Novel olivine and spinel LiMAsO4 (M = 3d-metal) as positive electrode materials in lithium cells

New olivines LiMAsO₄ (M = Mn, Fe, Co, and Ni) have been tested as positive electrode in lithium cells. Under the used experimental conditions we did not succeed to remove lithium ions from LiFeAsO₄, LiMnAsO₄ or LiNiAsO₄. More work is needed in order to verify whether the lack of electrochemical activity is intrinsic to these materials, or it is due to kinetical limitations such as particle size and poor conductivity. On the contrary lithium ions could be reversibly deinserted/inserted from/into LiCoAsO₄ at average voltages of 4.8 and 4.6 V respectively; the delithiated compound maintaining the olivine structural framework.The high pressure polymorph of LiMAsO₄ (M = Fe, Co, Ni) crystallizing with the spinel structure did not show any electrochemical activity potentially useful in rechargeable lithium batteries.     

Mesopore size dependence of the ionic diffusivity in alumina based composite lithium ionic conductors

Ordered-mesoporous Al₂O₃ was synthesized by a sol–gel method using neutral copolymer surfactants as structure-directing agents. The pore size was controlled over the 3–15 nm range by the use of various surfactants. Composites composed of the synthesized mesoporous Al₂O₃ and a lithium ion conductor (LiI) were prepared. The maximum dc electrical conductivity, 2.6 × 10^− 4 S cm^− 1 at 298 K, was observed for 50 LiI·50 Al₂O₃ composite with 4.2 nm average mesopore size, which was considerably higher than the previously reported LiI-alumina composites. A systematic dependence of conductivity upon pore size was observed, in which conductivity increased with decreasing pore size, except for samples with a pore size of 2.8 nm. The lithium ion diffusion coefficient determined by the ⁷Li pulsed field gradient nuclear magnetic resonance (PFG-NMR) showed excellent agreement with the measured conductivity calculated by the Nernst-Einstein equation. On the other hand, lithium migration activation energies obtained by quasielastic neutron scattering (QENS) and ⁷Li NMR spin-lattice relaxation time (T₁) were considerably smaller than those obtained from electrical conductivity and PFG-NMR. This could be explained by the ion migration mechanism in heterogeneous composites and a possible enhancement of conductivity in mesoscopically confined spaces.     

Microstructure evolution process of Ferro-Aluminum based sandwich composite for electromagnetic shielding

In this paper, sandwich composite (SWC) with Fe–Al soft magnetic alloy sandwiched between pure iron substrates was proposed and fabricated by hot pressing and diffusion treatment. The microstructure evolution process of the composite was investigated. Fe/Fe₂Al₅/Fe diffusion couple was obtained at 700 °C and subsequently kept at 900 °C for further isothermal diffusion. During the diffusion reactive process, we confirmed that major FeAl₂ and minor Fe₄Al₁₃ were produced when Fe₂Al₅ dissolved. After 10 h of diffusion treatment, FeAl and α-Fe(Al) were the only two intermetallic phases left. Except FeAl₂, the thickness of each intermetallic layer held good parabolic relationship with the diffusion annealing time.     

Evaluation of Gibbs free energies of formation of Ce–Cd intermetallic compounds using electrochemical techniques

Gibbs free energies of formation of six Ce–Cd intermetallic compounds, CeCd, CeCd₂, CeCd₃, CeCd_58/13, CeCd₆ and CeCd₁₁, were evaluated systematically using electrochemical techniques in the temperature range of 673–923 K in the LiCl–KCl–CeCl₃–CdCl₂ molten salt bath. The linear dependence of the Gibbs free energies of formation on temperature yields to the enthalpies and entropies of formation of these intermetallic compounds. By extrapolating the Gibbs free energy of Ce–Cd intermetallic compounds to the Cd distillation temperature, it was clear that the Gibbs free energy of Ce–Cd intermetallic compounds decreases gradually from CeCd₆ to CeCd₂ and attains minimum value at CeCd₂. This suggests on the Cd distillation from the U–Pu–Ce–Cd alloy that the dissolution of U or Pu into CeCd₂ should be mostly taken into consideration.     

