Crystal structures of the new fluorophosphates Li9Mg 3[PO4]4F3 and Li 2Mg[PO4]F and ionic conductivities of selected compositions

Hamdi Yahia, Masahiro Shikano, Tomonari Takeuchi, Hironori Kobayashi, Mitsuru Itoh

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The new compounds Li2Mg[PO4]F and Li 9Mg3[PO4]4F3 have been synthesized by a solid state reaction route. The crystal structures were determined from single-crystal X-ray diffraction data. Li2Mg[PO 4]F crystallizes with the orthorhombic Li2Ni[PO 4]F structure, space group Pnma, a = 10.7874(3), b = 6.2196(5), c = 11.1780(4) Å, V = 721.13(10) Å3, and Z = 8, whereas Li9Mg3[PO4]4F3 crystallizes with hexagonal symmetry, space group P63, with a = 12.6159(6), c = 5.0082(4) Å, V = 690.32(7) Å3, and Z = 2. A merohedral twinning was taken into account for its structural refinement. The structure of Li2Mg[PO4]F contains MgO3F chains made up of edge-sharing MgO4F2 octahedra. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg[PO4]F framework. The lithium atoms occupy mainly three distinct crystallographic sites. The structure of Li9Mg3[PO4] 4F3 consists of corner-sharing MgO4F 2 octahedra forming MgO4F chains running along the c axis. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg 3[PO4]4F3 framework with hexagonal and pentagonal tunnels, in which are located the Li atoms. This study reveals also a strong relationship between Li2Mg[PO4]F-, Mg 1-xFexAl3[BO3][SiO 4]O2- and P21/c-Li5V[PO 4]2F2- structures; and between P6 3-Li9Mg3[PO4]4F 3 and P21/c-Na2Mn[PO4]F. The ionic conductivities σ of the composite material Li6Mg 4[PO4]3[SO4]F3 and Li9Mg3[PO4]4F3, estimated using electrochemical impedance spectroscopic analyses at 300 °C, are 3.9 × 10-5 and 10-4 S cm-1 with activation energies of 0.524 eV and 0.835 eV, respectively.

Original languageEnglish
Pages (from-to)5858-5869
Number of pages12
JournalJournal of Materials Chemistry A
Volume2
Issue number16
DOIs
Publication statusPublished - 28 Apr 2014
Externally publishedYes

Fingerprint

fluorophosphate
Ionic conductivity
Crystal structure
Atoms
Twinning
Chemical analysis
Solid state reactions
Lithium
Tunnels
Activation energy
Single crystals
X ray diffraction
Composite materials

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

Crystal structures of the new fluorophosphates Li9Mg 3[PO4]4F3 and Li 2Mg[PO4]F and ionic conductivities of selected compositions. / Yahia, Hamdi; Shikano, Masahiro; Takeuchi, Tomonari; Kobayashi, Hironori; Itoh, Mitsuru.

In: Journal of Materials Chemistry A, Vol. 2, No. 16, 28.04.2014, p. 5858-5869.

Research output: Contribution to journalArticle

Yahia, Hamdi ; Shikano, Masahiro ; Takeuchi, Tomonari ; Kobayashi, Hironori ; Itoh, Mitsuru. / Crystal structures of the new fluorophosphates Li9Mg 3[PO4]4F3 and Li 2Mg[PO4]F and ionic conductivities of selected compositions. In: Journal of Materials Chemistry A. 2014 ; Vol. 2, No. 16. pp. 5858-5869.
@article{a7cee9ea1e8440bfa38642f1a646f553,
title = "Crystal structures of the new fluorophosphates Li9Mg 3[PO4]4F3 and Li 2Mg[PO4]F and ionic conductivities of selected compositions",
abstract = "The new compounds Li2Mg[PO4]F and Li 9Mg3[PO4]4F3 have been synthesized by a solid state reaction route. The crystal structures were determined from single-crystal X-ray diffraction data. Li2Mg[PO 4]F crystallizes with the orthorhombic Li2Ni[PO 4]F structure, space group Pnma, a = 10.7874(3), b = 6.2196(5), c = 11.1780(4) {\AA}, V = 721.13(10) {\AA}3, and Z = 8, whereas Li9Mg3[PO4]4F3 crystallizes with hexagonal symmetry, space group P63, with a = 12.6159(6), c = 5.0082(4) {\AA}, V = 690.32(7) {\AA}3, and Z = 2. A merohedral twinning was taken into account for its structural refinement. The structure of Li2Mg[PO4]F contains MgO3F chains made up of edge-sharing MgO4F2 octahedra. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg[PO4]F framework. The lithium atoms occupy mainly three distinct crystallographic sites. The structure of Li9Mg3[PO4] 4F3 consists of corner-sharing MgO4F 2 octahedra forming MgO4F chains running along the c axis. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg 3[PO4]4F3 framework with hexagonal and pentagonal tunnels, in which are located the Li atoms. This study reveals also a strong relationship between Li2Mg[PO4]F-, Mg 1-xFexAl3[BO3][SiO 4]O2- and P21/c-Li5V[PO 4]2F2- structures; and between P6 3-Li9Mg3[PO4]4F 3 and P21/c-Na2Mn[PO4]F. The ionic conductivities σ of the composite material Li6Mg 4[PO4]3[SO4]F3 and Li9Mg3[PO4]4F3, estimated using electrochemical impedance spectroscopic analyses at 300 °C, are 3.9 × 10-5 and 10-4 S cm-1 with activation energies of 0.524 eV and 0.835 eV, respectively.",
author = "Hamdi Yahia and Masahiro Shikano and Tomonari Takeuchi and Hironori Kobayashi and Mitsuru Itoh",
year = "2014",
month = "4",
day = "28",
doi = "10.1039/c3ta15264b",
language = "English",
volume = "2",
pages = "5858--5869",
journal = "Journal of Materials Chemistry A",
issn = "2050-7488",
publisher = "Royal Society of Chemistry",
number = "16",

