AgI-type solid electrolytes

doi:10.1016/0079-6786(76)90001-7

Progress in Solid State Chemistry

Volume 11, Part 4, 1976, Pages 345-402

https://doi.org/10.1016/0079-6786(76)90001-7 Get rights and content

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Ag<inf>3</inf>AsS<inf>3</inf>-As<inf>2</inf>S<inf>3</inf> composite: Detailed impedance spectroscopy study
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The 90% Ag₃AsS₃-10 % As₂S₃ composite and Proustite (Ag₃AsS₃) were investigated by impedance spectroscopy. Electrical properties of single crystal Proustite were investigated by 2 and 4 probe methods in the frequency range 10 Hz to 2 MHz and in the temperature interval from 300 K up to 480 K. The 90% Ag₃AsS₃-10 % As₂S₃ composite was investigated by 2 electrode method in the frequency range 10 Hz to 3 GHz and in the temperature interval from 300 K up to 400 K. Equivalent circuit explaining electrical conductivity mechanism in Ag₃AsS₃-As₂S₃ composite, taking in to account possible microstructure of the obtained sample and the interrelation of the composite constituents, was proposed. It was suggested that overall electrical conductivity of Ag₃AsS₃-As₂S₃ composite can be increased by small amount of As₂S₃, which gets doped with Ag⁺ ions from Ag₃AsS₃.
Density functional study on Ag<inf>8-x</inf>Cu<inf>x</inf>I<inf>8</inf> (0≤x≤8)
2021, Physica B: Condensed Matter
Citation Excerpt :
γ-phase of AgI has the zinc blende structure which resembles wurtzite structure. The α-AgI phase is known to be the best superionic conductors and therefore studied a lot [7]. Transition of AgI from β→α increases the conductivity nearly 3 times [8–13].
Ab-initio calculations are performed to investigate the effect of defects on structural, electronic and optical properties of Ag_8-xCu_xI₈ (0 ≤x ≤ 8). Initially AgI geometrically optimized and Ag atoms are replaced successively by Cu atoms. AgI is thermodynamically most stable, it exhibits low defect formation energy and fast ion conduction. The forbidden energy gap successively decreases with x. There is higher Ag⁺ ions formation than Cu⁺ ions. In the optical study, by increasing x, peaks of imaginary and real dielectric functions are shifted towards lower frequency regions, with Ag/Cu defects, there is slight shifting towards higher energy region, gradual increase in refractive index, and the reflectivity peaks are shifted towards higher energy.
Silver-ion dynamics close to the superionic phase transition of γ −RbAg<inf>4</inf>I<inf>5</inf> with segregated Ag<sup>+</sup>
2019, Physica B: Condensed Matter
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The AgI-based solid ionic conductors are the most common physical model for the cation motion in solid state [1,2].
The silver-ion dynamics in γ −RbAg₄I₅ with segregated microcrystals of AgI system was investigated by admittance spectroscopy in its normal phase but close to the superionic phase transition at 120 K. The electrical conductivity relaxation is well described using the conductivity formalism in the frequency domain $σ^{⋆} [ω] = σ_{0} {1 + {(ȷ ω / ω_{p})}^{n}} (n = 1 - β)$ but showing a decrease of the exponent β as the temperature increases toward 120 K, thus indicating stronger correlation between silver ions. The real part of the conductivity follows the dispersive behavior exp[(−t∕τ)^β] in a wide range of frequency and the temperature derivative of the dc conductivity, E_a = d(ln[σ₀])∕d(1∕T), increases with temperature in the same transition region below 120 K. The observed behavior in conductivity in the normal phase, close to the superionic transition at 120 K when compared with that of pure γ −RbAg₄I₅, is attributed to an increase of mobile silver-ion defects concentration with increasing temperature due to the presence of the AgI phase. At low temperatures, these defects populate most of the surface of the crystalline grains and they continue to be thermally generated and propagate toward the interior of the grains on increasing temperature, thus increasing ions jumps and correlation among them.
The effect of the nanodiamonds additive on ionic conductivity of silver iodide
2019, Materials Today: Proceedings
Citation Excerpt :
Silver iodide has long attracted attention because its α–AgI superionic modification stable at temperatures 147–555 °C has an extremely high ionic conductivity σ ∼1.3 S/cm at 147 °C with low activation energy [1].
Composite solid electrolytes AgI-C_ND (C_ND is nanodiamonds powder) were prepared and their properties were investigated by methods of X-ray diffraction, differential scanning calorimetry (DSC) and impedance spectroscopy. It was found that the addition of C_ND results in a strong increase in the ionic conductivity of AgI at temperatures below phase transition to the α-AgI phase. According to the results of DSC, no strong changes in thermodynamic properties of the salt in the composites occur. Therefore, in contrast to the AgI-oxide composites, the most probable reason of the conductivity increase in AgI-C_ND composites is formation of stable network of intergrains and anti-phase domain boundaries acting as conductivity pathways in the composites. Due to the particle-reinforcement effect on nanodiamond particles the AgI matrix in the composites may undergo strong local stresses leading to the stabilization of the polytypes. The peaks of such phases are detected in X-ray diffractograms of the composites. The maximum conductivity of AgI-C_ND composites, 5.6·10⁻⁴ S/cm at 31 °C observed in the composites containing 80 mol % C_ND, is comparable to the best values obtained for oxide-based composites with silver iodide. Thus, nanodiamonds is the first non-oxide additive which caused a strong enhancement of the ionic conductivity of AgI low temperatures.
Synergistic silver storage in the composite RbAg<inf>4</inf>I<inf>5</inf>:graphite: Thermodynamics and kinetics
2017, Solid State Ionics
The thermodynamics and kinetics of silver stoichiometry change in RbAg₄I₅:graphite composites briefly reported in a previous contribution are treated in detail. The stoichiometric variations occurring at the interface are achieved electrochemically and chemically. In samples that are not deliberately compacted samples, Stranski-Krastanov wetting of RbAg₄I₅ on carbon enables measurement of heterogeneous ambipolar Ag diffusion along the interface. If samples are deliberated compacted, the interfacial storage occurs through supercapacitive charging through the bulk path. The application of composites as electrodes in supercapacitor or battery mode underscores the very fast kinetics.
Anomalous temperature-dependent electrical properties of Na<inf>2</inf>MnP<inf>2</inf>O<inf>7</inf>
2017, Solid State Ionics
Na₂MnP₂O₇ is a promising sodium-ion battery cathode material. In our work we analyse electrical properties of Na₂MnP₂O₇ ceramics by impedance spectroscopy in the broad frequency range from 10 Hz to 10 GHz. Temperature dependencies of conductivity indicated a phase transition taking place in the grains of ceramics at 663 K, which was also evidenced by differential thermal analysis and thermal X-ray diffraction. In addition, close to the room temperature protonic conductivity strongly influences the total conductivity of the ceramics. Both newly observed phenomena may be important for overall sodium battery performance.

