Spatially limited diffusion coupled with ohmic potential drop and/or slow interfacial exchange: a new method to determine the diffusion time constant and external resistance from potential step (PITT) experiments

Vorotyntsev, Mikhail A.; Levi, Mikhael D.; Aurbach, Doron

doi:10.1016/j.jelechem.2003.12.014

Cited by 58 publications

(54 citation statements)

References 24 publications

(54 reference statements)

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“…This approach is described in detail in a number of publications of the authors Levi et al [27,37,61,64,[80][81][82]. It is based on the microscopic Lattice gas model.…”

Section: Resultsmentioning

confidence: 99%

“…Montella et al [44][45][46][47][48][49][50] and Churikov et al [6,42,[51][52][53][54][55] independently proposed analytical solutions of ion transport task in intercalation electrode having slow kinetics of the transfer in surface layer and subsequently distributed these concepts to other cases of diffusion space geometry. Levi et al [28,35,[56][57][58][59][60][61][62][63][64] showed a decisive influence of the thermodynamic factors on the transport processes in the intercalation electrode, and modified the theory of PITT and GITT methods taking into account the sorption isotherm of the intercalation electrode, a general view of which can be described the most accurately by the Frumkin intercalation isotherm. Also, they have developed notions of the interparticle interactions in the structure of intercalation materials based on lattice gas model, which allowed them to theoretically explain the shape of the concentration dependence of the lithium diffusion coefficient.…”

Section: Introductionmentioning

confidence: 99%

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Lithium diffusion in Li3V2(PO4)3-based electrodes: a joint analysis of electrochemical impedance, cyclic voltammetry, pulse chronoamperometry, and chronopotentiometry data

Ivanishchev

Чуриков

Ivanishcheva

et al. 2015

Ionics

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In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li 3 V 2 (PO 4 ) 3 ), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry ( C V ) , p u l s e c h r o n o a m p e r o m e t r y ( P I T T ) , a n d chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material's particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10 −9 and 3 × 10 −10 cm 2 s −1 , respectively, for transfer in the bulk and 10 −12 cm 2 s −1 for transfer in the thin surface layer of material's particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5-5.8 × 10 −10 and 0.9-5 × 10 −10 cm 2 s −1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10 −10 cm 2 s −1 for lithiated (at a potential of 3.5 V) and 2.3 × 10 −9 cm 2 s −1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10 −11 cm 2 s −1 for anodic and 3.4 × 10 −11 cm 2 s −1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li 3 V 2 (PO 4 ) 3 electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.

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“…This approach is described in detail in a number of publications of the authors Levi et al [27,37,61,64,[80][81][82]. It is based on the microscopic Lattice gas model.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Lithium diffusion in Li3V2(PO4)3-based electrodes: a joint analysis of electrochemical impedance, cyclic voltammetry, pulse chronoamperometry, and chronopotentiometry data

Ivanishchev

Чуриков

Ivanishcheva

et al. 2015

Ionics

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“…The understanding of the charge transport through conductive polymers, and specifically through polyaniline films, has attracted substantial research efforts [59,60]. The kinetics of the electron transport through the conductive polymers can be characterized by the use of chronoamperometry [61].…”

Section: à2mentioning

confidence: 99%

Enhanced Bioelectrocatalysis Using Single‐Walled Carbon Nanotubes (SWCNTs)/Polyaniline Hybrid Systems in Thin‐Film and Microrod Structures Associated with Electrodes

et al. 2006

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The charge transport properties in composites consisting of pyrene sulfonic acid-functionalized single-walled carbon nanotubes embedded in polyaniline, PAn/SWCNTs, and polystyrene sulfonate-doped PAn, PAn/PSS, are compared in thin-film and microrods configurations. The PAn/SWCNTs and PAn/PSS microrods were prepared by the electropolymerization of the respective components in porous alumina membranes coated with a conductive gold support, followed by the dissolution of the membrane template. The charge transport upon the oxidation of the PAn/ SWCNTs planar film or microrods structures is ca. 3.5 -4.0-fold faster than upon the oxidation of the PAn/PSS planar film or microrods structures, respectively. The faster charge transport in the PAn/SWCNTs films and microrods is used to enhance the mediated bioelectrocatalyzed oxidation of glucose in the presence of glucose oxidase (GOx). The bioelectrocatalyzed oxidation of glucose in the presence of the PAn/SWCNTs in the planar film and microrods structures is ca. 2-fold and up to 6-fold (depending on the potential) enhanced as compared to the respective PAn/PSS configurations.

