Ionic conduction in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals doped with Cr and Mn ions

The electrical conductivity σ of crystals of lithium heptagermanate Li₂Ge₇O₁₅ doped with Cr and Mn is measured in an alternating-current field with a frequency of 1 kHz in the temperature range 300–700 K. It is found that doping strongly affects the electrical conductivity. It is established that the addition of 0.1 wt % Cr leads to an increase in the electrical conductivity σ by almost one order of magnitude, whereas the introduction of 0.03 wt % Mn substantially reduces the electrical conductivity along particular crystallographic directions. Data available on the incorporation of Cr and Mn impurity atoms into the lattice suggests that the electrical conductivity is determined by lithium ions hopping over interstitial positions along the structural channels.     

Influence of composition nonstoichiometry on the electrical conductivity of LiNaGe4O9 crystals

The electrical conductivity σ of Li_{2 ? x} Na _x Ge₄O₉ (x = 1, 0.5, 0.2) crystals in an alternating-current electric field has been investigated at a frequency of 1 kHz in the temperature range of 300–800 K. A considerable anisotropy of the electrical conductivity has been revealed for crystals with a sodium concentration x = 1 at T > 500 K. It has been shown that the electrical conductivity σ along certain crystallographic directions increases by more than three orders of magnitude with a change in the sodium concentration from x = 1 to x = 0.2. The results have been discussed taking into account the specific features of the structure of the crystals under investigation. Presumably, the major charge carriers are interstitial Li ions migrating along channels of the framework structure of the Li_{2 ? x} Na _x Ge₄O₉ crystals.     

Thermal and electrical properties of glass-ceramics based on lithium heptagermanate

Glass-ceramic samples based on lithium heptagermanate Li₂Ge₇O₁₅ have been prepared by rapid quenching and subsequent heat treatment. The calorimetric measurements have revealed that Li₂Ge₇O₁₅ crystallizes from the glass phase in two stages. An intermediate state is characterized by a significant increase in the electrical conductivity of the glass-ceramic materials.     

Ion conduction and space-charge polarization processes in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The electrical properties of a lithium heptagermanate (Li₂Ge₇O₁₅) crystal have been studied in DC and AC measuring fields at temperatures from 500 to 700 K. In a DC field, a substantial decrease of electrical conductivity σ with time has been detected. On the basis of kinetic dependences σ(t), estimates of the charge carrier diffusion coefficient D have been obtained. In the frequency range 10¹–10⁵ Hz, the spectra of complex impedance ρ*(f) have been measured. The analysis of diagrams in the complex plane (ρ″–ρ′) has been performed within the equivalent circuit approach. It has been shown that, in the considered temperature and frequency intervals, the electrical properties of Li₂Ge₇O₁₅ crystals have been determined by the hopping conduction of interstitial lithium ions A _Li and accumulation of charge carriers near the blocking Pt electrodes.     

Optical second harmonic generation study of the ferroelectric phase transition in crystals and nanocrystals of lithium heptagermanate

The D _2h -C _2v ferroelectric phase transition in crystals of lithium heptagermanate Li₂Ge₇O₁₅ was revealed by the optical second harmonic generation technique. The phase transition temperature T _c was observed to shift from 10 to 6°C when the samples were doped with chromium (0.05%). No second harmonic signal was detected in the ferroelectric phase of nanocrystalline Li₂Ge₇O₁₅ samples.     

EPR study of copper ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The EPR spectra of Cu²⁺ ions (² D _5/2) located at two structurally nonequivalent positions Cu1 and Cu2 in crystals of lithium heptagermanate Li₂Ge₇O₁₅ are recorded. The angular dependences of the EPR spectrum are measured in the paraelectric phase of the Li₂Ge₇O₁₅ compound (T = 300 K). The components of the g factor and the hyperfine interaction tensor A are determined, and the orientation of the magnetic axes with respect to the crystallographic basis is established. The EPR spectra are recorded in the temperature range in the vicinity of the temperature T _C = 283 K of the transition from the paraelectric phase to the ferroelectric phase. The position symmetry of the Cu1 and Cu2 centers is determined at temperatures above and below the phase transition temperature T _C . The localization of paramagnetic centers in the structure is discussed, An analysis of the results obtained demonstrates that the Cu1 and Cu2 centers in the Li₂Ge₇O₁₅ crystal lattice replace lithium ions located at two structurally nonequivalent positions with the symmetries described at temperatures above T _C by the triclinic C _i and monoclinic C ₂ point groups, respectively.     

