Synthesis and electrochemical behavior of nanosized LiNi1−xCaxO2 cathode materials for high voltage secondary lithium-ion cells

A new class of LiNi_1−xCa_xO₂ (x = 0.0, 0.1, 0.2, 0.3 and 0.5) layered oxide materials has been synthesized by a simple low temperature solid-state route with mixed nitrates/urea with glycerol as the starting materials. First we have taken TG/DTA for observing the phase transformations of LiNi_0.9Ca_0.1O₂. The structure of the synthesized oxides was analyzed using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) to identify the crystal structure and cation environment, respectively. The synthesized ceramic oxide battery materials were examined by using transmission electron microscope (TEM), scanning electron microscope (SEM) analysis to determine the particle size, nature and morphological structure. SEM with energy dispersive X-ray spectroscopic analysis (EDAX) analysis was carried out to explore the composition of the prepared materials. The electrochemical performance of LiNi_1−xCa_xO₂ electrodes was analyzed using cyclic voltammetry (CV) and galvanostatic charge-discharge cycling studies in the voltage range 3.0-4.5 V. Electrode made with cathode active material, acetylene black and poly(vinylidene difluoride) yield a discharge capacity of 178.1 mAh g⁻¹ (x = 0.2) with good specific capacity over several charge-discharge cycles. These results have been also supported by cyclic voltammograms.     

Hydrothermal synthesis of nanocrystalline MxZn1−xFe2O4 (M=Ni, Mn, Co; x=0.40-0.60) powders

A series of nanocrystalline M_xZn_1−xFe₂O₄ (M=Ni, Mn and Co; x=0.40-0.60) powders have been successfully prepared via hydrothermal process and characterized by XRD, TEM and IR techniques. The effects of reaction temperature and the initial pH value of the starting suspension solution on the particulate properties such as the particle size and morphology are discussed. IR spectra indicate that there are no hydroxyl in as-prepared Ni_xZn_1−xFe₂O₄ and Co_xZn_1−xFe₂O₄ powders, while there are obvious hydroxyl adsorption on the IR spectrum of Mn_xZn_1−xFe₂O₄ powder.     

Electrical conductivity of yttrium-doped SrTiO3: influence of transition metal additives

The electrical conductivity of yttrium-doped SrTiO₃ with transition metals added as acceptor dopants (V, Mn, Fe, Co, Ni, Cu, Zn, Mo, Mg, Zr, Al, or Ga) was measured by the dc four-probe method at 600-900°C in reducing atmospheres. The replacement of 5 mol% titanium by acceptors leads to a decrease of conductivity of Sr_1−1.5xY_xTiO_3−δ. The degree of the decrease depends strongly on the type of dopant. Of the 5 mol% acceptor-doped compositions, the system Sr_0.85Y_0.10Ti_0.95Co_0.05O_3−δ had the highest conductivity of 45 S/cm at 800°C and oxygen partial pressure of 10⁻¹⁹ atm. The oxidation kinetics of yttrium-doped SrTiO₃ was significantly retarded by the addition of cobalt or manganese dopants. The ionic conductivity of SrTiO₃ doped with 5 mol% acceptors at Ti-sites was estimated from the total conductivity to lie in the vicinity of 10⁻⁴ S/cm, depending on oxygen partial pressure and temperature.     

Electrochemical behaviors of Li[Li(1−x)/3Mn(2−x)/3Nix/3Cox/3]O2 cathode series (0 < x < 1) synthesized by sucrose combustion process for high capacity lithium ion batteries

A mixed cathode material between Li₂MnO₃ and Li[Mn_1/3Ni_1/3Co_1/3]O₂ for high capacity lithium secondary batteries was introduced in this study. It was prepared using the sucrose combustion process because this is a simple process. The oxidation states of Mn, Co and Ni ions in the pristine Li[Li_(1−x)/3Mn_(2−x)/3Ni_x/3Co_x/3]O₂ compounds were confirmed to be tetravalent, trivalent and divalent, respectively, via XANES measurements. Electrochemical charge/discharge studies showed that the highest first discharge capacity of 224 mAh/g was obtained in composition of x = 0.5 at a 0.2 C rate. The oxidation state of the Co and Ni ions in the Li[Li_1/6Mn_1/2Ni_1/6Co_1/6]O₂ changed to higher oxidation states, but that of the Mn ions did not change.     

