Significant role of nanoscale Bi-rich phase in optimizing thermoelectric performance of Mg_3Sb_2

Mg_3Sb_(1.5)Bi_(0.5)-based alloys have received much attention, and current reports on this system mainly focus on the modulation of doping. However, there lacks the explanation for the choice of Mg_3Sb_(1.5)Bi_(0.5) as matrix. Here in this work,the thermoelectric properties of Mg_3Sb_(2-x)Bi_x(0.4 ≤ x ≤ 0.55) compounds are systematically investigated by using the first principles calculation combined with experiment. The calculated results show that the band gap decreases after Bi has been substituted for Sb site, which makes the thermal activation easier. The maximum figure of merit(ZT) is 0.27 at 773 K,which is attributed to the ultra-low thermal conductivity 0.53 W·m~(-1)·K~(-1) for x = 0.5. The large mass difference between Bi and Sb atoms, the lattice distortion induced by substituting Bi for Sb, and the nanoscale Bi-rich particles distributed on the matrix are responsible for the reduction of thermal conductivity. The introduction of Bi into Mg_3Sb_2-based materials plays a vital role in regulating the transport performance of thermoelectric materials.     

Enhanced thermoelectric performance through homogenously dispersed MnTe nanoparticles in p-type Bi_(0.52)Sb_(1.48)Te_3 nanocomposites

In this work,we report that the thermoelectric properties of Bi_(0.52)Sb_(1.48)Te_3alloy can be enhanced by being composited with Mn Te nano particles(NPs)through a combined ball milling and spark plasma sintering(SPS)process.The addition of Mn Te into the host can synergistically reduce the lattice thermal conductivity by increasing the interface phononscattering between Bi_(0.52)Sb_(1.48)Te_3 and MnTe NPs,and enhance the electrical transport properties by optimizing the hole concentration through partial Mn~(2+)acceptor doping on the Bi~(3+)sites of the host lattice.It is observed that the lattice thermal conductivity decreases with increasing the percentage of Mn Te and milling time in a temperature range from 300 Kto 500 K,which is consistent with the increasing of interfaces.Meanwhile,the bipolar effect is constrained to high temperatures,which results in the figure of merit z T peak shifting toward higher temperature and broadening the z T curves.The engineering z T is obtained to be 20%higher than that of the pristine sample for the 2-mol%Mn Te-added composite at a temperature gradient of 200 K when the cold end temperature is set to be 300 K.This result indicates that the thermoelectric performance of Bi_(0.52)Sb_(1.48)Te_3 can be considerably enhanced by being composited with Mn Te NPs.     

Improved thermoelectric performance in p-type Bi_(0.48)Sb_(1.52)Te_3 bulk material by adding MnSb_2Se_4

Bismuth telluride(Bi_2Te_3) based alloys, such as p-type Bi_(0.5)Sb_(1.5)Te_3, have been leading candidates for near room temperature thermoelectric applications. In this study, Bi_(0.48)Sb_(1.52)Te_3 bulk materials with MnSb_2Se_4 were prepared using high-energy ball milling and spark plasma sintering(SPS) process. The addition of MnSb_2Se_4 to Bi_(0.48)Sb_(1.52)Te_3 increased the hole concentration while slightly decreasing the Seebeck coefficient, thus optimising the electrical transport properties of the bulk material. In addition, the second phases of MnSb_2Se_4 and Bi_(0.48)Sb_(1.52)Te_3 were observed in the Bi_(0.48)Sb_(1.52)Te_3 matrix. The nanoparticles in the semi-coherent second phase of MnSb_2Se_4 behaved as scattering centres for phonons,yielding a reduction in the lattice thermal conductivity. Substantial enhancement of the figure of merit, ZT, has been achieved for Bi_(0.48)Sb_(1.52)Te_3 by adding an Mn_(0.8)Cu_(0.2)Sb_2Se_4(2mol%) sample, for a wide range of temperatures, with a peak value of 1.43 at 375 K, corresponding to ~40% improvement over its Bi_(0.48)Sb_(1.52)Te_3 counterpart. Such enhancement of the thermoelectric(TE) performance of p-type Bi_2Te_3 based materials is believed to be advantageous for practical applications.     