}

TY - JOUR

T1 - Crystal structures of the new fluorophosphates Li9Mg 3[PO4]4F3 and Li 2Mg[PO4]F and ionic conductivities of selected compositions

AU - Yahia, Hamdi

AU - Shikano, Masahiro

AU - Takeuchi, Tomonari

AU - Kobayashi, Hironori

AU - Itoh, Mitsuru

PY - 2014/4/28

Y1 - 2014/4/28

N2 - The new compounds Li2Mg[PO4]F and Li 9Mg3[PO4]4F3 have been synthesized by a solid state reaction route. The crystal structures were determined from single-crystal X-ray diffraction data. Li2Mg[PO 4]F crystallizes with the orthorhombic Li2Ni[PO 4]F structure, space group Pnma, a = 10.7874(3), b = 6.2196(5), c = 11.1780(4) Å, V = 721.13(10) Å3, and Z = 8, whereas Li9Mg3[PO4]4F3 crystallizes with hexagonal symmetry, space group P63, with a = 12.6159(6), c = 5.0082(4) Å, V = 690.32(7) Å3, and Z = 2. A merohedral twinning was taken into account for its structural refinement. The structure of Li2Mg[PO4]F contains MgO3F chains made up of edge-sharing MgO4F2 octahedra. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg[PO4]F framework. The lithium atoms occupy mainly three distinct crystallographic sites. The structure of Li9Mg3[PO4] 4F3 consists of corner-sharing MgO4F 2 octahedra forming MgO4F chains running along the c axis. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg 3[PO4]4F3 framework with hexagonal and pentagonal tunnels, in which are located the Li atoms. This study reveals also a strong relationship between Li2Mg[PO4]F-, Mg 1-xFexAl3[BO3][SiO 4]O2- and P21/c-Li5V[PO 4]2F2- structures; and between P6 3-Li9Mg3[PO4]4F 3 and P21/c-Na2Mn[PO4]F. The ionic conductivities σ of the composite material Li6Mg 4[PO4]3[SO4]F3 and Li9Mg3[PO4]4F3, estimated using electrochemical impedance spectroscopic analyses at 300 °C, are 3.9 × 10-5 and 10-4 S cm-1 with activation energies of 0.524 eV and 0.835 eV, respectively.

AB - The new compounds Li2Mg[PO4]F and Li 9Mg3[PO4]4F3 have been synthesized by a solid state reaction route. The crystal structures were determined from single-crystal X-ray diffraction data. Li2Mg[PO 4]F crystallizes with the orthorhombic Li2Ni[PO 4]F structure, space group Pnma, a = 10.7874(3), b = 6.2196(5), c = 11.1780(4) Å, V = 721.13(10) Å3, and Z = 8, whereas Li9Mg3[PO4]4F3 crystallizes with hexagonal symmetry, space group P63, with a = 12.6159(6), c = 5.0082(4) Å, V = 690.32(7) Å3, and Z = 2. A merohedral twinning was taken into account for its structural refinement. The structure of Li2Mg[PO4]F contains MgO3F chains made up of edge-sharing MgO4F2 octahedra. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg[PO4]F framework. The lithium atoms occupy mainly three distinct crystallographic sites. The structure of Li9Mg3[PO4] 4F3 consists of corner-sharing MgO4F 2 octahedra forming MgO4F chains running along the c axis. These chains are interlinked by PO4 tetrahedra forming a 3D-Mg 3[PO4]4F3 framework with hexagonal and pentagonal tunnels, in which are located the Li atoms. This study reveals also a strong relationship between Li2Mg[PO4]F-, Mg 1-xFexAl3[BO3][SiO 4]O2- and P21/c-Li5V[PO 4]2F2- structures; and between P6 3-Li9Mg3[PO4]4F 3 and P21/c-Na2Mn[PO4]F. The ionic conductivities σ of the composite material Li6Mg 4[PO4]3[SO4]F3 and Li9Mg3[PO4]4F3, estimated using electrochemical impedance spectroscopic analyses at 300 °C, are 3.9 × 10-5 and 10-4 S cm-1 with activation energies of 0.524 eV and 0.835 eV, respectively.

UR - http://www.scopus.com/inward/record.url?scp=84896920185&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84896920185&partnerID=8YFLogxK

U2 - 10.1039/c3ta15264b

DO - 10.1039/c3ta15264b

M3 - Article

AN - SCOPUS:84896920185

VL - 2

SP - 5858

EP - 5869

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

SN - 2050-7488

IS - 16

ER -