Synthesis and electrochemical properties of Li8 − x Zr1 − x Nb x O6 solid solutions

New lithium-conducting solid solutions based on lithium orthozirconate have been synthesized by mutual doping of the related structures Li₈ZrO₆ and Li₇NbO₆. The main factor determining the increase in the electrical conductivity of the Li_{8 ? x} Zr_{1 ? x} Nb _x O₆ solid solutions is the formation of lithium vacancies in the tetrahedral and octahedral layers. The practical stability of the Li_{8 ? x} Zr_{1 ? x} Nb _x O₆ ceramics to metallic lithium has been studied.     

Heat transport over nonmagnetic lithium chains in LiCuVO<Subscript>4</Subscript>, a new one-dimensional superionic conductor

The thermal conductivity of three single-crystal samples of the quasi-one-dimensional spin system of LiCuVO₄ with different concentrations of defects (primarily, vacancies on the lithium sublattice) was measured along the crystallographic a axis (along the nonmagnetic lithium chains) in the temperature interval 5–300 K. An increase in thermal conductivity from that of the crystal lattice was revealed for T>150–200 K. This increase can be accounted for only by assuming LiCuVO₄ to be a superionic conductor. This assumption was confirmed by measuring its electrical conductivity in the temperature interval 300–500 K. Li⁺ ions move over vacancies on the lithium sublattice (conducting channels) and act as charge carriers in LiCuVO₄. It is shown that LiCuVO₄ is a fairly good superionic conductor with application potential.     

Semiconductor-metal transition in defect lithium cobaltite

The magnetic susceptibility, electrical conductivity, and x-ray photoelectron and x-ray absorption spectra of defect lithium cobaltites of the general formula Li_{1 ? x} CoO₂ are investigated. It is found that, for lithium cobaltites with x > 0.25, the magnetic susceptibility increases abruptly and the conductivity type changes at T ～ 150 K. The assumption is made that the semiconductor-metal transition in defect lithium cobaltite is caused by the increase in the diffusion mobility of lithium ions with an increase in the temperature when there is a correlation between spatial distributions of lithium vacancies and “electron” holes.     

Interrelation of structural features and vibrational dynamics of atoms in the crystal lattice of lithium orthogermanate in the superionic state

The crystal structure and vibrational dynamics of lithium atoms in Li_3.75Ge_0.75V_0.25O₄ and Li_3.70Ge_0.85W_0.15O₄ solid electrolytes in the superionic state are investigated using neutron diffraction and nuclear magnetic resonance (NMR) spectroscopy. It is found that, in the crystal lattice, lithium ions occupy four nonequivalent positions in the tetrahedral and octahedral oxygen ion environment with vacancies in the octahedra. These findings are in good agreement with the NMR data on the dynamic inhomogeneity of lithium cations in the lattice. It is shown that the origin of the superionic state in the studied compounds is associated primarily with the geometric factor, i.e., with an increase in the size of cavities in the oxygen polyhedra surrounding lithium cations.     

Electrical behaviour of Li2O-ZnO-SiO2 glass and glass-ceramics system

Sealing quality lithium zinc silicate (LZS) glasses of compositions (wt.%) (a) LZSL- Li₂O: 12.65, ZnO: 1.85, SiO₂: 74.4, Al₂O₃: 3.8, K₂O: 2.95, P₂O₅: 3.15, B₂O₃: 1.2 (low ZnO), and (b) LZSH- Li₂O: 8.9, ZnO: 24.03, SiO₂: 53.7, Na₂O: 5.42, P₂O₅: 2.95, B₂O₃: 5 (high ZnO) were prepared by conventional melt-quench technique and converted to glass-ceramics by controlled crystallization process. The electrical properties of these samples were measured using ac impedance spectroscopy technique over a frequency range of 10 Hz-15 MHz at several temperatures in the range of 323-673 K. The ac conductivity, dc conductivity, dielectric constant and loss factor were obtained from these measurements. The dc conductivity (σ_dc) follows the Arrhenius behaviour with temperature. It is observed that σ_dc in LZSL glass is significantly higher than in the LSZH glass and the activation energies for σ_dc for LZSL and LZSH glasses are 0.59 and 1.08 eV, respectively. It further observed that the conductivity value decreases nearly one order of magnitude on conversion to glass-ceramics. The behaviour is explained on the basis of distributions and nature of alkali ions and network structures in these samples.     

