Impedance spectroscopy analysis of Li<Subscript>2</Subscript>SnO<Subscript>3</Subscript>

In this work, Li₂SnO₃ has been synthesized by the sol–gel method using acetates of lithium and tin. Thermogravimetric analysis (TGA) has been applied to the precursor of Li₂SnO₃ to determine the suitable calcination temperature. The formation of the compound calcined at 800 °C for 9 h has been confirmed by X-ray diffraction (XRD) analysis. The Li₂SnO₃ is then pelletized and electrically characterized by using electrochemical impedance spectroscopy (EIS) in the frequency range from 50 Hz to 1 MHz. The complex impedance spectra clearly show the dominating presence of the grain boundary effect on electrical properties whereas the complex modulus plots reveal two semicircles which are due to the grain (bulk) and grain boundary. The spectra of imaginary parts of both impedance and modulus versus frequency show the existence of peaks with the modulus plots exhibiting two peaks that are ascribed to the grain and grain boundary of the material. The peak maximum shifts to higher frequency with an increase in temperature and the broad nature of the peaks indicates the non-Debye nature of Li₂SnO₃. The activation energy associated with the dielectric relaxation obtained from the electrical impedance spectra is 0.67 eV. From the electric modulus spectra, the activation energies related to conductivity relaxation in the grain and grain boundary of Li₂SnO₃ are 0.59 and 0.69 eV, respectively. The conductivity–temperature relationship is thermally assisted and obeys the Arrhenius rule with the activation energy of 0.66 eV. The conduction mechanism of Li₂SnO₃ is via hopping.     

Electrochemical comparison between SnO2 and Li2SnO3 synthesized at high and low temperatures

Li₂SnO₃ has been synthesized at 1000 °C from Li₂CO₃ and SnO₂ (high temperature form - HT) and it has also been prepared from ball-milled SnO₂ and Li₂CO₃ at 650 °C (low temperature form - LT). The Li₂SnO₃ materials have been tested as a negative electrode for possible use in a Li-ion cell and their electrochemical behaviour has been compared with that of SnO₂. In theory, Li₂SnO₃ and SnO₂ should be able to cycle the same number of lithium atoms per tin atom but on the initial discharge SnO₂ has inserted more lithium than Li₂SnO₃. During the initial discharge of SnO₂ and Li₂SnO₃, a side electrochemical reaction seems to be occurring. The resultant compound apparently inserts lithium reversibly for potentials around 1 V; however, cycling from 0.02–2 V significantly degrades performance compared to 0.02–1 V. Li₂SnO₃ (HT) allows the de-insertion of more lithium than Li₂SnO₃ (LT) and SnO₂ in the first charge. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Structural and electrical characterization of the NASICON-type Li2FeZr(PO4)3 and Li2FeTi(PO4)3 compounds

In order to develop new electrolytes for all-solid-state rocking chair lithium batteries, the NASICON-type compounds Li₂FeZr(PO₄)₃ and Li₂FeTi(PO₄)₃ were investigated by powder X-ray diffraction technique and impedance spectroscopy. Li₂FeZr(PO₄)₃ is orthorhombic Pbna (a=8.706(3), b=8.786(2), c=12.220(5) Å) and Li₂FeTi(PO₄)₃ is orthorhombic Pbca (a=8.557(3), b=8.624(3), c=23.919(6) Å). They show no phase transitions from RT to 800 °C. In the same temperature range logσT vs. 1/T show no slope variations. The activation energies for the ionic conductivity were 0.62 and 0.64 eV for Li₂FeTi(PO₄)₃ and Li₂FeTi(PO₄)₃, respectively. In order to better evaluate the present results they were compared with those of α and β-LiZr₂(PO₄)₃ phases, which were also prepared and characterised. A change of activation energy from 0.47 eV to 1.03 eV was observed in the case of β phase, at about 300 °C; attributed to the β (orthorhombic) ? β′ (monoclinic) phase transition. In the α phase the activation energy 0.47 eV in the temperature range 150 – 850 °C. The Li₂FeZr(PO₄)₃ and Li₂FeTi(PO₄)₃ compounds can be interesting for applications as solid electrolytes in high temperature (>300 °C) lithium batteries.     