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AgI-type solid electrolytes

First page preview

Solid State Comm.

Phys. Rev.

Progress in Solid State Chemistry

J. Elchem. Soc.

Phys. Rev.

Ber. Bunsenges. physik. Chem.

Trans. Faraday Soc.

Science

Acta Cryst.

Z. Naturforsch.

Ber. Bunsenges. physik. Chem.

Diffusion in Solids, Liquids, Gases

Phys. Rev.

Z. physik. Chem.

Z. physik. Chem.

Leitfähigkeit und Überführungszahlen in festen Elektrolyten

Z. physik. Chem.

Z. physik. Chem.

Z. physik. Chem.

J. Phys. Soc. Japan

J. Chem. Phys.

Relationship between Structure and Anomalously Fast Ion Diffusion

Z. physik. Chem. NF

Helv. Phys. Acta

J. Solid State Chem.

J. Solid State Chem.

J. Solid State Chem.

Chem. Rev.

Z. Naturforsch.

phys. stat. sol. (a)

Progress in Solid State Chemistry

Ber. Bunsenges. physik. Chem.

Phys. Rev. Letters

J. Appl. Phys.

J. Electron. Spectrosc. and Relat. Phenom.

J. Appl. Elchem.

Nachr. Akad. Wiss. Göttingen

Z. Naturforsch.

Ber. Bunsenges. physik. Chem.

Z. Naturforsch.

phys. stat. sol. (a)

phys. stat. Sol (b)

Springer Tracts in Modern Physics

Solid State Comm.

J. Solid State Chem.

Phys. Rev. Letters

Z. Naturforsch.

Z. physik. Chem. NF

J. Appl. Phys.