Phase-Controlled Electrochemical Activity of Epitaxial Mg-Spinel Thin Films.

We report an approach to control the reversible electrochemical activity (i.e., extraction/insertion) of Mg(2+) in a cathode host through the use of phase-pure epitaxially stabilized thin film structures. The epitaxially stabilized MgMn2O4 (MMO) thin films in the distinct tetragonal and cubic phases are shown to exhibit dramatically different properties (in a nonaqueous electrolyte, Mg(TFSI)2 in propylene carbonate): tetragonal MMO shows negligible activity while the cubic MMO (normally found as polymorph at high temperature or high pressure) exhibits reversible Mg(2+) activity with associated changes in film structure and Mn oxidation state. These results demonstrate a novel strategy for identifying the factors that control multivalent cation mobility in next-generation battery materials.

Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity.

Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.

Phase characterization, thermal stability, high-temperature transport properties, and electronic structure of rare-earth Zintl phosphides Eu3M2P4 (M = Ga, In).

Two rare-earth-containing ternary phosphides, Eu3Ga2P4 and Eu3In2P4, were synthesized by a two-step solid-state method with stoichiometric amounts of the constitutional elements. Refinements of the powder X-ray diffraction are consistent with the reported single-crystal structure with space group C2/c for Eu3Ga2P4 and Pnnm for Eu3In2P4. Thermal gravimetry and differential scanning calorimetry (TG-DSC) measurements reveal high thermal stability up to 1273 K. Thermal diffusivity measurements from room temperature to 800 K demonstrate thermal conductivity as low as 0.6 W/m·K for both compounds. Seebeck coefficient measurements from room temperature to 800 K indicate that both compounds are small band gap semiconductors. Eu3Ga2P4 shows p-type conductivity and Eu3In2P4 p-type conductivity in the temperature range 300-700 K and n-type conductivity above 700 K. Electronic structure calculations result in band gaps of 0.60 and 0.29 eV for Eu3Ga2P4 and Eu3In2P4, respectively. As expected for a valence precise Zintl phase, electrical resistivity is large, approximately 2600 and 560 mΩ·cm for Eu3Ga2P4 and Eu3In2P4 at room temperature, respectively. Measurements of transport properties suggest that these Zintl phosphides have potential for being good high-temperature thermoelectric materials with optimization of the charge carrier concentration by appropriate extrinsic dopants.

Crystal structure and a giant magnetoresistance effect in the new Zintl compound Eu3Ga2P4.

Single-crystalline samples of a new Zintl compound, Eu(3)Ga(2)P(4), have been synthesized by a Ga-flux method. Eu(3)Ga(2)P(4) is found to crystallize in a monoclinic unit cell, space group C2/c, isostructural to Ca(3)Al(2)As(4). The structure is composed of a pair of edge-shared GaP(4) tetrahedra, which link by corner-sharing to form Ga(2)P(4) two-dimensional layers, separated by Eu(2+) ions. Magnetic susceptibility showed a Curie-Weiss behavior with an effective magnetic moment consistent with the value for Eu(2+) 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 H = 2 T at T = 100 K, suggesting strong coupling of carriers with the Eu(2+) magnetic moment.

Synthesis, structure, magnetism, and high temperature thermoelectric properties of Ge doped Yb14MnSb11.

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.

Cu nanoparticles derived from CuO electrodes in lithium cells.

Nanosheet cupric oxide (CuO) was synthesized by a hydrothermal synthesis method and its electrochemical performance was tested with Li metal as the reference anode. This CuO electrode showed a good capacity retention with a reversible capacity of 400 mA h g(-1) during up to 100 cycles. Copper (Cu) nanoparticles were produced and separated from the lithiated CuO electrode. Structural analyses by means of electron microscopy (field emission scanning electron microscopy and transmission electron microscopy) indicated that rather uniform spherical copper particles of 30-40 nm were obtained. These copper nanoparticles were collected as the lithiation product and this electrochemical reduction method was put forward as a new approach for synthesizing metal nanoparticles.