2O5 glass-ceramics

The crystallization mechanism and conductivity of lithium aluminum germanium phosphate [LAGP] glass-ceramics fabricated from Li_1+xAl_xGe_2−x(PO₄)₃ (x=0.0-0.7) glass system were investigated as a function of Al₂O₃ additions. A non-isothermal analysis was performed to study the crystallization behavior of LAGP glass-ceramics at various heating rates (5-25K min⁻¹) by the Kissinger equation and the Augis-Bennett equation, illustrating volume crystallization for the glass-ceramics. The crystal identification and microstructure in glass-ceramics containing various Al₂O₃ contents were analyzed by means of XRD and FESEM. The main phase of the glass-ceramics was found to be LiGe₂(PO₄)₃, with AlPO₄ as the impurity phase. Additionally the highest total ionic conductivity (5.8×10⁻⁴ S/cm) at room temperature was obtained when x=0.5 for Li_1+xAl_xGe_2−x(PO₄)₃ (x=0.0-0.7) glass-ceramics, suggesting that it was a promising electrolyte for practical application in all-solid-state lithium batteries.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

Li0.5Fe2.5−xMnxO4 ferrite sintered from microwave-induced combustion

Li_0.5Fe_2.5−xMn_xO₄ (0≦x≦1.0) powders with small and uniformly sized particles were successfully synthesized by microwave-induced combustion, using lithium nitrate, ferric nitrate, manganese nitrate and carbohydrazide as the starting materials. The process takes only a few minutes to obtain as-received Mn-substituted lithium ferrite powders. The resultant powders annealed at 650 ^°C for 2 h and were investigated by thermogravimeter/differential thermal analyzer (TG/DTA), X-ray diffractometer (XRD), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), and thermomagnetic analysis (TMA). The results revealed that the Mn content were strongly influenced the magnetic properties and Curie temperature of Mn-substituted lithium ferrite powder. As for sintered Li_0.5Fe_2.5−xMn_xO₄ specimens, substituting an appropriate amount of Mn for Fe in the Li_0.5Fe_2.5−xMn_xO₄ specimens markedly improved the complex permeability and loss tangent.     

Green and red up-conversion emissions of Er-Yb-codoped Al2O3 powders prepared by the nonaqueous sol-gel method

The 1 mol% Er³⁺- and 0-20 mol% Yb³⁺-codoped Al₂O₃ powders have been prepared by the nonaqueous sol-gel process using aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium and ytterbium nitrate as dopant under isopropanol environment. The two crystalline types of doped Al₂O₃, γ and θ, and a stoichiometric compound, (Yb,Er)₃Al₅O₁₂, were obtained for all the Er³⁺-Yb³⁺-codoped Al₂O₃ powders at the sintering temperature of 1000 °C. The maximal intensity of both the green and red up-conversion emissions centered at about 523, 545, and 660 nm was observed for the 1 mol% Er³⁺- and 10 mol% Yb³⁺-codoped Al₂O₃ powders. The intensity ratio of the red to green up-conversion emission (I_red/I_green) increased with increasing the Yb³⁺ doping concentration for the Er³⁺-Yb³⁺-codoped Al₂O₃ powders. Furthermore, the intensity ratio of the green up-conversion emission at about 523 to 545 nm (I₅₂₃/I₅₄₅) was proportional to the Yb³⁺ doping concentration and pump electric current, which was associated with the elevated temperature of powders.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.     

Effects of dopant on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials

The effects of dopant on the electrochemical properties of spinel-type Li_3.97M_0.1Ti_4.94O₁₂ (M = Mn, Ni, Co) and Li_(4-x/3)Cr_xTi_(5-2x/3)O₁₂(x = 0.1, 0.3, 0.6, 0.9, 1.5) were systematically investigated. Charge-discharge cycling were performed at a constant current density of 0.5 mA/cm² between the cut-off voltages of 3.0 and 1.0 V, the experimental results showed that Cr³⁺ dopant improved the reversible capacity and cycling stability over the pristine Li₄Ti₅O₁₂. The substitution of the Mn³⁺ and Ni³⁺ slightly decreased the capacity of the Li₄Ti₅O₁₂. Dopants such as Co³⁺ to some extent worsened the electrochemical performance of the Li₄Ti₅O₁₂.     

Properties of vanadium-doped SrBi4Ti4O15 ferroelectric ceramics

Using the standard solid-state reaction method, several vanadium-doped ferroelectric ceramics of type SrBi_4−x/3Ti_4−xV_xO₁₅ (SBTV−x) were synthesized. The vanadium doping content, x, rangs from 0.00 to 0.06. The crystal structure of SrBi₄Ti₄O₁₅ is not affected by V-doping. The electric breakdown voltage of the samples increases with V content. Meanwhile, V-doping results in a notable enlargement of remnant polarization (2P_r). The 2P_r of STBV−0.03 reaches a very large value, which is over 50 μC/cm² and is nearly twice greater than that at zero doping. The Curie temperatures of V-doped samples decrease slightly in comparison with that of SrBi₄Ti₄O₁₅. V-doping can improve the electric properties of SrBi₄Ti₄O₁₅ without sacrificing its thermal stableness.     

Molten salt synthesis of Li1 + x (Ni0.5Mn0.5)1 − xO2 as cathode material for Li-ion batteries

Li_1 + x(Ni_0.5Mn_0.5)_1 − xO₂ cathode material for Li-ion batteries has been prepared by a molten salt method using Li₂CO₃ salt. The influences of synthetic temperature and time have been intensively investigated. It is easy to obtain materials with a hexagonal α-NaFeO₂ structure except broad peaks between 20° and 25°. Nickel in Li_1 + x(Ni_0.5Mn_0.5)_1 − xO₂ is oxidized to a trivalent state while manganese maintained a tetravalent state. It is found that the discharge capacities of all samples increase with cycling. The sample prepared at 850 °C for 5 h has a discharge capacity of 130 mAh g^− 1 between 2.5 and 4.5 V versus V_Li+/Li at a specific current of 0.13 mA cm^− 2 after 50 cycles at 25 °C.     

Properties of vanadium-doped SrBi4Ti4O15 ferroelectric ceramics

Using the standard solid-state reaction method, several vanadium-doped ferroelectric ceramics of type SrBi_4−x/3Ti_4−xV_xO₁₅ (SBTV-x) were synthesized. The vanadium doping content, x, ranges from 0.000 to 0.06. The crystal structure of SrBi₄Ti₄O₁₅ is not affected by V-doping. The electric breakdown voltage of the samples increases with V content. Meanwhile, V-doping results in a notable enlargement of remnant polarization (2P_r). The 2P_r of STBV-0.03 reaches a very large value, which is over 50 μC/cm² and is nearly twice greater than that at zero doping. The Curie temperatures of V-doped samples decrease slightly in comparison with that of SrBi₄Ti₄O₁₅. V-doping can improve the electric properties of SrBi₄Ti₄O₁₅ without sacrificing its thermal stableness.     

Spinel-type solid solutions involving Mn and Ti:Crystal chemistry, magnetic and electrochemical properties

This study reports the structural and magnetic properties of spinel systems Li₄Mn_5−xTi_xO₁₂ (“4-5-12” series) and LiNi_0.5Mn_1.5−xTi_xO₄ (“LNMTO” series), both based on Mn⁴⁺ substitution by Ti⁴⁺. Intermediate compositions covering the whole range of compositions (0≤x≤5 and 0≤x≤1.5, respectively) were prepared by solid state reaction. The 4-5-12 system forms a continuous spinel solid solution, whereas the spinel phase range in LNMTO stops before the end member “LiNi_0.5Ti_1.5O₄”, which is multi-phased with a major hexagonal phase component. Cell parameters and (Mn,Ti)-O distances increase monotonically with titanium content in both series. In the LNMTO series, the end member LiNi_0.5Mn_1.5O₄ is known to form a superstructure with Ni/Mn cation ordering. Neutron diffraction and Raman spectroscopy show that this order is lost when Ti is substituted, even at low level (x=0.15). The LNMTO crystal chemistry is also complicated by the presence of partial cation inversion, and the presence of a secondary rocksalt-type phase that modifies the spinel stoichiometry. Magnetic properties are characterized by a competition between ferromagnetic and antiferromagnetic interactions; no magnetic ordering is achieved, in agreement with B-site cation frustration and disorder. Electrochemical measurements show that the Ti^3+/4+ and Mn^3+/4+ redox couples behave independently in the 4-5-12 series, and that titanium decreases the high-potential electrochemical redox activity of LNMTO because of its blocking character for electron transfer to and from the nickel sites in the spinel structure.     

Structural and electrical transport properties of ZnxFe3−xO4 thin film deposited on Si (1 1 1) by pulsed-laser deposition

Polycrystalline thin films of Fe_3−xZn_xO₄ (x = 0.0, 0.01 and 0.02) were prepared by pulsed-laser deposition technique on Si (1 1 1) substrate. X-ray diffraction studies of parent as well as Zn doped magnetite show the spinel cubic structure of film with (1 1 1) orientation. The order–disorder transition temperature for Fe₃O₄ thin film with thickness of 150 nm are at 123 K (Si). Zn doping leads to enhancement of resistivity by Zn²⁺ substitution originates from a decrease of the carrier concentration, which do not show the Verwey transition. The Raman spectra for parent Fe₃O₄ on Si (1 1 1) substrate shows all Raman active modes for thin films at energies of T_2g¹, T_2g³, T_2g², and A_1g at 193, 304, 531 and 668 cm⁻¹. It is noticed that the frequency positions of the strongest A_1g mode are at 668.3 cm⁻¹, for all parent Fe₃O₄ thin film shifted at lower wave number as 663.7 for Fe_2.98Zn_0.02O₄ thin film on Si (1 1 1) substrate. The integral intensity at 668 cm⁻¹ increased significantly with decreasing doping concentration and highest for the parent sample, which is due to residual stress stored in the surface.