The determination of hopping rates and carrier concentrations in ionic conductors by a new analysis of ac conductivity

The a.c. conductivity σ(ω) of ionic materials takes the form, σ(ω) = σ(0) + Aωⁿ. The carrier hopping rate, ω_p, is obtained from the new expression σ(0) = A ω_pⁿ and the carrier concentration is estimated from σ(0). The contribution of creation and migration terms to the activation energy for conduction may be determined from the thermal activation of σ(0) and ω_p and the corresponding entropy terms quantified. Data have been analyzed for four widely different ionic materials: single crystal Na β-alumina, polycrystalline Li₄SiO₄, Ag₇l₄AsO₄ glass and Ca(NO₃)₂/KNO₃ glass and melt. For each, the carrier concentration and hopping rates have been obtained.     

Mixed polaronic-ionic conduction in lithium borate glasses and glass-ceramics containing copper oxide

The effect of electric field strength on conduction in lithium borate glasses doped with CuO with different concentration was studied and the value of the jump distance of charge carrier was calculated. The conductivity measurements indicate that the conduction is due to non-adiabatic hopping of polarons and the activation energies are found to be temperature and concentration dependent. Lithium borate glasses are subjected to carefully-programmed thermal treatments which cause the nucleation and growth of crystalline phases. X-ray diffraction analysis confirmed the amorphous nature for the investigated glass sample and the formation of crystalline phase for annealed samples at 650 °C. The main separated crystalline phase is Li₂B₈O₁₃. The scanning electron micrographs of some selected glasses showed a significant change in the morphology of the films investigated due to heat treatment of the glass samples. It was found that the dc-conductivity decreases with an increase of the HT temperature. The decrease of dc conductivity, with an increase of the HT temperature, can be related to the decrease in the number of free ions in the glass matrix. There is deviation from linearity at high temperature regions in the logσ-1/T plots for all investigated doped samples at a certain temperature at which the transition from polaronic to ionic conduction occurs. The hopping of small polarons is dominant at low temperatures, whereas the hopping of Li⁺ ions dominates at high temperatures. PACS 71.55.Jv; 72.60.+g; 72.80.Ng     

Effect of the film thickness on the impedance behavior of sol–gel Ba0.6Sr0.4TiO3 thin films

Perovskite Ba_0.6Sr_0.4TiO₃ sol–gel thin films with different thicknesses are fabricated as MFM configuration to study the effect of the film thickness on the dielectric relaxation phenomenon and the ionic transport mechanism. The frequency dependent impedance, electric modulus, permittivity and AC conductivity have been investigated in this context. Z? plane for all the tested samples shows two regions, corresponding to the bulk mechanism and the distribution of the grain boundaries–electrodes process. Electric modulus versus frequency plots reveal non-Debye relaxation peaks. The observed decrease in both the impedance and permittivity with the increase in film thickness is attributed to the grain size effect. The frequency dependent conductivity plots show three regions of conduction processes, i.e. low-frequency region due to DC conduction, mid-frequency region due to translational hopping motion and high-frequency region due to localized hopping and/or reorientational motion.     

Ionic conductivity of pure and doped Li3N

The ionic conductivity of Li₃N crystals doped with various metal ions (magnesium, copper and aluminum) or hydrogen has been investigated. The metal ions have a negative effect on the conductivity whereas hydrogen increases it. The intrinsic Li⁺ ionic conductivity of pure Li₃N is (2·-4)×10^-4Ω^-1cm^-1 at room temperature with an activation energy of 0.26?0.27 eV. Doping with hydrogen to a maximum level of 0.5?1.0 atom% results in a conductivity of 6×10^-3Ω^-1cm^-1 and an activation energy which has been lowered to 0.20 eV. A model is proposed for the action of hydrogen whereby the Li-N bonds next to an NH^2- group are weakened thereby facilatating the creation of Li⁺ Frenkel defects and the vacancy migration. Hydrogen-doped Li₃N is termed an enhanced intrinsic conductor.     

Non-adiabatic polaron hopping conduction in CaMn1−xCrxO3 (0?x?0.3)

DC electrical conductivity (σ_dc) of electron-doped antiferromagnetic CaMn_1−xCr_xO₃ (0?x?0.3) has been discussed elaborately in the light of polaron hopping conduction. The increase in Cr doping concentration increases the conductivity and decreases the activation energy. Non-adiabatic polaron hopping conduction is observed in all the manganites at high temperatures. The analysis of σ_dc data shows that small polarons are formed at lower concentrations (?5%) of Cr doping and undoped samples. However, large polarons are materialized at higher doping (?10%) concentrations. This is consistent with the fact that doped Cr³⁺ has larger ionic size compared to that of Mn⁴⁺. Again, strong electron-phonon (e-ph) interaction is perceived in undoped and 5% Cr-doped samples but not in manganites with larger doping concentration. This also confirms the formation of larger polarons with the increase of x. Mott's variable range hopping (VRH) model can elucidate the dc conductivity at very low temperatures. It has been detected that single phonon-assisted hopping is responsible for the dc conduction in the Cr-doped CaMnO₃ manganites.     

