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The formation of an electric double‐layer (EDL) is an important phenomenon for many research areas, including energy storage technology. Although EDL is well‐known in electrochemistry, most of the studies involve the characterization of liquid electrolyte/electrode interfaces, and only a limited number of studies in solid‐solid contacts, such as solid electrolyte/electrode interface are available. This paper employed electrochemical impedance spectroscopy (EIS) to systematically investigate the influence of experimental factors in the interfacial capacitance arising from the electrode polarization in a lithium disilicate glass/gold electrode interface. It analyzed the influence of a.c. input voltage amplitude, samples' roughness (mechanical and chemomechanical polishing) and thickness, range of applied frequency and temperature, and the number of impedance cycles. In short, it was found that an input voltage range of 15–60 mV is indicated to minimize potential electrochemical processes during electrode polarization, where the data is reproducible from the second measurement cycle onward. Smoother surfaces closely approximated ideal electrode spike behavior, with surface treatment exhibiting influence on interfacial capacitance values. Moreover, as expected, we observed an increase in relative permittivity values with increasing thickness, accompanied by decreased capacitance values. Finally, by employing optimal experimental conditions and analyzing the inflection frequency (finflection${{f}_{inflection}}$) of the ε′$\varepsilon ^{\prime}$ versus log(f$f$) curve, we determined that the ratio between effective charge carriers (ne${{n}_e}$) and the total number of charge carriers (nt${{n}_t}$) nent$\frac{{{{n}_e}}}{{{{n}_t}}}$ falls within the range of 5–12% between 130°C and 280°C. [ABSTRACT FROM AUTHOR]

Garnet-type solid electrolytes stand out as promising Li-ion conductors for the next-generation batteries. It has been demonstrated that the inherent properties of garnets can be tailored by introducing various dopants into their crystal structures. Recently, there has been a growing interest in the concept of high entropy stabilization for materials design. In this study, we synthesized high-entropy garnets denoted as Li6La3Zro.7Tio.3Tao.5Sbo.5Oi2 (LLZTTSO), wherein Ti, Sb, and Ta occupy the Zr site. The formation of the cubic garnet phase in LLZTTSO was confirmed through X-ray diffraction (XRD), and the resulting lattice parameter agreed with predictions made using computational methods. Despite the substantial porosity (relative density 80.6%) attributed to the low sintering temperature, LLZTTSO exhibits a bulk ionic conductivity of 0.099 mS cm-1 at 25°C, and a total ionic conductivity of 0.088 mS cm-1, accompanied by an activation energy of 0.497 eV. Furthermore, LLZTTSO demonstrates a critical current density of 0.275mAcm-2 at 25°C, showcasing its potential even without any interfacial modification. [ABSTRACT FROM AUTHOR]

This study explores multi-component garnet-based materials as solid electrolytes for all-solid-state lithium batteries. Through a combination of computational and experimental approaches, we investigate the thermodynamic and structural properties of lithium lanthanum zirconium oxide garnets doped with various elements. Applying density functional theory, the influence of dopants on the thermodynamic stability of these garnets was studied. Probable atomic configurations and their impact on materials' properties were investigated with the focus on understanding the influence of these configurations on structural stability, phase preference, and ionic conductivity. In addition to the computational study, series of cubic-phase garnet compounds were synthesized and their electrochemical performance was evaluated experimentally. Our findings reveal that the stability of cubic phase in doped Li-garnets is primarily governed by enthalpy, with configurational entropy playing a secondary role. Moreover, we establish that the increased number of doping elements significantly enhances the cubic phase's stability. This in-depth understanding of materials' properties at atomic level establishes the basis for optimizing high-entropy ceramics, contributing significantly to the advancement of solid-state lithium batteries and other applications requiring innovative material solutions. [ABSTRACT FROM AUTHOR]

Garnet-type solid electrolytes stand out as promising Li-ion conductors for the next-generation batteries. It has been demonstrated that the inherent properties of garnets can be tailored by introducing various dopants into their crystal structures. Recently, there has been a growing interest in the concept of high entropy stabilization for materials design. In this study, we synthesized high-entropy garnets denoted as Li6La3Zr0.7Ti0.3Ta0.5Sb0.5O12 (LLZTTSO), wherein Ti, Sb, and Ta occupy the Zr site. The formation of the cubic garnet phase in LLZTTSO was confirmed through X-ray diffraction (XRD), and the resulting lattice parameter agreed with predictions made using computational methods. Despite the substantial porosity (relative density 80.6%) attributed to the low sintering temperature, LLZTTSO exhibits a bulk ionic conductivity of 0.099 mS cm−1 at 25°C, and a total ionic conductivity of 0.088 mS cm−1, accompanied by an activation energy of 0.497 eV. Furthermore, LLZTTSO demonstrates a critical current density of 0.275 mA cm−2 at 25°C, showcasing its potential even without any interfacial modification.

