Preparation, characterization and electrical conductivity studies of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics

Several compositions of NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb_1−xGd_xZr₂O₇ ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb_1−xGd_xZr₂O₇ (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb_0.5Gd_0.5Zr₂O₇ composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb_1−xGd_xZr₂O₇ ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb_1−xGd_xZr₂O₇ ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10⁻² S cm⁻¹ at 1173 K for NdYb_0.3Gd_0.7Zr₂O₇ composition.     

Synthesis and tunable thermal expansion properties of Sc2−xYxW3O12 solid solutions

A new series of rare earth solid solutions Sc_2−xY_xW₃O₁₂ was successfully synthesized by the conventional solid-state method. Effects of doping ion yttrium on the crystal structure, morphology and thermal expansion property of as-prepared Sc_2−xY_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TG), field emission scanning electron microscope (FE-SEM) and thermal mechanical analyzer (TMA). Results indicate that the obtained Sc_2−xY_xW₃O₁₂ samples with Y doping of 0≤x≤0.5 are in the form of orthorhombic Sc₂W₃O₁₂-structure and show negative thermal expansion (NTE) from room temperature to 600 °C; while as-synthesized materials with Y doping of 1.5≤x≤2 take hygroscopic Y₂W₃O₁₂·nH₂O-structure at room temperature and exhibit NTE only after losing water molecules. It is suggested that the obvious difference in crystal structure leads to different thermal expansion behaviors in Sc_2−xY_xW₃O₁₂. Thus it is proposed that thermal expansion properties of Sc_2−xY_xW₃O₁₂ can be adjusted by the employment of Y dopant; the obtained Sc_1.5Y_0.5W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.00683×10⁻⁶ °C⁻¹ in the 25–250 °C range.     

Raman and dielectric investigation of (Ba0.9−xSrxCa0.1)(Ti0.8Zr0.2)O3 ferroelectric ceramics

Solid solutions of (Ba_0.9−xSr_xCa_0.1)(Ti_0.8Zr_0.2)O₃ (BSCTZ) (0.1≤x≤0.4) were prepared using the conventional solid state reaction method. The effects of the substitution content on the crystallographic structure, phase transition and dielectric properties of the samples were investigated by dielectric and Raman spectroscopy over a wide temperature range from 100 to 500 K. All the samples were noted to undergo a diffuse phase transition from the tetragonal to the cubic phase and to exhibit a relaxor ferroelectric behavior.     

Electrochemical and thermal studies of Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 (x = 1/12, 1/4, 5/12, and 1/2)

Samples of the layered cathode materials, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (x = 1/12, 1/4, 5/12, and 1/2), were synthesized at 900 °C. Electrodes of these samples were charged in Li-ion coin cells to remove lithium. The charged electrode materials were rinsed to remove the electrolyte salt and then added, along with EC/DEC solvent or 1 M LiPF₆ EC/DEC, to stainless steel accelerating rate calorimetry (ARC) sample holders that were then welded closed. The reactivity of the samples with electrolyte was probed at two states of charge. First, for samples charged to near 4.45 V and second, for samples charged to 4.8 V, corresponding to removal of all mobile lithium from the samples and also concomitant release of oxygen in a plateau near 4.5 V. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples with x = 1/4, 5/12 and 1/2 charged to 4.45 V do not react appreciably till 190 °C in EC/DEC. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples charged to 4.8 V versus Li, across the oxygen release plateau, start to significantly react with EC/DEC at about 130 °C. However, their high reactivity is similar to that of Li_0.5CoO₂ (4.2 V) with 1 μm particle size. Therefore, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples showing specific capacity of up to 225 mAh/g may be acceptable for replacing LiCoO₂ (145 mAh/g to 4.2 V) from a safety point of view, if their particle size is increased.     

Study on the rapid synthesis of LiNi1−xCoxO2 cathode material for lithium secondary battery

LiNi_1−xCo_xO₂ (x = 0, 0.1, 0.2) cathode materials were successfully synthesized by a rheological phase reaction method with calcination time of 0.5 h at 800 °C. All obtained powders are pure phase with α-NaFeO₂ structure (R-3m space group). The samples deliver an initial discharge capacity of 182, 199 and 189 mAh g⁻¹ (25 mA g⁻¹, 4.35-3.0 V), respectively. The reaction mechanism was also discussed, which consists of a series of defect reactions. As a result of these defect reactions, the reaction of forming LiNi_1−xCo_xO₂ takes place in high speed.     