First-principles calculations of the effect of Ge content on the electronic,mechanical and acoustic properties of Li17Si4-xGex

The electronic, mechanical and acoustic properties of Li₁₇Si_4-xGe_x (x = 0, 2.3, 3.08, 3.53, and 4) have been investigated by using first-principles calculations based on the density functional theory (DFT). The research shows that the bulk modulus B, Young's modulus E, shear modulus G, and hardness H_v gradually decrease with the increasing Ge content. Li₁₇Si_4-xGe_x have the brittle nature from the analysis of B/G ratio and Cauchy pressure. The maximum Young's moduli are all along [1 1 0] plane, and the sequence of degree of anisotropic property is Li₁₇Ge₄ > Li₁₇Si_0.48Ge_3.52 > Li₁₇Si_0.92Ge_3.08 > Li₁₇Si_1.7Ge_2.3 > Li₁₇Si₄. The analysis of acoustic velocity shows that all the sound velocities decrease with the increasing Ge content for Li₁₇Si_4-xGe_x (x = 0, 2.3, 3.08, 3.53, and 4), and the longitudinal wave along [111] direction is fastest for the studied compounds. Debye temperature Θ_D, v_t and v_l decrease with the increasing Ge content. The minimum thermal conductivity decreases with the increasing Ge content, and Li₁₇Si_4-xGe_x have low thermal conductivities and are not potential thermal conductors. The analysis of electronic properties indicates that Li₁₇Si_4-xGe_x have the metal nature and anisotropic electrical conductivity. The electric conduction is improved with the increasing Ge content.     

Factors affecting ionic conductivity in the lithium conducting glassy solid electrolytes

The electrical conductivity results of lithium borosilicate glasses with addition of Li₂SO₄ and LiCl have been critically analyzed. In general, it is observed that the factors viz. lithium fraction, f_Li and the number of non-bridging oxygens (NBOs) govern the ionic conductivity in the lithium conducting glasses. For the same f_Li, the presence of mixed formers in the glass gives higher conductivity compared to that of the glass with only one former. Thus the competitive network of glass in mixed former systems provides higher mobilities for lithium ions and hence high ionic conductivity. The addition of Li₂SO₄ and LiCl in the lithium borosilicate glasses gave enhancement in the conductivity. However, the mechanism of enhancement in conductivity is different in the two glass systems. The comparison of the result of binary, ternary and quaternary glass systems suggests that in general, the decrease in activation energy, increase in f_Li and increase in NBOs gives rise to enhancement in conductivity. For the same value of f_Li the higher conductivity is exhibited by glasses with lower value of K (K=SiO₂/B₂O₃). Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

An EPR study of local fluctuations in the vicinity of the ferroelectric phase transition in Li2Ge7O15

EPR spectra of Mn²⁺ ions have been studied in the temperature interval containing the ferroelectric transition in crystalline lithium heptagermanate Li₂Ge₇O₁₅. The EPR linewidth and shape were measured as functions of temperature and orientation. It is shown that the critical resonance-line broadening observed to occur in the vicinity of the phase transition is due to fluctuations in the local order parameter with frequencies below 10⁷ Hz.     

Mixed ion-polaron transport in lithium vanadium–molybdenum tellurite glasses

The electrical properties of mixed ion-polaron conducting vanadium tellurite glasses of the form XLi₂O·(1 − X)[0.5V₂O₅·0.5MoO₃]2TeO₂ have been studied by using the impedance spectroscopy in a wide range of temperature and composition. The obtained results confirm the existence of a transition from a typically electronic (polaronic) conductive regime when the molar fraction (X) of Li₂O is equal to 0, to an ionic conductive regime when X tends to 1. This transition is characterised by a deep minimum in the electrical conductivity of about 3 orders of magnitude. The correlated behaviour between conductivity and the mean distance between lithium ions and between vanadium ions reinforces the key idea of two independent migrating paths for both electrons and ions, respectively.     