Dielectric-spectroscopic and a.c. conductivity studies on layered Na2-XKXTi3O7 (X=0.2, 0.3, 0.4) ceramics

The dependence of loss tangent (tanδ) and relative permittivity (ε_r) on temperature and frequency has been reported for Na_2-XK_XTi₃O₇ (with X=0.2, 0.3, 0.4) ceramics. The losses are characteristic of dipole mechanism and electrical conduction. The peaks of ε_r at high temperature indicate a possible ferroelectric phase transition for all three compositions. The results of a.c. conductivity studies on the same samples have also been reported. The corresponding ln(σT) versus 1000/T plots have been divided into five regions namely I, II, III, IV and V. The various conduction mechanisms in the different regions have been stressed. Furthermore, the log(σ) versus frequency plots for all the above samples reveal that the electronic hopping (polaron) conduction, which diminishes with the rise in temperature, is dominant in the lower temperature region. The interlayer ionic conduction seems to play a major role in conduction towards higher temperature.     

Effect of Li2O on the structure,electrical and dielectric properties of xLi2O·(20−x)CaO·30P2O5·30V2O5·20Fe2O3 glasses

Glasses of the general formula xLi₂O·(20?x)CaO·30P₂O₅·30V₂O₅·20Fe₂O₃ with x=0, 5, 10, 15 and 20 mol% were prepared; IR, density, electrical and dielectric properties have been investigated. Lithia-containing glasses revealed more (P₂O₇)^4?, FeO₆, V–O^? and PO^? groups and mostly have lower densities than those of lithia-free ones. The electrical properties showed random behavior by replacing Li₂O for CaO, which has been assigned to the change of the glass structure. The results of activation energy and frequency-dependent conductivity indicate that the conduction proceeds via electronic and ionic mechanisms, the former being dominant. The mechanism responsible for the electronic conduction is mostly thermally activated hopping of electrons from Fe(II) ions to neighboring Fe(III) sites and/or from V⁴⁺ to V⁵⁺. The dielectric constant (ε′) showed values that depend on the structure of glass according to its content of Li₂O. The (ε′) values are ranging between 3 and 41 at room temperature for 1 kHz, yet at high temperatures, glass with 20 mol Li₂O exhibits values of 110 and 3600 when measurement was carried out in the range 0.1–1 kHz, and at 5 MHz, respectively.     

NMR study of Li+-ion diffusion in the solid solution Li3+x(P1−x,Six)O4> with the γII-Li3PO4 structure

Diffusive motion of a Li⁺ ion in the solid solution of Li₃+x(P₁?x, Si_x)O₄ (0?x?0.4) with the γ_II-Li₃PO₄ structure was studied by the measurement of the ⁷Li spin-lattice relaxation time. The observed motion was a local motion instead of a long-range one. In comparison with the previous study on the solid solution of Li₄?x(P_x, Si₁?x)O₄ with the Li₄SiO₄ structure, it is noticeable that the activation energy is low and almost independent of the composition and that the attempt frequency is smaller in this phase. These characteristics were attributed to the availability of a large interstitial void in the γ_II-Li₃PO₄ structure. The low values of activation energy for the Li⁺ ionic conduction may be explained on the same basis.     

Breakdown of absolute rate theory and prefactor anomalies in superionic conductors

We suggest that the anomalously low prefactors observed for the ionic hopping rate in defect-structure superionic conductors are due to a breakdown of absolute rate theory. A treatment that takes dissipative processes into account is introduced and a new expression for the prefactor is obtained. We present NMR data on the superionic conductor Li₂Ti₃O₇ that supports these ideas and extract the value of the elemental energy transfer per collision.     

