Ionic conductivity of substituted Li2SO4 phases

Lithium ion conductivity of Li₂SO₄-Y₂(SO₄)₃, Li₂SO₄-La₂(SO₄)₃ and Li₂SO₄-Li₃PO₄ systems has been measured as a function of composition and temperature using AC complex impedance methods. Substitution of the trivalent cations results in a small enhancement of the ionic conductivity within the limit of solid solution formation. Considerable increase of the conductivity results by substitution of PO₄^3? for SO₄^2?. The maximum conductivity observed is $\text{1.1×10}{}^{\mathrm{?3}}\text{(Ω}\text{cm}\text{)}{}^{\mathrm{?1}}$ at 300°C for the composition Li_2.2S_0.8P_0.2O₄ with E_a = 0.8 eV. These results are discussed in terms of the structural properties.     

Phase diagram of the LISICON,solid electrolyte system,Li4GeO4Zn2GeO4

The phase diagram of the system Li₄GeO₄Zn₂GeO₄ is fairly similar to the corresponding silicate system and contains a wide range of solid solutions that extend to either side of the composition Li₂ZnGeO₄. These solid solutions are polymorphic. The high temperature ^γII solid solutions have a crystal structure derived from that of ^γII Li₃PO₄ and a formula, Li_{2 + 2x}Zn_1?xGeO₄ : ?0.36 < x < +0.87. LISICON, x = 0.75, is one member of the ^γII solid solution series. The compositional extent of the ^γII solid solutions is temperature dependent and eg. the LISICON composition is stable as a single phase γII structure only ? 630°C. On annealing LISICON and other lithiumrich, ^γII solid solutions in the range ～100 to 600°C, various reactions occur, including 1) precipitation of Li₄GeO₄, 2) phase transition(s) to metastable low temperature, γ-derivative structure(s) and 3) atmospheric attack to give Li₂GeO₃, Li₂CO₃ and other phases. The low temperature ^βII, ^βII′ solid solutions occur over a much smaller range of compositions to either side of Li₂ZnGeO₄ and have a crystal structure derived from that of ^βII Li₃PO₄. Li₄GeO₄ forms a short range of solid solutions.     

Lithium insertion into Li2Ti3O7

Li₂Ti₃O₇ with the ramsdellite-type structure undergoes lithium insertion reactions with n-BuLi. Li_2+xTi₃O₇ phases form with x = 0.5 and 1.0 at room temperature and at 50°C, respectively. The ESR spectrum of Li₃Ti₃O₇ confirms the partial reduction of Ti⁴⁺ ions to Ti³⁺. The electrical conductivity of the fully lithiated phase is several orders of magnitude higher than that of the host compound, suggesting charge hopping in the mixed valent lithiated compound.     

Ionic conductivities of Na2Ti3O7, K2Ti4O9 and their related materials

Ionic conductivities were measured on the polycrystalline samples of layered titanates, Na₂Ti₃O₇ and K₂Ti₄O₉, and their derivatives. The activation energies and the prefactors of the conductions were 0.70 eV and 7.9 × 10 (Ωcm)^?1K for Na₂Ti₃O₇ and 0.81 eB and 1.1 × 10³ (Ωcm)^?1K for K₂Ti₄O₉. A small amount of Nb₂O₅ was doped to these titanates substituting TiO₂. Remarkable enhancements of ionic conductivities were observed with the doping. A new metastable phase, Li₂Ti₃O₇, was prepared by ion-exchange of Na₂Ti₃O₇ and its ionic conductivity was measured.     

Structure and lithium ion conductivity of garnet-like Li5La3Sb2O12 and Li6SrLa2Sb2O12

Oxides with the nominal chemical compositions Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were prepared by solid-state reaction. The structures were refined by the Rietveld method using powder X-ray diffraction data. The synthesis of Li₅La₃Sb₂O₁₂ resulted in the well known garnet-related structure plus 5 wt.% of La₂LiSbO₆ in the bulk. In contrast to that, Li₆SrLa₂Sb₂O₁₂ could be synthesised in single garnet-related type phase. Lithium ion conductivities of Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂ were studied by the ac impedance method. The grain-boundary contribution to the total (bulk + grain-boundary) resistance is very small and about 5 and 3% for Li₅La₃Sb₂O₁₂ and Li₆SrLa₂Sb₂O₁₂, respectively, at 24 °C and decreases further with increase in temperature. Among the investigated compounds, Li₅La₃Sb₂O₁₂ exhibits the highest total (bulk + grain-boundary) and bulk ionic conductivity of 7.8 × 10⁻⁶ and 8.2 × 10⁻⁶ S cm⁻¹, respectively, at 24 °C. The structural data indicate that the coupled substitution Li + Sr ⇒ La leads to a closure of the bottle neck like O-O distances of the shared edges of neighbouring Li octahedra and therefore reduces the mobility of Li ions in Li₆SrLa₂Sb₂O₁₂. Scanning electron microscope (SEM) images of the Li₆SrLa₂Sb₂O₁₂ compound revealed well crystallised large homogeneous grains (∼4.8 μm) and the grains were in good contact with the neighbouring grain, which leads to a smaller grain-boundary contribution to the total resistance.     

