Search

To improve the thermoelectric (TE) properties of melt-grown higher manganese silicides MnSiγ, dissipation of MnSi precipitates that deteriorate the electrical conductivity is required. We have investigated the effects of light cobalt (Co) substitution on TE properties and MnSi precipitates of MnSiγ. A 4% substitution of Mn with Co is an effective approach to eliminate MnSi precipitates from melt-grown MnSiγ, which is confirmed by powder x-ray diffraction and energy-dispersive spectroscopy measurements. Furthermore, this light Co substitution leads to increase of the hole carrier concentration, resulting in a great increase in the electrical conductivity from 24 × 103 S/m to 54 × 103 S/m at 700 K. The resulting power factor exhibits 1.9 × 10−3 W/mK2 around 700 K. Moreover, the lattice thermal conductivity is greatly decreased by partial Co substitution compared with that of Co-free MnSiγ. Consequently, the dimensionless figure-of-merit zT of (Mn1−xCox)Siγ samples increases from 0.27 for x = 0 to 0.50 for x = 0.04 in the vicinity of 800 K.

The thermoelectric properties of ternary full-Heusler alloys, Co2 YZ, which are in a ferromagnetic state up to high temperature above 300 K, were measured and are discussed in terms of the crystal structure and electronic states. Among the full-Heusler alloys studied, the Co2MnSi sample exhibited the highest absolute value of Seebeck coefficient and also the highest electrical conductivity in the temperature range from 300 K to 1023 K. The highest power factor of 2.9 × 10−3 W/m-K2 was obtained for the Co2MnSi sample at 550 K, demonstrating the potential of half-metallic full-Heusler alloys as thermoelectric materials.

To further enhance the thermoelectric (TE) properties of higher manganese silicides (HMSs), dissipation of layered precipitates of MnSi phase as well as optimization of hole carrier concentration are critical. We have prepared a lightly vanadium-substituted solid solution of HMS, (Mn1−xVx)Siγ, by a melt growth method. A 2% substitution of manganese with vanadium is found to dissipate MnSi precipitates effectively, resulting in a substantial increase in the electrical conductivity from 280 S/cm to 706 S/cm at 800 K. The resulting TE power factor reaches 2.4 mW/K2-m at 800 K, more than twice that of the V-free sample. The total thermal conductivity did not change significantly with increasing x owing to a reduction of the lattice contribution. As a consequence, the dimensionless figure of merit zT of the melt-grown samples increased from 0.26 ± 0.01 for x = 0 to 0.59 ± 0.01 for x = 0.02 at around 800 K.

Hexagonal A-Mg-Si with A = Sr and Ba Zintl phases are promising candidates for p-type magnesium silicides usable with n-Mg2Si under 900 K. We synthesized p-type A-Mg-Si Zintl phases by the spark plasma synthesis procedure. Mg2Si and Mg2A powders were mixed at the ratio of 1−x/x with x = 0.3–0.4. Two-step synthesis was performed at 850 K for 20 min and 1100 K for 20 min under uniaxial pressure at 30 MPa. Sintered pellets exhibited a stable p-type thermoelectric property. These pellets consisted of several unknown phases. We found two semiconductor phases, namely A2Mg4Si3 and A2Mg12Si7. The crystal structures of the 2/4/3- and 2/12/7-phases were \( P\bar{6}2m\) (No. 189)- and \( P6_{3} /m\) (No. 176)-types, respectively. Sr0.70Mg2Si, Ba3Mg10Si7 and Sr3Mg10Si7 phases are newly found and characterized by a single crystal diffraction study. Previously found Sr2Mg4Si3 single phase polycrystalline 30φ × 10 mm pellets were successfully synthesized. The thermoelectric performance of the Sr2Mg4Si3 single phase sample was tested. The pellets exhibit p-type behavior from room temperature to 700 K. The thermal conductivity, κ, was almost constant at 1.1 W/mK from 350 K to 700 K.

The crystal structure, thermoelectric properties, and microstructure of polycrystalline samples with nominal compositions Mg2+x Si (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) have been investigated. It is revealed that the Mg2+x Si samples were composites consisting of Mg2Si matrix with dispersed Mg metal. The Mg2Si crystals contained a small amount of Mg atoms at interstitial (1/2 1/2 1/2) site (Mgi). In addition, Mg metal was present at grain boundaries between Mg2Si crystal grains (MgGB). Regarding thermoelectric properties, the electrical conductivity and Seebeck coefficient of Mg2+x Si were measured and their x dependences were discussed in terms of the amounts of Mgi and MgGB. The amount of MgGB and the electrical conductivity indicate quite similar x dependences.

