Crystal structure and cation transport properties of the layered monodiphosphates: Li{sub 9}M{sub 3}(P{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2} (M = Al, Ga, Cr, Fe)
Journal Article
·
· Journal of Solid State Chemistry
- Univ. Paris-Sud, Orsay (France). Lab. de Chimie des Solides
- Faculte des Sciences Pharmaceutiques et Biologiques, Chatenay-Malabry (France). Lab. de Cristallographic Bioinorganique
A new series of isotypic monodiphosphates of general formula Li{sub 9}M{sub 3}(P{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2} with M = Al, Ga, Cr, Fe was synthesized by flux methods. The crystal structure of the aluminum and iron members is described here. They crystallize in the trigonal space group P{bar 3}c1 with a = 9.553(1), C = 13.492(2) {angstrom} (M = Al), a = 9.726(1), c = 13.615(2) {angstrom} (M = Fe) and z = 2. The structure consists of {infinity}{sup 2}[(MP{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2}]{sup 9{minus}} corrugated layers, parallel to (001), separated by lithium ions. The layers are built up of MO{sub 6} octahedra sharing corners with PO{sub 4} tetrahedra and P{sub 2}O{sub 7} groups. Three nonequivalent lithium ions are present according to the structural formula Li(1){sub 1}Li(2){sub 2}Li(3){sub 6}[MP(2){sub 2}O{sub 7}]{sub 3}[P(1)O{sub 4}]{sub 2}. The crystal exhibit a lithium ion conduction mainly parallel to (001) but with rather low conductivity values: {sigma}{sub {parallel}(0001)} = 1.3 {times} 10{sup {minus}4} and 3.0 {times} 10{sup {minus}6} {Omega}{sup {minus}1} cm{sup {minus}1} at 300 C for M = Fe and M = Al, respectively. In the presence of acidic aqueous solutions, Li{sub 9}Fe{sub 3}(P{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2} undergoes an ion-exchange reaction between Li{sup +} and H{sup +} with the introduction of water molecules, which causes a one-dimensional expansion of the crystals perpendicular to the layers.
- OSTI ID:
- 642220
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 138; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis and characterization of phosphates in molten systems Cs{sub 2}O-P{sub 2}O{sub 5}-CaO-M{sup III}{sub 2}O{sub 3} (M{sup III}-Al, Fe, Cr)
Crystal structures and electronic properties for the over-lithiated and Li–Ag substituted phases of Li{sub 9}V{sub 3}(P{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2} insertion electrode system
A Mixed {alpha}/{beta} Superstructure in NASICON Ionic Conductors: Neutron Diffraction Study of Li
Journal Article
·
Tue Mar 15 00:00:00 EDT 2011
· Journal of Solid State Chemistry
·
OSTI ID:21494220
Crystal structures and electronic properties for the over-lithiated and Li–Ag substituted phases of Li{sub 9}V{sub 3}(P{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2} insertion electrode system
Journal Article
·
Fri Nov 14 23:00:00 EST 2014
· Journal of Solid State Chemistry
·
OSTI ID:22443462
A Mixed {alpha}/{beta} Superstructure in NASICON Ionic Conductors: Neutron Diffraction Study of Li
Journal Article
·
Wed Jan 31 23:00:00 EST 2001
· Journal of Solid State Chemistry
·
OSTI ID:784083