Electrochemical characterization on layered lithium ruthenate for electrochemical supercapacitors

Electrochemical characteristics of lithium ruthenate (Li_xRuO_2+0.5x·nH₂O) for electrochemical capacitors' electrode material were first examined in this paper by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge tests. Results show that Li_xRuO_2+0.5x·nH₂O has electrochemical capacitive characteristic within the potential range of − 0.2–0.9 V (vs. SCE) in 1 M Li₂SO₄ solution. The capacitance mainly arises from pseudo-capacitance caused by lithium ions' insertion/extraction into/out of the Li_xRuO_2+0.5x·nH₂O electrode. The specific capacitance of 391 F g^− 1 can be delivered at 1 mA charge–discharge current for Li_xRuO_2+0.5x·nH₂O electrode with an energy density of 65.7 W h kg^− 1. This material also exhibits an excellent cycling performance and there is no attenuation of capacitance over 600 cycles.     

Structural and electrochemical properties of LiNi0.5Mn0.5 − xAlxO2 (x = 0, 0.02, 0.05, 0.08, and 0.1) cathode materials for lithium-ion batteries

Layered LiNi_0.5Mn_0.5 ? xAl_xO₂ (x = 0, 0.02, 0.05, 0.08, and 0.1) series cathode materials for lithium-ion batteries were synthesized by a combination technique of co-precipitation and solid-state reaction, and the structural, morphological, and electrochemical properties were examined by XRD, FT-IR, XPS, SEM, CV, EIS, and charge–discharge tests. It is proven that the aliovalent substitution of Al for Mn promoted the formation of LiNi_0.5Mn_0.5 ? xAl_xO₂ structures and induced an increase in the average oxidation number of Ni, thereby leading to the shrinkage of the lattice volume. Among the LiNi_0.5Mn_0.5 ? xAl_xO₂ materials, the material with x = 0.05 shows the best cyclability and rate ability, with discharge capacities of 219, 169, 155, and 129 mAh g^? 1 at 10, 100, 200, and 400 mA g^? 1 current density respectively. Cycled under 40 mA g^? 1 in 2.8–4.6 V, LiNi_{0. 5}Mn_0.45Al_0.05O₂ shows the highest discharge capacity of about 199 mAh g^? 1 for the first cycle, and 179 mAh g^? 1 after 40 cycles, with a capacity retention of 90%. EIS analyses of the electrode materials at pristine state and state after first charge to 4.6 V indicate that the observed higher current rate capability of LiNi_{0. 5}Mn_0.45Al_0.05O₂ can be understood due to the better charge transfer kinetics.     

Low temperature synthesis of layered LiNiO2 cathode material in air atmosphere by ion exchange reaction

The layered LiNiO₂ cathode material for lithium ion battery was synthesized by ion-exchange reaction at low temperature in air atmosphere. The influence of synthesis conditions on the electrochemical performance of the resulting LiNiO₂ was investigated. The LiNiO₂ samples were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM) and infrared (IR) analysis. The results indicate that low temperature fabricated LiNiO₂ powders keep a single layered hexagonal structure and homogenous spheric shape like the raw material NiOOH. Charge and discharge tests show that the resultant LiNiO₂ exhibits good electrochemical properties. The first charge and discharge capacities of the sample are 183.4 mA h g^− 1 and 169.5 mA h g^− 1 at 0.5 mA cm^− 2, respectively. Galvanic charge/discharge and cyclic voltammetry tests reflect that LiNiO₂ electrode exhibits good cycle reversibility.     

Magnetic properties of rare-earth transition metal aluminides R6T4Al43 with Ho6Mo4Al43-type structure