A single-phase sample of a Nowotny chimney–ladder phase known as V17Ge31 has been prepared and its modulated crystal structure has been determined by means of a (3+1)-dimensional superspace approach. As in the case of higher manganese silicides (HMSs) MnSiγ, the compound consists of two tetragonal subsystems of [V] and [Ge] with an irrational c-axis ratio $$\gamma $$ = $$c_{\rm{V}}$$ / $$c_{\rm{Ge}} \sim $$ 1.82, and hence the structure formula is represented as VGe γ . As expected from the valence electron count estimated from the refined γ, the present germanide exhibits a metallic behavior with the electrical conductivity σ = 6.25 × 103 S/cm and the Seebeck coefficient S = 10.2 μV/K at 900 K. The resulting thermoelectric power factor of $$S^2\sigma $$ = 6.56 × 10-5 W/mK2 and the dimensionless figure-of-merit, ZT, = 3.7 × 10-3 at 900 K demonstrate that the germanide is not a promising thermoelectric material. However, as the determined lattice thermal conductivity is comparable to that of HMSs, thermoelectric properties can be maximized through the partial substitution of V with group 6–8 elements to decrease hole carrier concentration.

This research aims to develop a direct-contact manganese silicon p/n multilayer-type thermoelectric power generation block. p-type MnSi1.74 and n-type Mn0.7Fe0.3Si1.68 ball-milled powders with diameter of about 10 μm or less were mixed with polyvinyl butyl alcohol diluted with methylbenzene at pigment volume concentration of approximately 70%. The doctor-blade method produced 45-μm-thick p- and n-type pigment plates. The insulator, i.e., powdered glass, was mixed with cellulose to form insulator slurry. Lamination of manganese silicide pigment layers and screen-printed insulator layers was carried out to fabricate multilayer direct-contact thermoelectric devices. Hot pressing and spark plasma sintering were carried out at 450°C and 900°C, respectively. Four to 30 thermoelectric (TE) p/n pairs were fabricated in a 10 mm × 10 mm × 10 mm sintered TE block. The maximum output was 11.7 mW/cm2 at a temperature difference between 20°C and 700°C, which was about 1/85 of the ideal power generation estimated from the thermoelectric data of the bulk MnSi1.74 and Mn0.7Fe0.3Si1.68 materials. A power generation test using an engine test bench was also carried out.

Organic thin films have been viewed as potential thermoelectric (TE) materials, given their ease of fabrication, flexibility, cost effectiveness, and low thermal conductivity. However, their intrinsically low electrical conductivity is a main drawback which results in a relatively lower TE figure of merit for polymer-based TE materials than for inorganic materials. In this paper, a technique to enhance the ion transport properties of polymers through the introduction of ionic liquids is presented. The polymer is in the form of a nanofiber scaffold produced using the electrospinning technique. These fibers were then soaked in different ionic liquids based on substituted imidazolium such as 1-ethyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium bromide. This method was applied to electrospun polyacrylonitrile and a mixture of polyvinyl alcohol and chitosan polymers. The ion transport properties of the membranes have been observed to increase with increasing concentration of ionic liquid, with maximum electrical conductivity of 1.20 × 10−1 S/cm measured at room temperature. Interestingly, the maximum electrical conductivity value surpassed the value of pure ionic liquids. These results indicate that it is possible to significantly improve the electrical conductivity of a polymer membrane through a simple and cost-effective method. This may in turn boost the TE figures of merit of polymer materials, which are well known to be considerably lower than those of inorganic materials. Results in terms of the Seebeck coefficient of the membranes are also presented in this paper to provide an overall representation of the TE potential of the polymer-scaffolded ionic liquid membranes.

