Phase boundary propagation mode in nano-sized electrode materials evidenced by potentiostatic current transients analysis: Li-rich LiFePO4 case study

Sumanov, Vasiliy D.; Tyablikov, Oleg A.; Morozov, Anatoly V.; Fedotov, Stanislav S.; Vassiliev, Sergey Yu.; Nikitina, Victoria A.

doi:10.1016/j.electacta.2020.137627

Cited by 13 publications

(13 citation statements)

References 65 publications

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“…Moreover, low diffusion coefficient of Li + ion (approximately 10 −14 cm 2 /s) of LiFePO 4 may result in poor cyclability and subsequently capacity fading [75]. On a positive note, the reduction of the LiFePO 4 particles to the nanosize provides short Li + -ion diffusion paths within the positive electrode [76][77][78]. Additionally, the conductivity of LiFePO 4 is improved through coating of the material with a conductive carbon between particles providing high diffusion kinetics and preventing particles agglomeration [74,[77][78][79][80][81].…”

Section: Olivine Cathode Materialsmentioning

confidence: 99%

A Comparative Review of Metal Oxide Surface Coatings on Three Families of Cathode Materials for Lithium Ion Batteries

et al. 2021

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In the recent years, lithium-ion batteries have prevailed and dominated as the primary power sources for mobile electronic applications. Equally, their use in electric resources of transportation and other high-level applications is hindered to some certain extent. As a result, innovative fabrication of lithium-ion batteries based on best performing cathode materials should be developed as electrochemical performances of batteries depends largely on the electrode materials. Elemental doping and coating of cathode materials as a way of upgrading Li-ion batteries have gained interest and have modified most of the commonly used cathode materials. This has resulted in enhanced penetration of Li-ions, ionic mobility, electric conductivity and cyclability, with lesser capacity fading compared to traditional parent materials. The current paper reviews the role and effect of metal oxides as coatings for improvement of cathode materials in Li-ion batteries. For layered cathode materials, a clear evaluation of how metal oxide coatings sweep of metal ion dissolution, phase transitions and hydrofluoric acid attacks is detailed. Whereas the effective ways in which metal oxides suppress metal ion dissolution and capacity fading related to spinel cathode materials are explained. Lastly, challenges faced by olivine-type cathode materials, namely; low electronic conductivity and diffusion coefficient of Li+ ion, are discussed and recent findings on how metal oxide coatings could curb such limitations are outlined.

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Section: Olivine Cathode Materialsmentioning

confidence: 99%

A Comparative Review of Metal Oxide Surface Coatings on Three Families of Cathode Materials for Lithium Ion Batteries

et al. 2021

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“…In this respect, Sumanov proposed a hybrid model based on potentiostatic measurements taking into account the chemical reaction limitations from both nucleation and diffusion. 8 These findings highlight the ambivalent mechanistic complexity of LFP, which would be limited by nucleation at a low current density but would become limited by diffusion at high charge/discharge rates. For an LFP sample having a similar morphology and particle size as the one used is the current study, Sumanov derived a diffusion coefficient of about 2•10 −12 cm 2 •s −1 .…”

Section: Introductionmentioning

confidence: 79%

“…These findings highlight the ambivalent mechanistic complexity of LFP, which would be limited by nucleation at a low current density but would become limited by diffusion at high charge/discharge rates. For an LFP sample having a similar morphology and particle size as the one used is the current study, Sumanov derived a diffusion coefficient of about 2·10 –12 cm 2 ·s –1 …”

Section: Introductionmentioning

confidence: 82%

“…Whichever the kinetic model selected, the lithium internal diffusion is always an important step of the mechanisms proposed, although nucleation has also been considered by some authors as the limiting mechanism. In this respect, Sumanov proposed a hybrid model based on potentiostatic measurements taking into account the chemical reaction limitations from both nucleation and diffusion . These findings highlight the ambivalent mechanistic complexity of LFP, which would be limited by nucleation at a low current density but would become limited by diffusion at high charge/discharge rates.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics, Mechanism, and Optimization Modeling of a Green LFP Delithiation Process Developed for Direct Recycling of Lithium-Ion Batteries

Larouche

Voisard

Amouzegar

et al. 2023

Ind. Eng. Chem. Res.

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Orthorhombic LiFePO4 (LFP) offers highly reversible redox reactions, making it an attractive cathodic material for lithium-ion batteries. This electrochemical property was exploited to develop an environmentally benign selective lithium extraction process based on CO2 and hydrogen peroxide that can be applied to direct LFP recycling. The proof of concept of this green delithiation process was demonstrated in a previously published paper, while the process optimization and the establishment of the reaction kinetic mechanism are addressed in the current paper. First, the effects of solid to liquid ratio (S/L), temperature, CO2 pressure, and initial H2O2 to LFP molar ratio were studied through an orthogonal design of experiments. In the range of conditions studied and considering the objective of maximizing the S/L ratio, the optimal conditions are a temperature of 20 °C, a CO2 pressure of 2 atm, and a H2O2 to LFP molar ratio of 1.25. In addition, reaction kinetic models were used to determine the reaction mechanism. The activation energies obtained based on rate constants from shrinking core and Avrami models are 15.7 and 13.9 kJ mol–1, respectively. While these values reveal a mixed or diffusion-controlled heterogeneous reaction, the analysis of half-delithiated LFP particles under scanning–transmission electron microscopy revealed the reaction being controlled by nucleation rather than diffusion. In this context, the Avrami model that accounts for nucleation and growth in solid-state reactions proved the most appropriate. Further, the reaction mechanism is concluded to be limited by nucleation of FP phase within the body of LFP during the early reaction stage and to sequentially shift to the one-dimensional diffusion-limited crystallite growth regime. Finally, it is shown that CO2 acts as a buffering agent by neutralizing the LiOH formed by Fenton-like reactions between H2O2 and ferric iron in LFP.

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“…Typically, there are three typical shrinking core models to describe the leaching process, including external diffusion, internal diffusion and chemical reaction. 38,39 Each of them can be the rate controlling step of the leaching reaction respectively under certain circumstances. According to the optimal leaching conditions, the leaching kinetics of the process at different reaction temperatures (20 °C, 30 °C, 40 °C, and 50 °C) and oxidation times (0 min-30 min) have been studied, and the kinetics fitting is carried out according to the corresponding kinetics equations (Table S6 †).…”

Section: Resultsmentioning

confidence: 99%

Start from the source: direct treatment of a degraded LiFePO₄ cathode for efficient recycling of spent lithium-ion batteries

Qiu

Zhang

et al. 2022

Green Chem.

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Phase boundary propagation mode in nano-sized electrode materials evidenced by potentiostatic current transients analysis: Li-rich LiFePO4 case study

Cited by 13 publications

References 65 publications

A Comparative Review of Metal Oxide Surface Coatings on Three Families of Cathode Materials for Lithium Ion Batteries

A Comparative Review of Metal Oxide Surface Coatings on Three Families of Cathode Materials for Lithium Ion Batteries

Kinetics, Mechanism, and Optimization Modeling of a Green LFP Delithiation Process Developed for Direct Recycling of Lithium-Ion Batteries

Start from the source: direct treatment of a degraded LiFePO₄ cathode for efficient recycling of spent lithium-ion batteries

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Phase boundary propagation mode in nano-sized electrode materials evidenced by potentiostatic current transients analysis: Li-rich LiFePO4 case study

Cited by 13 publications

References 65 publications

A Comparative Review of Metal Oxide Surface Coatings on Three Families of Cathode Materials for Lithium Ion Batteries

A Comparative Review of Metal Oxide Surface Coatings on Three Families of Cathode Materials for Lithium Ion Batteries

Kinetics, Mechanism, and Optimization Modeling of a Green LFP Delithiation Process Developed for Direct Recycling of Lithium-Ion Batteries

Start from the source: direct treatment of a degraded LiFePO4 cathode for efficient recycling of spent lithium-ion batteries

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Product

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Start from the source: direct treatment of a degraded LiFePO₄ cathode for efficient recycling of spent lithium-ion batteries