Effect of Co content on performance of LiAl1/3−xCoxNi1/3Mn1/3O2 compounds for lithium-ion batteries

Layered LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ (0  x  1/3) compounds were studied via the combination of computational and experimental approach. The calculated voltage curve of LiNi_1/3Al_1/3Mn_1/3O₂ compound is presented, indicating it is of great potential for a cathode material of lithium-ion batteries. Unfortunately, it was found that the LiNi_1/3Al_1/3Mn_1/3O₂ compound without impurity phase could not be synthesized via a sol–gel process. To obtain a layered compound without impurity phase, partial of Al is replaced by Co in LiNi_1/3Al_1/3Mn_1/3O₂ compound in this study. Layered LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ (0  x  1/3) compounds were synthesized via sol–gel reaction at 900 °C under a oxygen stream. Single phase of the LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ in 1/6  x  1/3 region could be prepared successfully. The discharge capacity and conductivity increased with an increase in the Co-substitution content. The enhancement of the conductivity and phase purity by the introduction of Co content shows profound influence on the performance of the LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ compounds.     

THM growth and characterization of CuGaxIn1−xSe2 solid solutions

Growth of CuGa_xIn_1−xSe₂ single crystals by THM (traveling heater method) has been investigated. On the basis of the relation between the composition x of grown crystal CuGa_xIn_1−xSe₂ and y of CuGa_yIn_1−ySe₂ solute in 60 mol% In solution, THM growth of CuGa_xIn_1−xSe₂ (x = 0, 0.2, 0.4, 0.7, 1) was performed using a zone ingot which was prepared in advance. Bulk single crystals with 10 mm in diameter and 20–30 mm in length have been obtained by the THM growth, and their electrical and optical properties have been studied.     

Preparation and properties of LiCoyMnxNi1−x−yO2 as a cathode for lithium ion batteries

The preparation of LiCo_yMn_xNi_1−x−yO₂ from LiOH·H₂O, Ni(OH)₂ and γ-MnOOH in air was studied in detail. Single-phase LiCo_yMn_xNi_1−x−yO₂ (0y0.3 and x=0.2) is obtained by heating at 830–900°C. The optimum heating temperatures are 850°C for y=0–0.1 and 900°C for y=0.2–0.3. Excess lithium (1z1.11 for y=0.2) and the Co doping level (0.05y0.2) do not significantly affect the discharge capacity of Li_zCo_yMn_0.2Ni_0.8−yO₂. The doping of Co into LiMn_0.2Ni_0.8O₂ accelerates the oxidation of the transition metal ion, and suppresses partial cation mixing. Since the valence of the manganese ion in LiMn_0.2Ni_0.8O₂ is determined to be 4, the formation of a solid solution between LiCo_yNi_1−yO₂ and Li₂MnO₃ is confirmed.     

Phase transitions and phase decomposition of La1−xSrxCoO3−δ in low oxygen partial pressures

High-temperature X-ray diffraction has been used to investigate the phase stability of lanthanum strontium cobalt oxide (LSC) for a range of materials with the formula La_1−xSr_xCoO_3−δ (x = 0.7, 0.4, and 0.2). The stability of LSC increases with La content in low oxygen partial pressures at high temperature. Oxygen vacancy ordering has been observed for all three compositions in either low oxygen pressure or under reducing gas, as evidenced by the formation of the brownmillerite phase. The crystal structure of the vacancy-ordered phase was determined using Rietveld analysis of synchrotron X-ray diffraction data. The decomposition products under low oxygen pressure and in reducing conditions have been identified and characterized, including the phase transition and thermal expansion of the primary decomposition products, LaSrCoO₄ and LaSrCoO_3.5.     

Structural and electrochemical properties of Li1+xNi0.5Mn0.5O2+δ (0 ≤ x ≤ 0.7) cathode materials for lithium-ion batteries

A comparative analysis of the properties of LiNi_0.5Mn_0.5O₂ and Li_1+xNi_0.5Mn_0.5O₂ (0.2 ≤ x ≤ 0.7) powders, obtained by the freeze drying method, was performed. Lattice parameters of Li_1+xNi_0.5Mn_0.5O₂ decreased considerably with growing amounts of Li until x = 0.3; at x > 0.5 trace amounts of Li₂MnO₃ are observed by X-ray diffraction (XRD) patterns. X-ray photoelectron spectroscopy (XPS) analysis displayed an increase of Ni³⁺/Ni²⁺ ratio at 0.3 < x < 0.5, while Mn 2p spectra were almost identical in all samples. Rechargeable capacity values (V = 2.5–4.6 V) increased systematically with x reaching its maximum (185–190 mAh g⁻¹) at x = 0.5. Samples with superstoichiometric lithium content also demonstrated good C rate characteristics.     

Electrochemical supercapacitor behavior of nanoparticulate rutile-type Ru1−xVxO2

Rutile-type Ru_1−xV_xO₂ nanoparticles possessing high surface area were prepared by a polymerizable-complex method and its electrochemical supercapacitor behavior was studied. X-ray diffractometry, energy-dispersive X-ray analysis, and N₂ adsorption/desorption measurements were used to characterize the structure of the products. The electrochemical supercapacitor behavior of thick and thin films was studied by cyclic voltammetry in various acidic, neutral, and alkaline electrolytes. Ru_1−xV_xO₂ exhibited extremely enhanced supercapacitive properties compared to pure RuO₂. The highest surface redox activity was achieved with an acidic electrolyte. Ru_1−xV_xO₂ showed negligible surface redox activity in neutral electrolytes.     

IrxCo1−x (x = 0.3–1.0) alloy electrocatalysts, catalytic activities, and methanol tolerance in oxygen reduction reaction

Novel methanol-tolerant catalysts for oxygen reduction reaction (ORR), Ir_xCo_1−x/C (x = 0.3–1.0), were synthesized by a conventional impregnation method. These carbon-supported catalysts showed particle sizes of 2.7–5.0 nm. The catalyst activity and the catalyzed ORR kinetics were characterized by cyclic voltammetry and rotating disk electrode methods. Among these Ir_xCo_1−x/C catalysts, the alloy with a formula of Ir_xCo_1−x/C with x value in the range of 0.7–0.8 exhibited the highest mass and specific activities. Compared to a Pt/C catalyst, these alloy catalysts have much stronger methanol tolerance in terms of ORR onset potential (or open-circuit potential). Based on the rotating disk electrode measurements, it was confirmed that these Ir_xCo_1−x/C alloy catalysts could catalyze a complete four-electron transfer reaction of oxygen to water. These results strongly suggest that the novel Ir–Co metal alloy catalysts synthesized in this work could be promising for DMFC cathodes.     

Cycle characterizations of LiMxMn2−xO4 (M=Co, Ni) materials for lithium secondary battery at wide voltage region

LiM_xMn_2−xO₄ (M=Co, Ni) materials have been synthesized by a melt-impregnation method using γ-MnOOH as the manganese source. Highly crystallized LiM_xMn_2−xO₄ compounds were synthesized at a calcination temperature of 800°C for 24 h in air. All compounds show a single phase except for LiNi_0.5Mn_1.5O₄ based on the X-ray diffraction (XRD) diagram. With the increase of the doping content from 0.1 to 0.5, the capacity of doping materials decreases mainly in the 4 V region.

Although LiM_0.5Mn_1.5O₄ (M=Co, Ni) compound shows a small capacity in the (3+4) V region compared with parent LiMn₂O₄, it is a very effective material in reducing capacity loss in the 3 V region that is caused by the Jahn–Teller distortion. The doping of Co and Ni ions in the LiMn₂O₄ cathode material promotes the stability of this structure and provides an excellent cyclability.     

Preparation of Culn(SxSe1−x)2 thin films by sulfurization and selenization

A CuIn(S_xSe_1−x)₂ alloy thin-film was prepared by selenization of CuInS₂: its composition ratio x can be controlled by the number of selenization cycles implemented. Crystallinity of the films was improved by annealing in vacuum. The resistivity of the film was about 1 Ω cm and increased by one to two orders of magnitude after KCN treatment. An 8.1 % efficiency solar cell was obtained by using this annealed alloy thin-film.     

On the computer simulation of the P–C isotherms of ZrFe2 type hydrogen storage materials

This paper deals with computer simulation of the P–C isotherms of some ZrFe₂ type (Zr(Fe_1−xCr_x)₂, Zr_1−xTi_xFe_1.4Cr_0.6, Zr_1−2xMm_xTi_xFe_1.4Cr_0.6 : x00.4) of hydrogen storage materials. A feasible mathematical model has been developed to simulate the P–C isotherms. The randomized variables in the model applied for simulating the P–C isotherms of the above-mentioned ZrFe₂ type hydrogen storage materials correspond to change in enthalpy (ΔH) and entropy (ΔS) of hydride formation. Several ZrFe₂ type materials as in above have been synthesized and their P–C isotherms, enthalpy and entropy change has been evaluated experimentally in order to have input data for simulation. A special software was developed to simulate the P–C isotherms using the said model. A close match between the experimentally observed and simulated P–C isotherms for the above said ZrFe₂ type alloys has been obtained.     

Characterization of Cu(InxGa1−x)2Se3.5 thin films prepared by rf sputtering

Cu(In_xGa_1−x)₂Se_3.5 thin films were fabricated by rf sputtering from CuIn_xGa_1−xSe₂ and Na mixture target by controlling the mixture ratio. X-ray diffraction analyses show that the structure of Cu(In_xGa_1−x)₂Se_3.5, thin films is different from chalcopyrite structure: especially, CuIn₂Se_3.5 thin films have a defect chalcopyrite structure. The lattice parameters for Cu(In_xGa_1−x)₂Se_3.5 thin film are slightly smaller than those for CuIn_xGa_1−xSe₂ thin film and linearly decreased with increasing Ga content. The optical absorption coefficients for Cu(In_xGa_1−x)₂Se_3.5, thin films exceed 2 × 10⁴ cm⁻¹ in energy region above the fundamental band edge. The band gap for Cu(In_xGa_1−x)₂Se_3.5 thin films is larger than that for CuIn.Ga_1−x2Se₂ with the same Ga content and increased with increasing Ga content.     

Effect of substituting Mm with La on the electrochemical performances of Co-free LaxMm1−x(NiMnSiAlFe)4.9 (x = 0–1) electrode alloys prepared by casting and rapid quenching

In order to enhance the electrochemical capacity of the Co-free AB₅-type electrode alloy, Mm in the alloys was substituted with La and Co-free La_xMm_1−x(NiMnSiAlFe)_4.9 (x = 0, 0.45, 0.75, 1.0) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the substituting Mm with La on the electrochemical performances of the as-cast and quenched alloys were investigated in detail. The obtained results show that substituting Mm with La can enhance markedly the capacities of the as-cast and quenched alloys. When the amount of substituting Mm with La, x increased from 0 to 1.0, the maximum capacity of the as-cast alloys at 0.2C rate increased from 273.45 to 304.47 mAh g⁻¹, and the capacity retaining rate (R_h) increased from 59.16 to 59.86%. The capacity of the as-quenched alloys with a quenching rate of 10 m s⁻¹ increased from 236.83 to 300.31 mAh g⁻¹, and the capacity retaining rate (R_h) decreased from 78.69 to 62.29%. The substituting Mm with La had an insignificant effect on the activation capabilities of the as-cast and quenched alloys.     

