Effect of ruthenium substitution in layered sodium cobaltate NaxCoO2: Synthesis, structural and physical properties

Solid-state synthesis of Na_0.71Co_1−xRu_xO₂ compositions shows that ruthenium can be substituted for cobalt in the hexagonal Na_0.71CoO₂ phase up to x=0.5. The cell expands continuously with increasing ruthenium content. All mixed Co-Ru phases show a Curie-Weiss behaviour with no evidence of magnetic ordering down to 2 K. Unlike the parent phase Na_0.71CoO₂, ruthenium-substituted phases are all semiconducting. They exhibit high thermoelectric power, with a maximum of 165 μV/K at 300 K for x=0.3. The Curie constant C and Seebeck coefficient S show a non-monotonic evolution as a function of ruthenium content, demonstrating a remarkable interplay between magnetic properties and thermoelectricity. The presence of ruthenium has a detrimental effect on water intercalation and superconductivity in this system. Applying to Ru-substituted phases the oxidative intercalation of water known to lead to superconductivity in the Na_xCoO₂ system yields a 2-water layer hydrate only for x=0.1, and this phase is not superconducting down to 2 K.     

Crystal structure of the parent misfit-layered cobalt oxide [Sr2O2]qCoO2

The crystal structure of our newly discovered Sr-Co-O phase is investigated in detail through high-resolution electron microscopy (HREM) techniques. Electron diffraction (ED) measurement together with energy dispersive X-ray spectroscopy (EDS) analysis show that an ampoule-synthesized sample contains an unknown Sr-Co-O ternary phase with monoclinic symmetry and the cation ratio of Sr/Co=1. From HREM images a layered structure with a regular stacking of a CdI₂-type CoO₂ sheet and a rock-salt-type Sr₂O₂ double-layered block is observed, which confirms that the phase is the parent of the more complex “misfit-layered (ML)” cobalt oxides of [M_mA₂O_m+2]_qCoO₂ with the formula of [Sr₂O₂]_qCoO₂, i.e. m=0. It is revealed that the misfit parameter q is 0.5, i.e. the two sublattices of the CoO₂ sheet and the Sr₂O₂ block coexist to form a commensurate composite structure. We propose a structural model with monoclinic P2₁/m symmetry, which is supported by simulations of ED patterns and HREM images based on dynamical diffraction theory.     

Preparation and thermoelectric properties of AgPbmSbSem+2 materials

Hydrothermally synthesized AgPb_mSbSe_m+2 (m=10, 12, 16, 18) nanoparticles with diameters of 20-50 nm were compacted by pressureless sintering. The Seebeck coefficient and electrical conductivity of the samples were measured from room temperature up to ∼750 K. The samples show large and positive values of the Seebeck coefficient and moderate electrical conductivity. The thermoelectric properties of Ag_xPb₁₈SbSe₂₀ (x=0.8, 0.85) and AgPb₁₈SbSe_20−yTe_y (y=1, 3) samples have also been studied. It has been found that Ag_0.85Pb₁₈SbSe₂₀ sample has a higher thermoelectric power factor. A significant difference in thermoelectric properties has also been observed for the AgPb₁₈SbSe₂₀ samples prepared with pressureless sintering and spark plasma sintering.     

Charge compensation and oxidation in NaxCoO2−δ and LixCoO2−δ studied by XANES

A comparative study on the oxidation and charge compensation in the A_xCoO_2−δ systems, A=Na (x=0.75, 0.47, 0.36, 0.12) and Li (x=1, 0.49, 0.05), using X-ray absorption spectroscopy at O 1s and Co 2p edges is reported. Both the O 1s and Co 2p XANES results show that upon removal of alkali metal from A_xCoO_2−δ the valence of cobalt increases more in Li_xCoO_2−δ than in Na_xCoO_2−δ. In addition, the data of O 1s XANES indicate that charge compensation by oxygen is more pronounced in Na_xCoO_2−δ than in Li_xCoO_2−δ.     

