Effect of PbTe on Thermoelectric Properties of Co<Subscript>0.88</Subscript>Ni<Subscript>0.12</Subscript>Sb<Subscript>2.91</Subscript>Sn<Subscript>0.09</Subscript>

The Co_0.88Ni_0.12Sb_2.91Sn_0.09 compound was synthesized by a metallurgical route, and PbTe powder was prepared by the low-temperature aqueous chemical method. Composite materials (xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09) were prepared by the ball-milling and the hot-pressed process. Electrical conductivities of xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09 hot-pressed samples decrease with increase of PbTe content, but their thermal conductivities were effectively improved due to induction of disperse phase. Due to agglomeration of the disperse phase, little thermal conductivity improvement occurs for composite material with low PbTe content. The ZT values of xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09 samples were hardly enhanced due to the negative contribution of electrical conductivity.     

High-pressure and high-temperature synthesis of stable SxCo3.6Ni0.4Sb12 skutterudite compounds

Compared to Te, Ni is found in abundance in the earth's crust. At the same time, the mechanical properties of Ni atom-substituted skutterudite are significantly improved. In this study, a series of S-filled Ni-substituted skutterudite compounds were synthesized by a high-pressure and high-temperature (HPHT) method in the synthesis pressure range of 1.0–3.0 GPa. The phase composition, microscopic morphology, and electrothermal transmission properties of the S_xCo_3.6Ni_0.4Sb₁₂ (x = 0, 0.05, 0.10, 0.20) samples were systematically characterized. Phase composition analysis showed that the introduction of S atoms into the intrinsic pores of skutterudite can improve the solid solution limit of Ni atoms in the Co sites of skutterudite. The filling limit of S increased with the synthetic pressure. Moreover, microscopic morphology analysis revealed that the filling of S atoms inhibited the growth of grains. A large number of lattice fringes in different directions were found in the sample, containing abundant microstructures such as lattice distortions and dislocation defects. Compared with the synthesized samples, S_0.05Co_3.6Ni_0.4Sb₁₂ synthesized at 1.0 GPa had a maximum room temperature power factor of 7.98 × 10^?4 Wm^?1K^?2. The electrical properties of S_0.05Co_3.6Ni_0.4Sb₁₂ samples stored for 6 months without any protective measures were tested at room temperature. No obvious changes in performance were observed, which proved that the HPHT method can synthesize stable samples. After several thermal cycles, the electrical properties of the S_0.05Co_3.6Ni_0.4Sb₁₂ sample was tested for variable temperature, and it was found that the sample still had good stability. How the substitution of S atoms with Ni atoms reduces the lattice thermal conductivity can be explained by fitting the Callaway model. The S_0.05Co_3.6Ni_0.4Sb₁₂ sample synthesized at 1.0 GPa had a maximum zT value of 0.46 at the test temperature of 773 K, which decreased to 0.43 after multiple thermal cycles at the same temperature.     

S0.05Co4Sb11.6Te0.4 skutterudite introduced into graphene at high pressure and high temperature and its thermoelectric performance enhancement

A series of graphene-S_0.05Co₄Sb_11.6Te_0.4 (C_x-S_0.05Co₄Sb_11.6Te_0.4) composite polycrystalline skutterudite materials with graphene stoichiometric ratio of x = 0, 0.05, 0.10, 0.20 have been successfully prepared by high pressure and high temperature (HPHT) technology. Graphene is a two-dimensional material with large carrier mobility and large specific surface area. Through microscopic observation, it is found that graphene is attached to the grains in the sample. At the same time, with the increase of graphene content, grain growth is inhibited. Graphene addition reduces the thermal conductivity of skutterudite by increasing grain boundaries and achieves the purpose of optimizing its thermoelectric properties. At the same time, there are numerous lattice defects and distortions introduced in skutterudite synthesized by HPHT technology. Finally, the samples were synthesized under the conditions of 1.5 GPa and 900 K. The lattice thermal conductivity of the graphene composite sample C_x-S_0.05Co₄Sb_11.6Te_0.4 with x = 0.10 reaches a minimum of 0.99 at 773 K, and the zT value of this sample is 1.25 at 773 K, which is greater than pure S_0.05Co₄Sb_11.6Te_0.4, its zT value is 1.00 at 773 K. Compared with the method of synthesizing skutterudite under normal pressure, the HPHT technology can dramatically reduce the reaction time from several days to less than 30 min, while forming a high-pressure airtight reaction environment, which can effectively prevent the volatilization and oxidation of samples during the reaction process, thus providing a convenient method for synthesizing thermoelectric materials quickly and efficiently.     

Thermoelectric Properties of <Emphasis Type="Italic">x</Emphasis>PbTe/Yb<Subscript>0.2</Subscript>Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript> Hot-Pressed Samples

The xPbTe/Yb_0.2Co₄Sb₁₂ compounds were prepared by the ball-milling and hot-pressed process. Electrical conductivity of the composite samples are reduced with a increase in PbTe content; and, their temperature dependence coefficients show the positive values. The maximum electrical conductivity of composite materials is ~80000 Sm⁻¹ at 800 K. The Seebeck coefficient (absolute value) of the composite material is obviously improved with an increase in the dispersed phase (PbTe) content; the Seebeck coefficient (absolute value) of the 10PbTe sample is ~260 μVK⁻¹ at 700 K, which increases by 13.6% relative to that of the Yb_0.2Co₄Sb₁₂ sample. The thermal conductivity of the composite samples is improved due to introduction of PbTe, and the thermal conductivity of the 10PbTe sample is ~3 Wm⁻¹ K⁻¹ at 550 K. The maximum value of ZT is 0.78 at 700 K for the 2.5PbTe sample.     

Synergistic optimization of electrical-thermal properties of dual vacancy Bi1−x-yPbyCu1−xSeO by improving mobility and reducing lattice thermal conductivity

We fabricate Bi_1?x-yPb_yCu_1?xSeO (x = 0, 0.03, 0.06, y = 0, 0.10) samples via 4 min-microwave synthesis combined with 5 min-spark plasma sintering. The phase composition, microstructure, valence, and electrical and thermal transport properties of the samples are investigated at 298–873 K. Pb doping provides impurity carriers and increases the concentration to 0.9–3.0 × 10²⁰ cm^-³ . Bi and Cu vacancy could provide a carrier transport channel to reduce carrier scattering probability, leading to improved mobility. Twin crystals, stacking faults, and grain boundary segregation are observed in Bi_0.87Pb_0.10Cu_0.97SeO on scanning transmission electron microscopy. Bi and Cu vacancy increase the sample point defects in Pb-doped or undoped samples which results in a decrease in lattice thermal conductivity. The lattice thermal conductivity of Bi_0.87Pb_0.10Cu_0.97SeO is decreased to an extremely low value of 0.13 Wm^?1 K^?1 and a maximum ZT value of 1.09 is achieved at 873 K.     

Enhancement of Ca3Co4O9+δ thermoelectric properties by dispersing SiC nanoparticles

Misfit-layered oxides Ca₃Co₄O_9+δ + z wt% SiC (z = 0.00, 0.025, 0.05, 0.1, 0.2) samples were synthesized using solid-state sintering method and the effects of SiC nanoparticles diapersion on the thermoelectric properties were investigated. Thermoelectric properties of Ca₃Co₄O_9+δ + z wt% SiC (z = 0.00, 0.025, 0.05, 0.1, 0.2) were investigated up to 923 K. Compared with pure sample, the electrical resistivity of SiC-added samples reduces, for Ca₃Co₄O_9+δ + z wt% SiC (z = 0.00, 0.025, 0.05, 0.1, 0.2) ceramic samples with x ≤ 0.05, the electrical resistivity decreases with increasing SiC nanoparticles adding amounts. And, the electrical resistivity exists transition from semiconductor to metal conduction mechanism. While, the thermal conductivity also decreases due to the addition of SiC nanoparticles. As a result, the Ca₃Co₄O_9+δ + 0.2 wt% SiC sample had the lowest thermal conductivity of 1.47 W/Km at 923 K, which was 18.4% lower than that of the Ca₃Co₄O_9+δ sample. The ZT value of Ca₃Co₄O_9+δ + 0.05 wt% SiC can reach 0.218, which is 40.9% higher than the pure Ca₃Co₄O_9+δ sample.     

