Short-range electron-ion interaction effects in charging the electroactive polymer films

Воротынцев, М. А.; Badiali, J.P.

doi:10.1016/0013-4686(94)80064-2

Cited by 90 publications

(86 citation statements)

References 42 publications

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“…(33), (30) and (34) were used in this calculation (W i = 1). The halfpeak width of the differential intercalation capacity peak strongly depends on the interaction parameter g, as was previously discussed [4,23,24]. At the critical value, g crit = −4 (ideal first-order phase transition), the value of C int at the peak potential is infinitely high whereas D ei → 0.…”

Section: Relation Of the Classical "Enhancement Factor" W I To Particmentioning

confidence: 66%

“…A simplest Frumkin-type intercalation isotherm with an interaction constant g (which is independent of X) has the following form [23,24]:…”

Section: The "Enhancement Factor" and Intercalation Isothermsmentioning

confidence: 99%

“…the current collector/host and host/solution interface, should be polarized, and the changes in the interfacial potentials across these interfaces should be equal [25]. In this case the simple Frumkin isotherm is no more valid, and we have to use a more general equation instead of equation (28) [4,23]:…”

Section: Relation Of the Classical "Enhancement Factor" W I To Particmentioning

confidence: 99%

“…The differential intercalation capacity corresponding to this isotherm can be written with a certain modification of equation (33) [4,23]:…”

Section: Relation Of the Classical "Enhancement Factor" W I To Particmentioning

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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Section: Relation Of the Classical "Enhancement Factor" W I To Particmentioning

confidence: 66%

“…A simplest Frumkin-type intercalation isotherm with an interaction constant g (which is independent of X) has the following form [23,24]:…”

Section: The "Enhancement Factor" and Intercalation Isothermsmentioning

confidence: 99%

Section: Relation Of the Classical "Enhancement Factor" W I To Particmentioning

confidence: 99%

“…The differential intercalation capacity corresponding to this isotherm can be written with a certain modification of equation (33) [4,23]:…”

Section: Relation Of the Classical "Enhancement Factor" W I To Particmentioning

confidence: 99%

See 2 more Smart Citations

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

Lévi¹,

Aurbach²,

Vorotyntsev³

2002

Condens. Matter Phys.

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“…In other words, the redox process is not reversible, i.e., not close enough to thermodynamic equilibrium. Some authors proposed explanations for this abnormal behavior of ECP redox mechanisms such as conformational change of polymeric chains, [1][2][3] solvent and electrolyte movements, 1,[13][14][15] relaxation effects, 1,16,17 phase transition 1,7,18 or inter-site interactions, 19 and, more recently, dimerizable redox sites. 20 The aim of this work was to study the hysteresis phenomenon observed in charge-potential curves derived from cyclic voltammetry experiments performed on two ECPs, namely PANI and P3MT.…”

Section: Introductionmentioning

confidence: 99%

Analysis of hysteresis phenomenon as observed from voltammetric data of conducting polymers: part I

Matencio¹,

Pernaut²,

Vieil³

2003

J. Braz. Chem. Soc.

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Estudamos o fenômeno de histerese inerente aos processos redox dos polímeros condutores eletrônicos (PCE). As histereses foram separadas em duas classes: i) as histereses dinâmicas constituídas por componentes cinéticas e ôhmicas e ii) as histereses estacionárias ou termodinâmicas. Efetuamos uma análise matemática das histereses dinâmicas observadas nos voltamogramas cíclicos de dois polímeros: a polianilina (PANI) e o poli(3-metiltiofeno) (P3MT). Mostrou-se que no caso do P3MT a histerese é principalmente cinética devido à velocidade de uma das etapas do processo redox com também uma componente ôhmica relacionada à existência de uma impedância elétrica em serie com o sistema eletroquímico. No caso da PANI, observou-se que a histerese é independe da corrente, o que é característico de uma histerese termodinâmica.The hysteresis phenomenon inherent to redox processes of Electronic Conducting Polymers (ECP) has been studied. Hysteresis was divided into two classes: i) dynamic hysteresis, containing a kinetic and an ohmic component and ii) stationary or thermodynamic hysteresis. A mathematical analysis was performed on the dynamic hysteresis observed in cyclic voltammograms of two polymers: polyaniline (PANI) and poly(3-methylthiophene) (P3MT). It has been shown that in the case of P3MT, the hysteresis is mainly kinetic due to the rate of one of the steps of the redox process. However, an ohmic component related to the existence of an electrical impedance in series with the electrochemical system is also present. As for PANI, hysteresis is current independent, which is characteristic of thermodynamic hysteresis.

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Potentiostatic and Galvanostatic Intermittent Titration Techniques

Levi¹,

Aurbach²

2012

Characterization of Materials

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This article is concentrated on the essentials of potential and current pulses techniques, commonly known as potentiostatic and galvanostatic intermittent titration techniques (PITT and GITT, respectively). They were introduced around 35 years ago to provide thermodynamic and kinetic characterization of two‐ and three‐component metallic alloys with Li, and were thereafter widely used for studies of Li‐ion insertion into a variety of intercalation‐type anodes andcathodes. Emphasis is given to description of ion diffusion in finite (confined) space versus semi‐infinite diffusion in classical electrochemical cells. Special attention is also paid to intrinsic link between the diffusion time constant obtained from different electroanalytical techniques used and its dependence on the shape of the related ion intercalation isotherm. We also discuss the advantages and disadvantages in using separate incremental titration techniques as well as electrochemical impedance spectroscopy for detecting diffusion coefficients.

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Short-range electron-ion interaction effects in charging the electroactive polymer films

Cited by 90 publications

References 42 publications

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

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

Analysis of hysteresis phenomenon as observed from voltammetric data of conducting polymers: part I

Potentiostatic and Galvanostatic Intermittent Titration Techniques

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