Selective sodium-ion diffusion channels in Na2-xFe3(PO4)3 positive electrode for Na-ion batteries

Rachid Essehli, Hamdi Yahia, R. Amin, Fadwa El-Mellouhi, I. Belharouak

Research output: Contribution to journalArticle

Abstract

The electrochemical community around the world is focusing heavily on sodium-ion batteries R&D due to the huge abundance of sodium and need for large scale deployment of safe and inexpensive batteries for the electrical grid energy storage. We report on the characterization of model parameters such as ionic diffusivity and interfacial kinetics, for a potential sodium-ion battery cathode material, Na2-xFe3(PO4)3, using experimental and computational investigations. The Na2-xFe3(PO4)3 structure is characterized by two distinct one-dimensional (1-D) Na diffusion channels. Density Functional Theory (DFT) calculation reveals that Na is first fully removed from one of the channels followed by the subsequent removal of Na from the second channel. The experimental investigation reveals that, in the beginning of Na removal at 0 ≤ x ≤ 0.5; the sodium ion diffusivity is of the order of ~10−11 cm2s−1 and then slightly decreases. This is further confirmed by comparing the calculated sodium diffusion barriers along the individual 1-D channels as well as between the channels. Nevertheless, the exchange current density slowly increases up to x = 1.0 and remains quite constant thereafter. The magnitude of exchange current density is very low suggesting that the interfacial kinetics are the rate limiting factor. The obtained results suggest that Na2-xFe3(PO4)3 could achieve better rate performance with long cycling stability through engineering of the particle morphology and microstructure.

Original languageEnglish
JournalEnergy Storage Materials
DOIs
Publication statusPublished - 1 Jan 2019

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Sodium Channels
Sodium
Ions
Electrodes
Current density
Kinetics
Diffusion barriers
Energy storage
Density functional theory
Cathodes
Microstructure

Keywords

  • Alluaudite structure
  • Batteries
  • DFT calculations
  • Ionic diffusivity
  • Na-ion
  • Rietveld refinement

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)
  • Energy Engineering and Power Technology

Cite this

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title = "Selective sodium-ion diffusion channels in Na2-xFe3(PO4)3 positive electrode for Na-ion batteries",
abstract = "The electrochemical community around the world is focusing heavily on sodium-ion batteries R&D due to the huge abundance of sodium and need for large scale deployment of safe and inexpensive batteries for the electrical grid energy storage. We report on the characterization of model parameters such as ionic diffusivity and interfacial kinetics, for a potential sodium-ion battery cathode material, Na2-xFe3(PO4)3, using experimental and computational investigations. The Na2-xFe3(PO4)3 structure is characterized by two distinct one-dimensional (1-D) Na diffusion channels. Density Functional Theory (DFT) calculation reveals that Na is first fully removed from one of the channels followed by the subsequent removal of Na from the second channel. The experimental investigation reveals that, in the beginning of Na removal at 0 ≤ x ≤ 0.5; the sodium ion diffusivity is of the order of ~10−11 cm2s−1 and then slightly decreases. This is further confirmed by comparing the calculated sodium diffusion barriers along the individual 1-D channels as well as between the channels. Nevertheless, the exchange current density slowly increases up to x = 1.0 and remains quite constant thereafter. The magnitude of exchange current density is very low suggesting that the interfacial kinetics are the rate limiting factor. The obtained results suggest that Na2-xFe3(PO4)3 could achieve better rate performance with long cycling stability through engineering of the particle morphology and microstructure.",
keywords = "Alluaudite structure, Batteries, DFT calculations, Ionic diffusivity, Na-ion, Rietveld refinement",
author = "Rachid Essehli and Hamdi Yahia and R. Amin and Fadwa El-Mellouhi and I. Belharouak",
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T1 - Selective sodium-ion diffusion channels in Na2-xFe3(PO4)3 positive electrode for Na-ion batteries

AU - Essehli, Rachid

AU - Yahia, Hamdi

AU - Amin, R.

AU - El-Mellouhi, Fadwa

AU - Belharouak, I.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - The electrochemical community around the world is focusing heavily on sodium-ion batteries R&D due to the huge abundance of sodium and need for large scale deployment of safe and inexpensive batteries for the electrical grid energy storage. We report on the characterization of model parameters such as ionic diffusivity and interfacial kinetics, for a potential sodium-ion battery cathode material, Na2-xFe3(PO4)3, using experimental and computational investigations. The Na2-xFe3(PO4)3 structure is characterized by two distinct one-dimensional (1-D) Na diffusion channels. Density Functional Theory (DFT) calculation reveals that Na is first fully removed from one of the channels followed by the subsequent removal of Na from the second channel. The experimental investigation reveals that, in the beginning of Na removal at 0 ≤ x ≤ 0.5; the sodium ion diffusivity is of the order of ~10−11 cm2s−1 and then slightly decreases. This is further confirmed by comparing the calculated sodium diffusion barriers along the individual 1-D channels as well as between the channels. Nevertheless, the exchange current density slowly increases up to x = 1.0 and remains quite constant thereafter. The magnitude of exchange current density is very low suggesting that the interfacial kinetics are the rate limiting factor. The obtained results suggest that Na2-xFe3(PO4)3 could achieve better rate performance with long cycling stability through engineering of the particle morphology and microstructure.

AB - The electrochemical community around the world is focusing heavily on sodium-ion batteries R&D due to the huge abundance of sodium and need for large scale deployment of safe and inexpensive batteries for the electrical grid energy storage. We report on the characterization of model parameters such as ionic diffusivity and interfacial kinetics, for a potential sodium-ion battery cathode material, Na2-xFe3(PO4)3, using experimental and computational investigations. The Na2-xFe3(PO4)3 structure is characterized by two distinct one-dimensional (1-D) Na diffusion channels. Density Functional Theory (DFT) calculation reveals that Na is first fully removed from one of the channels followed by the subsequent removal of Na from the second channel. The experimental investigation reveals that, in the beginning of Na removal at 0 ≤ x ≤ 0.5; the sodium ion diffusivity is of the order of ~10−11 cm2s−1 and then slightly decreases. This is further confirmed by comparing the calculated sodium diffusion barriers along the individual 1-D channels as well as between the channels. Nevertheless, the exchange current density slowly increases up to x = 1.0 and remains quite constant thereafter. The magnitude of exchange current density is very low suggesting that the interfacial kinetics are the rate limiting factor. The obtained results suggest that Na2-xFe3(PO4)3 could achieve better rate performance with long cycling stability through engineering of the particle morphology and microstructure.

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