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Title: Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2

Abstract

The compound NaFe2(PO4)(SO4)2 is successfully synthesized via a solid state reaction route and its crystal structure is determined using powder X-ray diffraction data. NaFe2(PO4)(SO4)2 phase is also characterized by cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy. NaFe2(PO4)(SO4)2 crystallizes with the well-known NASICON-type structure. SAED and HRTEM experiments confirm the structural model, and no ordering between the PO4-3 and SO4-2 polyanions is detected. The electrochemical tests indicate that NaFe2(PO4)(SO4)2 is a 3 V sodium intercalating cathode. The electrical conductivity is relatively low (2.2 × 10-6 Scm-1 at 200 °C) and the obtained activation energy is ~0.60eV. The GITT experiments indicate that the diffusivity values are in the range of 10-11-10-12 cm2/s within the measured sodium concentrations.

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [3];  [4]
  1. Hamad Bin Khalifa Univ., Doha (Qatar). Qatar Environment and Energy Research Inst.
  2. Univ. Complutense, Madrid (Spain). Dept. de Química Inorgánica Facultad de Químicas
  3. National Inst. of Advanced Science and Technology, Osaka (Japan). Research Inst. of Electrochemical Energy
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Energy and Transportation Science Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1495971
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 382; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ben Yahia, Hamdi, Essehli, Rachid, Amin, Ruhul, Boulahya, Khalid, Okumura, Toyoki, and Belharouak, Ilias. Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2. United States: N. p., 2018. Web. doi:10.1016/j.jpowsour.2018.02.021.
Ben Yahia, Hamdi, Essehli, Rachid, Amin, Ruhul, Boulahya, Khalid, Okumura, Toyoki, & Belharouak, Ilias. Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2. United States. https://doi.org/10.1016/j.jpowsour.2018.02.021
Ben Yahia, Hamdi, Essehli, Rachid, Amin, Ruhul, Boulahya, Khalid, Okumura, Toyoki, and Belharouak, Ilias. Thu . "Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2". United States. https://doi.org/10.1016/j.jpowsour.2018.02.021. https://www.osti.gov/servlets/purl/1495971.
@article{osti_1495971,
title = {Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2},
author = {Ben Yahia, Hamdi and Essehli, Rachid and Amin, Ruhul and Boulahya, Khalid and Okumura, Toyoki and Belharouak, Ilias},
abstractNote = {The compound NaFe2(PO4)(SO4)2 is successfully synthesized via a solid state reaction route and its crystal structure is determined using powder X-ray diffraction data. NaFe2(PO4)(SO4)2 phase is also characterized by cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy. NaFe2(PO4)(SO4)2 crystallizes with the well-known NASICON-type structure. SAED and HRTEM experiments confirm the structural model, and no ordering between the PO4-3 and SO4-2 polyanions is detected. The electrochemical tests indicate that NaFe2(PO4)(SO4)2 is a 3 V sodium intercalating cathode. The electrical conductivity is relatively low (2.2 × 10-6 Scm-1 at 200 °C) and the obtained activation energy is ~0.60eV. The GITT experiments indicate that the diffusivity values are in the range of 10-11-10-12 cm2/s within the measured sodium concentrations.},
doi = {10.1016/j.jpowsour.2018.02.021},
journal = {Journal of Power Sources},
number = C,
volume = 382,
place = {United States},
year = {2018},
month = {2}
}

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Works referenced in this record:

Rhombohedral Form of Li 3 V 2 (PO 4 ) 3 as a Cathode in Li-Ion Batteries
journal, November 2000

  • Gaubicher, J.; Wurm, C.; Goward, G.
  • Chemistry of Materials, Vol. 12, Issue 11
  • DOI: 10.1021/cm000345g

Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries
journal, January 2012


A nasicon-type phase as intercalation electrode: NaTi2(PO4)3
journal, May 1987


Discovery of a Sodium-Ordered Form of Na 3 V 2 (PO 4 ) 3 below Ambient Temperature
journal, August 2015


Luminescence properties and energy transfer studies of color tunable Tb3+-doped RE1/3Zr2(PO4)3 (RE = Y, La, Gd and Lu)
journal, November 2016


CO-sensing properties of a NASICON-based gas sensor attached with Pt mixed with Bi2O3 as a sensing electrode
journal, February 2015


Preliminary results on the leaching process of phosphate ceramics, potential hosts for actinide immobilization
journal, August 2001