Effect of B-site doping on Sm0.5Sr0.5MxCo1−xO3−δ properties for IT-SOFC cathode material (M = Fe, Mn)

The crystal structure, thermal expansion rate, electrical conductivity and electrochemical performance of Sm_0.5Sr_0.5M_xCo_1−xO_3−δ (M = Fe, Mn) have been investigated. Two crystal structures have been observed in the specimens of Sm_0.5Sr_0.5Fe_xCo_1−xO_3−δ (SSFC) at room temperature, the perovskite structure of SSFC has an orthorhombic symmetry for 0 ≤ x ≤ 0.4 and a cubic symmetry for 0.5 ≤ x ≤ 0.9. The specimens of Sm_0.5Sr_0.5Mn_xCo_1−xO_3−δ (SSMC) crystallize in an orthorhombic structure. The adjustment of thermal expansion rate to electrolyte, which is one of the main problems of SSC, can be achieved to lower TEC values with more Fe and Mn substitution. Especially, Sm_0.5Sr_0.5Mn_0.8Co_0.2O_3−δ exhibits good thermal compatibility with La_0.8Sr_0.2Ga_0.8Mg_0.2O₃. High electrical conductivities are obtained for all the specimens and they demonstrate above 100 S/cm at 800 °C in SSFC system. The polarization resistance increases with increasing Mn content, Nevertheless, the polarization resistance of SSFC increases with increasing Fe content, but when the amount of Fe reaches to 0.4, the maximum is obtained while the resistance will decrease when the amount of Fe reaches above 0.4. Sm_0.5Sr_0.5Fe_0.8Co_0.2O_3−δ electrode exhibits high catalytic activity for oxygen reduction operating at temperature from 700 to 800 °C.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Effects of Co content and annealing temperature on the structure and optical properties of CoxMg1−xAl2O4 nanoparticles

Co_xMg_1−xAl₂O₄ (x = 0–0.8) nanoparticles were synthesized by sol–gel method, and characterized by X-ray powder diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy and ²⁷Al solid-state NMR spectroscopy were performed to study the chemical environments of cations in the nanoparticles as a function of cobalt content and annealing temperature. The results show that the crystallite size of the particles is about 20–40 nm. Besides the tetrahedral and octahedral coordinations, the second octahedrally coordinated Al³⁺ ions are observed in the samples. The inversion parameter (two times the fraction of Al³⁺ ions in tetrahedral sites) decreases with the increase of annealing temperature and cobalt content. The fraction of octahedral Mg²⁺ decreases with the increase of Co concentration. The absorption spectra indicate that Co²⁺ ions are located in the tetrahedral sites as well as in the octahedral sites in the nanoparticles. The intensity of the absorption peak corresponding to octahedral Co²⁺ ions (300–500 nm) decreases with increasing annealing temperature.     

Thermal stability against reduction of LaMn1−yCoyO3 perovskites

Thermal and reduction-oxidation stability of substituted LaMn_1−yCo_yO₃ perovskite-type oxides (0.0 ≤ y_Co ≤ 1.0) prepared by the citrate route have been studied by means of surface area, X-ray diffraction, FTIR spectroscopy and magnetic properties. The perovskite orthorhombic structure is found for y_Co ≤ 0.5, with the exception of y_Co = 0.1, which corresponds better to rhombohedral LaMnO_3.15. For y_Co > 0.5 the diffraction profiles are quite similar to the cobaltite’s rhombohedral structure. Magnetic iso-field studies (ZFC-FC) reveal that, for y_Co ≤ 0.50, the system presents an antiferromagnetic canted-like ordering of the Mn/Co sublattice, in which the presence of divalent Co ion creates Mn³⁺-Mn⁴⁺ pairs that interact ferromagnetically through the oxygen orbital. This interpretation is confirmed by the magnetization loops, in which the magnetic moment increases when substituting Mn for Co. Therefore, the general trend is: for y_Co ≤ 0.5, the Co ions are inserted in the manganite structure and for y_Co > 0.5, the Mn ions are inserted in cobaltite structure. The enhancement of the ferromagnetic properties and the thermal stability against reduction for y_Co = 0.5 is attributed to optimized Co²⁺-Mn⁴⁺ interactions.     

Preparation and chemical properties of the skutterudites (Ce-Yb)yFe4−x(Co/Ni)xSb12

The double-filled skutterudites Ce_y/2Yb_y/2Fe_4−xCo_xSb₁₂ and Ce_y/2Yb_y/2Fe_4−xNi_xSb₁₂ have been synthesized as single phase materials. The evolution of the lattice parameters and of the filling fractions with substitutions on the transition metal site have been studied by X-ray diffraction and electron probe microanalysis, respectively. Both results were compared to that of single filled series (Ce/Yb)_yFe_4−x(Co/Ni)_xSb₁₂. It shows that double-filled skutterudites can be understood as a solid solution between single filled ones. The valence states of Ce and Yb in all series have been studied using X-ray absorption spectroscopy at the L₃ edges, and we discuss their relationships with structural parameters. Ce is always trivalent, whereas Yb valence state decreases as Yb fraction increases. No distortion of the environment or sub-position of Yb in the cage have been seen by neutron diffraction. The Seebeck coefficient has been measured using a home made apparatus from 120 K to 300 K. It shows a crossover from p- to n-type conductivity for Co or Ni rich skutterudites in the six series. We discuss the influence on the room temperature thermopower of valence states, filling fractions and substitution rate on the transition metal site. Thermopower seems to be only driven by charge carriers concentration.     

High frequency magnetic mechanism of Ni-substituted Co2Z hexagonal ferrite

The magnetic properties, especially the high frequency magnetic mechanism, of Ni-substituted Co₂Z hexagonal ferrite were studied. The polycrystalline Z-type hexagonal ferrite of Ba₃Ni_xCo_2−xFe₂₄O₄₁ (0 ≤ x ≤ 2) were prepared by solid-state reaction. The results indicate that Ni-substituted Co₂Z samples all exhibit typical soft magnetic character. Substitution of Ni for Co will turn the planar magnetocrystalline anisotropy of Co₂Z to uniaxial anisotropy when x ≥ 1, so that the permeability drops dramatically and domain wall resonance appears in the frequency spectra. With the rise of Ni amount or sintering temperature, domain wall resonance strengthens gradually.     

Post-synthetic treatments on NixMnxCo1 − 2x(OH)2 for the preparation of lithium metal oxides

A series of hydroxides Ni_xMn_xCo_(1−2x)(OH)₂ for x = 0.00–0.50 were prepared. These hydroxides were used as the precursors in the synthesis of electrochemical active lithiated mixed metal oxides, LiNi_xMn_xCo_{(1 − 2x)}O₂. The traditional co-precipitation method was used to synthesize the hydroxides and the effect of different post-synthetic treatments were tested. The solutions after co-precipitation of the hydroxides were heated under hydrothermal or microwave assisted hydrothermal conditions at 180 °C. All samples were analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. We observed that the hydroxides undergo oxidation to an oxyhydroxide phase as the stoichiometry varies during their synthesis and with post-synthetic treatments. As the concentration of Ni and Mn increases in the sample, a mixture of both hydroxide and oxyhydroxide phases is obtained. SEM images demonstrate a sintering effect on the hydroxide particles after post-synthetic treatment, while XRD measurements on these samples show an increase in crystallinity and reduced turbostratic disorder. The oxides synthesized from these precursors demonstrate similar electrochemical performance with one another.     

Structural, magnetic and dielectric properties of Bi1−ySryFe(1−y)(1−x)Sc(1−y)xTiyO3 (x = 0-0.2, y = 0.1-0.3) ceramics

In this study, bulk ceramics with general formula Bi_1−ySr_yFe_{(1−y)(1−x)}Sc_(1−y)xTi_yO₃ (x = 0-0.2, y = 0.1-0.3 mol%) were prepared by traditional solid-state reaction method. As a comparison, bulk BiFeO₃ (BF) was also sintered by rapid sintering method. Their structural, magnetic, dielectric properties were investigated. X-ray diffraction analysis indicated that apart from a small amount of secondary phase detected in BF, all other samples crystallized in pure perovskite structure and maintained original R3c space group. The room temperature M-H curves were obtained. While BF had a coercive magnetic field (H_c) of 150 Oe, Bi_1−ySr_yFe_1−yTi_yO₃ solid solutions had a much larger value (for y = 0.1, 0.2, 0.3, H_c were 4537, 5230 and 3578 Oe, respectively). Sc³⁺ substitution decreased the H_c values of these solid solutions remarkably, and resulted in soft magnetic properties, as well as a decrease of the dielectric loss. At 1 MHz, the tan δ of Bi_0.7Sr_0.3Fe_0.7(1−x)Sc_0.7xTi_0.3O₃ with x = 0.05, 0.1, 0.15, 0.2 were 0.1545, 0.1078, 0.1046 and 0.1701, respectively.     

