Structural assessment of the electrochemical performance of LixCoO2 membrane electrodes by X-ray diffraction and absorption refinements

Li_xCoO₂ samples with different nominal load x were prepared submitting HT-LiCoO₂ membrane electrodes to electrochemical polarisation, followed by aging in open circuit conditions. Care was taken to obtain samples for both positive and negative overcharge beyond the canonical regime (0.6≤x≤1) of the Li_xCoO₂ electrode. For 11 samples in the range 0.37≤x≤1.43, Rietveld refinements of X-ray diffraction data were performed, with Li at 3a, Co at 3b and O at 6c in the space group R-3m as starting model. In the range 0.37≤x≤1, results show a continuous variation of theac unit cell and structural parameters such as the lithium site occupancy and the Li-O and Co-O interatomic distances. For samples in the range 1≤x≤1.43, Li₂CO₃ was detected as an impurity which might be due to decomposition of the electrolyte, and, if the negative overcharge was high enough, an abnormally high electron density at the 3a site indicates some Li→Co substitution. Results from Co-K edge X-ray absorption spectroscopy for the samples with x=0.37, 0.89, 1 and 1.43 show a clear shift of the absorption maximum with the oxidation state of Co and support the conclusions from Rietveld refinement. GNXAS refinement of EXAFS spectra for the samples with x=0.37 and 1 suggest that cation disordering may occur also for deep lithium deintercalation (positive overcharge), a fact which was not detectable from diffraction data.     

Structural and electrical characterization of MxNb3Se4 (M = Cu, H)

The compounds Cu_xNb₃Se₄ (0≤x≤0,45) and H_xNb₃Se₄ (0≤x≤2·10⁻³) were prepared by electrochemical titration from Nb₃Se₄. The samples were characterized by X-ray analysis and q-probe conductivity measurements as a function of temperature. The Cu-compound is isostructural with Nb₃Se₄ for 0≤x≤0.2 and shows new phases for 0,2≤x≤0,45. The H-compound shows an impurity controlled conductivity in the temperature range from 20 to 200 °C and an intrinsic type conductivity in the temperature range from 330 to 450 °C. The activation engines are 0 and 0.15 eV, respectively. Rapid proton conduction in H_xNb₃Se₄ makes it difficult to control the composition as demonstrated by exposure of the samples to different atmospheres. An increasing H-concentration decreases drastically the conductivity by several orders of magnitude.     

NMR study of local magnetic properties of beryllium substituted copper ferrite

The spin echo NMR spectra of⁵⁷Fe have been taken at 77 K to describe the local magnetic properties of beryllum substituted copper ferrite Cu_1−xBe_xFe₂O₄ for 0≤x≤0.2. From the spectra the concentration dependence of hyperfine magnetic fields for tetrahedral and octahedral sites have been derived. The results show that statistical distribution of beryllium atoms over magnetic sublattices takes place and suggest that only below x=0.2 solid solutions of beryllium copper ferrites can exist.     

Frequency response analysis of ionically conducting mixed system (1-x)CuI - xAg2MoO4 (0.15 ≤ x ≤ 0.55)

A systematic analysis of the electrical response of the mixed system (1-x)CuI — xAg₂MoO₄ (0.15≤x≤0.55) over the temperature range 297 – 447 K in the 20 Hz — 1 MHz frequency domain has been reported. Relaxation processes associated with individual compositions of this heterogeneous mixture of polycrystalline samples have been identified through a combined analysis of modulus and impedance spectral formalisms. The detailed analysis of these relaxation processes has indicated that AgI and Ag₂MoO₄ phases are the predominant sources of electric conduction in the case of samples in the composition region 0.33≤x≤0.55 whereas in those samples having x<0.33, the presence of Cu₂MoO₄ phase in the mixture is found to make a definite contribution to their effective electric conduction.     

Structural and conductivity investigations of doped Li-titanates

Polycrystalline lithium lanthanum titanates, Li_xLa_yTiO₃ (0<x<0.5, 0.5<y<0.7) show high ionic conductivity (10⁻⁴ to 10⁻³ S/cm, depending on x and y) at room temperature. Doping the lithium lanthanum titanates by Co and Ni results in perovskite-like structures, which may be readily synthesized by solid state reaction. Structural and conductivity characterizations are reported. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 999.     