Synthesis and physicochemical properties of Li2 Me x Zr1 − x O3 − δ (Me = Nb,Ti; x = 0.05, 0.1) solid solutions

Complex lithium metallates Li₂ Me _x Zr_{1 ? x} O_{3 ? δ} (Me = Nb, Ti, x = 0.05, 0.1) with iso-and heterovalent substitutions for Zr⁴⁺ ions in lithium zirconate are synthesized for the first time using a citrate technique. The inclusion of Ti⁴⁺ and Nb⁵⁺ ions in the crystal structure of Li₂ZrO₃ is confirmed by means of X-ray diffraction and NMR. It is shown that in the temperature range of 750–820 K, Li₂Ti_0.1Zr_0.9O₃ solid solution has higher conductivity than phases of undoped lithium zirconate.     

Electrical conductivity and dielectric properties of β-BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> crystal in the temperature range 90–300 K

The electrical conductivity σ and dielectric properties (?, tanδ) of β-BaB₂O₄ were studied in the temperature range 90–300 K. The quantities σ, ?, and tanδ were measured at frequencies of 0.1, 1, and 10 kHz and 1 MHz. The dielectric permittivity and electrical conductivity were found to grow with increasing temperature at all frequencies. The permittivity decreases and the electrical conductivity increases (by several orders of magnitude) with increasing frequency. Maxima were observed in the σ=f(T) and tanδ=f(T) curves for all frequencies; the maxima shift toward higher temperatures with increasing frequency.     

Dielectric relaxation of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> pair centers in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The temperature-frequency dependences of the permittivity of crystals of lithium heptagermanate Li₂Ge₇O₁₅ doped with Cr³⁺ ions are investigated. A dielectric response to reorientation of the dipole moments of the chromium impurity centers is revealed. Anomalies of the permittivity are described within the model of a Debye relaxator.     

Lithium-ionic diffusion and electrical conduction in the Li7La3Ta2O13 compounds

The electrical properties and the mechanism of lithium ionic diffusion in the Li₇La₃Ta₂O₁₃ compounds were investigated. The bulk and total conductivity at 300 K of the Li₇La₃Ta₂O₁₃ compound are about 3.3 × 10^? 6 S/cm and 2.6 × 10^? 6 S/cm, respectively. The activation energy of bulk and total conductivity is in the range of 0.38–0.4 eV. A prominent internal friction peak in Li₇La₃Ta₂O₁₃ compounds was observed around 280 K at 0.5 Hz, which is actually composed of two subpeaks (P₁ peak at lower temperature and P₂ peak at higher temperature). From the shift of peak position with frequency, the activation energy of 1.0 eV and the pre-exponential factor of relaxation time in the order of 10^? 18–10^? 21 s were obtained if one assumes Debye relaxation processes. These values of relaxation parameters strongly suggest the existence of interaction between the relaxation species (here lithium ions or vacancies). Based on the coupling model, the relaxation activation energies are deduced as 0.45 eV and the pre-exponential factor of relaxation time as 10^? 15 s. Judging from these relaxation parameters and the similarity of structure between Li₇La₃Ta₂O₁₃ and Li₅La₃Ta₂O₁₂ compounds, the P₁ and P₂ peaks are suggested to be related with the lithium ionic diffusion between 48g?48g and 24d?48g.     

Li4SiO4-Li3VO4赝二元系和Li4GeO4-Li4SiO4-Li3VO4赝三元系中新的锂离子导体

本文在室温到300℃的温度范围内研究了Li₄SiO₄-Li₃VO₄和Li₄GeO₄-Li₄SiO₄-Li₃VO₄体系中的离子导电性,发现γ_II相固溶体Li_3+xV_1-xSi_xO₄是好的锂离子导体。所研究的成分中Li_3.3V_0.7Si_0.3O₄的离子电导率最高,室温下为1×10^-5Ω^-1·cm^-1,在42—192℃的电导激活能为0.36eV,电子电导率可以忽略,因而这是迄今所发现的最好的锂离子导体之一。粗略确定了Li₄GeO₄-Li₄SiO₄-Li₃VO₄三元系中电导率高的范围,发现在Li_3.5V_0.5Ge_0.5O₄中Si部分取代Ge可以使电导率进一步提高,Li_3.5V_0.5Ge_0.4Si_0.1O₄的室温电导率可达1.3×10^-5Ω^-1·cm^-1,电导激活能为0.40eV。 关键词：