Chapter 3. Dispersive kinetics in condensed phases

Płonka, Andrzej

doi:10.1039/pc9888500047

Cited by 57 publications

(52 citation statements)

References 7 publications

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“…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: 97%

“…directly gives a stretched‐exponential expression similar to Equation (1) by Equation :

c_{normalA} (t) = c_{normalA} (0) normale normalx normalp [- {((), \frac{t}{τ})}^{α}]

…”

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: 97%

“…directly gives a stretched‐exponential expression similar to Equation (1) by Equation :

c_{normalA} (t) = c_{normalA} (0) normale normalx normalp [- {((), \frac{t}{τ})}^{α}]

…”

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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“…We note that degradation and ageing phenomena often obey a "universal relaxation law" [48]. The specific case of dispersive chemical kinetics has been explored in a series of review papers by Plonka [49][50][51][52][53], which may give points of departure for elucidating Eq. (1).…”

Section: Ni-oxide-based Films: Power-law Decay Of the Charge Density Exchangementioning

confidence: 99%

Electrochromics for energy efficient buildings: Towards long-term durability and materials rejuvenation

Wen

Arvizu

Niklasson

et al. 2015

Surface and Coatings Technology

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Electrochromic devices such as "smart windows" for energy efficient windows must be durable enough for many years of practical use. Typical devices employ films based on W oxide and Ni oxide, and this paper surveys recent progress on durability-related issues for these materials. In the case of W oxide, we discuss the beneficial effects of Ti addition, and we describe recent and unexpected progress concerning galvanostatic rejuvenation of aged W oxide films. For Ni oxide, we report how charge exchange declination during extended voltammetric cycling can be modeled in terms of a power law.

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“…This results in the formation of "tracks" and "spurs", but generally these simply add to the ESR intensities for the species ultimately trapped but do not seem to give rise to pairwise radical trapping. Certain more subtle aspects of the saturation behaviour, especially cross relaxation between different species are, however, best explained in terms of near neighbours formed in spurs [22]. …”

Section: Radical Pairsmentioning

confidence: 99%

ESR spectroscopy applied to the study of radiation mechanisms

Symons

1992

Appl. Magn. Reson.

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ESR spectroscopy is a powerful tool for detecting radicals or radical-ions trapped in solids, and in many cases "primary" electron-gain and -loss centres can be identified and their structures elucidated. Sometimes these primary centres are trapped in pairs, separated by ca. 5 to 15 A giving triplet state ESR spectra. The significance of pair-trapping in relation to current theo¡ for the action of ionizing radiation will be discussed with reference to several recent examples. Generally, the primary centres are well separated and ESR does not give useful information about spurs or local regions of high radical densities. Reasons for trapping will be summarized with specific reference to DNA and proteins. The question of electron-return will be discussed, and several examples of this will be reported.

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Chapter 3. Dispersive kinetics in condensed phases

Cited by 57 publications

References 7 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

Electrochromics for energy efficient buildings: Towards long-term durability and materials rejuvenation

ESR spectroscopy applied to the study of radiation mechanisms

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