Two parallel diffusion paths model for interpretation of PITT and EIS responses from non-uniform intercalation electrodes

Levi, Mikhael D.; Wang, C; Aurbach, Doron

doi:10.1016/j.jelechem.2003.07.014

Cited by 52 publications

(42 citation statements)

References 32 publications

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“…This work is a further development of the authors' view to the problem of impedance data analysis, which they reported in their earlier works [27,28]. The authors [26] analyzed their own data using the impedance models of the following researchers: Meyers et al [29], Pajkossy [30], Dokko et al [31].…”

Section: Introductionmentioning

confidence: 76%

“…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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Section: Introductionmentioning

confidence: 76%

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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show abstract

“…Distribution of the electrode layer thicknesses, as was recently shown in [18,19], complicates significantly the estimation of the effective chemical diffusion coefficients, so that different values of the diffusion coefficients can be obtained from the short-and the long-time domains. Due both to the above effect of the electrode inhomogeneity and to some specific complications related to the long time titration experiments, the most suitable for quantitative treatments seems to be the short-time behavior of chronoamperometric curves.…”

Section: Introductionmentioning

confidence: 99%

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

Levi

Aurbach

2004

Journal of Electroanalytical Chemistry

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“…Rct models the charge transfer resistance. A classical finite-space diffusion model (Ws) was used to describe diffusion impedance [25]. Rw, Cw and n w represent diffusion impedance, capacitance and exponent of capacitance, respectively.…”

Section: Model and Testingmentioning

confidence: 99%

EIS investigation of the deposition of trivalent chromium coatings on Al 6063 alloy

Chen

Shi

et al. 2008

J Appl Electrochem

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The influence of five variables (i.e. deposition temperature, time, bath pH, and concentrations of Cr 3? compound (KCr(SO 4 ) 2 ) and H 3 PO 4 ) on the preparation of Cr 3? coating on Al 6063 alloy was investigated using AC impedance spectroscopy (EIS) in 3.5 wt% NaCl. The optimal conditions were determined by AC impedance spectroscopy. The results indicated that the formation and quality of the coating were very sensitive to the deposition bath pH. A mechanism was proposed to explain the results. A simple model was derived and experimentally tested in terms of an equivalent circuit. Good agreement was found between the model predictions and the experimental results. The morphologies of the coated and uncoated electrodes were examined by scanning electron microscopy (SEM), and the results also support the proposed surface model.

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Two parallel diffusion paths model for interpretation of PITT and EIS responses from non-uniform intercalation electrodes

Cited by 52 publications

References 32 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

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

EIS investigation of the deposition of trivalent chromium coatings on Al 6063 alloy

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