Stability of some ternary and quaternary CeNi5-based and PrNi5-based hydride systems

The Ce_1−xR_xNi_2.5Cu_2.5 (R = La,Pr; 0.8 x 0.3) and PrNi_5−xM_x (M = Cu, Fe; 0.5 x 2.5) alloys were investigated for their hydriding characteristics in the temperature range 0–70°C and hydrogen pressure range 0.01–50 atm. The nonlinear behaviour of unit cell volume vs x in Ce_1–xLa_xNi_2.5Cu_2.5 suggests that both size and electronic effects are involved. The partial replacement of Ce by La and Ni by Cu in CeNi₅ causes a substantial reduction in the hydrogen sorption pressures without significantly impairing its hydrogen capacity. It was observed that Fe is more effective than Cu in stabilizing PrNi₅-H₂. The high values of the molar entropy of hydrogen of the β-hydrides studied, S^β_H, are attributed to extensive hydrogen disorder in the interstitial sites of the host lattice. A linear correlation between the hydride decomposition pressures (or free energy) and the unit cell volume. V_c, of the host alloys was observed. This behavior is helpful in predicting the stabilities of new hydrides in a given substitutional alloy series.     

Crystal growth of CuGaxIn1−xSe2 by horizontal bridgman method

Single crystals of CuGa_xIn_1−xSe₂ were grown from stoichiometric melt by horizontal Bridgman method. An non-contact carbon coating method was used to avoid sticking between quartz ampoule and the melt. The composition variations along the as-grown ingots were studied as a function of Ga content. X-ray powder diffraction measurements were carried out to determine the lattice constants.     

On the reversibility of hydrogen storage in Ti- and Nb-catalyzed Ca(BH4)2

The hydrogen sorption properties of calcium borohydride (Ca(BH₄)₂) catalyzed with a small amount of TiF₃, TiCl₃, NbF₅ or NbCl₅ are investigated using thermal analyses and X-ray diffraction. NbF₅ exhibits the best performance among all the catalysts; it causes a decrease in the hydrogen desorption temperature which leads to hydrogen absorption at practical temperature and pressure conditions. The hydrogen content of Ca(BH₄)₂ with NbF₅ reaches about 5.0 wt.% after hydrogen absorption at 693 K for 24 h under 90 bar of hydrogen. The main dehydrogenation product of Ca(BH₄)₂ with NbF₅ is a CaH_2−xF_x solid solution with a CaF₂ (C1) structure, while pure Ca(BH₄)₂ produces CaH₂ after hydrogen desorption.     

Layered alkali titanates (A2TinO2n+1): possible uses for energy/environment issues

Uses of layered alkali titanates (A₂Ti_nO_2n+1; Na₂Ti₃O₇, K₂Ti₄O₉, and Cs₂Ti₅O₁₁) for energy and environmental issues are summarized. Layered alkali titanates of various structural types and compositions are regarded as a class of nanostructured materials based on titanium oxide frameworks. If compared with commonly known titanium dioxides (anatase and rutile), materials design based on layered alkali titanates is quite versatile due to the unique structure (nanosheet) and morphological characters (anisotropic particle shape). Recent development of various synthetic methods (solid-state reaction, flux method, and hydrothermal reaction) for controlling the particle shape and size of layered alkali titanates are discussed. The ion exchange ability of layered alkali titanate is used for the collection of metal ions from water as well as a way of their functionalization. These possible materials design made layered alkali titanates promising for energy (including catalysis, photocatalysts, and battery) and environmental (metal ion concentration from aqueous environments) applications.     

Electrochemical performance of Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes in intermediate temperature solid oxide fuel cells

The electrochemical performances of Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes have been investigated in intermediate temperature solid oxide fuel cells. The Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag cathodes prepared by ball milling followed by firing at 920 °C show the maximum performance (power density: 0.15 W cm⁻² at 800 °C) at 3 wt.% Ag. On the other hand, the Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes with 0.1 mg cm⁻² (0.5 wt.%) Ag that were prepared by an impregnation of Ag into Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ followed by firing at 700 °C (but the electrolyte–Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ assembly was prepared first by firing at 1100 °C) exhibit much better performance (power density: 0.27 W cm⁻² at 800 °C) than the composite cathodes prepared by ball milling, despite a much smaller amount of Ag due to a better dispersion and an enhanced adhesion. AC impedance analysis indicates that the Ag catalysts dispersed in the porous Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ cathode reduce the ohmic and the polarization resistances due to an increased electronic conductivity and enhanced electrocatalytic activity.     

A new way of obtaining LixNi1−xO cathodes for molten-carbonate fuel cells

An unsintered nickel plaque containing Li₂CO₃ and an organic binder were tested as a cathode in a molten-carbonate fuel cell. Organic burnout, nickel oxidation,lithium carbonate decomposition and Li_xNi_1−xO solid-solution formation occurred during the start-up of the cell. The in-cell test showed good performance after a short time of operation, and a limited performance decay after 3500 h.     

Electrochemical impedance spectroscopy of BaCeO3 modified by Ti and Y

Barium cerate exhibits high protonic conductivity, especially when modified by trivalent dopant such as Y, Yb, Nd, Sm or Dy. Unfortunately, the poor chemical stability in the presence of CO₂ is the main disadvantage of this material. One of the possible approach to get the stable protonic conductor is the preparation of solid solutions. For example, doping of BaCeO₃ with Zr leads to the improvement of the chemical stability, but the electrical properties are simultaneously corrupted.In the present work the influence of Ti, per analogy to Zr, and Y dopants on electrical properties of BaCeO₃ was investigated using the electrochemical impedance spectroscopy (EIS) technique. BaCe_1−xTi_xO_3−δ (0 ≤ x ≤ 0.3) and Ba(Ce_0.95Ti_0.05)_0.95Y_0.05O_3−δ solid electrolytes were prepared by solid-state reaction method. It was found that the changes of electrical properties due to the introduction of Ti into the BaCeO₃ lattice is caused predominantly by the modification of the grain boundary properties. The Ti doping leads to the substantial decrease of grain boundary electrical conductivity, comparing to undoped material. The introduction of yttrium dopant to the BaCe_0.95Ti_0.05O₃ lattice has the opposite effect. The total electrical conductivity increases, due to significant modification of grain boundary electrical properties.     

Electrochromic properties of lithiated Co-oxide (LixCoO2) and Ni-oxide (LixNiO2) thin films prepared by the sol–gel route

Layered Li_xCoO₂ and Li_xNiO₂ thin films (x1) were prepared by a peroxo wet chemistry route from Li(I), Co(II) and Ni(II) acetate precursors and the addition of H₂O₂. Structural changes during the processing of xerogel to final oxide were followed by X-ray diffraction and infrared spectroscopy. Electrochromic properties were determined with in-situ potentiodynamic, potentiostatic and galvanostatic spectroelectrochemical measurements. Single dipped films with composition Li_0.99Co_1.01O₂ or Li_0.94Ni_1.06O₂ exhibited stable voltammetric response in 1 M LiClO₄/propylene carbonate electrolyte after about 60 cycles. The total charge exchanged in a reversible charging/discharging cycle was about ±30 mC cm⁻² for Li_0.99Co_1.01O₂ and ±20 mC cm⁻² for Li_0.94Ni_1.06O₂ oxide films. Galvanostatic measurements showed that about 1/2 (x0.5) and 2/3 (x0.3) of Li⁺ ions could be reversibly removed from the structure of Li_0.99Co_1.01O₂ and Li_0.94Ni_1.06O₂ films, respectively. Practical applicability of Li_0.99Co_1.01O₂ and Li_0.94Ni_1.06O₂ oxide films was studied in electrochromic devices with WO₃(H⁺)Li⁺ormolyteLi_0.99Co_1.01O₂ and WO₃(H⁺)Li⁺ormolyteLi_0.94Ni_1.06O₂ configuration. The monochromatic transmittance T_s (λ=633 nm) of dark blue coloured devices was extremely low (T_s3%), whereas in bleached state the value reached around T_s70%.