Fast Na+-ion transport in skeleton structures
journal, February 1976


The Crystal Structure of NaM2IV(PO4)3; MeIV = Ge, Ti, Zr.
journal, January 1968


A wide-ranging review on Nasicon type materials
journal, February 2011

  • Anantharamulu, N.; Koteswara Rao, K.; Rambabu, G.
  • Journal of Materials Science, Vol. 46, Issue 9
  • DOI: 10.1007/s10853-011-5302-5

High temperature neutron diffraction study of sodium di-tin tri-phosphate
journal, September 1992


High-pressure crystal chemistry and phase transition of RbTi 2 (PO 4 ) 3
journal, February 1994

  • Hazen, R. M.; Palmer, D. C.; Finger, L. W.
  • Journal of Physics: Condensed Matter, Vol. 6, Issue 7
  • DOI: 10.1088/0953-8984/6/7/006

The Structure of Na5Ti(PO4)3
journal, August 1993

  • Krimi, S.; Mansouri, I.; El Jazouli, A.
  • Journal of Solid State Chemistry, Vol. 105, Issue 2
  • DOI: 10.1006/jssc.1993.1248

La 3+ Diffusion in the NASICON-Type Compound La 1/3 Zr 2 (PO 4 ) 3 :  X-ray Thermodiffraction, 31 P NMR, and Ionic Conductivity Investigations
journal, October 2006

  • Barré, M.; Le Berre, F.; Crosnier-Lopez, M. P.
  • Chemistry of Materials, Vol. 18, Issue 23
  • DOI: 10.1021/cm061610m

The crystal structure of a nonstoichiometric NASICON
journal, June 1985


A Powder Neutron Diffraction Investigation of the Two Rhombohedral NASICON Analogues:  γ-Na 3 Fe 2 (PO 4 ) 3 and Li 3 Fe 2 (PO 4 ) 3
journal, February 2000

  • Masquelier, C.; Wurm, C.; Rodríguez-Carvajal, J.
  • Chemistry of Materials, Vol. 12, Issue 2
  • DOI: 10.1021/cm991138n

The crystal structure of the monoclinic Fe 2 (SO 4 ) 3
journal, August 1975


The crystal structure of rhombohedral Fe 2 (SO 4 ) 3
journal, January 1976


Tuning the Position of the Redox Couples in Materials with NASICON Structure by Anionic Substitution
journal, January 1998

  • Padhi, A. K.
  • Journal of The Electrochemical Society, Vol. 145, Issue 5
  • DOI: 10.1149/1.1838513

Polyanionic (Phosphates, Silicates, Sulfates) Frameworks as Electrode Materials for Rechargeable Li (or Na) Batteries
journal, June 2013

  • Masquelier, Christian; Croguennec, Laurence
  • Chemical Reviews, Vol. 113, Issue 8
  • DOI: 10.1021/cr3001862

Phase transitions and ionic conduction in 3D skeleton phosphates A3M2(PO4)3 : A = Li, Na, Ag, K ; M = Cr, Fe
journal, December 1983


NaFe 2 PO 4 (SO 4 ) 2 : a potential cathode for a Na-ion battery
journal, January 2016

  • Shiva, Konda; Singh, Preetam; Zhou, Weidong
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE01093H

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993


Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database
journal, August 1985

  • Brown, I. D.; Altermatt, D.
  • Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4
  • DOI: 10.1107/S0108768185002063

Bond-valence parameters for solids
journal, April 1991

  • Brese, N. E.; O'Keeffe, M.
  • Acta Crystallographica Section B Structural Science, Vol. 47, Issue 2
  • DOI: 10.1107/S0108768190011041

Unveiling the sodium intercalation properties in Na1.86□0.14Fe3(PO4)3
journal, August 2016


Works referencing / citing this record:

Sodium iron sulfate alluaudite solid solution for Na-ion batteries: moving towards stoichiometric Na 2 Fe 2 (SO 4 ) 3
journal, January 2019

  • Jungers, Thomas; Mahmoud, Abdelfattah; Malherbe, Cedric
  • Journal of Materials Chemistry A, Vol. 7, Issue 14
  • DOI: 10.1039/c9ta00116f

Facile aqueous synthesis of high performance Na 2 FeM(SO 4 ) 3 (M = Fe, Mn, Ni) alluaudites for low cost Na-ion batteries
journal, January 2020

  • Plewa, Anna; Kulka, Andrzej; Hanc, Emil
  • Journal of Materials Chemistry A, Vol. 8, Issue 5
  • DOI: 10.1039/c9ta11565j