Transmission Electron Microscope Studies of LiNi1/3Mn1/3Co1/3O2 before and after Long-Term Aging at 70°C

LiNi1/3Mn1/3Co1/3O2 is a potential cathode material for high-power applications in lithium-ion batteries. While cation ordering on a sqrt(3)×sqrt(3) R30° in-plane superlattice was proposed for the layered structure, the experimental data do not fully support this model. Here, we present a systematic electron diffraction study of LiNi1/3Mn1/3Co1/3O2 in the pristine state and after aging. Our results show that a mixture of different phases in the starting material transforms to the O3-type phase and the cubic spinel phase after aging, accompanied by an increase in the percentage of polycrystals

Microstructural Investigations of the Layered Cathode Materials LiCoO2 and LiNi1/3Mn1/3Co1/3O2

Both LiCoO2 and LiNi1/3Mn1/3Co1/3O2 layered cathode materials are investigated in our studies. P3 phase of CoO2, the end member of the LixCoO2, is found in both chemically and electrochemically delithiated materials. Delithiated LixCoO2 specimens decompose into fine Co3O4 and LiCoO2 particles starting at around 200 °C. This decomposing reaction is proved by in-situ X-ray diffraction and in-situ transmission electron microscopy investigations. The structures of pristine and cycled LiNi1/3Mn1/3Co1/3O2 are investigated by electron diffraction. Single and polycrystalline crystals are found in this material. The partial substitution of Co by Ni and Mn in LiNi1/3Mn1/3Co1/3O2 opens up the possibility of different cation configurations in the crystal lattice. Both 3Rm symmetry and superlattices are identified in this material. The number of particles with superlattices in pristine material (40%) is much bigger than cycled material at discharge state (10%)

High-Temperature Transport Properties of the Zintl Phases Yb_(11)GaSb_9 and Yb_(11)InSb_9

Two rare-earth Zintl phases, Yb_(11)GaSb_9 and Yb_(11)InSb_9, were synthesized in high-temperature self-fluxes of molten Ga and In, respectively. Structures were characterized by both single-crystal X-ray diffraction and powder X-ray diffraction and are consistent with the published orthorhombic structure, with the space group Iba2. High-temperature differential scanning calorimetry (DSC) and thermal gravimetry (TG) measurements reveal thermal stability to 1300 K. Seebeck coefficient and resistivity measurements to 1000 K are consistent with the hypothesis that Yb_(11)GaSb_9 and Yb_(11)InSb_9 are small band gap semiconductors or semimetals. Low doping levels lead to bipolar conduction at high temperature, preventing a detailed analysis of the transport properties. Thermal diffusivity measurements yield particularly low lattice thermal conductivity values, less than 0.6 W/m K for both compounds. The low lattice thermal conductivity suggests that Yb_(11)MSb_9 (M = Ga, In) has the potential for high thermoelectric efficiency at high temperature if charge-carrier doping can be controlled

Joint spectrum shrinking maps on projections

Let $\mathcal H$ be a finite dimensional complex Hilbert space with dimension $n \ge 3$ and $\mathcal P(\mathcal H)$ the set of projections on $\mathcal H$. Let $\varphi: \mathcal P(\mathcal H) \to \mathcal P(\mathcal H)$ be a surjective map. We show that $\varphi$ shrinks the joint spectrum of any two projections if and only if it is joint spectrum preserving for any two projections and thus is induced by a ring automorphism on $\mathbb C$ in a particular way. In addition, for an arbitrary $k \ge 3$, $\varphi$ shrinks the joint spectrum of any $k$ projections if and only if it is induced by a unitary or an anti-unitary. Assume that $\phi$ is a surjective map on the Grassmann space of rank one projections. We show that $\phi$ is joint spectrum preserving for any $n$ rank one projections if and only if it can be extended to a surjective map on $\mathcal P(\mathcal{H})$ which is spectrum preserving for any two projections. Moreover, for any $k >n$, $\phi$ is joint spectrum shrinking for any $k$ rank one projections if and only if it is induced by a unitary or an anti-unitary.Comment: 14 page

Synthesis, structure, magnetism, and high temperature thermoelectric properties of Ge doped Yb_(14)MnSb_(11)