Phase equilibria in the La-Me-Co-O (Me=Ca, Sr, Ba) systems

The phase equilibria of the La-Me-Co-O systems (Me = Ca, Sr and Ba) were studied in air at 1100 °C. Two types of solid solution of general composition La_1−xMe_xCoO_3−δ and (La_1−y Me_y)₂CoO₄ were found to exist in the systems. The limiting composition of La_1−xMe_xCoO_3−δ lies at x=0.8 for Me = Sr, Ba and between 0.3–0.5 for Me = Ca. It is shown that the rhombohedral distortion of the perovskite type La_1−xMe_xCoO_3−y decreases while x increases. La_1−xMe_xCoO_3−δ (Me = Sr, Ba) shows an ideal cubic structure at x=0.5. The stability range of (La_1−yMe_y)₂CoO₄ was found to be 0.25≤y≤0.35 for Me = Ca, 0.3≤y≤0.55 for Me = Sr and 0.3≤y≤0.375 for Me = Ba. All phases have tetragonal K₂NiF₄-type crystal structure. Based on the XRD and neutron diffraction patterns of quenched samples, the phase diagrams (Gibbs triangles) are constructed for all systems. The phase equilibrium at low oxygen pressure is shown for the example of the La-Sr-Co-O system. The decomposition mechanism of La_1−xSr_xCoO_3−δ at 1100 °C for the samples with 0.5<x<0.8 within the oxygen pressure range −0.678>log(Po₂)>−2.25 can be written as follows: La_1−x′ Sr_x′CoO_3−δ′=n La_1−x″Sr_x″CoO_3−δ″+m SrCoO_2.5+q/2 O₂ where x′>x″. The decomposition mechanism of La_1−xSr_xCoO_3−δ for the samples with x < 0.5 within the oxygen pressure range −2.25>log(Po₂)>−3.55 changes and can be written as follows: La_1−xSr_xCoO_3−δ′=r La_1−x′Sr_x′CoO_3−δ″+w (La_1−y′Sr_y′)₂CoO₄+v CoO+f/2 O₂. The results are shown in “logPo₂-composition” diagrams. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Short range order in sputtered Fe-B and Fe-Zr films

We report on the amorphous Fe_1−xB_x (0.12≤x≤0.60) and Fe_1−xZr_x (0.10≤x≤0.46) alloys obtained by rf-sputtering The P(H) distribution function changes versus atomic concentration are interpreted in terms of resultant atomic structure changes of the amorphous alloy and a tendency towards chemical short range order of the relevant crystalline phases.     

A study of iso- and alio-valent cation doped Ag2SO4 solid electrolyte

2 SO₄. The solid solubility limits up to x≤3 mole% for monovalent, x≤5.27 mole% for divalent and x≤3.63 mole% for trivalent cation doped Ag₂SO₄ are set with XRD, SEM, IR and DSC techniques. A predominant dependence of conductivity on the ionic size of iso- and alio-valent cations is observed. In particular, the conductivity enhances in both α and β phases, despite having a lower ionic-size dopant cation (relative to that of Ag⁺) in the transition element cation doped Ag₂SO₄. Ca²⁺, Ba²⁺, Y³⁺ and Dy³⁺ doped samples show depature from the regular behaviour in the β-phase. The conductivity behaviour is discussed considering ionic size, valence and electronic structure of the guest cations. Received: 3 February 1997/Accepted: 27 May 1997     

Synthesis and electrical characterisation of different doped magnesium titanates

The synthesis and characterization are reported for the cubic spinel titanate Mg_(2−x)Ni_xTiO₄ (x≤0.25) and Mg_(2−x)Mn_xTiO₄ (x≤1). Single phase samples were observed for Mg_(2−x)Ni_xTiO₄ and with x≤0.4 for Mg_(2−x)Mn_xTiO₄. AC measurements were carried out on four different compositions (x=0.01, 0.03, 0.04 and 0.15) in the Mg_(2−x)Ni_xTiO₄ series and for Mg_1.9Mn_0.1TiO₄. For all these compounds, increasing conductivity with temperature and Arrhenius conductivity dependence are observed, the activation energy is around 0.28 eV for the Ni compounds and is 0.184 eV for Mg_1.9Mn_0.1TiO₄. The DC conductivity was recorded over a range of oxygen partial pressures (10⁻¹⁹ to 1 atm) at 930 °C. The Mg_(2−x)Ni_xTiO₄ compounds show a n-type behaviour whereas the Mg_(2−x)Mn_xTiO₄ show a p-type behaviour at high p(O₂) and n-type at low p(O₂). The stability under reduced conditions was checked and discussed for the different synthesized compounds. Paper presented at the 5th Euroconference onSolid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Progress in the lithium insertion mechanism in Cu3P