Enhanced rate performance of lithium titanium oxide anode material by bromine doping

Br-doped lithium titanium oxide (Li₄Ti₅O₁₂) particles in the form of Li₄Ti₅Br _x O_12-x (x?=?0, 0.1, 0.2, 0.3, 0.4) are synthesized via a simple liquid deposition reaction, followed by a high-temperature treatment. The effects of bromine (Br) doping on the structures and electrochemical properties of Li₄Ti₅O₁₂ are extensively studied. It is found that Br atoms can enter the lattice structure and enlarge the lattice parameters of Li₄Ti₅O₁₂. Although Br doping has not changed the phase composition, obvious effects on the particle’s morphology and size have been observed. Electrochemical test results indicate that the rate capability of Li₄Ti₅O₁₂ has been evidently improved by Br doping at an appropriate concentration. The as-synthesized Li₄Ti₅O_11.8Br_0.2 electrode presents much higher discharge capacity and better cycle stability than that of the other electrodes. The greatly enhanced electrochemical performance of Li₄Ti₅O_11.8Br_0.2 may be attributed to the improved dispersion of nanoparticles and increased electrical conductivity.     

Enhanced thermoelectric performance of PEDOT: PSS films via ionic liquid post-treatment

Thermoelectric(TE)energy harvesting can effectively convert waste heat into electricity,which is a crucial technology to solve energy concerns.As a promising candidate for energy conversion,poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)has gained significant attention owing to its easy doping,high transparency,and solution processability.However,the TE performance of PEDOT:PSS still needs to be further enhanced.Herein,different approaches have been applied for tuning the TE properties:(i)direct dipping PEDOT:PSS thin films in ionic liquid;(ii)post-treatment of the films with concentrated sulfuric acid(H₂SO₄),and then dipping in ionic liquid.Besides,the same bis(trifluoromethanesulfonyl)amide(TFSI)anion and different cation salts,including 1-ethyl-3-methylimidazolium(EMIM+)and lithium(Li+),are selected to study the influence of varying cation types on the TE properties of PEDOT:PSS.The Seebeck coefficient and electrical conductivity of the PEDOT:PSS film treated with H2SO4EMIM:TFSI increase simultaneously,and the resulting maximum power factor is 46.7μW·m^-1·K^-2,which may be attributed to the ionic liquid facilitating the rearrangement of the molecular chain of PEDOT.The work provides a reference for the development of organic films with high TE properties.     

Sb_2Te_3热电薄膜的离子束溅射制备与表征

采用离子束溅射技术交替沉积Sb-Te-Sb多层薄膜后进行高真空热处理,直接制备Sb2Te3薄膜.利用X射线衍射(XRD)仪、霍尔系数测试仪、薄膜Seebeck系数测量系统对所制备的薄膜特性进行表征.XRD测量结果显示,薄膜的主要衍射峰与Sb2Te3标准衍射峰相同,在[101]/[012]晶向取向明显,存在较多的Te杂质峰;霍尔系数测试结果表明,薄膜为p型半导体薄膜,薄膜电阻率较低,其电导率接近于金属电导率,载流子浓度量级为1023cm-3,具有良好的电学性能;Seebeck系数测量结果显示,薄膜具有良好的热电性能,在不同条件下制备的薄膜的Seebeck系数在7.8—62μV/K范围;在所制备的薄膜中,退火时间为6h、退火温度为200℃的薄膜其Seebeck系数达到最大,约为62μV/K,且电阻率最小.     

Optimize the thermoelectric performance of CdO ceramics by doping Zn

The thermoelectric performance of CdO ceramics was enhanced by simultaneously optimizing the electrical and thermal transport properties via a small amount of Zn doping(≤3%). The introduction of Zn can obviously increase the electrical conductivity of CdO due to the simultaneous increase of carrier concentration and mobility, and eventually results in an improvement in power factor. Zn doping is also effective in suppressing the thermal conductivity of CdO because of stronger phonon scatterings from point defects, Zn-riched second phase, and grain boundaries. A best ZT of about 0.45 has been achieved in the Cd_(1-x)Zn_xO systems at about 1000 K, which is comparable to the highest values reported for other n-type oxide TE materials.     

Enhanced thermoelectric performance of P-type Sb2Te3 thin films through organic-inorganic hybridization on flexible substrate

In this work, a new idea of organic-inorganic hybridization was proposed to fabricate flexible p-type - Sb₂Te₃/CH₃NH₃I thin films. The CH₃NH₃I has a strong adsorption which can promote the growth of organic molecules, improve the crystallization, and finally increase electrical conductivity. Post-annealing of the fabricated films increased the phonon scattering, thus resulting in a reduction of thermal conductivity and an increased ZT value. The annealed hybrid-composite film showed a significant enhancement in thermoelectric performance, with a maximum ZT value of 0.94 at a temperature of 413 K, which is twice as large as that of the as-deposited film.     