Electrochemical and structural study of Ce0.8Sm0.2−xLaxO1.9 electrolyte materials for SOFC

Ce_0.8Sm_0.2−xLa_xO_1.9 powders, denoted as La_xSDC (for x=0, 0.01, 0.03, 0.05, 0.07 and 0.1), were synthesized via the mechanical milling reaction method. The La³⁺ doping content has a remarkable influence on structural and electrical properties. The phase identification and morphology were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Lattice parameters were calculated by the Rietveld method. It was observed that the lattice parameter values in Ce_0.8Sm_0.2−xLa_xO_1.9 systems obey Vegard's law. The pellets were then sintered at 1500 °C in air for 7 h. The relative densities of these pellets were over 93.7%.The electrical conductivity was studied using two-probe impedance spectroscopy and results showed that the conductivity of Ce_0.8Sm_0.2−xLa_xO_1.9 first increased and then decreased with La dopant content x. Results also showed that Ce_0.8Sm_0.17La_0.03O_1.9 had the highest electrical conductivity, σ₇₀₀ °C equal to 3.8×10⁻² Scm⁻¹ and an activation energy equal to 0.77 eV. It was therefore concluded that co-doping with the appropriate amount of La can further improve the electrical properties of ceria electrolytes.     

Synthesis and microstructure of (LaSr)MnO3 and (LaSr)FeO3 ceramics by a reaction-sintering process

(La_xSr_1−x)MnO₃ (LSMO) and (La_xSr_1−x)FeO₃ (LSFO) (x = 0.2–0.4) ceramics prepared by a simple and effective reaction-sintering process were investigated. Without any calcination involved, La₂O₃ and SrCO₃ were mixed with MnO₂ (LSMO) or Fe₂O₃ (LSFO) then pressed and sintered directly. LSMO and LSFO ceramics were obtained after 2 and 4 h sintering at 1350–1400 and 1200–1280 °C, respectively. Grain size decreased as La content increased in LSMO and LSFO ceramics.     

Evolution of the local structure and electrochemical properties of spinel LiNixMn2−xO4 (0 ≤ x ≤ 0.5)

A series of Ni substituted spinel LiNi_xMn_2−xO₄ (0 ≤ x ≤ 0.5) have been synthesized to study the evolution of the local structure and their electrochemical properties. X-ray diffraction showed a few Ni cations moved to the 8a sites in heavily substituted LiNi_xMn_2−xO₄ (x ≥ 0.3). X-ray photoelectron spectroscopy confirmed Ni²⁺ cations were partially oxidized to Ni³⁺. The local structures of LiNi_xMn_2−xO₄ were studied by analyzing the and A_1g Raman bands. The most compact [Mn(Ni)O₆] octahedron with the highest bond energy of Mn(Ni)O was found for LiNi_0.2Mn_1.8O₄, which showed a Mn(Ni)O average bond length of 1.790 Å, and a force constant of 2.966 N cm⁻¹. Electrolyte decomposition during the electrochemical charging processes increased with Ni substitution. The discharge capacities at the 4.1 and 4.7 V plateaus obeyed the linear relationships with respect to the Ni substitution with the slopes of −1.9 and +1.9, which were smaller than the theoretical values of −2 and +2, respectively. The smaller slopes could be attributed to the electrochemical hysteresis and the presence of Ni³⁺ in the materials.     

Influence of A-site Ba substitution on microwave dielectric properties of (BaxMg1−x)(A0.05Ti0.95)O3 (A=Zr,Sn) ceramics

The microwave dielectric properties of (Ba_xMg_1−x)(A_0.05Ti_0.95)TiO₃ (A=Zr, Sn) ceramics were investigated with regard to substitution of Ba for Mg of A-site. The microwave dielectric properties were correlated with the Ba content. With an increase in Ba content from 0.01 to 0.1, the dielectric constant and the τ_f value increased, but the Q×f value decreased. The sintered (Ba_xMg_1−x)(Zr_0.05Ti_0.95)TiO₃ (called B_xMZT) ceramics had a permittivity in the range of 19.1−20.6, quality factor from 180,000 to 25,000 GHz, and variation in temperature coefficient of resonant frequency from −35 to −39 ppm/°C with increasing composition x. For sintered (Ba_xMg_1−x)(Sn_0.05Ti_0.95)TiO₃ (called B_xMST) ceramics, the dielectric constant increased from 19 to 20.5, Q×f value increased from 120,000 to 37,000 (GHz), and the τ_f value increased from −50 to −3.3 ppm/°C as the x increased from 0.01 to 0.1. When A=Sn and x=0.1, (Ba_0.1Mg_0.9)(Sn_0.05Ti_0.95)TiO₃ ceramics exhibited dielectric constant of 20.5, Q×f value of 37,000 (GHz), and a near-zero τ_f value of −3.3 ppm/°C sintered at 1210 °C for 4 h.     

