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.
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 Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- DE-AC02-06CH11357
- OSTI ID:
- 961118
- Report Number(s):
- ANL/MSD/JA-44764; CMATEX; TRN: US201010%%944
- Journal Information:
- Chem. Mater., Vol. 14, Issue 2002; ISSN 0897-4756
- Country of Publication:
- United States
- Language:
- ENGLISH
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