Enhanced thermoelectric figure of merit in indium and ytterbium double-filled skutterudite bulk materials through simultaneously optimising power factor and reducing thermal conductivity

In this study, Yb_xCo₄Sb₁₂ and In_xYb_0.3Co₄Sb₁₂ bulk materials were fabricated via microwave synthesis combined with spark plasma sintering. Based on ytterbium single filling, indium was further filled into the voids of CoSb₃. Carrier concentration and mobility were regulated as 1.6–1.8 × 10²⁰ cm^-³ and ∼30 cm²V⁻¹S⁻¹, respectively, resulting in an improved power factor of ∼4900 μWm⁻¹K⁻². The phonon-resonant scattering, caused by indium and ytterbium double filling, was combined with other phonon scattering mechanisms such as nano-inclusion, dislocation, and grain boundary segregation, which resulted in a significantly decreased lattice thermal conductivity of 0.72–2.08 Wm⁻¹K⁻¹. Owing to the improvements in carrier concentration and phonon transport, excellent thermoelectric performance, reflected by ZT = 1.38 at 773 K, was achieved in In_0.4Yb_0.3Co₄Sb₁₂.     

Enhanced thermoelectric efficiency of Cu2−xSe–Cu2S composite by incorporating Cu2S nanoparticles

The study of thermoelectric transport properties in Cu_2−xSe and Cu₂S has gained an importance in the thermoelectric research during last few years due to their superionic behavior and low cost. Here, we reported a facile method to enhance the thermoelectric efficiency of Cu_2−xSe by introducing Cu₂S nanoparticles (NPs) in the matrix of Cu_2−xSe. The observed efficiency is a direct result of simultaneous improvement of Seebeck coefficient (S) because of the external strain induced by Cu₂S nanoinclusions in Cu_2−xSe and decline in the total thermal conductivity by suppressing both electronic and lattice thermal contributions. Such higher S and lower thermal conductivity is realized for a composite structure with 10 wt% nanoinclusions of Cu₂S which effectively contributed to higher ZT value of 0.90 at moderate temperature of 773 K. Thus, it is believed that the proposed hybrid structure is a promising p-type thermoelectric material for mid-temperature range energy harvesting applications.     

Hydrothermal method for the synthesis of Sb2Te3, and Bi0.5Sb1.5Te3 nanoplates and their thermoelectric properties

In this study, a modified hydrothermal method is reported for the preparation of Sb₂Te₃ and Bi_0.5Sb_1.5Te₃ nanoplates and their bulk samples was prepared by spark plasma sintering (SPS). The crystal structure, morphology, and thermoelectric properties were investigated. The microstructure results indicate that the bulk samples consisted nanograins after SPS. The presence of nanograins, high Seebeck coefficient (181 μV/K), high electrical conductivity (763 Ω^?1 cm^?1), and low thermal conductivity (1.15 W/mK) has been achieved in Sb₂Te₃ nanoplate bulk samples. As a result, the dimensionless thermoelectric figure of merit (ZT) of 0.55 at 400 K was achieved. Moreover, the peak ZT shifted to higher temperature compared with other reported results found in literature.     

Enhancing the thermoelectric performance of cold sintered calcium cobaltite ceramics through optimised heat-treatment

Cold sintering is a promising technology for preparing electronic materials, enabling densification at low temperature, but rarely employed for thermoelectrics. Herein, high-quality Ca_2.7Bi_0.3Co_3.92O_9+δ ceramics were synthesised by a combination of cold sintering and annealing processes. Stoichiometric mixtures of raw materials were calcined once or twice at 1203 K for 12 h in air, and then cold sintered at 673 K for 60 min under a pressure of 85 MPa, followed by annealing at 1203 K for 12 h or 24 h in air. The effects of the calcination processes and annealing conditions on the thermoelectric performance of cold sintered samples were investigated. By optimising heat-treatment, the formation of secondary phases, texture development and porosity were controlled, leading to enhanced electrical conductivity and reduced thermal conductivity. Consequently, at 800 K there was 85% increase in power factor and 35% increase in ZT (value of 0.15) compared to previous studies.     