Thermoelectric properties of polycrystalline La1−xSrxCoO3

Thermoelectric properties of polycrystalline La_1−xSr_xCoO₃, where Sr²⁺ is substituted in La³⁺ site in perovskite-type LaCoO₃, have been investigated. Sr-doping increases the electrical conductivity (σ) of La_1−xSr_xCoO₃, and also decreases the Seebeck coefficient (S) for 0.01?x?0.40. A Hall coefficient measurement reveals that the increase in electrical conductivity arises from increases in both carrier concentration and the Hall mobility. The decrease in the Seebeck coefficient is caused by a decrease in carrier effective mass as well as increase in carrier concentration. The highest power factor (σS²) is 3.7×10⁻⁴ W m⁻¹ K⁻² at 250 K for x=0.10. The thermal conductivity (κ) is about 2 W m⁻¹ K⁻¹ at 300 K for 0?x?0.04, and increases for x?0.05 because of an increase in heat transport by conductive carrier. The thermoelectric properties of La_1−xSr_xCoO₃ are improved by Sr-doping, and the figure of merit (Z=σS² κ⁻¹) reaches 1.6×10⁻⁴ K⁻¹ for x=0.06 at 300 K (ZT=0.048). For heavily Sr-doped samples, the thermoelectric properties diminish mainly because of the decrease in the Seebeck coefficient and the increase in thermal conductivity.     

Structural, magnetic, and electrochemical studies on lithium insertion materials LiNi1−xCoxO2 with 0≤x≤0.25

The structural, magnetic, and electrochemical properties of the LiNi_1−xCo_xO₂ samples with x= 0, 0.05, 0.1, and 0.25 have been investigated by powder X-ray diffraction analyses, magnetic susceptibility (χ) measurements, and electrochemical charge and discharge test in non-aqueous lithium cell. According to the structural analyses using a Rietveld method, the occupancy of the Ni ions in the Li layer was estimated to be below 0.01 for all the samples and was eventually independent of x. The temperature (T) dependence of χ⁻¹ obtained with the magnetic field H=10 kOe indicated that all the samples are a Curie-Weiss paramagnet down to . At low T, all the samples entered into a spin-glass-like phase below T_f. The magnitude of T_f was found to decrease almost linearly with x, as in the case for the x dependences of the lattice parameters of a_h- and c_h-axes, Weiss temperature, and effective magnetic moment. It is, therefore, found that the change of the magnetic properties with x is simply explained by a dilution effect due to the increase of the quantity of Co³⁺ ions. On the other hand, the electrochemical measurements demonstrated that the irreversible capacity at the initial cycle is drastically decreased by the small amount of Co ions. Furthermore, the discharge capacity (Q_dis) for the x=0.05 and 0.1 samples are larger than that for the x=0 sample; namely, Q_dis=180 mAh g⁻¹ for x=0, Q_dis=217 mAh g⁻¹ for x=0.05, and Q_dis=206 mAh g⁻¹ for x=0.1. Comparing with the past results, the amount of Ni ions in the Li layer is found to play a significant role for determining the magnetic and electrochemical properties of LiNi_1−xCo_xO₂.     

New misfit-layered cobalt oxide (CaOH)1.14CoO2

We synthesized a new cobalt oxide (CaOH)_1.14CoO₂ by utilizing a high-pressure technique. X-ray and electron diffraction studies revealed that the compound has a layered structure that consists of CdI₂-type CoO₂ layers and rock-salt-type double CaOH atomic layers. The two subcells have incommensurate periodicity along the a-axis, resulting in a misfit-layered structure. From resistivity and Seebeck coefficient measurements, we have shown that the two-dimensional (2-D) variable-range hopping (VRH) regime with hole conduction is dominant at low temperature for this compound. As temperature increases, the conduction mechanism undergoes crossover from the 2-D VRH regime to a thermal activation-energy-type regime.     

Monoclinic phase of the misfit-layered cobalt oxide (Ca0.85OH)1.16CoO2

A monoclinic phase of the misfit-layered cobalt oxide (Ca_0.85OH)_1.16CoO₂ was successfully synthesized and characterized. It was found that this new material is a poly-type phase of the orthorhombic form of (CaOH)_1.14CoO₂, recently discovered by the present authors. Both the compounds consist of two interpenetrating subsystems: CdI₂-type CoO₂ layers and rock-salt-type double-atomic-layer CaOH blocks. However, these two phases exhibit a different stacking structure. By powder X-ray and electron diffraction (ED) studies, it was found that the two subsystems of (Ca_0.85OH)_1.16CoO₂ have c-centered monoclinic Bravais lattices with common a=4.898 Å, c=8.810 Å and β=95.8° lattice parameters, and different b parameters: b₁=2.820 Å and b₂=4.870 Å. Chemical analyses revealed that the monoclinic phase has a cobalt valence of +3.1-3.2. Resistivity of the monoclinic phase is approximately 10¹-10⁵ times lower than that of the orthorhombic phase. This suggests that the monoclinic phase is a hole-doped phase of the insulating orthorhombic phase. Furthermore, large positive Seebeck coefficients (∼100 μV/K) were observed near room temperature.     