Dielectric and ferroelectric properties of Ba0.8Sr0.2Ti1−5x/4NbxO3 ceramics

Ba_0.8Sr_0.2Ti_1−5x/4Nb_xO₃ ceramics, x = 0, 0.01, 0.05, 0.10, were fabricated by conventional solid-state reaction. With increasing niobium content the ferroelectric phase transition temperature decreases linearly, and the dispersivity of the transition increases. Niobium B-site decreases transition temperature more pronounced than Sr²⁺ at A-site. The heterovalent substitution of Nb⁵⁺ in low content causes local defect dipole, while more substitutions introduce disorder to disturb the long-range dipole correlation. Ba_0.8Sr_0.2Ti_1−0.5/4Nb_0.1O₃ ceramic shows weak ferroelectric loop at room temperature far from its transition temperature, 153 K.     

Combustion synthesis of (Ti1−xNbx)2AlC solid solutions from elemental and Nb2O5/Al4C3-containing powder compacts

Preparation of the (Ti_1−xNb_x)₂AlC solid solution (formed from the M_n+1AX_n or MAX carbides, where n = 1, 2, or 3, M is an early transition metal, A is an A-group element, and X is C) with x = 0.2-0.8 was investigated by self-propagating high-temperature synthesis (SHS). Nearly single-phase (Ti,Nb)₂AlC was produced through direct combustion of constituent elements. Due to the decrease of reaction exothermicity, the combustion temperature and reaction front velocity decreased with increasing Nb content of (Ti_1−xNb_x)₂AlC formed from the elemental powder compacts. In addition, the samples composed of Ti, Al, Nb₂O₅, and Al₄C₃ were adopted for the in situ formation of Al₂O₃-added (Ti,Nb)₂AlC. The SHS process of the Nb₂O₅/Al₄C₃-containing sample involved aluminothermic reduction of Nb₂O₅, which not only enhanced the reaction exothermicity but also facilitated the evolution of (Ti,Nb)₂AlC. Based upon the XRD analysis, two intermediates, TiC and Nb₂Al, were detected in the (Ti,Nb)₂AlC/Al₂O₃ composite and their amounts were reduced by increasing the extent of thermite reduction involved in the SHS process. The laminated microstructure characteristic of the MAX carbide was observed for both monolithic and Al₂O₃-added (Ti,Nb)₂AlC solid solutions synthesized in this study.     

Effects of B-site ion (M) substitution on the ionic conductivity of (Li3xLa2/3−x)1+y/2(MyTi1−y)O3 (M=Al, Cr)

Effect on the ionic conductivity of B-site ion (M) substitution in (Li_3xLa_2/3−x)_1+y/2M_yTi_1−yO₃ (M=Al, Cr) has been investigated. It has been found that partial substitution of smaller Al³⁺ for Ti⁴⁺ is effective to enhance the ionic conductivity of Li_3xLa_2/3−xTiO₃. At 300 K, the maximum bulk conductivity of (1.58±0.01)×10⁻³ S cm⁻¹ is observed from the composition of (Li_0.39La_0.54)_1−y/2Al_yTi_1−yO₃ with y=0.02 (x=0.13), that is the highest yet reported for known perovskite solutions at room temperature. The conductivity enhancement is interpreted as being due to the substitution-induced bond-strength change rather than due to bottleneck size change for Li migration, TiO₆-octahedron tilting or A-site cation ordering.     

Preparation and cycling performance of Aland F co-substituted compounds Li4AlxTi5−xFyO12−y

Li₄Al_xTi_5−xF_yO_12−y compounds were prepared by a solid-state reaction method. Phase analyses demonstrated that both Al³⁺ and F⁻ ions entered the structure of spinel-type Li₄Ti₅O₁₂. Charge-discharge cycling results at a constant current density of 0.15 mA cm⁻² between the cut-off voltages of 2.5 and 0.5 V showed that the Al³⁺ and F⁻ substitutions improved the first total discharge capacity of Li₄Ti₅O₁₂. However, Al³⁺ substitution greatly increased the reversible capacity and cycling stability of Li₄Ti₅O₁₂ while F⁻ substitution decreased its reversible capacity and cycling stability slightly. The electrochemical performance of the Al³⁺-F⁻-co-substituted specimen was better than the F⁻-substituted one but worse than the Al³⁺-substituted one.     

