No Arabic abstract
We present a structural and magnetic study on two batches of polycrystalline LiNi$_{0.8}$Mn$_{0.1}$Co$_{0.1}$O$_2$ (commonly known as Li NMC 811), a Ni-rich Li ion battery cathode material, using elemental analysis, X-ray and neutron diffraction, magnetometry, and polarised neutron scattering measurements. We find that the samples, labelled S1 and S2, have the composition Li$_{1-x}$Ni$_{0.9+x-y}$Mn$_y$Co$_{0.1}$O$_2$, with $x = 0.025(2)$, $y = 0.120(2)$ for S1 and $x = 0.002(2)$, $y = 0.094(2)$ for S2, corresponding to different concentrations of magnetic ions and excess Ni$^{2+}$ in the Li$^+$layers. Both samples show a peak in the zero-field cooled (ZFC) dc susceptibility at 8.0(2) K but the temperature at which the ZFC and FC (field-cooled) curves deviate is substantially different: 64(2) K for S1 and 122(2) K for S2. Ac susceptibility measurements show that the transition for S1 shifts with frequency whereas no such shift is observed for S2 within the resolution of our measurements. Our results demonstrate the sample dependence of magnetic properties in Li NMC 811, consistent with previous reports on the parent material LiNiO$_2$. We further establish that a combination of experimental techniques are necessary to accurately determine the chemical composition of next generation battery materials with multiple cations.
We present a study of the electronic structure and magnetism of Co$_2$MnAl, CoMnVAl and their heterostructure. We employ a combination of density-functional theory and dynamical mean-field theory (DFT+DMFT). We find that Co$_2$MnAl is a half-metallic ferromagnet, whose electronic and magnetic properties are not drastically changed by strong electronic correlations, static or dynamic. Non-quasiparticle states are shown to appear in the minority spin gap without affecting the spin-polarization at the Fermi level predicted by standard DFT. We find that CoMnVAl is a semiconductor or a semi-metal, depending on the employed computational approach. We then focus on the electronic and magnetic properties of the Co$_2$MnAl/CoMnVAl heterostructure, predicted by previous first principle calculations as a possible candidate for spin-injecting devices. We find that two interfaces, Co-Co/V-Al and Co-Mn/Mn-Al, preserve the half-metallic character, with and without including electronic correlations. We also analyse the magnetic exchange interactions in the bulk and at the interfaces. At the Co-Mn/Mn-Al interface, competing magnetic interactions are likely to favor the formation of a non-collinear magnetic order, which is detrimental for the spin-polarization.
The electronic and magnetic properties of clinopyroxene CaMnGe$_2$O$_6$ were studied using density function calculations within the GGA+U approximation. It is shown that anomalous ferromagnetic ordering of neighboring chains is due to a common-enemy mechanism. Two antiferromagnetic exchange couplings between nearest neighbours within the Mn-Mn chain and interchain coupling via two GeO$_4$ tetrahedra suppress antiferromagnetic exchange via single GeO$_4$ tetrahedron and stabilize ferromagnetic ordering of Mn chains.
We present a novel hydrated layered manganate MgMn$_3$O$_7$$cdot$3H$_2$O as a maple-leaf-lattice (MLL) antiferromagnet candidate. The MLL is obtained by regularly depleting 1/7 of the lattice points from a triangular lattice so that the magnetic connectivity $z = 5$ and is thus intermediately frustrated between the triangular ($z = 6$) and kagome ($z = 4$) lattices. In MgMn$_3$O$_7$$cdot$3H$_2$O, the Mn$^{4+}$ ions, carrying Heisenberg spin 3/2, form a regular MLL lattice in the quasi-two-dimensional structure. Magnetization and heat capacity measurements using a hydrothermally-prepared powder sample reveal successive antiferromagnetic transitions at 5 and 15 K. A high-field magnetization curve up to 60 T at 1.3 K exhibits a multi-step plateau-like anomaly. We discuss the unique frustration of the MLL antiferromagnet in which the chiraldegree of freedom may play an important role.
Neutron diffraction and magnetic susceptibility studies show that orthorhombic single-crystals of topological semimetals ${rm Sr(Mn_{0.9}Cu_{0.1})Sb_2}$ and ${rm Sr(Mn_{0.9}Zn_{0.1})Sb_2}$ undergo three dimensional C-type antiferromagnetic (AFM) ordering of the Mn$^{2+}$ moments at $T_N = 200pm10$ and $210pm12$ K, respectively, significantly lower than that of the parent SrMnSb$_2$ with $T_N=297 pm 3$ K. Magnetization versus applied magnetic field (perpendicular to MnSb planes) below $T_N$ exhibits slightly modified de Haas van Alphen oscillations for the Zn-doped crystal as compared to that of the parent compound. By contrast, the Cu-doped system does not show de Haas van Alphen magnetic oscillations, suggesting that either Cu substitution for Mn changes the electronic structure of the parent compound substantially, or that the Cu sites are strong scatterers of carriers that significantly shorten their mean free path thus diminishing the oscillations. Density functional theory (DFT) calculations including spin-orbit coupling predict the C-type AFM state for the parent, Cu-, and Zn-doped systems and identify the $a$-axis (i.e., perpendicular to the Mn layer) as the easy magnetization direction in the parent and 12.5% of Cu or Zn substitutions. In contrast, 25% of Cu content changes the easy magnetization to the $b$-axis (i.e., within the Mn layer). We find that the incorporation of Cu and Zn in SrMnSb$_2$ tunes electronic bands near the Fermi level resulting in different band topology and semi-metallicity. The parent and Zn-doped systems have coexistence of electron and hole pockets with opened Dirac cone around the Y-point whereas the Cu-doped system has dominant hole pockets around the Fermi level with a distorted Dirac cone. The tunable electronic structure may point out possibilities of rationalizing the experimentally observed de Haas van Alphen magnetic oscillations.
We have studied low-temperature magnetic properties as well as high-temperature lithium ion diffusion in the battery cathode materials LixNi1/3Co1/3Mn1/3O2 by the use of muon spin rotation/relaxation. Our data reveal that the samples enter into a 2D spin-glass state below TSG=12 K. We further show that lithium diffusion channels become active for T>Tdiff=125 K where the Li-ion hopping-rate [nu(T)] starts to increase exponentially. Further, nu(T) is found to fit very well to an Arrhenius type equation and the activation energy for the diffusion process is extracted as Ea=100 meV.