Structure of lithium nitride and transition-metal-doped derivatives, Li{sub 3-x-y}Mn{sub x}N (M = Ni, Cu) : a powder neutron diffraction study.

Journal Article · Tue Jan 01 04:00:00 EST 2002 · Chem. Mater.

DOI:https://doi.org/10.1021/cm010718t· OSTI ID:961118

Gregory, D H; O'Meara, P M; Gordon, A G; Hodges, J P; Short, S; Jorgensen, J D; ORNL,

Structures of lithium nitride ({alpha}-Li{sub 3}N) and ternary nitridometalates Li{sub 3-x-y}M{sub x}N (M = Ni, Cu) have been refined from time-of-flight powder neutron diffraction data using the Rietveld method. The parent binary nitride was synthesized by reaction of lithium metal with nitrogen using liquid sodium as a solvent. The ternary nitrides were prepared by reaction of Li{sub 3}N with the respective transition metals under nitrogen. Refined data confirm the hexagonal structure previously reported by single-crystal X-ray diffraction for lithium nitride (P6/mmm, a = 3.6576(1) {angstrom}, c = 3.8735(1) {angstrom}, Z = 1) and show that the {alpha}-Li{sub 3}N phase contains close to 3% Li vacancies at room temperature. The substituted nitridometalates, Li{sub 1.36}Ni{sub 0.79}N and Li{sub 2.21}Cu{sub 0.40}N, both form structures analogous to {alpha}-Li{sub 3}N (P6/mmm, a = 3.7697(1) {angstrom}, c = 3.5270(1) {angstrom} and a = 3.6791(1) {angstrom}, c = 3.7725(1) {angstrom}, respectively) in which the transition metal is disordered with Li between [Li{sub 2-y}N] planes and Li vacancies are disordered within these planes. The nickel and copper nitrides contain 43% (y = 0.85) and 16% (y = 0.32) Li vacancies, respectively, within the [Li{sub 2}N] planes and consequently contain transition metals predominantly in the +2 oxidation state.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: SC
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 961118
• Report Number(s): ANL/MSD/JA-44764
• Journal Information: Chem. Mater., Journal Name: Chem. Mater. Journal Issue: 2002 Vol. 14; ISSN CMATEX; ISSN 0897-4756
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

36 MATERIALS SCIENCE
COPPER NITRIDES
DOPED MATERIALS
LIQUIDS
LITHIUM
LITHIUM NITRIDES
METALS
NEUTRON DIFFRACTION
NICKEL
NITRIDES
NITROGEN
POWDERS
SODIUM
TRANSITION ELEMENT COMPOUNDS
VACANCIES
VALENCE
X-RAY DIFFRACTION