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.     

Improved thermoelectric properties of n-type Bi2S3 via grain boundaries and in-situ nanoprecipitates

To improve the thermoelectric properties of n-type Bi₂S₃ materials, a certain amount of SbCl₃ were added into Bi₂S₃ materials by a conventional melting method combined with plasma activated sintering (PAS) process. The Bi₂S₃-based materials evolve from the lamellar- to particle-like structures after SbCl₃ doping. The phonon scattering has strong enhancement through the increased grain boundaries and in-situ Bi₂S₃ nanoprecipitates, resulting in the low lattice thermal conductivity. Meanwhile, the high power factor is achieved because of the marked increase in the electrical conductivity. Hence, the synergistic effect of antimony and chlorine substitutions not only contribute to reduce the thermal conductivity but also tune the electrical transport properties, yielding a peak ZT value of ∼ 0.65 at 773 K for the Bi₂S₃-1%SbCl₃ sample.     

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.     

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.     

Thermoelectric performance of Ni,Co, and Fe nanoparticles incorporated into their metal borates glassy matrices

Here, we present our current attempt to intrinsically dope Ni⁰, Co⁰, and Fe⁰ nanoparticles within Ni^II-, Co^II-, and Fe^II-borate glassy matrices, respectively. The system was prepared by one-pot reaction of the desired M_T^II salt with excess NaBH₄ through an in-situ reduction and hydrolysis processes to afford metallic M_T⁰ nanoparticles dispersed into the M_T-BO₃ matrix. The composition and structural characteristics of these M_T⁰:M_T-BO₃ materials were identified by thermal oxidation, ATR-IR, X-ray powder diffraction, and magnetic techniques as glassy/amorphous borate matrices containing magnetic nanoparticles. The electrical conductivity (σ) of cold-pressed discs of these metal-doped composites shows that they behave as nonohmic semiconductors within the temperature range of 303 ≤ T ≤ 373 K suggesting a mixed electronic-ionic conduction. However, their thermal conductivity (κ) occurs through phonon lattice vibration dynamics rather than electronic. The σ/κ ratio shows a steep non-linear increase from 9.4 to 270 KV⁻² in Ni⁰:Ni-BO₃. In contrast, a moderate-weak increase is observed for Co⁰:Co-BO₃ and Fe⁰:Fe-BO₃ analogs. The obtained materials are examined for thermoelectric (TE) applications by determining their Seebeck coefficient (S) power factor (PF), figure of merit (ZT), and conversion efficiency (η%). All the TE data shows that Ni⁰:Ni-BO₃ (S, 80 μVK⁻¹; PF, 97.7 mWm⁻¹ K⁻¹; ZT 0.54; η, 2.15%) is a better TE semiconductor than the other two M_T⁰:M_T-BO₃. This finding shows that Ni⁰:Ni-BO₃ is a promising candidate to exploit low-temperature waste heat from body heat, sunshine, and small domestic devices for small-scale TE applications.     

Improved thermoelectric properties of SiC with TiC segregated network structure

A TiC segregated network structure (SNS) approach was utilised to improve the thermoelectric properties of SiC. Different amounts of TiC particles were dry coated on SiC granules to form electrically conductive SNS; then the powder mixtures were spark plasma sintered at 2200°C. The TiC-SNS simultaneously increased the electrical and decreased thermal conductivity of SiC but adversely affected the Seebeck coefficient. By adding 10 vol% TiC, an ≈ 800% increase in electrical conductivity and a ≈ 50% decrease in thermal conductivity were achieved, but the Seebeck coefficient deteriorated due to the metallic nature of the material. A maximum ZT of 5.04 × 10⁻³ was achieved at 923 K, by limiting the Seebeck coefficient's reduction by optimising TiC content to 1.5 vol% while simultaneously increasing the electrical conductivity by ≈ 100% and reducing thermal conductivity by ≈ 40%. This ZT value is almost 90% higher than any value recorded in the literature for SiC.     

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.     