The effect of Ag addition on electrical properties of the thermoelectric compound Ca3Co4O9

Ca₃Co₄O₉/Ag composites incorporating different amounts of Ag were synthesized by solid-state reaction. Scanning electron microscopy revealed Ag particles dispersed among and combined with Ca₃Co₄O₉ grains several times larger in size. The electrical resistivity (ρ) of the composites is favorably lower than that of Ca₃Co₄O₉ alone and decreases with increasing Ag content. It can thus be inferred that the highly conductive Ag particles between the oxide grains contribute to the reduction of ρ. Although minimal in smaller amounts, the addition of Ag also seems to have a negative impact on the Seebeck coefficient (S) of the composites due to its poor S. Since the reduction of ρ is more significant than the degradation of S, the power factor is found to be improved by the addition of 10 wt% Ag.     

Magnetic properties of the chemically delithiated LixMn2O4 with 0.07≤x≤1

Magnetism for the Li_xMn₂O₄ samples with 0.07≤x≤1, which are prepared by a chemical reaction in HNO₃ solution, is investigated by direct current susceptibility (χ) and muon-spin rotation/relaxation (μSR) measurements. The effective magnetic moment (μ_eff) of Mn ions decreases monotonically with decreasing x, indicating that Mn³⁺ ions with S=2 () are oxidized to Mn⁴⁺ ions with S=3/2 () with decreasing x. On the other hand, as x decreases from 1 to 0.6, the Curie-Weiss temperature (Θ_p) increases monotonically from ∼−260 to −100 K, and then levels off to −100 K with further decreasing x. This indicates that the antiferromagnetic interaction is dominant in the whole x range. For the x=0.48 sample, the temperature dependence of χ in field-cooling mode clearly deviates from that in zero-field-cooling mode below ∼63 K (=T_m). Furthermore, the hysteresis loop is observed in the magnetization vs. field curve at 5 K. Since the zero-field μSR spectrum is well fitted by a strongly damped oscillation function, the Mn moments for the x=0.48 sample are in a highly disordered fashion down to the lowest temperature measured.     

Construction of a double-layered tetrahedral network within a perovskite host: Two-step route to the alkali-metal-halide layered perovskite, (LixCl)LaNb2O7

A two-step topotactic route is used to construct lithium halide layers within a perovskite host. Initially RbLaNb₂O₇ is converted to (CuCl)LaNb₂O₇ by ion exchange and then reductive intercalation with n-butyllithium is used to form (Li_xCl)LaNb₂O₇. The copper metal byproduct from the reduction step is removed by treatment with iodine. Rietveld refinement of neutron powder diffraction data revealed that an alkali-halide double layer with LiO₂Cl₂ tetrahedra forms between the perovskite slabs. Compositional studies indicate that the range for x in (Li_xCl)LaNb₂O₇ is 2?x<4, which appears consistent with the neutron data where only one lithium site was found in the structure.     

Structure and basic magnetic properties of the honeycomb lattice compounds Na2Co2TeO6 and Na3Co2SbO6

The synthesis, structure, and basic magnetic properties of Na₂Co₂TeO₆ and Na₃Co₂SbO₆ are reported. The crystal structures were determined by neutron powder diffraction. Na₂Co₂TeO₆ has a two-layer hexagonal structure (space group P6₃22) while Na₃Co₂SbO₆ has a single-layer monoclinic structure (space group C2/m). The Co, Te, and Sb ions are in octahedral coordination, and the edge sharing octahedra form planes interleaved by sodium ions. Both compounds have full ordering of the Co²⁺ and Te⁶⁺/Sb⁵⁺ ions in the ab plane such that the Co²⁺ ions form a honeycomb array. The stacking of the honeycomb arrays differ in the two compounds. Both Na₂Co₂TeO₆ and Na₃Co₂SbO₆ display magnetic ordering at low temperatures, with what appears to be a spin-flop transition found in Na₃Co₂SbO₆.     

