Chapter 5. Dispersive kinetics

Płonka, Andrzej

doi:10.1039/pc9949100107

Cited by 50 publications

(23 citation statements)

References 256 publications

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“…where α is the power‐law exponent and E is a constant. Such power‐law dependencies frequently appear when the reaction is diffusion limited, for example when the diffusion of reactants is modeled by a random walk . Integration of the first‐order kinetic equation [Eq.…”

Section: Discussionmentioning

confidence: 88%

“…Next we discuss how the above reaction schemes can give rise to the degradation kinetics observed in this study, that is, those given by the power‐law and stretched‐exponential expressions in Equations (1) and (2), respectively. These expressions arise naturally in the case of so‐called dispersive chemical kinetics, as discussed in several comprehensive review papers by Plonka . Dispersive kinetics occurs when the rate constants K 1 and K 2 are time‐dependent and given by power‐law functions [Eq.…”

Section: Discussionmentioning

confidence: 99%

“…The dynamics of charge density degradation is described in terms of power‐law and stretched‐exponential decay and is influenced by the Ni 3+ concentration. The underlying causes of these functions are explored within the framework of dispersive chemical reaction kinetics, which allows us to discuss microscopic mechanisms for the charge density evolution. Degradation of optical modulation is due to increased optical transmittance in both bleached and colored states, thus indicating a critical depletion of Ni 3+ sites.…”

Section: Introductionmentioning

confidence: 99%

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Anodic Electrochromic Nickel Oxide Thin Films: Decay of Charge Density upon Extensive Electrochemical Cycling

2016

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Electrochromic (EC) Ni oxide thin film is a critical component in the "smart windows". However, long-term decay of the EC performance in aprotic electrolytes is persistent and poorly understood, and it is difficult to assess life-times of EC devices. Here we report on charge density decline upon electrochemical cycling. The charge density decay was modeled with a power law or, alternatively, a stretched exponential; both models describe a rapid drop of charge density during the first hundreds of cycles and a subsequent slower decline. The decay is independent of film composition and applied potential range as long as the upper limit of the potential is ≤4.4 V vs. Li/Li + . Our decay models are interpreted in terms of dispersive chemical reaction kinetics and point at ion diffusion as the rate-limiting step.Power-law exponents are consistent with diffusion. The results provide a framework for evaluating EC durability of Ni-oxide-based thin films and may be important for assessing the durability of EC devices.

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Section: Discussionmentioning

confidence: 88%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Anodic Electrochromic Nickel Oxide Thin Films: Decay of Charge Density upon Extensive Electrochemical Cycling

2016

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“…Several explanations have been put forward to explain the latter behaviour (see, e.g. [5][6][7][8][9][10] and references therein). In the case of processes taking place in constrained media (solutions of reacting species in viscous liquids, matrices, etc.…”

Section: Introductionmentioning

confidence: 99%

Non-Exponential Decays in First-Order Kinetic Processes. The Case of"Squeezed Exponential"

Sworakowski

Matczyszyn

2007

Acta Phys. Pol. A

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Dedicated to the memory of late Professor Jerzy ProchorowKinetics of processes, in which the reaction rate increases with conversion, is discussed and illustrated with an example of the chemical reaction of isomerization of an azobenzene derivative in a liquid crystalline matrix. A simple phenomenological model is put forward explaining the effect by dynamic changes of interactions between the reacting species and the matrix.

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“…Examples include models for dc [3][4][5] and ac conduction in disordered solids [6][7][8][9], protein dynamics [10][11][12], viscous flow of liquids close to the glass transition [ 13,14], diffusion in random flows [ 15], or rate processes controlled by the anomalous diffusion of reactants [16][17][18][19][20]. Usually, the complexity of a system is represented by some sort of randomness of the energy landscape.…”

Section: Introductionmentioning

confidence: 99%

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Jacobsen

Cheung

et al.

Principles and Applications of Distributed Event-Based Systems

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The universal time-dependence of the mean-square displacement for motion in a random energy landscape with equal minima is evaluated analytically and numerically in the percolation path approximation (PPA), which was recently shown by extensive computer simulations in two and three dimensions [Dyre and Schr~ler, cond-mat/9601052] to be more accurate than the standard effective medium approximation (EMA). According to the PPA the universal mean-square displacement in dimensionless units as function of time varies as 1 / In 2 ( t-~ ) for t ~ 0. This implies a quite different short-time behavior than predicted by the EMA, where the universal mean-square displacement varies as 1/ln(t -t) at short times [Dyre and Jacobsen, Phys. Rev. E 52 (1995) 2429].

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Chapter 5. Dispersive kinetics

Cited by 50 publications

References 256 publications

Anodic Electrochromic Nickel Oxide Thin Films: Decay of Charge Density upon Extensive Electrochemical Cycling

Anodic Electrochromic Nickel Oxide Thin Films: Decay of Charge Density upon Extensive Electrochemical Cycling

Non-Exponential Decays in First-Order Kinetic Processes. The Case of"Squeezed Exponential"

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