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.     

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.     

Synthesis and electrochemical studies of the 4 V cathode, Li(Ni2/3Mn1/3)O2

Layered Li(Ni_2/3Mn_1/3)O₂ compounds are prepared by freeze-drying, mixed carbonate and molten salt methods at high temperature. The phases are characterized by X-ray diffraction, Rietveld refinement, and other methods. Electrochemical properties are studied versus Li-metal by charge–discharge cycling and cyclic voltammetry (CV). The compound prepared by the carbonate route shows a stable capacity of 145 (±3) mAh g⁻¹ up to 100 cycles in the range 2.5–4.3 V at 22 mA g⁻¹. In the range 2.5–4.4 V at 22 mA g⁻¹, the compound prepared by molten salt method has a stable capacity of 135 (±3) mAh g⁻¹ up to 50 cycles and retains 96% of this value after 100 cycles. Capacity-fading is observed in all the compounds when cycled in the range 2.5–4.5 V. All the compounds display a clear redox process at 3.65–4.0 V that corresponds to the Ni^2+/3+–Ni^3+/4+ couple.     

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.     

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.     

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.     

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.     

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.     

Electrochemical properties of TiO2 hollow microspheres from a template-free and green wet-chemical route

Electrochemical properties of TiO₂ hollow microspheres from a green and template-free route were investigated by charge–discharge, cyclic voltammograms, cycle performance, and high rate capacities measurements. The storage capacity of Li ions in the first discharge process was 290.3 mAh g⁻¹. During the successive 10 cycles, the reversible capacity stayed in the range from 290 to 130 mAh g⁻¹ with a capacity fading of 8.96% per cycle. Cyclic voltammograms measurement exhibited only a pair of reduction/oxidation peaks, indicating TiO₂ hollow microspheres with a good crystalline quality was approached in this route.     

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.     

Electrochemical properties of the LaNi3.55Mn0.4Al0.3Co0.4Fe0.35 hydrogen storage alloy

The electrochemical properties of LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 hydrogen storage alloy have been studied through chronopotentiometric, chronoamperometric and cyclic voltammogram measurements. The maximum capacity value obtained was 265 mAh g⁻¹ at rate C/6 and the capacity decrease was recorded by 1.5% after 30 cycles. The values of the hydrogen diffusion coefficient D_H obtained through cyclic volammogram and chronoamperometric techniques were, respectively, 7.01 × 10⁻⁸ cm² s⁻¹ and 4.23 × 10⁻¹¹ cm² s⁻¹.     

Properties of BaCe1−xTixO3 materials for hydrogen electrochemical separators

In this work the structural, microstructural and electrical properties of BaCe_1−xTi_xO₃ materials were investigated. The series of materials with different titanium concentrations x (0–0.3) were prepared by solid-state reaction method. The structural studies by X-ray diffraction have shown that undoped material crystallizes in orthorhombic phase, while the increasing concentration of Ti dopant up to x = 0.2 leads to the ordering of the structure to phases with higher symmetries (tetragonal and even cubic). The estimated solubility limit was found to be not higher than 20 at.% of Ti. Microstructure observations by scanning electron microscopy and linear contraction determination have shown the strong influence of Ti dopant on microstructure and an improvement of sinterability. The DC four-probe electrical conductivity measurements accompanied by the potentiometric EMF measurements of solid-state electrochemical cells in controlled gas atmospheres (containing H₂, O₂ and H₂O) and temperatures (500–800 °C) allowed determination of the total and partial electrical conductivities of selected materials. It was found that the introduction of Ti dopant leads to a decrease in total electrical conductivity by ca. one order of magnitude compared to the undoped material, almost independently of Ti concentration. Also, the modification of transport properties after doping with titanium was determined.     

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.     

A new electrode material for nickel–metal hydride batteries: MgNiPt alloy prepared by ball-milling

In this paper, the effects of platinum addition on the structure and electrochemical properties of MgNiPt (Pt = 1.0, 2.0 and 3.0 at.%) metal hydride alloys are discussed. The ternary alloys were processed by mechanical alloying and had their structures characterized by X-ray diffraction, transmission electron microscopy and in situ X-ray absorption spectroscopy. It is observed that the structure of the alloys is formed by amorphous and nanocrystalline phases, with the size of the nano-grains close to 5 nm. The electrochemical properties were evaluated by galvanostatic charge and discharge cycles using different discharge rates in the range of 10–80 mA g⁻¹. The best result was obtained for the Mg_49.0Ni_49.0Pt_2.0 alloy, which showed smaller decay of the discharge capacity as a function of the charge/discharge cycle number, retaining 64% of its initial discharge capacity (364 mAh g⁻¹) after 10 cycles.     

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%.     

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.     

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.     

Crystal chemistry modification of lithium nickel cobalt oxide cathodes for lithium ion rechargeable batteries

As a cathode material for lithium ion rechargeable batteries, LiNi_0.8Co_0.2O₂ (LNCO) is one of the most attractive candidates for high power electronic devices. In the present work, we have synthesized LNCO powder by solid-state route. The discharge capacity and the capacity retention of LNCO cathode are found to be 100 mAh g⁻¹ and 63%, respectively. Molybdenum doping, replacing parts of cobalt ion in LNCO lattice increases the discharge capacity (157 mAh g⁻¹) and improve its capacity retention characteristics. Through X-ray Rietveld analyses, we have found that Mo doping increases the inter-slab spacing between the (Co,Ni)O₂ octahedral layers which provides easier Li¹⁺ intercalation leading to improved electrochemical properties in the modified cathode.     

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.     

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.