Copper phosphide, Cu₃P has been synthesized using a ceramic route, and its electrochemical behaviour versus lithium has been studied studied galvanostatic and potentiodynamic measurements and in situ X-ray diffraction analysis. The insertion/extraction mechanism proceeds with the formation of at least three different Li_xCu_3−xP (x=1, 2, 3) phases. The electrochemical behaviour of Cu₃P samples obtained from ceramic and solvothermal syntheses are compared to further understanding of the complex redox mechanism occurring during insertion/extraction. First-principle electronic structure calculations show that discharge probably begins with the formation of a solid solution Li_xCu_3−yP (x<0.5). Paper presented at the Patras Conference on Solid State Ionics-Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Investigation of impurity effects in La2?xSrxCu1?yMyO4 (M=Ga,Zn) by electronic specific heat

The electronic specific heat C_el was studied at T≤10K on Ga- and Zn-doped La_2−xSr_xCuO₄ (0.16≤x≤0.22). In pure La_2−xSr_xCuO₄ (0.16≤x≤0.22), the C_el at T<T_c contains only a T² component but no T-linear one, which is peculiar to a clean d-wave superconductor. Partial substitution of Ga or Zn for Cu changes the T²-term of C_el into a quite different one described by the sum of a T-linear and a nearly T³ term. The coefficient of the T-linear term, γ, markedly increases with Zn-or Ga-content. The λ/λ_N vs. T_c/T_co relation for Zn-doped samples with x≥0.2 is in good agreement with the theoretical curve for resonant impurity scattering in a d-wave superconductor, while those for Ga-doped samples and for Zn-doped samples with x<0.2 deviate slightly from the theoretical curve. Such a deviation will be discussed in relation to the change in the magnetic properties of the present system caused by impurity-doping.     

Structural and magnetic properties of nano-crystalline RuFe alloys prepared by organometallic synthesis

Nanoparticles of Ru_1-xFe_x (0≤x≤1) in a carbon matrix were synthesized over the entire composition range using organometallic precursors. For Fe concentrations with x<0.70, a hexagonal close-packed phase was formed whereas a body-centered cubic phase was observed for x>0.70. The crystallite sizes varied between 5–10 nm. In addition, multi-wall carbon nanotubes formed during the pyrolysis of the precursors. Increasing superparamagnetic order was observed with increasing Fe content.     

Microstructure,dielectric and piezoelectric properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>-Ba(Ti<Subscript>0.95</Subscript>Zr<Subscript>0.05</Subscript>)O<Subscript>3</Subscript> lead-free ceramics with CuO sintering aid

Using an ordinary ceramic fabrication technique, we fabricated lead-free (1-x)(K_0.5Na_0.5)NbO₃-xBa(Ti_0.95Zr_0.05)O₃ ceramics with CuO sintering aid . Ba(Ti_0.95Zr_0.05)O₃ diffuses into (K_0.5Na_0.5)NbO₃ to form a new solid solution. The ceramics with perovskite structure possess orthorhombic phase at x≤0.04 and become tetragonal phase at x≥0.06. Both the paraelectric cubic–ferroelectric tetragonal and the ferroelectric tetragonal–ferroelectric orthorhombic phase transition temperatures decrease with increasing the concentration of Ba(Ti_0.95Zr_0.05)O₃. The doping of CuO effectively promotes the densification of the ceramics. The coexistence of the orthorhombic and tetragonal phases at 0.04<x<0.06 and the improvement in sintering performances of the ceramics significantly enhance the piezoelectric and dielectric properties at room temperature. The ceramics with x=0.04–0.06 and y=0.75–1.50 possess excellent properties: d₃₃=119–185 pC/N, k_P=37–44%, k_t=35–49%, ε=341–1129, cosδ=0.7–4.4% and T_c=312–346 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Structural investigations of non-stoichiometric solid solutions (Bi2O3)1−x(M2O3)x (M=Y, La, Pr, Nd, Gd and Dy)

