Structure, stoichiometry and transport properties of lithium copper nitride battery materials: Combined NMR and powder neutron diffraction studies

Andrew S. Powell, Zlatka Stoeva, Ronald I. Smith, Duncan H. Gregory, Jeremy J. Titman

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

A combined NMR and neutron diffraction study has been carried out on three Li3-x-yCuxN materials with x = 0.17, x = 0.29 and x = 0.36. Neutron diffraction indicates that the samples retain the P6/mmm space group of the parent Li3N with Cu located only on Li(1) sites. The lattice parameters vary smoothly with x in a similar fashion to Li 3-x-yNixN, but the Li(2) vacancy concentration for the Cu-substituted materials is negligible. This structural model is confirmed by wideline 7Li NMR spectra at 193 K which show three different local environments for the Li(1) site, resulting from the substitution of neighbouring Li atoms in the Li(1) layer by Cu. Since the Cu-substituted materials are only very weakly paramagnetic, variable temperature 7Li wideline NMR spectra can be used to measure diffusion coefficients and activation energies. These indicate anisotropic Li+ diffusion similar to the parent Li3N with transport confined to the [Li2N] plane at low temperature and exchange between Li(1) and Li(2) sites dominant at high temperature. For the intra-layer process the diffusion coefficients at room temperature are comparable to Li3N and Li3-x-y Ni xN, while Ea decreases as x increases in contrast to the opposite trend in Ni-substituted materials. For the inter-layer process E a decreases only slightly as x increases, but the diffusion coefficients at room temperature increase rapidly with x.

Original languageEnglish
Pages (from-to)10641-10647
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number22
DOIs
Publication statusPublished - Jun 14 2011

Fingerprint

Neutron powder diffraction
Lithium
Nitrides
Stoichiometry
Transport properties
nitrides
neutron diffraction
electric batteries
Copper
stoichiometry
diffusion coefficient
lithium
transport properties
Nuclear magnetic resonance
copper
nuclear magnetic resonance
Neutron diffraction
room temperature
Temperature
lattice parameters

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Structure, stoichiometry and transport properties of lithium copper nitride battery materials : Combined NMR and powder neutron diffraction studies. / Powell, Andrew S.; Stoeva, Zlatka; Smith, Ronald I.; Gregory, Duncan H.; Titman, Jeremy J.

In: Physical Chemistry Chemical Physics, Vol. 13, No. 22, 14.06.2011, p. 10641-10647.

Research output: Contribution to journalArticle

Powell, Andrew S. ; Stoeva, Zlatka ; Smith, Ronald I. ; Gregory, Duncan H. ; Titman, Jeremy J. / Structure, stoichiometry and transport properties of lithium copper nitride battery materials : Combined NMR and powder neutron diffraction studies. In: Physical Chemistry Chemical Physics. 2011 ; Vol. 13, No. 22. pp. 10641-10647.
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