Dielectric,impedance and modulus spectroscopy of Ta-based layered perovskite

PbBi₂Ta₂O₉ ceramic samples were fabricated by high-temperature mixed oxide method. X-ray diffraction determines the structure as orthorhombic. The scanning electron microscopy confirms the formation of densely packed grains in the sample. The dielectric measurements, complex impedance and complex modulus study were carried out in a frequency range of 1?kHz–1?MHz and a temperature rangeof 25–500°C. The conduction mechanism of the material is discussed in details using variable range hoping, nearest neighbor hopping relaxation model and dc activation energy at two different temperature regimes. From the J-E characteristics studies, the occurrence of non-linear curves endorses the non-Ohmic nature of the material.     

Electrical properties of a-antimony selenide

This paper reports conduction mechanism in a-Sb₂Se₃ over a wide range of temperature (238 to 338 K) and frequency (5 Hz to 100 kHz). The d.c. conductivity measured as a function of temperature shows semiconducting behaviour with activation energy ΔE=0.42 eV. Thermally induced changes in the electrical and dielectric properties of a-Sb₂Se₃ have been examined. The a.c. conductivity in the material has been explained using modified CBH model. The band conduction and single polaron hopping is dominant above room temperature. However, in the lower temperature range the bipolaron hopping dominates.     

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：     

Impedance spectroscopy and dielectric analysis in KH2PO4 single crystal

Optical observation, differential scanning calorimetry, thermogravimetric analysis, and differential thermogravimetric measurements have been carried out on KH₂PO₄ single crystals. As compared with the optical observation of crystal under polarizing microscope, the dehydration process occurred gradually over the crystal surface at temperatures above 195 °C and then the interior of the sample. The ac impedance measurements were performed as a function of both frequency and temperature. The electrical conduction and dielectric relaxation have been studied. The activation energy of migration is 1.02 eV in the temperature range between 150 and 179 °C. The conduction mechanism in this temperature range is attributed to the hopping of proton among hydrogen vacancies. At temperatures above 186 °C, a higher conductivity activation energy with 2.94 eV is obtained. In addition to the proton conduction, the migration of the heavier ions (such as potassium ion) is also suggested.     

Ionic-electronic mixed conduction in LixV2O5

The dc conductivity of lithium vanadium bronze, Li_xV₂O₅ was measured on polycrystal prepared by solid-state reaction in the x region 0.25–0.70. Both electronic and ionic conduction was observed. The former increased with increase of lithium content and was nearly equal to the total conductivity 10^-1–10⁰ S/cm. The ionic conductivity (∽10^-4 S/cm) measured by dc four-probe technique decreased as the lithium content increased in the range 400–500°C. The apparent activation energy for ionic conduction varied from 57 kJ/mol for x of 0.25 to 82 kJ/mol for x of 0.50.     

Li2SO4—Li2B2O4,Li2SO4—(NH4)2SO4赝二元系相图及离子导电性研究

本文用差热分析和X射线衍射方法对Li₂SO₄-Li₂B₂O₄和Li₂SO₄-[NH₄]₂SO₄两个赝二元系相图进行了研究。Li₂SO₄-Li₂B₂O₄是共晶体系,共晶温度为720℃ 关键词：     

Proton and Li-7 NMR study on the effect of the OH− anion upon the Li+-ion conduction in the solid solution Li5NI2LiOH

From ¹H and ⁷LiNMR relaxation times T₁, T₂ and T_1ρ in Li₅NI₂ and the solid solution Li₅NI₂?0.77LiOH, the diffusive motion of the Li⁺ ion was studied to make clear the role of the OH^? ion in improving the Li⁺ ionic conduction. At temperatures as low as 140 K, each Li⁺ ion jumps among four available positions. Its activation energies are 9.26 and 11.8 kJ mol^?1 for Li₅NI₂ and Li₅NI₂?0.77LiOH, respectively. Diffusive motion was observed in T₂ and T_1ρ above 240 K. The mode of the cation distribution and the diffusion mechanism are not affected by the presence of the OH^? anion. The most noticeable fact is that the OH^? ion is substituted selectively for the N^3? ion that is the nearest neighbour of the Li⁺ ion. This selective substitution increases the concentration of the Li⁺ vacancy most effectively up to 4.2% of the total Li positions. At the same time it diminishes the strong attractive force of the N^3? anion binding the Li⁺ ion to the position, and thus the activation energy. For the diffusion, an anomalously low attempt frequency of 3&#x0303; × 10⁹Hz was obtained from T_1ρ, while the normal value of 4.8 × 10¹²Hz was obtained from the ionic conductivity. The large discrepancy was attributed to the collective nature of the Li⁺ diffusive motion.