The magnetic properties of 53 aluminium-rich intermetallic compounds R₆T₄Al₄₃ with R=rare-earth elements and T=Ti, V, Nb, Ta, Cr, Mo, W were investigated using polycrystalline samples and a SQUID magnetometer in the temperature range from 2 to 300 K with magnetic flux densities up to 5.5 T. The yttrium and lutetium compounds are Pauli paramagnetic, indicating that the transition metal atoms do not carry magnetic moments. The samarium compounds show van Vleck behavior and antiferromagnetic order with Néel temperatures of less than 12 K. Of these Sm₆Ti₄Al₄₃ becomes metamagnetic. The ytterbium compounds show a mixed or intermediate valent behavior and no magnetic order down to 2 K. All other compounds obey the Curie–Weiss law above 30 K. Their effective magnetic moments correspond to the theoretical moments of the rare-earth ions. They show ferromagnetic or metamagnetic behavior with ordering temperatures all below 20 K. The magnetization curves of most compounds (recorded up to 5.5 T) reach about 50% of the theoretical magnetization already at 0.5 T. The gadolinium compounds are exceptional in that they reach at 0.5 T only about 10% of their theoretical magnetization. The crystal structures of the isotypic compounds Yb₆V₄Al₄₃ and Yb₆Ta₄Al₄₃ were refined from single-crystal X-ray data.     

Diffusional mechanism of deintercalation in LiFe1 − yMnyPO4 cathode material

The paper presents the investigations on the structural, electrical and electrochemical properties of Mn substituted phospho-olivines LiFe_1 − yMn_yPO₄ and of W, Ti or Al doped LiFePO₄. The microscopic nature of the observed macroscopic, metallic-like conductivity of W, Ti, Al doped phospho-olivine samples is discussed. Some fundamental arguments against the bulk type conductivity are presented.A single phase, diffusional mechanism of deintercalation was found to appear for Mn-substituted LiFe_1 − yMn_yPO₄ samples in the whole range of lithium concentration, in contrast to the pure LiFePO₄, LiMnPO₄ and W, Ti, Al doped phospho-olivines, where a two-phase mechanism of electrochemical lithium extraction/insertion is observed.     

High-resolution transmission electron microscopy study on reversion of Al2CuMg precipitates in Al–Cu–Mg alloys under irradiation

Image deconvolution analyses showed that reversion of S-Al₂CuMg precipitates occurred in an Al–Cu–Mg alloy during high-resolution transmission electron microscopy observations. A fraction of Mg and Cu atoms in the precipitates diffused into Al matrix due to electron beam irradiation at 300 kV, resulting in structural/chemical reversion of the precipitates. The structural reversion of the S-Al₂CuMg precipitates is closely related with irradiation-induced displacement of atoms. The strong attraction between Cu and Mg atoms might assist the sub-threshold displacement of Cu atoms. One transitional structure is determined to be S′′-Al₁₀Cu₃Mg₃, a precursor of S-Al₂CuMg. Two other transitional structures, Al₃CuMg and Al₁₈Cu₅Mg₅ which have the same lattice parameters of a = c = 0.405 nm as that of S′′-Al₁₀Cu₃Mg₃, but different b values, are suggested.     

Effective utilization of spray pyrolyzed CeO2 as optically passive counter electrode for enhancing optical modulation of WO3

Nanocrystalline cerium oxide (CeO₂) thin films were deposited onto the fluorine doped tin oxide coated glass substrates using methanolic solution of cerium nitrate hexahydrate precursor by a simple spray pyrolysis technique. Thermal analysis of the precursor salt showed the onset of crystallization of CeO₂ at 300 °C. Therefore, cerium dioxide thin films were prepared at different deposition temperatures from 300 to 450 °C. Films were transparent (T ~ 80%), polycrystalline with cubic fluorite crystal structure and having band gap energy (Eg) in the range of 3.04–3.6 eV. The different morphological features of the film obtained at various deposition temperatures had pronounced effect on the ion storage capacity (ISC) and electrochemical stability. The larger film thickness coupled with adequate degree of porosity of CeO₂ films prepared at 400 °C showed higher ion storage capacity of 20.6 mC cm^? 2 in 0.5 M LiClO₄ + PC electrolyte. Such films were also electrochemically more stable than the other studied samples. The Ce⁴⁺/Ce³⁺ intervalancy charge transfer mechanism during the bleaching–lithiation of CeO₂ film was directly evidenced from X-ray photoelectron spectroscopy. The optically passive behavior of the CeO₂ film (prepared at 400 °C) is affirmed by its negligible transmission modulation upon Li⁺ ion insertion/extraction, irrespective of the extent of Li⁺ ion intercalation. The coloration efficiency of spray deposited tungsten oxide (WO₃) thin film is found to enhance from 47 to 53 cm² C^? 1 when CeO₂ is coupled with WO₃ as a counter electrode in electrochromic device. Hence, CeO₂ can be a good candidate for optically passive counter electrode as an ion storage layer.     

Rechargeability improvement of δ-type chemical manganese dioxide with the co-doping of Bi and Ni in alkaline electrolyte

δ-MnO₂ with the doping of Ni and Bi was prepared through a simple chemical precipitation/oxidation method. Its structure was confirmed by the X-ray diffraction tests. The results of cyclic voltammetry and galvanostatic charge–discharge tests showed that both the doping of Bi and Ni benefited the electrochemical activity of the MnO₂ electrode. Compared to the un-doped electrode, the Bi-doped one showed larger discharge capacity and the Ni-doped one showed higher discharge potential and better cycleability. With the co-doping of 5 wt% Bi and 10 wt% Ni, the discharge capacity of the MnO₂ electrode reached 252 mA h g^?1 at a 0.2C rate and 116 mA h g^?1 at a 1C rate, respectively. Its capacity remained in 105 mA h g^?1 after 50 cycles at a 1C rate, but the capacity of a commercial electrolytic MnO₂ electrode was only 37 mA h g^?1.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

Characterization of doped La0.7A0.3Cr0.5Mn0.5O3 − δ (A = Ca,Sr, Ba) electrodes for solid oxide fuel cells

Doped lanthanum manganese chromite based perovskite, La_0.7A_0.3Cr_0.5Mn_0.5O_3 ? δ (LACM, A = Ca, Sr, Ba), on yttria-stabilized zirconia (YSZ) electrolyte is investigated as potential electrode materials for solid oxide fuel cells (SOFCs). The electrical conductivity and electrochemical activity of LACM depend on the A-site dopant. The best electrochemical activity is obtained on the La_0.7Ca_0.3Cr_0.5Mn_0.5O_3 ? δ/YSZ (LCCM/YSZ) composite electrodes. The conductivity of LCCM is 29.9 S cm^? 1 at 800 °C in air, and the electrode polarization resistance (R_E) of the LCCM/YSZ composite cathode for the O₂ reduction reaction is 0.5 Ω cm² at 900 °C. The effect of Gd-doped ceria (GDC) impregnation on the LCCM cathode polarization resistances is also studied. GDC impregnation significantly enhances the electrochemical activity of the LCCM cathode. In the case of the 6.02 mg cm^? 2 GDC-impregnated LCCM cathode, R_E is 0.4 Ω cm² at 800 °C, ~ 60 times smaller than 24.4 Ω cm² measured on a LCCM cathode without the GDC impregnation. Finally the electrochemical activities of the doped lanthanum manganese chromites for the H₂ oxidation reaction are also investigated.     

Electrical conductivity and thermal expansion of the oxy-cuspidine Gd4Al2O9 substituted with Ca and Sr

The series of Gd_4 ? xM_xAl₂O_9 ? x/2 (M = Ca, Sr) with x = 0, 0.01, 0.05, 0.10 and 0.25 was prepared by the citrate complexation method. Both Gd_4 ? xCa_xAl₂O_9 ? x/2 and Gd_4 ? xSr_xAl₂O_9 ? x/2 show the monoclinic cuspidine structure with space group of P2₁/c up to 0.05–0.1 and 0.01–0.05 mol for Ca and Sr, respectively. Beyond the substitution limit of Gd₄Al₂O₉, GdAlO₃ and SrGd₂Al₂O₇ appear as additional phases. The highest electrical conductivity obtained at 900 °C yielded σ = 1.49 × 10^? 4 S/cm for Gd_3.95Ca_0.05Al₂O_8.98. In comparison, the conductivity of pure Gd₄Al₂O₉ was σ = 1.73 × 10^? 5 S/cm. The conductivities determined are in a similar range as those of other cuspidine materials investigated previously. The thermal expansion coefficient of Gd₄Al₂O₉ at 1000 °C was 7.4 × 10^? 6 K^? 1. The phase transition between 1100 and 1200 °C reported earlier changes with increasing substitution of Ca and Sr.     