This study explores multi-component garnet-based materials as solid electrolytes for all-solid-state lithium batteries. Through a combination of computational and experimental approaches, we investigate the thermodynamic and structural properties of lithium lanthanum zirconium oxide garnets doped with various elements. Applying density functional theory, the influence of dopants on the thermodynamic stability of these garnets was studied. Probable atomic configurations and their impact on materials’ properties were investigated with the focus on understanding the influence of these configurations on structural stability, phase preference, and ionic conductivity. In addition to the computational study, series of cubic-phase garnet compounds were synthesized and their electrochemical performance was evaluated experimentally. Our findings reveal that the stability of cubic phase in doped Li-garnets is primarily governed by enthalpy, with configurational entropy playing a secondary role. Moreover, we establish that the increased number of doping elements significantly enhances the cubic phase’s stability. This in-depth understanding of materials’ properties at atomic level establishes the basis for optimizing high-entropy ceramics, contributing significantly to the advancement of solid-state lithium batteries and other applications requiring innovative material solutions.

La2Mo2O9 based Tb-doped compound, La2-xTbxMo2O9 (x=0.1, 0.2, 0.5), was synthesized and characterised by EIS studies. The frequency and temperature dependent dielectric, electric modulus and ac conductivity studies have been done. Different formalisms have been used to understand relaxation mechanism in our compound. The conductivity in these specimens appears to be due to mobility of oxygen ions.

The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term ‘solid state ionics’ was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1–xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm–1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm–1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology.

The formation phenomena of silver carbonate (Ag2CO3)–silver iodide (AgI) solid solutions were investigated by X-ray diffraction, thermogravimetry-differential thermal analysis, and electrical conductivity measurement. Results revealed that AgI and Ag2CO3 reacted with each other when mixed at room temperature. The reaction products were classified into three types: (1) AgI-based solid solutions in the AgI-rich region for x = 10% or less in x Ag2CO3–(1 − x) AgI; (2) Ag2CO3-based solid solutions in the Ag2CO3-rich region for x = 60% or more; and (3) silver carbonate iodides in the intermediate range for x between 10% and 60%. For the AgI-based solid solutions, the incorporation of Ag2CO3 into the AgI lattice expanded the unit cell and enhanced electrical conductivity. The solubility limit of Ag2CO3 into the AgI lattice estimated from the differential thermal analysis was x ≈ 5%.

The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term 'solid state ionics' was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1-xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm-1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm-1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology. [ABSTRACT FROM AUTHOR]

Lithium superionic conductors with the Li10GeP2S12 (LGPS)-type structure are promising materials for use as solid electrolytes in next-generation lithium batteries. A novel member of the LGPS family, Li9.42Si1.02P2.1S9.96O2.04, and its solid solutions were synthesised by quenching from 1273 K in the Li2S–P2S5–SiO2 pseudoternary system. The material exhibited an ionic conductivity as high as 3.2×10−4 S cm−1 at 298 K, as well as the high electrochemical stability to lithium metal, which was improved by the introduction of oxygen into the LGPS-type structure. An all-solid-state cell with a lithium metal anode and Li9.42Si1.02P2.1S9.96O2.04 as the separator showed excellent performance with a high coulomb efficiency of 100%. Thus, oxygen doping is an effective way of improving the electrochemical stability of LGPS-type structure.

Lithium exchanged phases of amorphous and crystalline zirconium titanium phosphate have been synthesized by an ion exchange technique. These materials have been characterized by elemental analysis (ICP-AES and AAS), spectral analysis (FTIR), thermal analysis (TGA) and X-ray diffraction studies. The conductance properties of these materials have been explored by measuring specific conductance at different temperatures in the range of 30-250 °C at 10 °C intervals, using impedance analyzer over a frequency range 1 Hz - 32 MHz at a signal level below 1 V. Lithium exchanged phases of amorphous and crystalline zirconium phosphate and titanium phosphate have also been synthesized under identical conditions, characterized and their conductance properties investigated for comparative studies. It is observed that, in all cases, conductivity decreases with increasing temperature. Conductance performance is discussed based on conductivity data and activation energy. [ABSTRACT FROM AUTHOR]

Abstract: The selectivity of metal oxide gas sensors (MOG) can be improved significantly by forming composites with solid ionic conductor additives. First investigations were done using model composites of SnO2/Natrium Super Ionic Conductor (NASICON) with the result of a huge sensitivity enhancement to substances ending with R–OH, R–HO or R–COOH groups and a reduction of sensitivity to other gas components. This selectivity of the new composite to those functional groups could be confirmed by catalytic conversion measurements with FTIR-spectroscopy at three gas components, respectively. The specific conductivity of the NASICON containing composites is significantly lower than that of pure SnO2. Advanced studies show that the activation energy of the bulk-conductivity increases by approximately 30% in the presence of NASICON. In spite of high volume parts of NASICON (20%), no polarization effects were found (a complete Ohmic current–voltage behavior) and mainly the resistive part of the electrical impedance is influenced. [Copyright &y& Elsevier]

