Iron titanium phosphates as high-specific-capacity electrode materials for lithium ion batteries

Rachid Essehli, B. El Bali, A. Faik, M. Naji, S. Benmokhtar, Y. R. Zhong, L. W. Su, Z. Zhou, J. Kim, K. Kang, M. Dusek

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Two iron titanium phosphates, Fe0.5TiOPO4 and Fe 0.5Ti2(PO4)3, were prepared, and their crystal structures and electrochemical performances were compared. The electrochemical measurements of Fe0.5TiOPO4 as an anode of a lithium ion cell showed that upon the first discharge down to 0.5 V, the cell delivered a capacity of 560 mA h/g, corresponding to the insertion of 5 Li's per formula unit Fe0.5TiOPO4. Ex-situ XRD reveals a gradual evolution of the structure during cycling of the material, with lower crystallinity after the first discharge cycle. By correlating the electrochemical performances with the structural studies, new insights are achieved into the electrochemical behaviour of the Fe0.5TiOPO 4 anode material, suggesting a combination of intercalation and conversion reactions. The Nasicon-type Fe0.5Ti2(PO 4)3 consists of a three-dimensional network made of corners and edges sharing [TiO6] and [FeO6] octahedra and [PO4] tetrahedra leading to the formation of trimmers [FeTi 2O12]. The first discharge of lithium ion cells based on Fe0.5Ti2(PO4)3 materials showed electrochemical activity of Ti4+/Ti3+ and Fe 2+/Fe0 couples in the 2.5-1 V region. Below this voltage, the discharge profiles are typical of phosphate systems where Li 3PO4 is a product of the electrochemical reaction with lithium; moreover, the electrolyte solvent is reduced. An initial capacities as high as 1100 mA h g-1 can be obtained at deep discharge. However, there is an irreversible capacity loss in Fe0.5Ti2(PO 4)3 due to the occurrence of insulating products as Li3PO4 and a solid electrolyte interface.

Original languageEnglish
Pages (from-to)434-441
Number of pages8
JournalJournal of Alloys and Compounds
Volume585
DOIs
Publication statusPublished - 2014
Externally publishedYes

Fingerprint

Lithium
Phosphates
Iron
Titanium
Electrodes
Anodes
Ions
Solid electrolytes
Intercalation
Electrolytes
Crystal structure
Electric potential
Lithium-ion batteries
titanium phosphate

Keywords

  • Crystal structure
  • Electrolyte
  • Lithium-ion batteries
  • Nasicon
  • Oxyphosphate

ASJC Scopus subject areas

  • Mechanical Engineering
  • Mechanics of Materials
  • Materials Chemistry
  • Metals and Alloys

Cite this

Iron titanium phosphates as high-specific-capacity electrode materials for lithium ion batteries. / Essehli, Rachid; El Bali, B.; Faik, A.; Naji, M.; Benmokhtar, S.; Zhong, Y. R.; Su, L. W.; Zhou, Z.; Kim, J.; Kang, K.; Dusek, M.

In: Journal of Alloys and Compounds, Vol. 585, 2014, p. 434-441.

Research output: Contribution to journalArticle

Essehli, R, El Bali, B, Faik, A, Naji, M, Benmokhtar, S, Zhong, YR, Su, LW, Zhou, Z, Kim, J, Kang, K & Dusek, M 2014, 'Iron titanium phosphates as high-specific-capacity electrode materials for lithium ion batteries', Journal of Alloys and Compounds, vol. 585, pp. 434-441. https://doi.org/10.1016/j.jallcom.2013.09.093
Essehli, Rachid ; El Bali, B. ; Faik, A. ; Naji, M. ; Benmokhtar, S. ; Zhong, Y. R. ; Su, L. W. ; Zhou, Z. ; Kim, J. ; Kang, K. ; Dusek, M. / Iron titanium phosphates as high-specific-capacity electrode materials for lithium ion batteries. In: Journal of Alloys and Compounds. 2014 ; Vol. 585. pp. 434-441.
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abstract = "Two iron titanium phosphates, Fe0.5TiOPO4 and Fe 0.5Ti2(PO4)3, were prepared, and their crystal structures and electrochemical performances were compared. The electrochemical measurements of Fe0.5TiOPO4 as an anode of a lithium ion cell showed that upon the first discharge down to 0.5 V, the cell delivered a capacity of 560 mA h/g, corresponding to the insertion of 5 Li's per formula unit Fe0.5TiOPO4. Ex-situ XRD reveals a gradual evolution of the structure during cycling of the material, with lower crystallinity after the first discharge cycle. By correlating the electrochemical performances with the structural studies, new insights are achieved into the electrochemical behaviour of the Fe0.5TiOPO 4 anode material, suggesting a combination of intercalation and conversion reactions. The Nasicon-type Fe0.5Ti2(PO 4)3 consists of a three-dimensional network made of corners and edges sharing [TiO6] and [FeO6] octahedra and [PO4] tetrahedra leading to the formation of trimmers [FeTi 2O12]. The first discharge of lithium ion cells based on Fe0.5Ti2(PO4)3 materials showed electrochemical activity of Ti4+/Ti3+ and Fe 2+/Fe0 couples in the 2.5-1 V region. Below this voltage, the discharge profiles are typical of phosphate systems where Li 3PO4 is a product of the electrochemical reaction with lithium; moreover, the electrolyte solvent is reduced. An initial capacities as high as 1100 mA h g-1 can be obtained at deep discharge. However, there is an irreversible capacity loss in Fe0.5Ti2(PO 4)3 due to the occurrence of insulating products as Li3PO4 and a solid electrolyte interface.",
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AU - Essehli, Rachid