The Zintl phase Yb_(14)MnSb_(11) was successfully doped with Ge utilizing a tin flux technique. The stoichiometry was determined by microprobe analysis to be Yb_(13.99(14))Mn_(1.05(5))Sb_(10.89(16))Ge_(0.06(3)). This was the maximum amount of Ge that could be incorporated into the structure via flux synthesis regardless of the amount included in the reaction. Single crystal X-ray diffraction could not unambiguously determine the site occupancy for Ge. Bond lengths varied by about 1% or less, compared with the undoped structure, suggesting that the small amount of Ge dopant does not significantly perturb the structure. Differential scanning calorimetry/thermogravimetry (DSC/TG) show that the doped compound's melting point is greater than 1200 K. The electrical resistivity and magnetism are virtually unchanged from the parent material, suggesting that Yb is present as Yb^(2+) and that the Ge dopant has little effect on the magnetic structure. At 900 K the resistivity and Seebeck coefficient decrease resulting in a zT of 0.45 at 1100 K, significantly lower than the undoped compound

Microstructural Investigations of the Layered Cathode Materials LiCoO2 and LiNi1/3Mn1/3Co1/3O2

Both LiCoO2 and LiNi1/3Mn1/3Co1/3O2 layered cathode materials are investigated in our studies. P3 phase of CoO2, the end member of the LixCoO2, is found in both chemically and electrochemically delithiated materials. Delithiated LixCoO2 specimens decompose into fine Co3O4 and LiCoO2 particles starting at around 200 °C. This decomposing reaction is proved by in-situ X-ray diffraction and in-situ transmission electron microscopy investigations. The structures of pristine and cycled LiNi1/3Mn1/3Co1/3O2 are investigated by electron diffraction. Single and polycrystalline crystals are found in this material. The partial substitution of Co by Ni and Mn in LiNi1/3Mn1/3Co1/3O2 opens up the possibility of different cation configurations in the crystal lattice. Both 3Rm symmetry and superlattices are identified in this material. The number of particles with superlattices in pristine material (40%) is much bigger than cycled material at discharge state (10%)

Direct characterization of the Li intercalation mechanism into α-V \u3c inf\u3e 2 O \u3c inf\u3e 5 nanowires using in-situ transmission electron microscopy

© 2017 Author(s). The Li-V2O5 system has been well studied electrochemically, but there is a lack of systematic in-situ studies involving direct investigations of the structural changes that accompany the lithiation process. The open-cell battery setup inside a transmission electron microscope is ideal for studying the reaction pathway of intercalation of Li+ into nanowire cathodes. In this work, we utilize in-situ transmission electron microscopy to study the Li-V2O5 system. More specifically, we employ electron beam diffraction and electron energy-loss spectroscopy (EELS) in an open-cell battery setup to examine the phase changes within α-V2O5 nanowire cathodes upon in-situ lithiation. Our results suggest that the pristine α-V2O5 nanowire forms a Li oxide shell which then acts as a solid state electrolyte to conduct Li+ ions, and the bulk of the V2O5 nanowire undergoes transformation to the γ-Li2V2O5 phase

Crystal Structure and a Giant Magnetoresistance Effect in the New Zintl Compound Eu₃Ga₂P₄

Single-crystalline samples of a new Zintl compound, Eu₃Ga₂P₄, have been synthesized by a Ga-flux method. Eu₃Ga₂P₄ is found to crystallize in a monoclinic unit cell, space group <i>C</i>2/<i>c</i>, isostructural to Ca₃Al₂As₄. The structure is composed of a pair of edge-shared GaP₄ tetrahedra, which link by corner-sharing to form Ga₂P₄ two-dimensional layers, separated by Eu²⁺ ions. Magnetic susceptibility showed a Curie–Weiss behavior with an effective magnetic moment consistent with the value for Eu²⁺ magnetic ions. Below 15 K, ferromagnetic ordering was observed and the saturation magnetic moment was 6.6 μ_B. Electrical resistivity measurements on a single crystal showed semiconducting behavior. Resistivity in the temperature range between 280 and 300 K was fit by an activation model with an energy gap of 0.552(2) eV. The temperature dependence of the resistivity is better described by the variable-range-hopping model for a three-dimensional conductivity, suggesting that Eu–P bonds are involved in the conductivity. A large magnetoresistance, up to −30%, is observed with a magnetic field <i>H</i> = 2 T at <i>T</i> = 100 K, suggesting strong coupling of carriers with the Eu²⁺ magnetic moment