Preparation and characterization of novel spinel Li4Ti5O12−xBrx anode materials

Br-doped Li₄Ti₅O₁₂ in the form of Li₄Ti₅O_12−xBr_x (0 ≤ x ≤ 0.3) compounds were successfully synthesized via solid state reaction. The structure and electrochemical properties of the spinel Li₄Ti₅O_12−xBr_x (0 ≤ x ≤ 0.3) materials were investigated. The Li₄Ti₅O_12−xBr_x (x = 0.2) presents the best discharge capacity among all the samples, and shows better reversibility and higher cyclic stability compared with pristine Li₄Ti₅O₁₂, especially at high current rates. When the discharge rate was 0.5 C, the Li₄Ti₅O_12−xBr_x (x = 0.2) sample presented the excellent discharge capacity of 172 mAh g⁻¹, which was very close to its theoretical capacity (175 mAh g⁻¹), while that of the pristine Li₄Ti₅O₁₂ was 123.2 mAh g⁻¹ only.     

Amorphous LiCoO2 thin films on Li1+x+yAlxTi2−xSiyP3−yO12 prepared by radio frequency magnetron sputtering for all-solid-state Li-ion batteries

Amorphous LiCoO₂ thin films were deposited on the NASICON-type glass ceramics, Li_1+x+yAl_xTi_2−xSi_yP_3−yO₁₂ (LATSP), by radio frequency (RF) magnetron sputtering below 180 °C. The as-deposited LiCoO₂ thin films were characterized by X-ray diffraction, scanning electron microscopy and atomic force microscope. All-solid-state Li/PEO₁₈-Li (CF₃SO₂)₂N/LATSP/LiCoO₂/Au cells were fabricated using the amorphous film. The electrochemical performance of the cells was investigated by galvanostatic cycling, cyclic voltammetry, potentiostatic intermittent titration technique and electrochemical impedance spectroscopy. It was found that the amorphous LiCoO₂ thin film shows a promising electrochemical performance, making it a potential application in microbatteries for microelectronic devices.     

Combustion synthesis of Ca1−xCuxAl2O4 (x = 0.0, 0.4 and 0.8) copper doped calcium aluminate

We report the effect of Cu²⁺ ion on CaAl₂O₄ with different molar concentrations of 0.0, 0.4 and 0.8 M prepared by simple combustion method. The materials have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR) and scanning electron microscopy (SEM). DC electrical conductivity has also been measured to study the electrical behavior of the materials. The XRD patterns confirm the formation of single-phase CaAl₂O₄ along with some impurity phases like CaAl₄O₇, CaAl₁₂O₁₉ and Ca₁₂Al₁₄O₃₃. The FT-IR spectra show the stretching and bending vibrations of the synthesized compounds. DC electrical conductivity of the Ca_1−xCu_xAl₂O₄ is found to vary from 26.46 × 10⁻⁴ to 515.68 × 10⁻⁴ S cm⁻¹ for x = 0.0 to x = 0.8 at the measuring temperature of 1000 °C. SEM images show the morphological features of the compounds.     

Structural and magnetic characterization of MnxZn1 − xFe2O4 (x = 0.2; 0.35; 0.65; 0.8; 1.0) ferrites obtained by the citrate precursor method

In this work the microstructure and magnetic properties of Mn-Zn ferrites powders were investigated. Mn_xZn1 _− xFe₂O₄ powders where x = 0.2; 0.35; 0.5; 0.65; 0.8 and 1.0 were obtained by citrate precursor method. Citrate resin precursor was burned on air atmosphere at 400 °C for 3 h. Mn-Zn powders were calcined at 950 °C during 150 min under inert atmospheres: N₂ and rarefied atmosphere. Thermal analysis of precursor resin, phase evolution and microstructure of Mn-Zn ferrites powders were investigated by TG, DTA, XRD and SEM techniques. The powders calcined under rarefied atmosphere show spinel cubic structure and contamination of α-Fe₂O₃, while powders calcined under N₂ presents only the spinel cubic structure. Particle size was observed by SEM ranging from 80 to 150 nm. The magnetic properties were measured employing a vibrating sample magnetometer (VSM). It was observed that the saturation magnetization M_s increased with the increase of Mn content. The M_s of Mn_0.8Zn_0.2Fe₂O₄ calcined on rarefied atmosphere and Mn_0.8Zn_0.2Fe₂O₄ calcined on N₂ was 23.31 emu g⁻¹ and 56.23 emu g⁻¹, respectively.     