Structural and electrochemical properties of LiNi0.3Co0.7O2 synthesized by different low-temperature techniques

Single phase LiNi_1−yCo_yO₂ (y=0.7) with fine particles were prepared by two different low-temperature methods, namely sol–gel and combustion techniques. It was found that bulk quantities of submicron-sized particles of layered LiNi_0.3Co_0.7O₂ can be obtained at temperatures below 400°C by these solution techniques. The methods involved the mixing of either acetates or nitrates of the metals, Ni and Co, with a chelating agent, carboxylic acid (sol–gel method) or a complexing agent, glycine (combustion method) in an aqueous medium. Both carboxylic acid and glycine acted as fuels, decomposed the homogeneous precipitate of metal complexes at low temperature, and yielded the free impurity LiNi_0.3Co_0.7O₂ compound. The synthesized products were characterized by structural (XRD, SEM), spectroscopic (FTIR) and thermal (DTA-TG) analyses. The electrochemical performance of the synthesized products in rechargeable Lithium cells were evaluated using a non-aqueous organic electrolyte mixture of 1M LiPF₆ in EC+DMC. The electrochemical behavior of synthesized LiNi_0.7Co_0.3O₂ is discussed in relation with its synthesis procedures.     

Novel composite interconnecting ceramics La0.7Ca0.3CrO3−δ/Ce0.8Sm0.2O1.9 for solid oxide fuel cells

In this paper, an interconnecting ceramic for solid oxide fuel cells was developed, based on the modification from La_0.7Ca_0.3CrO_3−δ by addition of Ce_0.8Sm_0.2O_1.9. It is found that addition of small amount Ce_0.8Sm_0.2O_1.9 into La_0.7Ca_0.3CrO_3−δ dramatically increased the electrical conductivity. For the best system, La_0.7Ca_0.3CrO_3−δ + 5 wt.% Ce_0.8Sm_0.2O_1.9, the electrical conductivity reached 687.8 S cm⁻¹ at 800 °C in air. In H₂ at 800 °C, the specimen with 3 wt.% Ce_0.8Sm_0.2O_1.9 had the maximal electrical conductivity of 7.1 S cm⁻¹. With the increase of Ce_0.8Sm_0.2O_1.9 content the relative density increased, reaching 98.7% when the Ce_0.8Sm_0.2O_1.9 content was 10 wt.%. The average coefficient of thermal expansion at 30-1000 °C in air increased with Ce_0.8Sm_0.2O_1.9 content, ranging from 11.12 × 10⁻⁶ to 12.46 × 10⁻⁶ K⁻¹. The oxygen permeation measurement illustrated a negligible oxygen ionic conduction, indicating it is still an electronically conducting ceramic. Therefore, this material system will be a very promising interconnect for solid oxide fuel cells.     

The microwave-assisted synthesis and characterization of Zn1 − xCoxO nanopowders

In this paper, we present a simple microwave-assisted synthesis of Zn_1 − xCo_xO nanopowders. With the advantages of the microwave-assisted method, we have successfully synthesized good crystalline quality and good surface morphology Zn_1 − xCo_xO nanopowders. The nanopowders are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-VIS absorption, and micro-Raman spectroscopy. We found, in the synthesis process, the surfactant Triethanolamine (TEA) plays an important role on the morphology of Zn_1 − xCo_xO nanoparticles. The XRD study shows that for Co doping up to 5%, Co²⁺ ions are successfully incorporated into the ZnO host matrix. The absorption spectra of Zn_1 − xCo_xO (x = 1-5%) nanopowders show several peaks at 660, 611 and 565 nm, indicating the presence of Co²⁺ ions in the tetrahedral sites. The Raman study shows that the linewidth of E₂^low mode increases with Co concentration, which further indicates the incorporation of Co²⁺ ions into the ZnO host matrix.     

Dependence of optical properties on the composition of (Ba1−x−ySrxEuy)Si2O2N2 phosphors for white light emitting diodes

BaSi₂O₂N₂: Eu²⁺ is an efficient phosphor because of its high quantum yield and quenching temperature. Partial substitution of Ba²⁺ by Sr²⁺ is the most promising approach to tune the color of phosphors. In this study, a series of (Ba_1−x−ySr_xEu_y)Si₂O₂N₂ (x = 0.0–0.97, y = 0.00–0.10) phosphors are synthesized via high-temperature solid-state reactions. Intense green to yellow phosphors can be obtained by the partial substitution of the host lattice cation Ba²⁺ by either Sr²⁺ or Eu²⁺. The luminescent properties and the relationships among the lowest 5d absorption bands, Stokes shifts, centroid shifts, and the splitting of Eu²⁺ are studied systematically. Then, based on (Ba_1−x−ySr_xEu_y)Si₂O₂N₂ phosphors and near-ultraviolet (∼395 nm)/blue (460 nm) InGaN chips, intense green–yellow light emitting diodes (LEDs) and white LEDs are fabricated. (Ba_0.37Sr_0.60)Si₂O₂N₂: 0.03Eu²⁺ phosphors present the highest efficiency, and the luminous efficiency of white LEDs can reach 17 lm/w. These results indicate that (Ba_1−x−ySr_xEu_y)Si₂O₂N₂ phosphors are promising candidates for solid-state lighting.     

