title: Antifluorite-type lithium chromium oxide nitrides: synthesis, structure, order, and electrochemical properties.
abstract: Antifluorite-type lithium chromium oxide nitrides were prepared by solid-state reaction of Li(3)N, Li(2)O, and Cr(2)N. Depending on the reaction time and starting Li/Cr and O/Cr ratios, either an ordered or a disordered phase (or mixtures of both) is obtained. The formation of the former is favored by short reaction times and low Cr/O ratios whereas the formation of the latter is favored by higher Cr/O ratios and longer reaction times. The two phases were characterized, and the first one was confirmed to be the already reported Li(14)Cr(2)N(8)O phase, whereas the stoichiometry of the second is Li(10)CrN(4)O(2). Interestingly, even if both contain cationic vacancies in the structure, electrochemical lithium intercalation could only be achieved for Li(10)CrN(4)O(2). This phase exhibits a reversible capacity of 160 mAh/g very stable upon cycling. Bond valence and first-principles DFT calculations were carried out to understand the absence of lithium insertion in Li(14)Cr(2)N(8)O. Li-Li repulsion and destabilization of the tetrahedral CrN(4) units induced by occupation of the potential sites, as well as the absence of energetically favorable pathways for transport of the ions to these sites, are suggested to be the reasons.
authors.affiliation: Institut de Ciència de Materials de Barcelona, Campus UAB, 08193 Bellaterra, Catalonia, Spain, Institut Laue Langevin, 6 rue Jules Horowitz, 38042 Grenoble Cedex 9, France.
authors.forename: Jordi
authors.initials: J
authors.lastname: Cabana
authors.forename: Christopher D
authors.initials: CD
authors.lastname: Ling
authors.forename: Judith
authors.initials: J
authors.lastname: Oró-Solé
authors.forename: Damien
authors.initials: D
authors.lastname: Gautier
authors.forename: Gerard
authors.initials: G
authors.lastname: Tobías
authors.forename: Stefan
authors.initials: S
authors.lastname: Adams
authors.forename: Enric
authors.initials: E
authors.lastname: Canadell
authors.forename: M Rosa
authors.initials: MR
authors.lastname: Palacín