Measurements of Bleustein-Gulyaev waves in Li2B4O7 crystal

Properties of Bleustein-Gulyaev waves (BGW) in Li₂B₄O₇ crystal were determined from the measured parameters of a delay line with double electrode interdigital transducers (IDT). Since the frequency response at the third harmonic was in good agreement with the SAW equivalent circuit model, it was possible to determine the BGW parameters. It was found that the coupling coefficient of BGW is very sensitive to aluminum layer thickness variations. Good agreement was found between calculated and measured parameters of BGW from an extrapolation to the zero layer thickness     

Effect of preparative parameters on the electrical conductivity of Li2SO4-Al2O3 composites

The effect of various preparative parameters, such as the size and form of alumina and also the time of sintering, on the electrical conductivity of the Li₂SO₄-Al₂O₃ composite system has been investigated. The sintering time appears to be an insignificant preparative parameter. The role of different phases of Al₂O₃ on the electrical conductivity of the composite clearly establishes that the maximum enhancement is achieved for γ-Al₂O₃. The 50 m/o Al₂O₃ composition was found to exhibit the highest conductivity, an enhancement of three orders of magnitude at 500°C. The experimental data indicates higher conduction in the space charge layer near the surface to be the possible mechanism of conductivity enhancement.     

Ionic conductivity in Na5GdSi4O12

Na₅GdSi₄O₁₂ has been prepared by solid state reaction. Na⁺ ion conductivity is 3 × 10^?1 (ohm-cm)^?1 at 300° with an activation energy for conduction of 6.5 kcal/mole. The structure of isotypic Na₅YSi₄O₁₂ is characterized by Si₁₂O₃₆ rings stacked to form columns held apart by MO₆ octahedra. Immobile Na atoms are situated within the rings. The high conductivity arises from the presence of mobile Na atoms between the columns.     

Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

Subsolidus phase equilibria and the Li5Nd4FeO10 phase in the Li2O-Nd2O3-Fe2O3 system

A survey of the subsolidus phase equilibria in the system Li₂O-Nd₂O₃-Fe₂O₃ was made at subsolidus temperatures in the range 1000-1050 °C. A ternary phase was identified. The phase is centered on Li₅Nd₄FeO₁₀, with a cubic lattice a = 11.9494 Å. The compound melts incongruently at 1105 °C. The magnetic susceptibility was measured in the temperature range 4-300 K. The compound is paramagnetic in the temperature range 150-300 K and follows the Curie-Weiss law. At about T_N = 10 K, a long-range magnetic ordering is observed.     

New Li+ ion conductors in the system,Li4GeO4-Li3VO4

New Li⁺ ion conducting solid electrolytes have been found in the system Li₄GeO₄-Li₃VO₄. Of the compositions studied, Li_3.6Ge_0.6V_0.4O₄ has the highest conductivity with σ ～ 4 × 10^?5 ohm^?1cm^?1 at 18°C rising to ～ 10^?2 ohm^?1 cm^?1 at 190°C. The activation energy is ～0.44 eV. These conductivity values are among the highest yet found for Li⁺ ion conductors; the room temperature value is much higher than in LISICON, Li_3.5Zn_0.25GeO₄, or in Li_3.4Si_0.4P_0.6O₄ and is comparable to that in $\text{LiI/A}\text{l}{}_2\text{O}{}_3$ mixtures. These solid electrolytes are easy to synthesize, thermodynamically stable and insensitive to atmospheric attack. Structurally, they are solid solutions based on γ_II Li₃VO₄, a γ tetrahedral structure; high conductivity is due to the interstitial Li⁺ ions which are created during solid solution formation.     