The paper presents the results of research of properties of LaLiTiO 3 and β-Al 2 O 3 thin films for miniature thermobiosensors. The available thermoelectric semiconductor converters are not sensitive enough for registration of slight quantities of heat during biochemical reactions in the region of low-potential temperature differences. For this, we prepared new thin-film materials LaLiTiO 3 and β-Al 2 O 3 and studied their thermal and electrical properties. These materials are solid electrolytes with superionic conductivity. The vacuum methods of “explosive” evaporation and magnetron sputtering were used for depositing the films. For the first time thin films of β-Al 2 O 3 and LaLiTiO 3 were used as sensor based electrical converters for measuring the concentration of glucose, urine and heavy metal ions. [ABSTRACT FROM AUTHOR]

The influence of the sodium-ions in SnO2/NASICON (Na super ionic conductor) admixtures on the selectivity and sensitivity of metal oxide gas sensors was studied. NASICON (Na1+xZr2SixP3−xO12, 0≤x≤3) was chosen as a model substance in which the content of sodium ions can be varied in the range 0≤x≤3. For that purpose SnO2 powder was prepared and mixed in a volume ratio of 8:2 with NASICON powder, screen printed and sintered to obtain a gas sensitive thick film composite. A drastic improvement of the sensitivity to R&z.sbnd;OH, R&z.sbnd;CHO and R&z.sbnd;COOH ending molecules and a reduction of the sensitivity to molecules like CO, H2, NH3, propane, propene, 2-propanol and propanone was observed in comparison to pure SnO2. This effect is clearly pronounced with increasing concentration of the sodium ions in the NASICON structure. For comparison, admixtures with the anionic conductor yttrium stabilized zirconia (YSZ) and with the typical isolator Al2O3 showed equal or also higher sensitivities to the most tested substances compared to pure SnO2 but no pronounced selectivity. A preliminary model is presented which explains the unusual gas sensitivity of SnO2/NASICON composites to some individual gas components by specific molecular interactions at the NASICON-surface and by sensitivity amplification due to e−–Na+ interactions across the SnO2/NASICON interface. [Copyright &y& Elsevier]

The formation phenomena of silver carbonate (Ag2CO3)–silver iodide (AgI) solid solutions were investigated by X-ray diffraction, thermogravimetry-differential thermal analysis, and electrical conductivity measurement. Results revealed that AgI and Ag2CO3 reacted with each other when mixed at room temperature. The reaction products were classified into three types: (1) AgI-based solid solutions in the AgI-rich region for x = 10% or less in x Ag2CO3–(1 − x) AgI; (2) Ag2CO3-based solid solutions in the Ag2CO3-rich region for x = 60% or more; and (3) silver carbonate iodides in the intermediate range for x between 10% and 60%. For the AgI-based solid solutions, the incorporation of Ag2CO3 into the AgI lattice expanded the unit cell and enhanced electrical conductivity. The solubility limit of Ag2CO3 into the AgI lattice estimated from the differential thermal analysis was x ≈ 5%. [ABSTRACT FROM AUTHOR]

Two groups of hybrid organic-inorganic composites exhibiting ionic conduction properties, so called ORMOLYTES (organically modified electrolytes), have been prepared by the sol-gel process. The first group has been prepared from mixture of a lithium salt and 3-isocyanatopropyltriethoxysilane(IsoTrEOS),O,O′-bis(2-aminopropyl)polypropyleneglycol. These materials produce chemical bonds between the organic (polymer) and the inorganic (silica) phases. The second group has been prepared by an ultrasonic method from a mixture of tetraethoxysilane (TEOS), polypropyleneglycol and a lithium salt. The organic and inorganic phases are not chemically bonded in these samples. The Li+ ionic conductivity, σ, of all these materials has been studied by AC impedance spectroscopy up to 100°C. Values of σ up to 10−6 Ω−1 · cm−1 have been found at room temperature. A systematic study of the effects of lithium concentration, polymer chain length and the polymer to silica weight ratio on σ shows that there is a strong dependence of σ on the preparation conditions. The dynamic properties of the Li+ ion and the polymer chains as a function of temperature between −100 and 120°C were studied using 7Li solid-state NMR measurements. The ionic conductivity of both families are compared and particular attention is paid to the nature of the bonds between the organic and inorganic components. [ABSTRACT FROM AUTHOR]