Spark plasma sintered BaTiO3/graphene composites for thermoelectric applications

The viability of spark plasma sintered graphene/barium titanate ceramic matrix composites as thermoelectric materials is investigated. The temperature dependence of electrical conductivity, thermal conductivity and Seebeck coefficient was analyzed. The addition of low amounts of graphene oxide combined with the spark plasma sintering process increases electrical conductivity of pure BaTiO₃ several orders of magnitude, whereas the thermal conductivity shows only a moderate enhancement. The composites display a semiconducting behaviour, with the resistivity decreasing with increasing temperature and following a thermally activated temperature dependence at high T. A strong dependence of ZT figure of merit with the graphene concentration and the measurement temperature was found. Optimal values are found for 1.7 wt% graphene oxide at the maximum experimental temperature (600 K).     

Thermoelectric transport properties of boron-doped nanocrystalline diamond foils

Natural diamond is known for its outstanding thermal conductivity and electrical insulation. However, synthetic production allows for doping and tailoring microstructural and transport properties. Despite some motivation in the literature and the ongoing search for abundant and non-toxic thermoelectric materials, the first experimental study on a set of eight substrate-free boron-doped nanocrystalline diamond foils is presented herein. All transport coefficients were determined in the same direction within the same foils over a broad temperature range up to 900 °C. It is found that nanostructuring reduces the thermal conductivity by two orders of magnitude, but the mobility decreases significantly to around 1 cm² V⁻¹ s⁻¹, too. Although degenerate transport can be concluded from the temperature dependence of the Seebeck coefficient, charge carriers notably scatter at grain boundaries where sp²-carbon modifications and amorphous boron-rich phases form during synthesis. A detailed analysis of doping efficiency yields an acceptor fraction of only 8–18 at%, meaning that during synthesis excess boron thermodynamically prefers electrically inactive sites. Decent power factors above 10⁻⁴ W m⁻¹ K⁻² at 900 °C are found despite the low mobility, and a Jonker-type analysis grants a deeper insight into this issue. Together with the high thermal conductivity, the thermoelectric figure of merit zT does not exceed 0.01 at 900 °C.     

Enhanced thermoelectric properties of carbon fiber reinforced cement composites

Thermoelectric properties of carbon fiber reinforced cement composites (CFRCs) have attracted relevant interest in recent years, due to their fascinating ability for harvesting ambient energy in urban areas and roads, and to the widespread use of cement-based materials in modern society. The enhanced effect of the thin pyrolytic carbon layer (formed at the carbon fiber/cement interface) on transport and thermoelectric properties of CFRCs has been studied. It has been demonstrated that it can enhance the electrical conduction and Seebeck coefficient of CFRCs greatly, resulting in higher power factor 2.08 µW m⁻¹ K⁻² and higher thermoelectric figure of merit 3.11×10⁻³, compared to those reported in the literature and comparable to oxide thermoelectric materials. All CFRCs with pyrolytic carbon layer, exhibit typical semiconductor behavior with activation energy of electrical conduction of 0.228-0.407 eV together with a high Seebeck coefficient. The calculation through Mott’s formula indicates the charge carrier density of CFRCs (10¹⁴–10¹⁶ cm⁻³) to be much smaller than that of typical thermoelectric materials and to increase with the carbon layer thickness. CFRCs thermal conductivity is dominated by phonon thermal conductivity, which is kept at a low level by high density of micro/nano-sized defects in the cement matrix that scatter phonons and shorten their mean free path. The appropriate carrier density and mobility induced by the amorphous structure of pyrolytic carbon is primarily responsible for the high thermoelectric figure of merit.     

Fabrication and high-temperature thermoelectric properties of Ti-doped Sr0.9La0.1TiO3 ceramics

Ti-doped Sr_0.9La_0.1TiO₃ ceramics with high density were successfully prepared in argon atmosphere by conventional solid state reaction. The influences of titanium doping content on the microstructure and thermoelectric properties were investigated. The results showed that titanium was oxidized during the calcination procedure. TiO₂ phase survived and coexisted with Sr_0.9La_0.1TiO₃ phase in the sintered ceramics. The Seebeck coefficients were increased from −163 to −259 μV/K as the temperature increased from 350 K to 1073 K. The thermal conductivity can be significantly reduced by doping Ti. Thermoelectric figure of merit (ZT) first decreased and then increased with increasing Ti doping content. Ceramics showed the best thermoelectric properties when Ti doping amount was 5 wt%, the maximum PF was 7.13 μW/K²/cm, and ZT value was 0.144 at 1073 K.     