AU - El Bali, B.

AU - Faik, A.

AU - Naji, M.

AU - Benmokhtar, S.

AU - Zhong, Y. R.

AU - Su, L. W.

AU - Zhou, Z.

AU - Kim, J.

AU - Kang, K.

AU - Dusek, M.

PY - 2014

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N2 - Two iron titanium phosphates, Fe0.5TiOPO4 and Fe 0.5Ti2(PO4)3, were prepared, and their crystal structures and electrochemical performances were compared. The electrochemical measurements of Fe0.5TiOPO4 as an anode of a lithium ion cell showed that upon the first discharge down to 0.5 V, the cell delivered a capacity of 560 mA h/g, corresponding to the insertion of 5 Li's per formula unit Fe0.5TiOPO4. Ex-situ XRD reveals a gradual evolution of the structure during cycling of the material, with lower crystallinity after the first discharge cycle. By correlating the electrochemical performances with the structural studies, new insights are achieved into the electrochemical behaviour of the Fe0.5TiOPO 4 anode material, suggesting a combination of intercalation and conversion reactions. The Nasicon-type Fe0.5Ti2(PO 4)3 consists of a three-dimensional network made of corners and edges sharing [TiO6] and [FeO6] octahedra and [PO4] tetrahedra leading to the formation of trimmers [FeTi 2O12]. The first discharge of lithium ion cells based on Fe0.5Ti2(PO4)3 materials showed electrochemical activity of Ti4+/Ti3+ and Fe 2+/Fe0 couples in the 2.5-1 V region. Below this voltage, the discharge profiles are typical of phosphate systems where Li 3PO4 is a product of the electrochemical reaction with lithium; moreover, the electrolyte solvent is reduced. An initial capacities as high as 1100 mA h g-1 can be obtained at deep discharge. However, there is an irreversible capacity loss in Fe0.5Ti2(PO 4)3 due to the occurrence of insulating products as Li3PO4 and a solid electrolyte interface.

AB - Two iron titanium phosphates, Fe0.5TiOPO4 and Fe 0.5Ti2(PO4)3, were prepared, and their crystal structures and electrochemical performances were compared. The electrochemical measurements of Fe0.5TiOPO4 as an anode of a lithium ion cell showed that upon the first discharge down to 0.5 V, the cell delivered a capacity of 560 mA h/g, corresponding to the insertion of 5 Li's per formula unit Fe0.5TiOPO4. Ex-situ XRD reveals a gradual evolution of the structure during cycling of the material, with lower crystallinity after the first discharge cycle. By correlating the electrochemical performances with the structural studies, new insights are achieved into the electrochemical behaviour of the Fe0.5TiOPO 4 anode material, suggesting a combination of intercalation and conversion reactions. The Nasicon-type Fe0.5Ti2(PO 4)3 consists of a three-dimensional network made of corners and edges sharing [TiO6] and [FeO6] octahedra and [PO4] tetrahedra leading to the formation of trimmers [FeTi 2O12]. The first discharge of lithium ion cells based on Fe0.5Ti2(PO4)3 materials showed electrochemical activity of Ti4+/Ti3+ and Fe 2+/Fe0 couples in the 2.5-1 V region. Below this voltage, the discharge profiles are typical of phosphate systems where Li 3PO4 is a product of the electrochemical reaction with lithium; moreover, the electrolyte solvent is reduced. An initial capacities as high as 1100 mA h g-1 can be obtained at deep discharge. However, there is an irreversible capacity loss in Fe0.5Ti2(PO 4)3 due to the occurrence of insulating products as Li3PO4 and a solid electrolyte interface.

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