Prospective p-type magnesium-silicon compounds have been produced from mixed and sintered Mg2Si, Mg2Sr or Mg2Ba powders. The synthesis was carried out through the spark plasma sintering (SPS) process at 1123 K for 10 min at 50 MPa. p-Type thermoelectric performance was observed for samples prepared from sintered powder at nominal compositions (Mg2Si)0.7(Mg2Sr)0.3 and (Mg2Si)0.7(Mg2Ba)0.3. The maximum dimensionless figure of merit, ZT, of the former sample reached 0.24 at 700 K. The crystal structures and chemical contents were carefully elucidated by powder and single-crystal x-ray diffraction (XRD) measurements, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) with the use of energy-dispersive x-ray spectroscopy (EDS). The SPS samples consisted of two new unknown phases. Based on the single-crystal XRD data, the crystal structures of two different A(Sr or Ba)-Mg-Si crystals are successfully determined. The two structures are hexagonal P63/m-type A2Mg12Si7 and $$ {{P}}\bar{6}2{{m}} $$ (no. 189)-type A2Mg4Si3. The two structures consist of three-dimensionally interconnecting MgSi4 tetrahedron networks and alkaline-earth ion columns aligned parallel to the 4.3-A axes. Both phases have identical [(A2+, Mg2+)]2[Si4−]-type chemical formulae, being identified as a kind of Zintl phase.

Polycrystalline samples of misfit-layered sulfides [Ln2S2] p NbS2 (Ln = lanthanides) have been prepared using the CS2 sulfidation method. Except for Ln = Eu and Lu, single-phase samples were prepared. The compounds consist of an alternate stacking of a trigonal prism-type [NbS2] layer and a double-layered NaCl [rock salt (RS)]-type [Ln2S2] block, parallel to the c-axis. Three types of stacking modes of the [NbS2] layer and the RS-type block have been confirmed with a (3 + 1)-dimensional superspace group description: two face-centered orthorhombic structures and one face-centered monoclinic structure. Slightly cation-deficient samples with Ln = Yb exhibit the highest Seebeck coefficient S ≈ 59 μV/K. With electrical resistivity of $$\rho = 1.4 \,\hbox{m}{\Upomega}$$ cm and thermal conductivity of κ = 0.69 W/Km, this yields a dimensionless figure of merit of ZT = 0.11 at 300 K.

We have prepared the CuFe1−xMnxO2 solid solution to enhance the thermoelectric performance of CuFeO2 by reducing its thermal conductivity κ. With increasing x above 0.4, the crystal structure changes from delafossite \( \left( {R\overline{3} m} \right) \) to crednerite (C2/m). CuFe0.5Mn0.5O2 exhibits the lowest κ value of 2.28 W/m K at the theoretical density, being about one-quarter of that of the end members, CuFeO2 and CuMnO2. We discuss the temperature dependence of κ in terms of a classical phonon transport model, and conclude that local structural modulation due to the mixture of undistorted FeO6 octahedra and distorted MnO6 octahedra in CuFe1−xMnxO2 leads to the significant reduction of κ.

In this study, we investigated the chemical composition and electronic structure of the delafossite-type oxides CuFeO2 (CFO) and CuFe0.98Ni0.02O2 (CFNO). The hole carrier density in the Cu and FeO2 layers of CFNO was found to be different from that of CFO, leading to the enhancement of electrical conductivity by Ni substitution. In addition, thermoelectric properties were found to be affected by the surface treatment, possibly due to some surface contamination. An etched CFNO (E-CFNO) exhibited a higher electrical conductivity and a higher Seebeck coefficient relative to the polished CFNO (P-CFNO). The thermal conductivity did not change much between E-CFNO and P-CFNO. As a result, the thermoelectric performance of E-CFNO was higher than that of P-CFNO. This result indicates that etching is needed when we use CFNO as a p-leg in thermoelectric generators.

We have investigated the effects of Bi doping on the crystal structure and high-temperature thermoelectric properties of the n-type layered oxide Ca2MnO4−γ . The electrical conductivity σ and the absolute value of the Seebeck coefficient S were, respectively, found to increase and decrease with Bi doping. The thermal conductivity κ of doped Ca2MnO4−γ is relatively low, 0.5 W/m K to 1.8 W/m K (27°C to 827°C). Consequently, the ZT value, ZT = σS 2 T/κ, increases with Bi doping. The maximum ZT is 0.023 for Ca1.6Bi0.18MnO4−γ at 877°C, which is ten times higher than that of the end member, Ca2MnO4−γ . The increase of ZT mainly results from the considerable increase of σ, which can be explained in terms of structural change. The␣Mn-O(1) and the Mn-O(2) distances in the c-direction and ab-plane, respectively, increase with increasing Bi concentration, indicating that the valence state of Mn ions decreases with the increase of electron carriers in the CaMnO3 layers. In addition, the Mn-O(2)-Mn bond angle increases linearly with Bi doping, leading to an improvement of the electron carrier mobility.