The decisive role of electrostatic interactions in transport mode and phase segregation of lithium ions in LiFePO<sub>4</sub>

Wang, Xiaoxiao; Huang, Jun; Liu, Yuwen; Chen, Shengli

doi:10.1039/d3sc04297a

Chem. Sci.

2023

DOI: 10.1039/d3sc04297a

|View full text |Cite

The decisive role of electrostatic interactions in transport mode and phase segregation of lithium ions in LiFePO₄

Xiaoxiao Wang,

Jun Huang,

Yuwen Liu

et al.

Abstract: The Hamiltonian model reveals that ion–electron coupled transfer is the optimal reaction pathway with the lowest activation barrier, compared with separate electron tunneling or ion transport.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2024

Publication Types

Select...

Article2

Relationship

Self Cite0

Independent2

Authors

Journals

Cited by 2 publications

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Straightforward computational determination of energy-transfer kinetics through the application of the Marcus theory

Solé-Daura,

Maseras

2024

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Straightforward computational determination of energy-transfer kinetics through the application of the Marcus theory

Solé-Daura,

Maseras

2024

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Impact of temperature on short-range charge ordering in LiFePO4/FePO4

Hammadi,

Kullgren,

Wolf

et al. 2024

Phys. Rev. B

View full text Add to dashboard Cite

Energy is stored in a LiFePO4 battery electrode through the intercalation of Li. As Li incorporate into the crystal lattice of Fe(III)PO4, electrons reduce Fe(III) into Fe(II). The interactions of Li and its vacant site (Va) with these localized electrons (holes), so-called polarons, cause phase separation during battery operation. These fundamental interactions are however difficult to quantify using standard electronic structure calculations. In this paper, we utilize DFT+U with occupation matrix control to compute interaction energies at varying Li-Fe(II) and Va-Fe(III) pair separations. The increased energy with separation warrants the use of an electrostatic description. The DFT+U data are fitted to a Coulombic potential with two-body corrections and used in a Monte Carlo scheme. The coordination of the species determines their short-range ordering, showing that the Li and Va create chains bridged by their associated polarons which dissociate into dimers at higher temperatures. This dissociation happens at higher temperatures for Va than for Li, indicating a more pronounced clustering behavior during the formation of FePO4. Notably, a significant amount of uncoordinated Li exists at elevated temperatures, challenging the simplified picture of complete Li-Fe(II) pairing. Published by the American Physical Society 2024

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

The decisive role of electrostatic interactions in transport mode and phase segregation of lithium ions in LiFePO₄

Abstract: The Hamiltonian model reveals that ion–electron coupled transfer is the optimal reaction pathway with the lowest activation barrier, compared with separate electron tunneling or ion transport.

Cited by 2 publications

References 65 publications

Straightforward computational determination of energy-transfer kinetics through the application of the Marcus theory

Straightforward computational determination of energy-transfer kinetics through the application of the Marcus theory

Impact of temperature on short-range charge ordering in LiFePO4/FePO4

Contact Info

Product

Resources

About

The decisive role of electrostatic interactions in transport mode and phase segregation of lithium ions in LiFePO4

Abstract: The Hamiltonian model reveals that ion–electron coupled transfer is the optimal reaction pathway with the lowest activation barrier, compared with separate electron tunneling or ion transport.

Cited by 2 publications

References 65 publications

Straightforward computational determination of energy-transfer kinetics through the application of the Marcus theory

Straightforward computational determination of energy-transfer kinetics through the application of the Marcus theory

Impact of temperature on short-range charge ordering in LiFePO4/FePO4

Contact Info

Product

Resources

About

The decisive role of electrostatic interactions in transport mode and phase segregation of lithium ions in LiFePO₄