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 journalArticlepeer-review

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

All Science Journal Classification (ASJC) codes

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

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