ABSTRACT
Li2MnO3 with a S = 3/2 two-dimensional Mn honeycomb lattice has a Neel-type antiferromagnetic transition at TN = 36 K with a broad maximum in magnetic susceptibility at TM = 48 K. We have investigated site percolation effects by replacing Mn with nonmagnetic Ti, and completed a full phase diagram of Li2Mn1-xTixO3 solid solution systems to find that antiferromagnetic transition is continuously suppressed without a clear sign of changes in the Neel-type antiferromagnetic structure. The magnetic ordering eventually disappears at a critical concentration of xc = 0.7. This experimental observation is consistent with percolation theories for a honeycomb lattice when one considers up to 3rd nearest-neighbor interactions. This study highlights the importance of interaction beyond nearest neighbors even for the Mn element with relative localized 3d electrons in the honeycomb lattice.
ABSTRACT
Lithium-ion batteries, which have been widely used to power portable electronic devices, are on the verge of being applied to new automobile applications. To expand this emerging market, however, an electrode that combines fast charging capability, long-term cycle stability, and high energy density is needed. Herein, we report a novel layered lithium vanadium fluorophosphate, Li(1.1)Na(0.4)VPO(4.8)F(0.7), as a promising positive electrode contender. This new material has two-dimensional lithium pathways and is capable of reversibly releasing and reinserting ~1.1 Li(+) ions at an ideal 4 V (versus Li(+)/Li) to give a capacity of ~156 mAh g(-1) (energy density of 624 Wh kg(-1)). Moreover, outstanding capacity retentions of 98% and 96% after 100 cycles were achieved at 60°C and room temperature, respectively. Unexpectedly high rate capability was delivered for both charge and discharge despite the large particle size (a few microns), which promises further enhancement of power density with proper nano-engineering.
ABSTRACT
The crystal structure of the layered cobalt oxyfluoride Sr(2)CoO(3)F synthesized under high-pressure and high-temperature conditions has been determined from neutron powder diffraction and synchrotron powder diffraction data collected at temperatures ranging from 320 to 3 K. This material adopts the tetragonal space group I4/mmm over the measured temperature range and the crystal structure is analogous to n = 1 Ruddlesden-Popper type layered perovskite. In contrast to related oxyhalide compounds, the present material exhibits the unique coordination environment around the Co metal center: coexistence of square pyramidal coordination around Co and anion disorder between O and F at the apical sites. Magnetic susceptibility and electrical resistivity measurements reveal that Sr(2)CoO(3)F is an antiferromagnetic insulator with the Néel temperature T(N) = 323(2) K. The magnetic structure that has been determined by neutron diffraction adopts a G-type antiferromagnetic order with the propagation vector k = (1/2 1/2 0) with an ordered cobalt moment µ = 3.18(5) µ(B) at 3 K, consistent with the high spin electron configuration for the Co(3+) ions. The antiferromagnetic and electrically insulating states remain robust even against 15%-O substation for F at the apical sites. However, applying pressure exhibits the onset of the metallic state, probably coming from change in the electronic state of square-pyramidal coordinated cobalt.
ABSTRACT
The structure of a new layered oxyfluoride, viz. potassium strontium diniobium hexaoxide fluoride, KSrNb(2)O(6)F, was refined from powder neutron diffraction data in the orthorhombic space group Immm. The oxyfluoride compound is an n = 2 member of the Dion-Jacobson-type family of general formula A[A'(n-1)B(n)X(3n+1)], which consists of double layered perovskite slabs, [SrNb(2)O(6)F](-), between which K(+) ions are located. Within the perovskite slabs, the NbO(5)F octahedra are significantly distorted and tilted about the a axis. A bond-valence-sum calculation gives evidence for O/F ordering in KSrNb(2)O(6)F, with the F(-) ions located in the central sites of the corner-sharing NbO(5)F octahedra along the b axis. All atoms lie on special positions, namely Nb on m, Sr on mmm, K on m2m, F on mm2, and O on sites of symmetry m and m2m.
