LiMoN[sub 2]: The first metallic layered nitride

Journal Article · · Chemistry of Materials; (United States)

OSTI ID:7019682

Elder, S H; Doerrer, L H; DiSalvo, F J ^[1]; Parise, J B ^[2]; Guyomard, D; Tarascon, J M ^[3]

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1. Cornell Univ., Ithaca, NY (United States)
2. State Univ. of New York, Stony Brook, NY (United States)
3. Bell Communications Research, Redbank, NJ (United States)

The authors report the first example of a layered ternary lithium nitride in which the lithium can be deintercalated and reintercalated. The synthesis of LiMoN[sub 2] is also the first example of a ternary nitride formed from either the ammonolysis of a molecular organometallic molecule, Li[sub 2]Mo(N[sup t]Bu)[sub 4] or the ammonolysis of a ternary oxide, Li[sub 2]MoO[sub 4]. Elucidation of the unique structure, in a classic illustration, required both synchrotron X-ray and neutron diffraction data. The space group is R3 with lattice parameters ([angstrom]; from the neutron data) of a = 2.8674 (2) and c = 15.801 (2). The ideal structure consists of MoN[sub 2] layers with Mo in trigonal prismatic holes and Li in octahedral holes between the MoN[sub 2] layers. The presence of cation anti-site defects was clearly indicated by the joint X-ray/neutron data refinement; the structure is best described as (Li[sub 0.85]Mo[sub 0.15])[sub oct](Mo[sub 0.85]Li[sub 0.15])[sub tp]N[sub 2]. LiMoN[sub 2] is Pauli paramagnetic with [chi][sub 0] = 0.59 [times] 10[sup [minus]6] emu g[sup [minus]1]. The authors have employed a variety of different oxidizing agents for the deintercalation of the lithium from LiNoN[sub 2] and have been able to deintercalate up to 64% of the lithium. This disintercalated species can be reintercalated with n-butyllithium at room temperature. In contrast, electrochemical studies show a large hysteresis in the charge/discharge cycles with no reversibility. 44 refs., 10 figs., 5 tabs.

• OSTI ID: 7019682
• Journal Information: Chemistry of Materials; (United States), Journal Name: Chemistry of Materials; (United States) Vol. 4:4; ISSN CMATEX; ISSN 0897-4756
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360602 -- Other Materials-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
ALKALI METALS
BREMSSTRAHLUNG
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CLATHRATES
COHERENT SCATTERING
CRYSTAL STRUCTURE
DIFFRACTION
ELECTROMAGNETIC RADIATION
ELEMENTS
LITHIUM
LITHIUM COMPOUNDS
LITHIUM NITRIDES
METALS
MOLYBDENUM COMPOUNDS
MOLYBDENUM NITRIDES
NITRIDES
NITROGEN COMPOUNDS
PNICTIDES
RADIATIONS
REFRACTORY METAL COMPOUNDS
SCATTERING
SYNCHROTRON RADIATION
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION