α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf>

A dual positive/negative electrode material for sodium ion batteries

Rachid Essehli, I. Belharouak, Hamdi Yahia, R. Chamoun, B. Orayech, B. El Bali, K. Bouziane, X. L. Zhou, Z. Zhou

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

A new orthophosphate α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> was synthesized using a solid state reaction route, and its crystal structure was determined from powder X-ray diffraction data. The physical properties of α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> were studied by magnetic and electrochemical measurements and by Mössbauer and Raman spectroscopy. α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> crystallizes according to a stuffed α-CrPO<inf>4</inf>-type structure with the space group Imma and the cell parameters a = 10.42821(12), b = 13.19862(15), c = 6.47634(8) Å, and Z = 4. The structure consists of a 3D-framework of octahedra and tetrahedra sharing corners and/or edges with channels along [100] and [010], in which the sodium atoms are located. The <sup>57</sup>Fe Mössbauer spectrum indicates that the Fe<sup>3+</sup> cation is distributed over two crystallographic sites implying the presence of a Ni<sup>2+</sup>/Fe<sup>3+</sup> statistical disorder. Magnetic susceptibility follows the Curie-Weiss behavior above 100 K with θ = -114.3 K indicating the occurrence of predominant antiferromagnetic interactions. Electrochemical tests indicate that during the first discharge to 1 V vs. Na<sup>+</sup>/Na in a sodium cell, one Na<sup>+</sup> ion could be inserted into the α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> structure. This has led to the formation of a new phase Na<inf>3</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> which was found to be promising as a positive electrode material for sodium batteries. When α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> is further discharged to 0.03 V, it delivers a capacity of 960 mA h g<sup>-1</sup>. This corresponds to the intercalation of more than seven sodium atoms per formula unit which is an indication of a conversion-type behaviour with the formation of metallic Fe and Ni. When cycled in the voltage range 0.03-3 V vs. Na<sup>+</sup>/Na, at 20 °C, under the current rates of 50, 100, 200, and 400 mA g<sup>-1</sup>, reversible capacities of 238, 196, 153, and 115 mA h g<sup>-1</sup>, were obtained, respectively. This journal is

Original languageEnglish
Pages (from-to)4526-4532
Number of pages7
JournalDalton Transactions
Volume44
Issue number10
DOIs
Publication statusPublished - 14 Mar 2015

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Electrodes
Sodium
Ions
Atoms
Raman Spectrum Analysis
Intercalation
Solid state reactions
Magnetic susceptibility
X-Ray Diffraction
Powders
X ray powder diffraction
Raman spectroscopy
Cations
Physical properties
Crystal structure
Phosphates
Electric potential

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> A dual positive/negative electrode material for sodium ion batteries. / Essehli, Rachid; Belharouak, I.; Yahia, Hamdi; Chamoun, R.; Orayech, B.; El Bali, B.; Bouziane, K.; Zhou, X. L.; Zhou, Z.

In: Dalton Transactions, Vol. 44, No. 10, 14.03.2015, p. 4526-4532.

Research output: Contribution to journalArticle

Essehli, Rachid ; Belharouak, I. ; Yahia, Hamdi ; Chamoun, R. ; Orayech, B. ; El Bali, B. ; Bouziane, K. ; Zhou, X. L. ; Zhou, Z. / α-Na<inf>2</inf>Ni<inf>2</inf>Fe(PO<inf>4</inf>)<inf>3</inf> A dual positive/negative electrode material for sodium ion batteries. In: Dalton Transactions. 2015 ; Vol. 44, No. 10. pp. 4526-4532.
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abstract = "A new orthophosphate α-Na2Ni2Fe(PO4)3 was synthesized using a solid state reaction route, and its crystal structure was determined from powder X-ray diffraction data. The physical properties of α-Na2Ni2Fe(PO4)3 were studied by magnetic and electrochemical measurements and by M{\"o}ssbauer and Raman spectroscopy. α-Na2Ni2Fe(PO4)3 crystallizes according to a stuffed α-CrPO4-type structure with the space group Imma and the cell parameters a = 10.42821(12), b = 13.19862(15), c = 6.47634(8) {\AA}, and Z = 4. The structure consists of a 3D-framework of octahedra and tetrahedra sharing corners and/or edges with channels along [100] and [010], in which the sodium atoms are located. The 57Fe M{\"o}ssbauer spectrum indicates that the Fe3+ cation is distributed over two crystallographic sites implying the presence of a Ni2+/Fe3+ statistical disorder. Magnetic susceptibility follows the Curie-Weiss behavior above 100 K with θ = -114.3 K indicating the occurrence of predominant antiferromagnetic interactions. Electrochemical tests indicate that during the first discharge to 1 V vs. Na+/Na in a sodium cell, one Na+ ion could be inserted into the α-Na2Ni2Fe(PO4)3 structure. This has led to the formation of a new phase Na3Ni2Fe(PO4)3 which was found to be promising as a positive electrode material for sodium batteries. When α-Na2Ni2Fe(PO4)3 is further discharged to 0.03 V, it delivers a capacity of 960 mA h g-1. This corresponds to the intercalation of more than seven sodium atoms per formula unit which is an indication of a conversion-type behaviour with the formation of metallic Fe and Ni. When cycled in the voltage range 0.03-3 V vs. Na+/Na, at 20 °C, under the current rates of 50, 100, 200, and 400 mA g-1, reversible capacities of 238, 196, 153, and 115 mA h g-1, were obtained, respectively. This journal is",
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AU - Yahia, Hamdi

AU - Chamoun, R.

AU - Orayech, B.

AU - El Bali, B.

AU - Bouziane, K.

AU - Zhou, X. L.

AU - Zhou, Z.

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