Some features of the thermodynamics of solid electrolytes

Gurevich, Yu. Ya.; Kharkats, Yu. I.

doi:10.1016/0013-4686(77)80028-5

Cited by 11 publications

(12 citation statements)

References 10 publications

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“…In a simple model, obviously, V ≡ V (1) and V (2) ≡ 0. The potential in formula (1) can also be the effective single-particle potential V = V eff , which reflects simultaneously the role played by potentials V (1) and V (2) .…”

Section: The Stochastic Approach the Gurevich-kharkats Modelmentioning

confidence: 99%

“…Consider fundamental tenets of a stochastic method of description of the ion transfer on the basis of works [1][2][3]. The dynamics of ions in a field of forces that act in a regular potential V ( r ) is described by the Langevin equation (see for example [7,8])…”

Section: The Stochastic Approach the Gurevich-kharkats Modelmentioning

confidence: 99%

“…That is why this stochastic approach has a limited range of applications and in some cases may lead to wrong conclusions. Attention should be drawn to the fact that, prior to writing work [1], no rigorous analytical solution of the Kramers problem throughout the entire region of values of the friction coefficient was present in the literature, but a considerable progress occurred in the solution of this question in the last few years. The author is unaware of any attempts to revise stochastic model for the ion transfer [1,2] with allowance for this.…”

Section: Introductionmentioning

confidence: 99%

“…Gurevich and Yu.I. Kharkats [1,2] on the basis of a classic work by H.A. Kramers concerning the diffusion in a phase space [3].…”

Section: Introductionmentioning

confidence: 99%

“…The Kramers solutions of the problem concerning the overcoming of a potential barrier by a particle, which formed the cornerstone of [1,2], were derived for two extreme cases, specifically, for small and large friction. That is why this stochastic approach has a limited range of applications and in some cases may lead to wrong conclusions.…”

Section: Introductionmentioning

confidence: 99%

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On a Stochastic Theory of Ion Transfer at Intermediate Damping

Samgin

2005

Russ J Electrochem

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The stochastic method, which was formulated earlier by Gurevich and Kharkats on the basis of a classic solution of the Fokker-Planck equation in a phase space of coordinates and momenta, is developed to extend it to the case of intermediate damping. In contradistinction to the Gurevich-Kharkats model, the new theory is based on the Fokker-Planck equation in the energy-action coordinates. Analytical expressions for the exchange current and conductance are derived. The expressions are valid in a broad damping regime. As compared with the Gurevich-Kharkats model, the expression for the exchange current contains an additional factor, which depends on the energy losses sustained by the ion upon its collision with the cage of a crystal lattice. An explanation for the isotope effect in the high-temperature protonic conductors is suggested. It is demonstrated that the friction coefficient for these solid electrolytes may correspond to the underdamped-to-intermediatedamping regime. This fact makes it possible to put forth an explanation for the existing contradictions between their properties and simple hopping models, which ignore the interaction of ions with the crystal lattice.

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Section: The Stochastic Approach the Gurevich-kharkats Modelmentioning

confidence: 99%

Section: The Stochastic Approach the Gurevich-kharkats Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Gurevich and Yu.I. Kharkats [1,2] on the basis of a classic work by H.A. Kramers concerning the diffusion in a phase space [3].…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On a Stochastic Theory of Ion Transfer at Intermediate Damping

Samgin

2005

Russ J Electrochem

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Ionic conductivity in AgI1−xClx

Ihara

Warita

Suzuki

1984

Phys. Stat. Sol. (a)

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Experimental results are presented for the ionic conductivity of AgI1−xClx (0 < x < 0.1) in the temperature range 60 to 200 °C. It is found that the substitution of Cl− ions for I− ions in AgI leads to a substantial decrease in the temperature for β–α phase transition and also a large increase in the ionic conductivity in β‐phase. The effect of Cl− ions is more pronounced than that of Br− ions. This result is consistent with Shahi and Wagner's conjecture. A simple model is given which can explain the effect of Cl− ions.

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Phase Transitions in High-Temperature Fluorite-Struture Superionic Conductors

Mezrin

1989

Phys. Stat. Sol. (a)

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The thermodynamies of phase transitions associated with Frenkel aniondisorder in CaF2−type superionic conductors is considered. The short‐range order in the arrangement of vacancies in the main anion sublattice and of anions in the octahedral interstices is describedin a pairwise approximation (of the Bethe type) with allowance for intractions of is described in a pairwise appromean‐field approximation and the Frenkel‐pair formation entropoy phenomenologically, with retention of linear and quadratie terms in defect concentration. Genetically related first and second order and diffuse phase transitions may be realized within the model proposed. A satisfactory quantitative agreement is obtained between the theoretical temperature dependence of heat capacity and that observed experimentally for CaF2 type compounds on diffuse transition to superionic state. The reason is discussed why the classical theory of point defects cannot be applied to these systems over theentire transition range.

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Some features of the thermodynamics of solid electrolytes

Cited by 11 publications

References 10 publications

On a Stochastic Theory of Ion Transfer at Intermediate Damping

On a Stochastic Theory of Ion Transfer at Intermediate Damping

Ionic conductivity in AgI1−xClx

Phase Transitions in High-Temperature Fluorite-Struture Superionic Conductors

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