RESUMO
Transition-metal thiophosphates and selenophosphates are layered systems with the potential for displaying two-dimensional (2D) magnetic phenomena. We present the crystal structures and magnetic properties of two lithium transition-metal thiophosphates, Li1.56Co0.71P2S6 and Li2.26Fe0.94P2S6. The previously unreported Li1.56Co0.71P2S6 crystallizes in the trigonal space group P31m with lattice parameters a = 6.0193(6) Å and c = 6.5675(9) Å. The CoS6 octahedra are arranged in a honeycomb lattice and form 2D layers separated by lithium cations. The previously solved Li2.26Fe0.94P2S6 is isostructural to Li1.56Co0.71P2S6 but displays site mixing between the Li+ and Fe2+ cations within the thiophosphate layer. Unusually, Li1.56Co0.71P2S6 appears to have P2S63- and not P2S64- anions. We therefore term it a "noninnocent" anion because of the ambiguous nature of its oxidation state. Combined neutron diffraction and magnetization measurements reveal that both Li1.56Co0.71P2S6 and Li2.26Fe0.94P2S6 display magnetic anisotropy as well as no long-range magnetic order down to 5 K. In the iron thiophosphate, susceptibility indicates an effective moment of 5.44(3) µB, which may be best described by an S + L model, where S = 2 and L = 2, or close to the free ion limit. In the cobalt thiophosphate, we found the effective moment to be 4.35(2) µB, which would point to an S = 3/2 and L = 1 model due to octahedral crystal-field splitting.
RESUMO
We report a detailed investigation of the long-range magnetic ordering in polycrystalline samples of LiCoPO4 and LiMnPO4, which belong to a series of well-known olivine cathode materials LiMPO4 (M = Mn, Fe, Co, Ni). Samples were prepared by hydrothermal and solid state methods. The magnetic susceptibility is found to be strongly field-dependent, impacting the antiferromagnetic transition temperature and the bifurcation of the FC and ZFC curves. We discuss the role synthesis conditions have on impurity formation and particle size. We report neutron powder diffraction data for the samples prepared by solid state methods. Based upon representational analysis of the observed reflections, we affirm the magnetic structure Pnma' for LiCoPO4 and Pn'm'a' for LiMnPO4. The refined magnetic moments from these models are 3.28(4) µB for LiCoPO4 and 4.28(3) µB for LiMnPO4. We also study the onset of magnetic ordering in each sample and affirm that the ordering temperature is 22 K for LiCoPO4 and 34 K for LiMnPO4. The critical parameters describing those transitions are ßc = 0.21(4) (LiCoPO4) and ßc = 0.31(3) (LiMnPO4). These values are characteristic of a 3D Ising system for LiMnPO4 and intermediate behavior between a 2D and 3D Ising system for LiCoPO4. We compare these observations with other reports proposing lower magnetic symmetry.