The structural investigations of the non-stoichiometric solid solutions (Bi₂O₃)_1−x(M₂O₃)_x (M=Y, La, Pr, Nd, Gd and Dy) have been carried out. Polycrystalline samples have been synthesized using ceramic technique and the synthesis parameters have been optimized for each dopant concentration. The structural phase evolution studies with dopant concentrations have been performed using X-ray powder diffraction data over a wide range of compositions 0.10≤x≤0.40. The unit cell parameters have been obtained from the analysis of the data. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Synthesis and conductivities of the apatite-type systems, La9.33+xSi6−yMyO26+z (M=Co, Fe, Mn) and La8Mn2Si6O26

Apatite-type oxides of formula (La/Sr)_10−xSi₆O_26+y have been attracting significant interest recently, because of their high oxide ion conductivity. In this paper we report the synthesis and conductivities of phases based on doping La_9.33Si₆O₂₆ with Co, Fe, Mn on the Si site, according to the formula La_9.33+x/3Si_6−xM_xO₂₆ (M=Co, Fe, Mn). Substitution limits observed were x≤1.5 (Co), x≤1.25 (Fe), x≤0.5 (Mn). Higher Mn levels could be achieved by substituting onto the La site, with it being possible to prepare the phase La₈Mn₂Si₆O₂₆. The highest conductivities were observed for the Co doped samples, although investigations into the dependence of conductivity on p(O₂) (0.2–10⁻⁵ atm.) indicated that the conductivity was dominated by the electronic component in these cases. In contrast, the conductivities for the Fe and Mn doped samples were mainly ionic in the same p(O₂) range. Experiments into varying the oxygen content of these doped phases indicated that increasing the oxygen content above the nominally stoichiometric O₂₆ appears to increase the oxide ion conductivity. Preliminary studies of the reactivity of the electrolyte La_9.33Si₆O₂₆ with potential SOFC cathode materials (La_1−xSr_xMO₃; M=Co, Fe, Mn) suggests that reaction can occur at high temperatures leading to the incorporation of the transition metal into the apatite electrolyte. However, the fact that these doped phases exhibit high conductivities suggests that this may limit any problems caused by such a reaction at the electrolyte-electrode interface. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Synthesis and electrical characterisation of the perovskite niobate-titanates,Sr1−x/2Ti1−xNbxO3−δ

The synthesis and electrical characterisation over a range of oxygen partial pressures (10⁻²⁰ to 1 atm) are reported for the cubic perovskite niobate-titanates Sr_1−x/2Ti_1−xNb_xO_3−δ, which are proposed as potential anode materials for solid oxide fuel cells. Single phase samples were observed for 0≤x≤0.4, and phase purity was retained on annealing at both high and low oxygen partial pressures. Good electrical conductivity was observed on reduction in low oxygen partial pressures, with a maximum for the sample with 25% Nb (x=0.25), σ=5.6 Scm⁻¹ at 930°C (P (O₂)=10⁻¹⁸ atm). For dense samples the higher the Nb content the more resistant the reduced sample was to reoxidation as the oxygen partial pressure was increased. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Photoluminescent analysis of Zn1-xCdxO alloys

The photoluminescent (PL) spectra of Zn_1-xCd_xO (0≤x≤0.53) alloy films were obtained successfully. A new explanation from the viewpoint of band structure is brought forward to comprehend the PL nature of the alloy films. According to this explanation, the near-band-energy emissions of the Zn_1-xCd_xO (x>0) films are caused by the radiative transitions between the Zn4s–Cd5s hybrid level and the O2p level, and the broadenings of the two levels are responsible for the gradually increased line width of the PL peak of the film; Zn3d and Cd4d orbital levels have great effects on the band-gap variations of the alloys. In addition, a quadratic equation is put forward to depict the relationship between the band gaps E_g of the alloys and their Cd contents x, i.e. E_g(x)=3.30-1.22x+1.26x² (0≤x≤0.53). PACS 78.55.-m; 78.55.Et; 81.15.Cd     