Enhancement of Thermoelectric Performance in Hierarchical Mesoscopic Oxide Composites of Ca3Co4O9 and La0.8Sr0.2CoO3

The natural contradiction in enhancing electrical conductivity and thermopower in thermoelectric oxides makes it hard to improve the performance of a single thermoelectric oxide material. We report a facile method to construct a unique architecture of thermoelectric oxides that is promising to realize a simultaneous improvement of overall electrical conductivity and thermopower. Here, a series of two‐phase nanocomposites comprising of Ca₃Co₄O₉ (CCO) and La_0.8Sr_0.2CoO₃ (LSCO) has been synthesized through ball milling followed by spark plasma sintering (SPS) method. The electron microscope images reveal that the two constituents form the unique composites while retaining their individual crystalline and morphological identities. Owing to the hierarchical mesoscopic structure with nanoscale particles and submicrometer scale grain boundaries, an external strain is induced into the CCO grains by the LSCO nanoparticles to enhance the thermopower. The mesoscopic structure is also favorable for improving the electrical conductivity. Moreover, the long‐wavelength phonons can be scattered effectively from LSCO nanoparticles and the thermal conductivity is further suppressed. With compromises between power factor and thermal conductivity, the largest ZT achieved is up to 0.41 at 1000 K for the composites with 25 wt% of LSCO.     

Enhanced Thermoelectric Properties of Bi2O2Se Ceramics by Bi Deficiencies

Polycrystalline Bi_2?xO₂Se ceramics were synthesized by spark plasma sintering process. Their thermoelectric properties were evaluated from 300 to 773 K. All the samples are layered structure with a tetragonal phase. The introduction of Bi deficiencies will cause the orientation alignment and change of effective mass. As a result, a significant enhancement of thermoelectric performance was achieved. The maximum of Seebeck coefficient is ?568.8 μV/K for Bi_1.9O₂Se at 773 K, much larger than ?445.6 μV/K for pristine Bi₂O₂Se. Featured with very low thermal conductivity [~0.6 W·(m·K)^?1] and an optimized electrical conductivity, ZT at 773 K is significantly increased from 0.05 for pristine Bi₂O₂Se to 0.12 for Bi_1.9O₂Se by introducing Bi deficiencies, which makes it a promising candidate for medium temperature thermoelectric applications.     

Electrical properties of (La0.9Ca0.1)(Co1−xNix)O3−δ cathode materials for SOFCs

Modified perovskite ceramics (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ (x = 0–0.3) cathodes for solid oxide fuel cells (SOFCs) were synthesized by solid state reaction. The lattice parameters, electrical conductivity, activation energy, and microstructures of these specimens were investigated systematically in this study. The results exhibited that all specimens are rhombohedron structures and their tolerance factors were greater than 0.97, indicating that the perovskite was not distorted by Ni²⁺ cation substitution for the B site of (La_0.9Ca_0.1)CoO_3?δ. The microstructures of the (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ specimens showed good densification, and were well-sintered, with few pores. The electrical conductivity behavior conformed to the nature of a semiconductor, for all specimens. As x = 0.1, the electrical conductivity reached the maximum value of 750.3 S/cm at 800 °C, and the activation energy calculated from the Arrhenius plot of the electrical conductivity versus the reciprocal of temperature is 7.1 kJ/mol.The novelty of this study is its introduction of the concept of defect chemistry to explain the relationship between compensation mechanisms and electrical conductivity. The information gleaned regarding charge compensation mechanisms and defect formation may be valuable for a better understanding of the cathode of (La_0.9Ca_0.1)(Co_1?xNi_x)O_3?δ ceramics used for SOFCs. Moreover, the information about oxygen content versus temperature is useful for expressing the relationship between electrical conductivity and composition. Therefore, we also used thermogravimetric analysis combined with the room-temperature oxygen content which was determined by iodometric titration to investigate the oxygen content from room temperature to high temperature, in air. Based on the experimental results, the (La_0.9Ca_0.1)(Co_0.9Ni_0.1)O_3?δ specimen shows high electrical conductivity. Consequently, it is identified as a promising candidate for cathode SOFC applications.