Synthesis, structure and dielectric characterization of Ln2Ti2−2xM2xO7(Ln=Gd, Er; M=Zr, Sn, Si)

The progress in wireless communications and information access has demanded the use of electronic ceramics exhibiting desired properties. To further our understanding of these properties, compounds in the Ln₂Ti_2-2xM_2xO₇ (Ln=Gd, Er; M=Zr, Sn, Si) systems were synthesized by ceramic methods and characterized by powder X-ray diffraction. The ZrO₂-doped Gd₂Ti_2−2xZr_2xO₇ compounds adopt the pyrochlore structure type and form a complete solid solution. Er₂Ti_2−2xZr_2xO₇ forms a pyrochlore solid solution for x<0.1. However, stoichiometric Er₂Zr₂O₇ does not form; instead Er₄Zr₃O₁₂ forms a with defect fluorite structure. The Sn-doped Ln₂Ti_2−2xSn_2xO₇ (Ln=Gd, Er) compounds form complete solid solutions, and the Si compounds adopt the pyrochlore structure up to x=0.05. At ambient temperature, dielectric constants range from 10 to 61 for Er₂Ti_2−2xZr_2xO₇ and 16-31 for Gd₂Ti_2−2xZr_2xO₇ with low dielectric loss (1×10⁻³) at 1 GHz.     

Thermal, spectroscopic and magnetic properties of the CoxNi1−x(SeO3)·2H2O (x = 0, 0.4, 1) phases: Crystal structure of Co0.4Ni0.6(SeO3)·2H2O

The Co_xNi_1−x(SeO₃)·2H₂O (x = 0, 0.4, 1) family of compounds has been hydrothermally synthesized under autogeneous pressure and characterized by elemental analysis, infrared and UV-vis spectroscopies and thermogravimetric and thermodiffractometric techniques. The crystal structure of Co_0.4Ni_0.6(SeO₃)·2H₂O has been solved from single-crystal X-ray diffraction data. This phase is isostructural with the M(SeO₃)·2H₂O (M = Co and Ni) minerals and crystallizes in the P2₁/n space group, with a = 6.4681(7), b = 8.7816(7), c = 7.5668(7) Å, β = 98.927(9)° and Z = 4. The crystal structure of this series of compounds consists of a three-dimensional framework formed by (SeO₃)²⁻ selenite oxoanions and edge-sharing M₂O₁₀ dimeric octahedra in which the metallic cations are coordinated by the oxygens belonging to both the selenite groups and water molecules. The diffuse reflectance spectra show the essential characteristics of Co(II) and Ni(II) cations in slightly distorted octahedral environments. The calculated values of the Dq and Racah (B and C) parameters are those habitually found for the 3d⁷ and 3d⁸ cations in octahedral coordination. The magnetic measurements indicate the existence of antiferromagnetic interactions in all the compounds. The magnetic exchange pathways involve the metal orbitals from edge-sharing dimeric octahedra and the (SeO₃)²⁻ anions which are linked to the M₂O₁₀ polyhedra in three dimensions.     

Magnetic softness and interparticle exchange interactions of (Fe65Co35)1 − x(Al2O3)x (x = 0-0.50) nanogranular films

The effect of Al₂O₃ content on the structure, electrical properties, magnetic properties, and interparticle exchange interactions of (Fe₆₅Co₃₅)_1 − x(Al₂O₃)_x films with Al₂O₃ volume fractions x ranging from 0 to 0.50 was systematically investigated. Among the films with x between 0 and 0.25, the lowest coercivity of 0.56 kA/m was achieved in the (Fe₆₅Co₃₅)_0.82(Al₂O₃)_0.18 film. This is ascribed to the strongest exchange interactions between the Fe₆₅Co₃₅ nanoparticles in this film. Combined with the microstructure analysis of the (Fe₆₅Co₃₅)_1 − x(Al₂O₃)_x films, the modified Herzer's model was extended to interpret the variation of the coercivity with x and analyze the effect of the exchange interactions between the Fe₆₅Co₃₅ nanoparticles on the magnetic softness. The remanence curves confirm the existence of the exchange interactions and reveal the evolution of the exchange interaction strength with Al₂O₃ content.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.