Doped lithium nickel cobalt mixed oxides for the positive electrode in lithium ion batteries

Phase pure aluminium and magnesium doped lithium nickel cobalt mixed oxides Li(Ni,Co_0.1–0.2M_≤0.05)O₂ (M=Al, Mg) were synthesised in laboratory by a synthesis procedure adopted from H.C. Stark. Structural parameters were determined by Rietveld analysis of x-ray diffraction spectra. Electrochemical characterisation took place in three-electrode teflon cells and coin-type cells versus lithium metal. Thermal stability of cathodes without electrolyte was measured by DSC. For aluminium and magnesium doped lithium nickel cobalt mixed oxides Li(Ni,Co_0.1–0.2M_≤0.05)O₂ (M=Al, Mg) the layered structure is stabilised by both aluminium and magnesium. The lithium nickel disorder is decreased by cobalt and is nearly unaffected by aluminium. According to the Rietveld refinements, magnesium seems to reduce the lithium nickel disorder strongly, even though refinements are not totally reliable in this case. Initial capacity and reversibility in the first cycle are nearly unaffected by aluminium, but strongly inferred by magnesium. Both, aluminium and magnesium doping increase the cycling stability of lithium nickel cobalt mixed oxides. Increased thermal stability of charged electrodes without electrolyte by aluminium and magnesium doping seems to be due to limited delithiation. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16 – 22, 2001.     

Short-range magnetic order,irreversibility and giant magnetoresistance near the triple points in the (x,T) magnetic phase diagram of ZrMn<Subscript>6</Subscript>Sn<Subscript>6-x</Subscript>Ga<Subscript>x</Subscript>

We have studied pseudo-layered ZrMn₆Sn_6-xGa_x intermetallics (0.55 ≤ x ≤ 0.81) using magnetic, magnetoresistivity and powder neutron diffraction measurements. All the alloys studied have magnetic ordering temperatures in the 450-490 K temperature range. They present complex temperature-dependent partially disordered magnetic structures whose ferromagnetic component develops upon increasing the Ga content. ZrMn₆Sn_6-xGa_x alloys with x ≤ 0.69 are essentially collinear antiferromagnets at high-temperature and adopt antifan-like arrangements at low temperature. For x ≥ 0.75, the alloys order ferromagnetically and evolve to a fan-like structure upon cooling. The intermediate compositions (x = 0.71 and 0.73) present a canted fan-like order at high temperature and another kind of antifan-like arrangement at low temperature. The degree of short-range order tends to increase upon approaching the intermediate compositions. The (x, T) phase diagram contains two triple points (x ~ 0.70; T ~ 460 K and x ~ 0.74; T ~ 455 K), where the paramagnetic, an incommensurate and a commensurate phases meet, which possess some of the features of Lifshitz point. Irreversibilities manifest in the low-temperature magnetization curves at the antifan-fan or fan-ferromagnetic boundaries as well as inside the fan region. Giant magnetoresistance is observed, even above room temperature.     

Anomalous electrical behavior in ferromagnetic La1−xBaxCoO3−δ materials (0<x≤0.50)

We prepared in this work La_1−xBa_xCoO_3−δ (0<x≤0.50) compounds using the nitrate decomposition method, and focus in the study of the transport properties of the ferromagnetic compounds (x>0.15, T_c≈200 K) in the temperature range 77 K≤T≤300 K. We find that while for x<0.20 these materials show semiconducting behavior, their electrical conduction being dominated by small-polaron holes, for x>0.20 they show metallic behavior for T>100 K, with a transition to semiconducting behavior being observed for T ≤ 100 K. For x=0.20, small changes in the oxygen stoichiometry of the samples - due to slight variations in the thermal treatments - greatly affect the transport properties of the materials that can show either two metal-insulator transitions as the temperature increases or a semiconducting behavior. Very interestingly all these ferromagnetic samples are very sensitive to the polarity of the applied electrical current, and display peculiar “diodic” behaviors. All these observations are explained on the basis of an inhomogeneous electronic structure in the Ba-doped cobalt perovskites. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.