Synthesis and thermoelectric performance of Li-doped NiO ceramics

Ni_1?xLi_xO (x = 0, 0.03, 0.06, 0.09) powders were prepared by sol–gel method combined with sintering procedure using Ni(CH₃COO)₂·4H₂O and citric acid as the raw materials and alcohol as solvent. The crystal structures of the samples were investigated by X-ray diffraction and Raman spectroscopy. The thermoelectric properties, such as the electrical conductivity, the Seebeck coefficient and the thermal conductivity were measured. The results showed that all the samples are p-type semiconductors. The electrical conductivity increases with the increase of the temperature, which indicates that the substitution of Li⁺ for Ni²⁺ can increase the concentrations and mobility of the carriers. The thermal conductivity decreases remarkably with the increase of the Li doping content, which indicates that Li doping can enhance the scattering of phonon. However, the Seebeck coefficient will decline with the increase of the Li doping content. As results of the increase of electrical conductivity and reduction of thermal conductivity, Li doping can increase the figure of merit (ZT) of NiO, the ZT value reach 0.049 at 770 K for Ni_1?xLi_xO with x = 0.06.     

The effect of graphite oxide on the thermoelectric properties of polyaniline

Graphite oxide (GO)/ordered polyaniline (PANI) composites have been prepared through an in situ polymerization. TEM, XRD, FTIR and XPS analyses show that the PANI grew along the surface of exfoliated GO as a template to form a more ordered structure with high crystallinity during polymerization. Compared with pure PANI, both higher electrical conductivity and higher Seebeck coefficient of GO/PANI composites result from the increased carrier mobility, which is confirmed by Hall measurement. Strong interactions exist between graphene oxide and PANI, including electrostatic forces, hydrogen bonding and π–π stacking. There is no significant difference in thermal conductivity between GO/PANI composites and PANI. The maximum electrical conductivity and Seebeck coefficient of the composites reach 751 S m^?1 and 28.31 μV K^?1, respectively. The maximum thermoelectric figure of merit is up to 4.86 × 10^?4, 2 orders of magnitude higher than that of pure PANI.     

Thermoelectric properties of copper-deficient Cu2-xSe (0.05 ≤ x ≤ 0.25) binary compounds

Recently, many novel superionic thermoelectric materials have been discovered along the concept of “phonon-liquid electron-crystal” (PLEC). Among them, Cu_2-xSe-based liquid-like materials are typical examples. In this study, a series of copper-deficient Cu_2-xSe (0.05 ≤ x ≤ 0.25) materials were synthesized and used to study the role of Cu vacancies on the electrical and thermal transport properties. The X-ray photoelectron spectroscopy (XPS) measurements suggest that the valence states of Cu and Se are independent on the Cu/Se atomic ratio. With increasing the content of Cu vacancies, the hole concentration is monotonously increased, leading to the improved electrical conductivity and reduced Seebeck coefficient. Based on the single parabolic band model analysis, it is found that changing the content of Cu vacancies does not obviously modify the material's electronic band structure and effective mass. Due to the presence of highly mobile Cu ions inside the crystal structure, the lattice thermal conductivities of all Cu_2-xSe (0.05 ≤ x ≤ 0.25) materials are very low with values around 0.39 W m⁻¹ K⁻¹ at 500 K. Because of the significantly reduced Seebeck coefficient and increased electronic thermal conductivity, the thermoelectric figure of merit zTs are decreased when increasing x from 0.05 to 0.25. At 750 K, a maximum zT of 0.46 is obtained in Cu_1.95Se among all Cu_2-xSe (0.05 ≤ x ≤ 0.25) materials.     

Porous Ca3Co4O9 with enhanced thermoelectric properties derived from Sol–Gel synthesis

Highly porous Ca₃Co₄O₉ thermoelectric oxide ceramics for high-temperature application were fabricated by sol–gel synthesis and subsequent conventional sintering. Growth mechanism of misfit-layered Ca₃Co₄O₉ phase, from sol–gel synthesis educts and upcoming intermediates, was characterized by in-situ X-ray diffraction, scanning electron microscopy and transmission electron microscopy investigations. The Ca₃Co₄O₉ ceramic exhibits a relative density of 67.7%. Thermoelectric properties were measured from 373 K to 1073 K. At 1073 K a power factor of 2.46 μW cm⁻¹ K⁻², a very low heat conductivity of 0.63 W m⁻¹ K⁻¹ and entropy conductivity of 0.61 mW m⁻¹ K⁻² were achieved. The maintained figure of merit ZT of 0.4 from sol–gel synthesized Ca₃Co₄O₉ is the highest obtained from conventional, non-doped Ca₃Co₄O₉. The high porosity and consequently reduced thermal conductivity leads to a high ZT value.     

