New approach of electrochemical systems dynamics in the time domain under small-signal conditions: III – Discrimination between nine candidate models for analysis of PITT experimental data from LixCoO2 film electrodes

Montella, C.; Michel, Richard

doi:10.1016/j.jelechem.2009.01.012

Cited by 20 publications

(4 citation statements)

References 91 publications

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“…All models suggested in Ref. 42 were tested with our data, such as the model representing finite reaction kinetics together with finitelength Warburg diffusion (FLW) or anomalous diffusion (trapping and release of ions). The model that best fitted our current transients (0.005< χ2< 0.1 for I vs t in μA), is shown in the inset in Figure 8.…”

Section: Determination Of Kinetic Parameters By Pitt-mentioning

confidence: 99%

Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO₂Thin-Films

Moitzheim

Gendt

Vereecken

2019

J. Electrochem. Soc.

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Titania is considered an interesting anode candidate for Li + -ion batteries, as it offers a high theoretical capacity (1280 mAh cm −3 or 336 mAh g −1 ) and long term cycling stability. Unfortunately, the most commonly investigated anatase structure never reaches the theoretical capacity at practical charging rates (i.e. above 1 C). In this work, we compare amorphous (am-TiO 2 ) to anatase TiO 2 thin-films, and investigate the exceptional performance of am-TiO 2 as Li + -ion insertion electrode. An in-depth electrochemical characterization using cyclic voltammetry (CV), constant current lithiation and delithiation, and potentiostatic intermittent titration technique (PITT) is performed. From CV, the insertion and extraction kinetics of am-TiO 2 is found to be unrestricted by diffusion, contrary to anatase. Based on our combined electrochemical results, two different mechanisms are formulated for anatase and am-TiO 2 . Whereas anatase is filled from the "top-down", with a buildup of Li near the electrode/electrolyte interface, am-TiO 2 shows a "bottom-up" filling mechanism. This discrepancy is ascribed to the difference in diffusion coefficient measured for am-TiO 2 and anatase. This work highlights the differences of Li-ion insertion into amorphous TiO 2 compared to anatase, and gives guidance on material development for high capacity and fast charging electrodes.

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Section: Determination Of Kinetic Parameters By Pitt-mentioning

confidence: 99%

Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO₂Thin-Films

Moitzheim

Gendt

Vereecken

2019

J. Electrochem. Soc.

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“…Subsequently, the theoretical relations have been developed in the works of several researchers. 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.…”

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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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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“…6-9, and rigorous models of diffusion phenomena often require sophisticated numerical calculations. [9][10][11] The 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.…”

mentioning

confidence: 81%

“…5 The ion transport in host electrodes was reviewed in Refs. [6][7][8][9], and rigorous models of diffusion phenomena often require sophisticated numerical calculations. [9][10][11] The current transients for potential steps during the intercalation of Li-ions in Li 1−δ CoO 2 electrodes were found by Refs.…”

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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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New approach of electrochemical systems dynamics in the time domain under small-signal conditions: III – Discrimination between nine candidate models for analysis of PITT experimental data from LixCoO2 film electrodes

Cited by 20 publications

References 91 publications

Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO₂Thin-Films

Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO₂Thin-Films

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

Dynamics in Electrochromic Windows Interpreted with an Extended Logistic Model

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New approach of electrochemical systems dynamics in the time domain under small-signal conditions: III – Discrimination between nine candidate models for analysis of PITT experimental data from LixCoO2 film electrodes

Cited by 20 publications

References 91 publications

Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO2Thin-Films

Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO2Thin-Films

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

Dynamics in Electrochromic Windows Interpreted with an Extended Logistic Model

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Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO₂Thin-Films

Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO₂Thin-Films