Conductivity and space charge phenomena in solid electrolytes with one mobile charge carrier species, a review with original material

Kornyshev, A. A.; Воротынцев, М. А.

doi:10.1016/0013-4686(81)85017-7

Cited by 102 publications

(135 citation statements)

References 54 publications

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“…accommodation of the extra charge, is a much faster process). Such migration time, also known as RC-time of charging a capacitor trough a resistor, can be estimated as 44,45,46 ≈ ( • )/ , where is the diffusion coefficient of ions, is the characteristic thickness of the double layer -the Gouy length, and is the distance between the electrodes in the junction. Taking ~1 and as large as 5 , and ~5 × 10 −6 2 / , we obtain ≈ 10 −8 .…”

Section: Discussionmentioning

confidence: 99%

Principles of a Single-Molecule Rectifier in Electrolytic Environment

et al. 2016

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The idea of gating the electrical current across a single chain molecule, confined between and linking two electrodes in electrolytic solution, in order to achieve an asymmetric current-voltage plot, was first put forward and substantiated with a detailed theory by Kornyshev and Kuznetsov (ChemPhysChem, 2006), and Kornyshev, Kuznetsov, and Ulstrup (PNAS, 2006). However, not all aspects of that effect have been studied in those papers. Its experimental confirmation, published by Capozzi et al. (Nature Nanotech, 2015), enthused us to revisit that theory, extending it and exploring all the regimes of system operation. In this article we present such comprehensive analysis, which reveals a set of new features. An important finding is that the introduction of more refined models of the electric double layer (beyond linear response) results in stronger rectification effects, already for relatively dilute electrolyte concentrations. The theory equally applies to electrode systems with and without full electrochemical potential control and highlights important differences for these two scenarios, for example with regards to the effect of electrode surface area.

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Section: Discussionmentioning

confidence: 99%

Principles of a Single-Molecule Rectifier in Electrolytic Environment

et al. 2016

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“…This expression (14a) for the ion conductivity explains the reason of an unexpected behaviour of the conventional "enhancement factor", W i , in equation (22). Comparison of equations (14) and (14a) shows that the formally introduced "component diffusion coefficient", D i , represents a function of the ion concentration:…”

Section: The "Enhancement Factor" and Intercalation Isothermsmentioning

confidence: 87%

“…A similar relation between the diffusion coefficient and the conductivity also exists for materials possessing a single type of mobile charge carriers, either electronic or ionic ones [20][21][22]:…”

Section: Theoretical Model Of Coupled Electron-ion Transportmentioning

confidence: 94%

“…For the first problem one can use the argumentation derived for the systems with a pure ion conductivity [22]. If the ion subsystem is close to the saturation level one can consider this saturation limit (all possible sites are occupied by lithium cations) as the background point, to which a dilute lattice gas of vacancies in this cation lattice is added.…”

Section: The "Enhancement Factor" and Intercalation Isothermsmentioning

confidence: 99%

“…On the other hand, for low charging levels, the conductivity is proportional to the ion concentration, c i . Thus, the general expression for the conductivity of intercalated ions must have the form [22]:…”

Section: The "Enhancement Factor" and Intercalation Isothermsmentioning

confidence: 99%

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INTERPRETATION OF POTENTIAL INTERMITTENCE TITRATION TECHNIQUE EXPERIMENTS FOR VARIOUS Li-INTERCALATION ELECTRODES

Lévi¹,

Aurbach²,

Vorotyntsev³

2002

Condens. Matter Phys.

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In this paper we compare two different approaches for the calculation of the enhancement factor W i , based on its definition as the ratio of the chemical and the component diffusion coefficients for species in mixed-conduction electrodes, originated from the "dilute solution" or "lattice gas" models for the ion system. The former approach is only applicable for small changes of the ion concentration while the latter allows one to consider a broad range of intercalation levels. The component diffusion coefficient of lithium ions has been determined for a series of lithium intercalation anodes and cathodes. A new "enhancement factor" for the ion transport has been defined and its relations to the intercalation capacitance and the intercalation isotherm have been established. A correlation between the dependences of the differential capacitance and the partial ion conductivity on the potential has been observed. It is considered as a prove that the intercalation process is controlled by the availability of sites for Li-ion insertion rather than by the concurrent insertion of the counter-balancing electronic species.

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Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li⁺‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry

et al. 2021

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The future of mobility depends on the development of next‐generation battery technologies, such as all‐solid‐state batteries. As the ionic conductivity of solid Li+‐conductors can, in some cases, approach that of liquid electrolytes, a significant remaining barrier faced by solid‐state electrolytes (SSEs) is the interface formed at the anode and cathode materials, with chemical instability and physical resistances arising. The physical properties of space charge layers (SCLs), a widely discussed phenomenon in SSEs, are still unclear. In this work, spectroscopic ellipsometry is used to characterize the accumulation and depletion layers. An optical model is developed to quantify their thicknesses and corresponding concentration changes. It is shown that the Li+‐depleted layer (≈190 nm at 1 V) is thinner than the accumulation layer (≈320 nm at 1 V) in a glassy lithium‐ion‐conducting glass ceramic electrolyte (a trademark of Ohara Corporation). The in situ approach combining electrochemistry and optics resolves the ambiguities around SCL formation. It opens up a wide field of optical measurements on SSEs, allowing various experimental studies in the future.

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Conductivity and space charge phenomena in solid electrolytes with one mobile charge carrier species, a review with original material

Cited by 102 publications

References 54 publications

Principles of a Single-Molecule Rectifier in Electrolytic Environment

Principles of a Single-Molecule Rectifier in Electrolytic Environment

INTERPRETATION OF POTENTIAL INTERMITTENCE TITRATION TECHNIQUE EXPERIMENTS FOR VARIOUS Li-INTERCALATION ELECTRODES

Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li⁺‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry

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Conductivity and space charge phenomena in solid electrolytes with one mobile charge carrier species, a review with original material

Cited by 102 publications

References 54 publications

Principles of a Single-Molecule Rectifier in Electrolytic Environment

Principles of a Single-Molecule Rectifier in Electrolytic Environment

INTERPRETATION OF POTENTIAL INTERMITTENCE TITRATION TECHNIQUE EXPERIMENTS FOR VARIOUS Li-INTERCALATION ELECTRODES

Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li+‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry

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Product

Resources

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Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li⁺‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry