title: Correlations between lithium local structure and electrochemistry of layered LiCo(1-2x)Ni(x)Mn(x)O2 oxides: 7Li MAS NMR and EPR studies.
abstract: Advanced (7)Li MAS NMR technologies and high frequency EPR are combined to identify structural motifs and their relation to electrochemical properties of layered lithium-cobalt-nickel-manganese oxides LiCo1-2xNixMnxO2 (0 < x ≤ 0.5) used as cathode materials in lithium ion batteries. Structural-chemical shift regularities were established by systematic variation of the ratio of diamagnetic Co(3+) to paramagnetic Ni/Mn ions with variable valences. While EPR allows identifying the oxidation state of transition metal ions inside the layers, (7)Li NMR probes the local structure of Li with respect to transition metal ions located in two adjacent layers. For assignment of the lithium chemical shifts, we examine first magnetically diluted LiCo1-2xNixMnxO2 with x = 0.02, where paramagnetic ions are stabilized only in Mn(4+) and Ni(3+) form. Then the studies are extended towards the intermediate compositions with x = 0.10 and 0.33, containing simultaneously paramagnetic Mn(4+), Ni(3+) and Ni(2+) ions and diamagnetic Co(3+) ions. The benefit of using NMR with ultrafast spinning rates is demonstrated for the end composition LiNi0.5Mn0.5O2 having only paramagnetic Ni(2+) and Mn(2+) ions. The local structure of Li is quantified in respect of the number of Ni(2+) and Mn(4+) neighbors. It has been demonstrated that Ni(2+) and Mn(4+) are non-randomly distributed around Li and their distribution depends on the method of synthesis. The extent of local cationic order and its effect on the electrochemical properties of LiNi0.5Mn0.5O2 are discussed.
authors.affiliation: Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria. radstoy@svt.igic.bas.bg.
authors.forename: Radostina
authors.initials: R
authors.lastname: Stoyanova
authors.forename: Svetlana
authors.initials: S
authors.lastname: Ivanova
authors.forename: Ekaterina
authors.initials: E
authors.lastname: Zhecheva
authors.forename: Ago
authors.initials: A
authors.lastname: Samoson
authors.forename: Svetlana
authors.initials: S
authors.lastname: Simova
authors.forename: Pavleta
authors.initials: P
authors.lastname: Tzvetkova
authors.forename: Anne-Laure
authors.initials: AL
authors.lastname: Barra