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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. Here, we observe 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 exploration 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 indicate that Na2-xFe3(PO4)3more » could achieve better rate performance with long cycling stability through engineering of the particle morphology and microstructure.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Hamad Bin Khalifa Univ., Doha (Qatar)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE; National Priorities Research Program; Qatar National Research Fund (QNRF)
OSTI Identifier:
1566943
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Energy Storage Materials
Additional Journal Information:
Journal Volume: 24; Journal ID: ISSN 2405-8297
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Alluaudite structure; Rietveld refinement; Ionic diffusivity; DFT calculations; Na-ion; Batteries

Citation Formats

Essehli, Rachid, Ben Yahia, Hamdi, Amin, Ruhul, El-Mellouhi, Fadwa, and Belharouak, Ilias. Selective sodium-ion diffusion channels in Na2-xFe3(PO4)3 positive electrode for Na-ion batteries. United States: N. p., 2019. Web. doi:10.1016/j.ensm.2019.07.040.
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Essehli, Rachid, Ben Yahia, Hamdi, Amin, Ruhul, El-Mellouhi, Fadwa, & Belharouak, Ilias. Selective sodium-ion diffusion channels in Na2-xFe3(PO4)3 positive electrode for Na-ion batteries. United States. https://doi.org/10.1016/j.ensm.2019.07.040
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Essehli, Rachid, Ben Yahia, Hamdi, Amin, Ruhul, El-Mellouhi, Fadwa, and Belharouak, Ilias. Tue . "Selective sodium-ion diffusion channels in Na2-xFe3(PO4)3 positive electrode for Na-ion batteries". United States. https://doi.org/10.1016/j.ensm.2019.07.040. https://www.osti.gov/servlets/purl/1566943.
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@article{osti_1566943,
title = {Selective sodium-ion diffusion channels in Na2-xFe3(PO4)3 positive electrode for Na-ion batteries},
author = {Essehli, Rachid and Ben Yahia, Hamdi and Amin, Ruhul and El-Mellouhi, Fadwa and Belharouak, Ilias},
abstractNote = {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. Here, we observe 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 exploration 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 indicate that Na2-xFe3(PO4)3 could achieve better rate performance with long cycling stability through engineering of the particle morphology and microstructure.},
doi = {10.1016/j.ensm.2019.07.040},
journal = {Energy Storage Materials},
number = ,
volume = 24,
place = {United States},
year = {Tue Jul 30 00:00:00 EDT 2019},
month = {Tue Jul 30 00:00:00 EDT 2019}
}
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Publisher's Version of Record
https://doi.org/10.1016/j.ensm.2019.07.040
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Figures / Tables:

Table 1 Table 1: Crystallographic and structure refinements data for Na1.7Fe3(PO4)3.
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