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“…16 The three main models used in the literature to fit experimental data for insertion/extraction processes under the potential step chronoamperometry technique were discussed and compared. 17 The approaches/models listed above can describe electro intercalation dynamics for EC electrodes immersed in model electrolytes, which often requires solving a set of complex equations.…”

Section: -11mentioning

confidence: 99%

“…14 The kinetics limitations at the electrolyte/electrode interface as well as Ohmic drop effects were introduced in the diffusion model through a single dimensionless parameter, 15 and approximate expressions of the current transients were proposed. 16 The three main models used in the literature to fit experimental data for insertion/extraction processes under the potential step chronoamperometry technique were discussed and compared. 17 The approaches/models listed above can describe electro intercalation dynamics for EC electrodes immersed in model electrolytes, which often requires solving a set of complex equations.…”

mentioning

confidence: 99%

Dynamics in Electrochromic Windows Interpreted with an Extended Logistic Model

Roldán

Romanyuk

2016

J. Electrochem. Soc.

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Complete electrochromic (EC) devices based on tungsten oxide are characterized by the chronocoulometry technique in a wide range of applied voltage and time. An empirical model is proposed to approximate the recorded charge evolution over extended periods of time required for the full coloration transition. The model is described by an analytic expression based on the logistic population growth of tungsten bronzes that are responsible for the coloration upon ion intercalation into tungsten oxide, and just four parameters characterize the dynamics of the EC device. The model is verified by fitting experimental chronocoulograms recorded from two different commercial EC windows. It is discussed how the model can be used for the description of the coloration dynamics and estimation of the coloration efficiency. Switchable smart windows based on the electrochromic (EC) technology are becoming popular in the architectural sector as they offer potential energy savings and improved visual comfort.1 One of the key parameters of the EC device is its switching speed, i.e. time required to switch between the lightest and most intensive coloration. When compared to other "switchable" technologies like suspended particle devices (SPDs) or polymer dispersed liquid crystal devices, EC windows exhibit a relatively slow switching speed, on the order of 10 -20 min for the full color transition, which hinders a fast market penetration and still remains an important topic for research and development.An EC window contains typically tungsten oxide layer (WO 3 ) as the primary EC material, which changes its color due to the potentialinduced intercalation of protons or alkali ions into the WO 3 electrode resulting in the formation of so-called tungsten bronzes. Numerous approaches and models have been proposed to investigate electrointercalation into EC materials like WO 3 . Early studies focused on the bleaching and coloring of WO 3 electrodes immersed in various liquid electrolytes. The time dependence of the coloration of amorphous WO 3 at low voltages was described in terms of a barrier for current at the WO 3 -electrolyte interface.2,3 The coloring and bleaching processes of Li x WO 3 films were examined in short time ranges considering diffusion-limited process, 4 whereas the kinetics of electrochemical reactions in WO 3 was found to be governed by the resistance that depends on the conductivity of electrolyte, reduced forms of WO 3 and transparent conducting layers. 5 The ion transport in host electrodes was reviewed in Refs. 6-9, and rigorous models of diffusion phenomena often require sophisticated numerical calculations. 9-11The current transients for potential steps during the intercalation of Li-ions in Li 1−δ CoO 2 electrodes were found by Refs. 12,13 to deviate from the theoretical predictions. Their chronoamperometric data were interpreted in terms of the cell-impedance controlled diffusion of Li-ions. The diffusion flux of intercalated species at the electrode surface limited by the interfacial charge transfer kinetics ...

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Spatially limited diffusion coupled with ohmic potential drop and/or slow interfacial exchange: a new method to determine the diffusion time constant and external resistance from potential step (PITT) experiments

Cited by 58 publications

References 24 publications

Lithium diffusion in Li3V2(PO4)3-based electrodes: a joint analysis of electrochemical impedance, cyclic voltammetry, pulse chronoamperometry, and chronopotentiometry data

Lithium diffusion in Li3V2(PO4)3-based electrodes: a joint analysis of electrochemical impedance, cyclic voltammetry, pulse chronoamperometry, and chronopotentiometry data

Enhanced Bioelectrocatalysis Using Single‐Walled Carbon Nanotubes (SWCNTs)/Polyaniline Hybrid Systems in Thin‐Film and Microrod Structures Associated with Electrodes

Dynamics in Electrochromic Windows Interpreted with an Extended Logistic Model

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