Effect of Ti substitution for Nb in double perovskite-type Ba3CaNb2O9 on chemical stability and electrical conductivity

This paper reports the synthesis, structure, chemical stability and electrical transport properties of Ti substituted Ba₃CaNb₂O₉ (BCN) to develop electrolytes for proton conducting solid oxide fuel cells (H-SOFCs). The powder X-ray diffraction (PXRD) of Ba₃CaNb_2−xTi_xO_9−δ (x = 0.1, 0.15, 0.2, 0.25 and 0.3) and Ba₃Ca_1.18Nb_1.82−xTi_xO_9−δ (x = 0.15 and 0.25) showed formation of double perovskite-like structure with lattice constant comparable to that of Ba₃Ca_1.18Nb_1.82O_9−δ (BCN18). Scanning electron microscopy (SEM) showed dense and pore-free microstructure for Ba₃CaNb_1.75Ti_0.25O_8.875. PXRD and Fourier transform infrared (FTIR) spectroscopy data confirmed long-term stability of Ba₃CaNb_2−xTi_xO_9−δ and Ba₃Ca_1.18Nb_1.82−xTi_xO_9−δ in boiling H₂O and in CO₂ at elevated temperatures. The AC impedance investigation showed contribution due to bulk, grain-boundary and electrode effect at low temperatures. The electrical conductivity of studied materials were measured in different medium including dry air, dry H₂, wet H₂, wet N₂ and D₂O. Increase in conductivity in wet N₂ and decrease in conductivity in D₂O confirmed the proton conduction in Ba₃CaNb_1.75Ti_0.25O_9-δ. Among Ti-substituted compounds investigated in this study, Ba₃Ca_1.18Nb_1.57Ti_0.25O_8.605 showed the highest conductivity of 3.5 × 10⁻⁴ S cm⁻¹ at 400 °C in wet N₂ (3%H₂O), which is comparable to reported values of Ba₂Ca_0.79Nb_0.66Ta_0.55O_6−δ and BCN18.     

Synthesis of LiNi0.9Co0.1O2 from Li2CO3, NiO or NiCO3, and CoCO3 or Co3O4 and their electrochemical properties

Cathode active materials with a composition of LiNi_0.9Co_0.1O₂ were synthesized by a solid-state reaction method at 850 °C using Li₂CO₃, NiO or NiCO₃, and CoCO₃ or Co₃O₄, as the sources of Li, Ni, and Co, respectively. Electrochemical properties, structure, and microstructure of the synthesized LiNi_0.9Co_0.1O₂ samples were analyzed. The curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂ for the first charge–discharge and the intercalated and deintercalated Li quantity Δx were studied. The destruction of unstable 3b sites and phase transitions were discussed from the first and second charge–discharge curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂. The LiNi_0.9Co_0.1O₂ sample synthesized from Li₂CO₃, NiO, and Co₃O₄ had the largest first discharge capacity (151 mA h/g), with a discharge capacity deterioration rate of −0.8 mA h/g/cycle (that is, a discharge capacity increasing 0.8 mA h/g per cycle).     

Zr-doped Li[Ni0.5−xMn0.5−xZr2x]O2 (x = 0, 0.025) as cathode material for lithium ion batteries

Layered Li[Ni_0.5−xMn_0.5−xZr_2x]O₂ (x = 0, 0.025) have been prepared by the mixed hydroxide and molten-salt synthesis method. The individual particles of synthesized materials have a sub-microsize range of 200-500 nm, and LiNi_0.475Mn_0.475Zr_0.05O₂ has a rougher surface than that of LiNi_0.5Mn_0.5O₂. The Li/Li[Ni_0.5−xMn_0.5−xZr_2x]O₂ (x = 0, 0.025) electrodes were cycled between 4.5 and 2.0 V at a current density of 15 mA/g, the discharge capacity of both cells increased during the first ten cycles. The discharge capacity of the Li/LiNi_0.475Mn_0.475Zr_0.05O₂ cell increased from 150 to 220 mAh/g, which is 50 mAh/g larger than that of the Li/LiNi_0.5Mn_0.5O₂ cell. We found that the oxidation of oxygen and the Mn³⁺ ion concerned this phenomenon from the cyclic voltammetry (CV). Thermal stability of the charged Li[Ni_0.5−xMn_0.5−xZr_2x]O₂ (x = 0, 0.025) cathode was improved by Zr doping.