Synthesis, structure, and magnetic properties of Ba2Cu2US5

The alkaline-earth uranium chalcogenide Ba₂Cu₂US₅ was obtained in a two-step reaction from BaS, Cu₂S, and US₂. Ba₂Cu₂US₅ crystallizes in a new structure type in space group C2/m of the monoclinic system with two formula units in a cell of dimensions a=13.606(3) Å, b=4.0825(8) Å, c=9.3217(19) Å, and β=116.32(3)° (153 K). The structure consists of layers separated by Ba atoms in bicapped trigonal-prismatic coordination. The two-dimensional layer is built from US₆ octahedra and CuS₄ tetrahedra. The connectivity of the MS_n polyhedra within the layer in the [001] direction is oct tet tet oct tet tet. A μ_eff value of 2.69(2) μ_B/U was obtained from the magnetic susceptibility data. No magnetic transition was observed for Ba₂Cu₂US₅ down to 2 K.     

Mn environment in layered Li[Mg0.5−xNixMn0.5]O2 oxides monitored by EPR spectroscopy

X-band and high-frequency EPR spectroscopy were used for studying the manganese environment in layered Li[Mg_xNi_0.5−xMn_0.5]O₂, 0?x?0.5. Both layered LiMg_0.5Mn_0.5O₂ and monoclinic Li[Li_1/3Mn_2/3]O₂ oxides (containing Mn⁴⁺ ions only) were used as EPR standards. The EPR study was extended to the Ni-substituted analogues, where both Ni²⁺ and Mn⁴⁺ are paramagnetic. For LiMg_0.5−xNi_xMn_0.5O₂ and Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂, an EPR response from Mn⁴⁺ ions only was detected, while the Ni²⁺ ions remained EPR silent in the frequency range of 9.23-285 GHz. For the diamagnetically diluted oxides, LiMg_0.25Ni_0.25Mn_0.5O₂ and Li[Li_0.10Ni_0.35Mn_0.55]O₂, two types of Mn⁴⁺ ions located in a mixed (Mn-Ni-Li)-environment and in a Ni-Mn environment, respectively, were registered by high-field experiments. In the X-band, comparative analysis of the EPR line width of Mn⁴⁺ ions permits to extract the composition of the first coordination sphere of Mn in layered LiMg_0.5−xNi_xMn_0.5O₂ (0?x?0.5) and Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂ (x>0.2). It was shown that a fraction of Mn⁴⁺ are in an environment resembling the ordered “α,β”-type arrangement in Li_1−δ1Ni_δ1[Li_{(1−2x)/3+δ1}Ni_2x/3−δ1)_α(Mn_(2−x)/3Ni_x/3)_β]O₂ (where and δ₁=0.06 were calculated), while the rest of Mn⁴⁺ are in the Ni,Mn-environment corresponding to the Li_1−δ2Ni_δ2[Ni_1−yMn_y]O₂ () composition with a statistical Ni,Mn distribution. For Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂ with x?0.2, IR spectroscopy indicated that the ordered α,β-type arrangement is retained upon Ni introduction into monoclinic Li[Li_1/3Mn_2/3]O₂.     

The effect of Al substitution on the reactivity of delithiated LiNi1/3Mn1/3Co(1/3−z)AlzO2 with non-aqueous electrolyte

The high temperature reactions between 1 M LiPF₆ EC:DEC and Al-doped LiNi_1/3Mn_1/3Co_(1/3−z)Al_zO₂ charged to 4.3 V were studied by accelerating rate calorimetry (ARC) and compared with those of charged LiNi_1/3Mn_1/3Co_1/3O₂ and LiMn₂O₄. Al substitution for Co in LiNi_1/3Mn_1/3Co_1/3O₂ improves the thermal stability. Materials with z > 0.06 are less reactive with electrolyte than spinel LiMn₂O₄ at all temperatures studied. The maximum self-heating rate (SHR) attained and the specific capacity decrease as the Al content increases. There is a range of compositions near z = 0.1 that show excellent promise as materials which are both safer than and more energy dense than spinel LiMn₂O₄.     

MeV Si ions bombardments effects on thermoelectric properties of SiO2/SiO2+Ge nanolayers

The performance of the thermoelectric materials and devices is shown by a dimensionless figure of merit, ZT=S²σT/K, where S is the Seebeck coefficient, σ is the electrical conductivity, T is the absolute temperature and K is the thermal conductivity. ZT can be increased by increasing S, increasing σ, or decreasing K. We have prepared the thermoelectric generator device of SiO₂/SiO₂+Ge multilayer superlattice films using the ion beam assisted deposition (IBAD). The 5 MeV Si ion bombardments have been performed using the AAMU Pelletron ion beam accelerator at five different fluences to make quantum structures (nanodots and/or nanoclusters) in the multilayer superlattice thin films to decrease the cross plane thermal conductivity, increase the cross plane Seebeck coefficient and cross plane electrical conductivity. To characterize the thermoelectric generator devices before and after MeV Si ions bombardments at the different fluences we have measured the cross-plane Seebeck coefficient, the cross-plane electrical conductivity, and the cross-plane thermal conductivity, Raman spectra to get some information about the sample structure and bond structures among the used elements in the superlattice thin film systems.     

Structure and thermoelectric properties of the ordered skutterudite CoGe1.5Te1.5

The skutterudite-related material CoGe_1.5Te_1.5 has been synthesised and structurally characterised by powder neutron diffraction. Analysis of the high-resolution powder neutron diffraction data indicates that the structure of CoGe_1.5Te_1.5 retains the a⁺a⁺a⁺ tilt system of the ideal skutterudite structure, while the anions are ordered in layers perpendicular to the [111] direction of the skutterudite unit cell. This anion ordering results in a lowering of the symmetry from cubic to rhombohedral (space group , a=12.3270(5) and c=15.102(1) Å at 293 K). The electrical transport properties have been investigated using four-probe resistivity and Seebeck coefficient measurements. The temperature dependence of the electrical resistivity and the magnitude of the Seebeck coefficient indicate that CoGe_1.5Te_1.5 is an n-type semiconductor.     

Structural and magnetic study of the cation-ordered perovskites Ba2−xSrxErMoO6

A series of perovskite phases have been prepared from the appropriate carbonates and oxides by heating under reducing conditions at temperatures up to 1300 °C. Complete ordering between ErO₆ and MoO₆ octahedra and a disordered distribution of Sr²⁺ and Ba²⁺ occur in all compounds. Neutron powder diffraction experiments show that the substitution of Sr²⁺ into Ba₂ErMoO₆ introduces a progressive reduction in symmetry from Fm3¯m (x=0) to I4/m (x=0.5, 0.8) to P2₁/n (x=1.25, 1.75, 2.0). Magnetic susceptibility measurements indicate that all of these compounds show Curie-Weiss paramagnetism and that for x<1.25 this behaviour persists down to 2 K. The monoclinically distorted compounds show magnetic transitions at low temperature and neutron diffraction has confirmed the presence of long-range antiferromagnetic order below 2.5 and 4 K in Ba_0.25Sr_1.75ErMoO₆ and Sr₂ErMoO₆, respectively. Ba_0.75Sr_1.25ErMoO₆, Ba_0.25Sr_1.75ErMoO₆ and Sr₂ErMoO₆ do not undergo structural distortion on cooling from room temperature.     

Structural and magnetic properties of Pr18Li8Fe5−xMxO39 (M=Ru, Mn, Co)

A polycrystalline sample of Pr₁₈Li₈Fe₄RuO₃₉ has been synthesized by a solid state method and characterized by neutron powder diffraction, magnetometry and Mössbauer spectroscopy; samples of Pr₁₈Li₈Fe_5−xMn_xO₃₉ and Pr₁₈Li₈Fe_5−xCo_xO₃₉ (x=1, 2) have been studied by magnetometry. All these compounds adopt a cubic structure (space group , a₀∼11.97 Å) based on intersecting 〈111〉 chains made up of alternating octahedral and trigonal-prismatic coordination sites. These chains occupy channels within a Pr-O framework. The trigonal-prismatic site in Pr₁₈Li₈Fe₄RuO₃₉ is occupied by Li⁺ and high-spin Fe³⁺. The remaining transition-metal cations occupy the two crystallographically-distinct octahedral sites in a disordered manner. All five compositions adopt a spin-glass-like state at 7 K (Pr₁₈Li₈Fe₄RuO₃₉) or below.     

Effects of nano-TiO2 dispersion on the thermoelectric properties offilled-skutterudite Ba0.22Co4Sb12

Homogeneously dispersed nano-TiO₂ was introduced into the matrix of n-type barium-filled cobalt antimony (Ba_0.22Co₄Sb₁₂) via sol–gel method successfully. The Seebeck coefficients are improved and the lattice thermal conductivities are depressed with a proper addition of nano-TiO₂ not more than 0.8 vol.%, while the electrical conductivities nearly remain unchanged. The effects of n-type semiconductive nanoscale inclusions on the electrical and thermal transport characteristics are discussed. Microstructure analyses indicate that the fine nanoinclusions locate on the grain boundaries as well as inside grains, which serve as extra phonon scattering mode and new type energy filtering. As a result, the optimal ZT value was achieved for the sample of 0.4 vol.% TiO₂ composition.