Thermoelectric properties and figure of merit of perovskite-type Sr1−xLaxSnO3 ceramics

The thermoelectric properties of perovskite-type Sr_1−xLa_xSnO₃ ceramics with x=0.01–0.05 were evaluated from the Seebeck coefficient S, electrical conductivity σ, and thermal conductivity κ measured at high temperatures. The La-doped ceramics were n-type semiconductors exhibiting thermally activated electrical conduction behaviors in the temperature range of 473–1073 K. Eelectron carriers were introduced into the conduction band from doped La atoms up to x=0.03, which was the solubility limit of La at Sr site. The temperature dependence of the κ values for the ceramics was unaffected by both the La content and the microstructures. Estimations of the electronic thermal conductivities by the Wiedemann-Franz law revealed that the phonon thermal conductivities were dominant for all ceramics. The dimensionless figure of merit ZT increased with increasing temperature for all ceramics and reached 0.02–0.05 at 1073 K. In contrast to cubic Ba_1−xLa_xSnO₃ ceramics, bending of the Sn–O–Sn bonds due to octahedral tilting distortion in Sr_1−xLa_xSnO₃ lowered the electron mobility, decreasing the power factor S²σ and ZT values, although it effectively reduced the phonon mean free path, decreasing the κ values.     

Enhanced thermoelectric power factor and low thermal conductivity in one-dimensional Te/Ag2Te composites

We reports the synthesis and characterization of Te/Ag₂Te nanorod composites with various Ag₂Te contents. The composite samples were prepared by mixing Te and Ag₂Te nanorods synthesized by polyvinylpyrrolidone (PVP)-assisted solution-phase mixing. The thermoelectric properties of the prepared composites vary according to the Ag₂Te content. Furthermore, the samples exhibit an enhancement in electrical conductivity and a reduction in the Seebeck coefficient with increasing Ag₂Te content. The maximum power factor (350.71 µV/K at room temperature) is observed for the sample containing 30% Ag₂Te. The samples were assembled as 1D nanostructures, which led to a decrease in thermal conductivity owing to the strong phonon scattering effect. The maximum thermoelectric figure of merit (ZT) at room temperature, 0.34 was obtained for the sample with 30% Ag₂Te content. This value is 480% larger than that obtained for the pristine Te nanorod samples.     

Improvement of thermoelectric performance of oxygen reduced Sr0.7Ba0.3Nb2O6-δ ceramics by Lanthanides doping

Thermoelectric properties of lantanide doped Sr_0.7Ba_0.3Nb₂O₆ ceramics were investigated in the temperature range from 323 K to 1073 K. A better electrical conductivity is obtained in the sample with larger ionic radius of doping element. Thus, the highest PF value is achieved in La-doped sample. The NbO₂ second phase is counterproductive to reduce the lattice thermal conductivity, so La-doped sample without impurity shows low thermal conductivity. Thus, La-doped sample shows an excellent thermoelectric performance ZT ∼ 0.35. The small average grain size and the nano-sized phases are observed in Gd and Dy doped samples, both of which contribute to scattering phonons, resulting in low thermal conductivities.     

Thermoelectric Ca0.9Yb0.1MnO3−δ grain growth controlled by spark plasma sintering

n-Type Ca_0.9Yb_0.1MnO_3?δ thermoelectric (TE) powders were prepared by solid state synthesis (SSS) and co-precipitation method (Cop). The bulk TE materials were consolidated using conventional sintering (CS) and spark plasma sintering (SPS) respectively. The shrinkage behavior, as well as the sample densification strongly depends on the starting particle size. Consequently, the bulk samples from normal powder (SSS) and nano-powder (Cop) were prepared with similar density by using different sintering temperatures, of 1400 °C and 1200 °C, then 1200 and 950 °C for CS and SPS respectively. Such a decrease (up to 200 °C) of the sintering temperature is a consequent progress in terms of engineering for applications. Another advantage of the co-precipitation process compared to the conventional solid state synthesis is that, due to the small particle sizes and the decreased sintering temperature, grain growth was limited and TE properties were enhanced. The interest of the SPS process was also evidenced and we are presenting here the structural and microstructural investigations. In addition, the thermoelectric properties of samples prepared with two different processes were studied with the figure of merit of 0.18 at 750 °C.     

