Effect of temperature on the kinetics and thermodynamics of electrochemical insertion of Li-ions into a graphite electrode

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

doi:10.1016/j.jelechem.2003.08.032

Cited by 45 publications

(51 citation statements)

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“…Levi et al [27,[35][36][37][38][39][40][41] have developed the basis of CV method for kinetic and thermodynamic analysis of processes in application to various lithium intercalation materials. Churikov et al [33,42] proposed to modify the Randles-Shevchik equation by the introduction of a correction parameter z to account the differences between the concentration and the activity of the potential-defining particles.…”

Section: Introductionmentioning

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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Section: Introductionmentioning

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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“…A thin strip of Li RE was pressed onto a Ni wire and was isolated from both the electrodes and the stainless steel framework by a thin polypropylene tape (for details see Ref. [9]). The preparation of thin composite graphite electrodes has been described previously [9,10].…”

Section: Methodsmentioning

confidence: 99%

“…[9]). The preparation of thin composite graphite electrodes has been described previously [9,10]. The electrodes contained $1.8 mg of graphite powder (KS-15 from Timrex Inc., the average particle size close to 15 lm, specific surface area obtained by BET 12 m 2 g À1 ) and 10% (by weight) of PVdF binder.…”

Section: Methodsmentioning

confidence: 99%

“…For instance, phase transitions during electrochemical Li ion-insertion into graphite [9][10][11], Li x Mn 2 O 4 spinel [12] or Mg-ions insertion into Mg x Mo 6 S 8 Chevrel phase [13] start with a slow growth of nuclei of a new (more rich in ions content) phase in the bulk of the old (more diluted) one. This was identified by characteristic rising current transients in response to potential steps, similar in shape to current transients related to both cases of electrocrystallization of metals from liquid electrolyte solutions or the formation of intermetallic alloys.…”

Section: Introductionmentioning

confidence: 99%

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Chronoamperometric measurements and modeling of nucleation and growth, and moving boundary stages during electrochemical lithiation of graphite electrode

Levi

Markevich

Wang

et al. 2007

Journal of Electroanalytical Chemistry

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A Perspective on the Molecular Modeling of Electrolyte Decomposition Reactions for Solid Electrolyte Interphase Growth in Lithium‐Ion Batteries

Bin Jassar,

Michel,

Abada

et al. 2024

Adv Funct Materials

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The solid electrolyte interphase (SEI) is a thin heterogeneous layer formed at the anode/electrolyte interface in lithium‐ion batteries as a consequence of the reduction of the electrolyte. The initial formation of the SEI inhibits the direct contact between the electrode and the electrolyte and thus protects the battery. However, the composition, structure, and size of the SEI evolve over time and the growth of the SEI is considered the primary mechanism leading to the gradual deterioration of the battery performance. Despite the importance of the SEI and its growth, the atomistic understanding of the underlying elementary reaction steps remains partial. Molecular modeling of the electrolyte decomposition is key to gain detailed insights that are complementary to experiments for the reactions occurring in this heterogenous interphase. In this perspective, the electron transport mechanisms are first described from the anode to the electrolyte through the SEI and highlight the importance of the inorganic/organic interface within the heterogeneous SEI: it is where the electrolyte decomposition reactions are likely to occur. Finally, a view is provided on the current progress on molecular modeling techniques (e.g., Density Functional Theory, force fields, machine learning potentials) of the SEI and the challenges each method faces.

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Effect of temperature on the kinetics and thermodynamics of electrochemical insertion of Li-ions into a graphite electrode

Cited by 45 publications

References 46 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

Chronoamperometric measurements and modeling of nucleation and growth, and moving boundary stages during electrochemical lithiation of graphite electrode

A Perspective on the Molecular Modeling of Electrolyte Decomposition Reactions for Solid Electrolyte Interphase Growth in Lithium‐Ion Batteries

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