Structural and electrochemical characterization of mesoporous thin films of Nb2xV2 − 2xO5 upon lithium intercalation

Nb_2xV_2 ? 2xO₅ (0 ≤ x ≤ 1) powders were prepared by a synthetic route based on the inorganic polymerization of alkoxy-choride precursors and characterized by a combination of X-ray diffraction, ⁵¹V and ⁹³Nb NMR and Raman spectroscopy. Amorphous mesoporous thin films of similar compositions were successfully prepared by a modified Evaporation Induced Self Assembly method using polystyrene-b-polyethyleneoxide diblock copolymer as structuring agent. The electrochemical properties of the mesoporous films upon lithium insertion–deinsertion are investigated by cyclic voltammetry. This study highlights the advantages of such nanoarchitecture in terms of increased capacity to insert lithium.     

An efficient approach for the direct synthesis of lithium niobate powders

Lithium niobate powders from the raw powders of Li₂CO₃ and Nb₂O₅ are directly synthesized by a combustion method with urea as fuel. The synthesis parameters (e. g., the calcination temperature, calcination time, and urea-to-(Li₂CO₃ + Nb₂O₅) quantity ratio) are studied to reveal the optimized synthesis conditions for preparing high-quality lithium niobate powders. In our present work, it is found that a urea-to-(Li₂CO₃ + Nb₂O₅) ratio close to 3, calcination temperature at 550∼600 °C and reaction time around 2.5 h may lead to high-quality lithium niobate powders. The microstructure of synthesized powders is further studied; a possible mechanism of the involved reactions is also proposed.     

Giant magnetoresistance in Cu–Co films electrodeposited on n-Si

High quality Cu–Co alloy films with excellent metallic luster have been electrolytically deposited directly onto n-Si (1 0 0) substrate, thereby eliminating the need of a conducting seed layer, which is otherwise required when the films were grown on insulating substrates (Al₂O₃). The as-deposited Cu–Co films exhibit relatively higher magnetoresistance (MR) in comparison with the as-deposited films on Al₂O₃ under identical conditions. The observed increase in MR could be attributed to the reduced substrate current shunting. The MR further improves to 2.67% (at H=10 kOe) with vacuum annealing (at 425°C for 30 min) of the films on Si. This has been ascribed to the separation of Cu and Co phases resulting in a magnetic granular nanostructure. This value of MR of annealed films on Si is, however, lower in comparison with the value obtained for annealed films deposited on Al₂O₃. Glancing angle X-ray diffraction (GAXRD) has revealed the formation of copper silicide in these samples, which is responsible for the lower value of MR. Thus we have observed good MR with a copper silicide host matrix.     

Synthesis and characterization of Eu2+ activated X12Al10.6Si3.4O32Cl5.4 (X=Sr,Ca) phosphors

In this article, we have reported emission characteristics of Eu²⁺ activated Sr₁₂Al_10.6Si_3.4O₃₂Cl_5.4 and Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4 phosphors, prepared by combustion synthesis. The PL excitation was monitored at two different wavelengths 254 nm (mercury excitation) and 354 nm (mercury free excitation), which shows broad-blue emission bands at 432 nm, and 438 nm for 354 nm excitation wavelength. Under mercury excitation at 254 nm it shows emission wavelengths at 470 nm, 589 nm, 592 nm, and 617 nm for the prepared Sr₁₂Al_10.6Si_3.4O₃₂Cl_5.4 and Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4 phosphors. Further it was characterized by XRD, for the investigation of phase and purity of the phosphors. Thermal degradation of the phosphors was also studied at different temperatures.     

Self-assembled line growth of allyl alcohol on the H-terminated Si(100)-(2 × 1) surface

Using first-principles density-functional calculations, we investigate the growth mechanism of allyl alcohol (ALA) line on the H-terminated Si(100)-(2 × 1) surface. Unlike the allyl mercaptan (CH₂ = CH ? CH₂ ? SH) line, which was observed to grow across the Si dimer rows, we find that ALA (CH₂ = CH ? CH₂ ? OH) has the line growth along the Si dimer row. The self-assembled growth of ALA line occurs via the radical chain reaction mechanism, similar to the case of a typical alkene molecule, styrene. Our calculated energy profile along the reaction pathway shows that the different growth direction of ALA line compared with that of allyl mercaptan line is ascribed to the great instability of the oxygen radical intermediate, which prevents the line growth across the dimer rows.