Synthesis of n-type Bi2Te1-xSex compounds through oxide reduction process and related thermoelectric properties

We propose a new process for the fabrication of n-type Bi₂Te_3-xSe_x (x = 0, 0.25, 0.4, 0.7) compounds. The compounds could be synthesized successfully using only oxide powders as the starting materials via the mechanical milling, oxidation, reduction, and spark plasma sintering processes. The controllability of the Se content could be ascertained by structural, electrical, and thermal characterizations, and the highest thermoelectric figure of merit (ZT) of 0.84 was achieved in Bi₂Te_2.6Se_0.4 compound at 423 K without any intentional doping. This process provides a new route to fabricate n-type Bi₂Te_3-xSe_x compounds with competitive ZTs using all oxide starting materials.     

Thermoelectric properties of Yb-doped La0.1Sr0.9TiO3 ceramics at high temperature

The effect of ytterbium doping on the thermoelectric properties of La_0.1Sr_0.9TiO₃ ceramics has been investigated at the temperature range between 300 K and 1000 K. Samples with different ytterbium concentrations have been synthesized by the conventional solid state reaction technique. An X-ray diffraction pattern suggests that the dominant crystal structure is of perovskite, with a small amount of pyrochlore phase of Yb₂Ti₂O₇. The electrical resistivities of all samples exhibit a minimum in the temperature range between 300 K and 1000 K. The minimum values of electrical resistivity are 1.5 mΩ cm, 2.0 mΩ cm, 3.9 mΩ cm, 7.1 mΩ cm, and 9.0 mΩ cm for x=0.01, 0.03, 0.05, 0.07, and 0.10, respectively. With the increasing ytterbium content, the electrical resistivity enhanced dramatically, the Seebeck coefficients are increased marginally, and the thermal conductivities are reduced moderately. The lowest thermal conductivity of 3.9 W/mK is obtained in sample of La_0.1Sr_0.89Yb_0.01TiO₃, which exhibits maximum figure of merit 0.20 at 963 K.     

Promising high temperature thermoelectric properties of dense Ba2Co9O14 ceramics

Layered cobalt oxides have shown high thermoelectric properties. The n = 1 member of the Ba_n+1Co_nO_3n+3(Co₈O₈) family, Ba₂Co₉O₁₄, a new layered cobalt oxides family with Co(II) and Co(III) in the CdI₂ layers, has been synthesized by solid state reaction and sintered as dense ceramics (relative density ∼ 93%) by Spark Plasma Sintering. It presents promising p-type thermoelectric properties at high temperature. The dimensionless figure of merit ZT is 0.032 at 660 K and 0.04 at 1000 K, which is about one quarter to one third of the ZT value of Ca₃Co₄O₉ ceramics.     

Super-fast preparation of Nd-filled p-type skutterudite compounds with enhanced thermoelectric properties

P-type filled skutterudite materials have been gained considerable research interest in recent years due to their promising thermoelectric power generation applications at intermediate temperature. Herein, we systematically investigated the influence of Nd filling on the thermoelectric properties of Nd_xFe₂Co₂Sb₁₂ (x=0.4, 0.5 0.6, 0.7 and 0.8). Nd-filled skutterudites are synthesized using a simple and time-saving induction melt spinning technique followed by spark plasma sintering. The results show that Nd-filling leads to the significant reduction in the lattice thermal conductivity and enhancement of power factor over the entire temperature range. The most marked reduction in the lattice thermal conductivity is achieved with the value of 0.76 W/m K for x=0.7 sample, due to strengthened phonon scattering. Meanwhile, the highest ZT=0.98 is attained at 740 K for Nd_0.7Fe₂Co₂Sb₁₂. The rapid synthesis procedure provides an effective pathway for the fabrication of thermoelectric materials with high performance.     