Low temperature biomimetic synthesis of the Li2ZrO3 nanoparticles containing Li6Zr2O7 and high temperature CO2 capture

Li₂ZrO₃ nanoparticles containing Li₆Zr₂O₇ were prepared by a biomimetic soft solution route and characterized with X-ray diffraction (XRD), transmission electron microscope (TEM) and nitrogen adsorption. The results show that the tetragonal Li₂ZrO₃ nanoparticles containing monoclinic Li₆Zr₂O₇ can be obtained using this simple method. The mean diameter of the nanoparticles is approximately 90 nm and the corresponding specific surface area is 23.7 m² g^− 1. Moreover, the Li₂ZrO₃ nanoparticles obtained were thermally analyzed under a CO₂ flux to evaluate their CO₂ capture capacity at high temperature. It was found that the as-prepared Li₂ZrO₃ nanoparticles would be an effective acceptor for high temperature CO₂ capture.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

The perfection of bridgman-grown Bi4Ge3O12 crystals

Single crystals of Bi₄Ge₃O₁₂ were grown by the vertical Bridgman technique. As shown by X-ray diffraction line profiles these crystals exhibit a very high degree of perfection. Bi₄Ge₃O₁₂ is used as detector material for high energy radiation. Very perfect crystals are preferred because defects play a prominent role in radiation damage.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

The solid electrolyte system,Li3PO4Li4SiO4

The phase diagram of the system Li₄SiO₄Li₃PO₄ has been studied. At subsolidus temperatures, ? 1000°C, Li₄SiO₄ forms a short range of equilibrium solid solutions between 0 and ～ 12 mole % Li₃PO₄; γ-Li₃PO₄ forms a range of equilibrium solid solutions between ～ 58 and 100% Li₃PO₄. In addition to these equilibrium solid solutions, Li₄SiO₄ forms an extensive range of metastable solid solutions containing up to ～ 60% Li₃PO₄, on quenching melts from ? 1050°C. Hence compositions around 60% Li₃PO₄, 40% Li₄SiO₄ may be prepared in two structural forms, i.e. as solid solutions of either Li₄SiO₄ or γ Li₃PO₄. Conductivity measurements show that, at these compositions, the two solid solution structures have similar, high conductivity of Li⁺ ions.     

Valency states of Yb, Eu, Dy and Ti ions in Li2B4O7 glasses

Absorption and emission spectra of Eu and Dy, Yb and Ti ions in Li₂B₄O₇ glasses grown in oxygen and hydrogen gas atmospheres were measured for valency states and lattice-sites analysis. For the Li₂B₄O₇ glass doped with Eu²⁺, Eu³⁺ and Dy³⁺ ions which were grown in oxidizing and reducing atmospheres, absorption and emission bands due to these ions were investigated before and after γ-irradiation. For the Yb³⁺-doped Li₂B₄O₇ glass, a weak, broad band was observed near the sharp 976.3 nm absorption band. The origin of this band is discussed in comparison with other glasses. Moreover, irradiation experiments using γ-rays were also performed in order to investigate the possibility of valency change of Yb ions. It was found that Ti⁴⁺ ions, which are produced under oxidizing atmosphere, change to Ti³⁺ ions after γ-irradiation with a dose of 10⁵ Gy. An additional absorption band observed at about 500 nm is due to the Ti³⁺ ions accompanied by charge-compensating vacancy and does not give any emission.     

Pure-mode measurements of Li2B4O7material properties

Recent measurements of doubly rotated plate resonators have highlighted the need for more accurate material constants for use in dilithium tetraborate resonator design. In this paper, we report on the room-temperature determination of the elastic, piezoelectric, and dielectric constants of dilithium tetraborate using frequency domain measurements of primarily pure-mode vibrations in thin, flat plates     

Preparation of Li2B4O7 thin films by chemical solution decomposition method

Li₂B₄O₇ polycrystalline films on silica glass and Si(111) substrates were prepared by chemical solution decomposition(CSD) method. After spin coating, the wet film was dried at 200 °C, and then annealed at different temperatures to form polycrystalline Li₂B₄O₇ film. These annealed films were characterized by using X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), transmission electron microscope (TEM) and selective area electron diffraction (SAED). All these results show that the main component of the film is Li₂B₄O₇ crystalline phase and the average crystalline size of these films is in the range of 20-50 nm.     

Growth of BaAl2O4, SrAl12O19 & Mg2Ga4GeO10 crystals in molten bismuth germanate glasses

Small, well-formed BaAl₂O₄ blades (up to 0.5 mm), SrAl₁₂O₁₉ platelets (up to 0.01 mm), and Mg₂GeO₁₀ plates (up to 0.25 mm) can be precipitated at 1370, 1230, and 1300°C respectively from molten MO/Bi₂O₃/2 GeO₂ mixtures that contain either Al₂O₃ or Ga₂O₃. Similar experiments with PbO and CdO containing melts yielded only Al₂O₃ crystals. After quenching, all of these crystals can be separated from the adhering glass by appropriate dissolution techniques. Density, refraction, and infrared results confirm these findings.