Effect of Zn migration on the thermoelectric properties of Zn4Sb3 material

β-Zn₄Sb₃ is interesting as thermoelectric material at moderate temperature due to the extreme low thermal conductivity. Recent success in energy band engineering or nano-engineering led to a significant improvement in the thermoelectric properties of β-Zn₄Sb₃. In this work, we utilize the direct current to drive the migration of Zn by designing of sintering mould. Obvious Zn migration under the direct current applied in the plasma activated sintering (PAS) process is found in Zn₄Sb₃ compounds, and Zn exhibits significantly heterogeneous gradient composition distribution. At the top of sample, the single-phase Zn₄Sb₃ decomposes into ZnSb phase because of the loss of Zn, while Zn originated from lattice and interstitial sites in Zn₄Sb₃ is abundant in the bottom. The temperature-dependent transport measurements are also carried out at 323–673 K. Zn migration has a huge influence on the thermoelectric properties because of the sensitivity of Zn₄Sb₃. The maximum power factor can reach ~ 1.44 mW m⁻¹ K⁻² at 673 K due to the high Seebeck coefficient and low resistivity, which is one of the highest values in the reported results. The resulting peak ZT value of ~ 1.2 at 673 K is obtained. To control the Zn distribution by tuning the current is a feasible approach to improve the thermoelectric properties of Zn₄Sb₃ material.     

Enhanced thermoelectric properties of CNT dispersed and Na-doped Bi2Ba2Co2Oy composites

The thermoelectric properties of Bi₂Ba₂Co₂O_y and Bi_1.975Na_0.025Ba₂Co₂O_y+x wt% carbon nanotubes (CNT; x=0.00, 0.05, 0.10, 0.15, 0.5, and 1.0) ceramic samples synthesised by the solid-state reaction method were investigated from 300K to 950K. Na doping with a small amount played an important role in reducing resistivity and slightly reduced the Seebeck coefficients and the thermal conductivity. The CNT dispersant increased resistivity, but the thermal conductivity was reduced remarkably. In particular, the Bi_1.975Na_0.025Ba₂Co₂O_y+1.0wt% CNT sample exhibited an ultralow thermal conductivity of 0.39 W K⁻¹ m⁻¹ at 923K. This was attributed to the point defects caused by Na doping and the interface scattering caused by the CNT dispersant. The combination of Na doping and CNT dispersion had better effects on thermoelectric properties. The Bi_1.975Na_0.025Ba₂Co₂O_y+0.5wt% CNT sample exhibited a better dimensionless figure of merit (ZT) value of 0.2 at 923K, which was improved by 78.2%, compared with the undoped Bi₂Ba₂Co₂O_y sample.     

Effects of microstructure evolution on transport properties of thermoelectric nickel-doped zinc oxide

We investigate the effects of microstructure evolution on transport properties of nickel-doped ZnO for thermoelectric waste heat recovery at high temperatures. A 3 at.% supersaturated Ni-alloyed ZnO solid solution was prepared by sintering at 1400 °C followed by controlled nucleation and growth of sub-micrometer size NiO-precipitates by aging at 750, 800, and 900 °C for different durations. Minimum thermal conductivity as low as 8.0 W m⁻¹ K⁻¹ at 700 °C is obtained for samples aged at 750 °C for 16 h due to precipitates with high number density of 1.3·10²⁰ m⁻³, which initiate phonon scattering. In turn, as-quenched samples exhibit the highest electrical conductivity, ca. 17.9 S cm⁻¹ at 700 °C. Further nucleation and growth of precipitates taking place for longer annealing durations reduce electrical conductivity and increase Seebeck coefficients, which is associated with dilution of the ZnO-matrix from Ni-atoms. This study provides us with guidelines for optimization of thermoelectric Ni-doped ZnO.     

Thermoelectric properties of carbon nanotube reinforced cement-based composites fabricated by compression shear

Carbon nanotubes (CNTs) with weight percent of 5.0%, 10.0% and 15.0% were added into the cement matrix to fabricate CNT reinforced cement-based composites (CNTs/CC) by mixing and dry compression shear methods. Seebeck coefficient, electrical conductivity and thermal conductivity of the as-received CNTs/CC were measured and analyzed in detail. The CNTs/CC exhibits the thermoelectric behavior of p-type semiconductor. CNTs were dispersed uniformly in cement matrix by compression shear stress, which promoted a relatively high electrical conductivity (0.818 S/cm) and Seebeck coefficient (57.98 μV/°C) of CNTs/CC. Combining with their lower thermal conductivity ranged from 0.734 to 0.947 W m^?1 K^?1, the CNTs/CC shows the highest thermoelectric figure of merit (ZT) has reached 9.33 × 10^?5, Which is benefit to the applications in large-scale energy harvesting in the buildings and pavements with low cost in the future cities.