Enhanced thermoelectric performance of TiO_2-based hybrid materials by incorporating conducting polymer

In order to study the thermoelectric properties of TiO2-based hybrid materials, TiO2/polyparaphenylene(PPP)nanocomposites are fabricated by spark plasma sintering(SPS). The results show that the electrical conductivity follow percolation theory is enhanced due to the electron transfer highway provided by the conducting PPP phase. Furthermore,the thermal conductivity is reduced due to the drastic difference of vibrational spectra between organic and inorganic components. As a result, the greatest ZT= 0.24 is obtained for Ti O2/0.75 wt% PPP sample, which is 15-fold higher than pure Ti O2(ZT= 0.016).     

Excellent thermoelectric performance in weak-coupling molecular junctions with electrode doping and electrochemical gating

Excellent thermoelectric performance in molecular junctions requires a high power factor, a low thermal conductance, and a maximum figure of merit(ZT) near the Fermi level. In the present work, we used density functional theory in combination with a nonequilibrium Green's function to investigate the thermoelectric performance of carbon chain-graphene junctions with both strong-coupling and weak-coupling contact between the electrodes and the molecules. The results revealed that a room temperature ZT of 4 could be obtained for the weak-coupling molecular junction, approximately one order of magnitude higher than that reached by the strong-coupling junction. The reason for this is that strong interfacial scattering suppresses most of the phonon modes in weak-coupling systems, resulting in ultralow phonon thermal conductance. The influence of electrode width,electrode doping, and electrochemical gating on the thermoelectric performance of the weak-coupling system was also investigated, and the results revealed that an excellent thermoelectric performance can be obtained near the Fermi level.     

First principle investigation of the electronic and thermoelectric properties of Mg_2C

In this paper, electronic and thermoelectric properties of Mg_2C are investigated by using first principle pseudo potential method based on density functional theory and Boltzmann transport equations. We calculate the lattice parameters,bulk modulus, band gap and thermoelectric properties(Seebeck coefficient, electrical conductivity, and thermal conductivity) of this material at different temperatures and compare them with available experimental and other theoretical data. The calculations show that Mg_2C is indirect band semiconductor with a band gap of 0.75 eV. The negative value of Seebeck coefficient shows that the conduction is due to electrons. The electrical conductivity decreases with temperature and Power factor(PF) increases with temperature. The thermoelectric properties of Mg_2C have been calculated in a temperature range of 100 K–1200 K.     

Enhanced thermoelectric properties of p-type polycrystalline SnSe by regulating the anisotropic crystal growth and Sn vacancy

Thermoelectric selenides have attracted more and more attentions recently.Herein,p-type Sn Se polycrystalline bulk materials with good thermoelectric properties are presented.By using the SnSe_2 nanostructures synthesized via a wetchemistry route as the precursor,polycrystalline Sn Se bulk materials were successfully obtained by a combined heattreating process under reducing atmosphere and following spark plasma sintering procedure.As a reference,the Sn Se nanostructures synthesized via a wet-chemistry route were also fabricated into polycrystalline bulk materials through the same process.The thermoelectric properties of the Sn Se polycrystalline transformed from SnSe_2 nanostructures indicate that the increasing of heattreating temperature could effectively decrease the electrical resistivity,whereas the decrease in Seebeck coefficient is nearly invisible.As a result,the maximum power factor is enhanced from 5.06×10~(-4)W/m·K~2to 8.08×10~(-4)W/m·K~2at 612~?C.On the other hand,the reference sample,which was obtained by using Sn Se nanostructures as the precursor,displays very poor power factor of only 1.30×10~(-4)W/m·K~2at 537~?C.The x-ray diffraction(XRD),scanning electron microscope(SEM),x-ray fluorescence(XRF),and Hall effect characterizations suggest that the anisotropic crystal growth and existing Sn vacancy might be responsible for the enhanced electrical transport in the polycrystalline Sn Se prepared by using SnSe_2 precursor.On the other hand,the impact of heat-treating temperature on thermal conductivity is not obvious.Owing to the boosting of power factor,a high z T value of 1.07 at 612~?C is achieved.This study provides a new method to synthesize polycrystalline Sn Se and pave a way to improve the thermoelectric properties of polycrystalline bulk materials with similar layered structure.     

Ga掺杂对Cu_3SbSe_4热电性能的影响

采用熔融-淬火方法制备了Cu_(2.95)Ga_xSb_(1-x)Se_4(x=0,0.01,0.02和0.04)样品,系统地研究了Ga在Sb位掺杂对Cu_3SbSe_4热电性能的影响.研究结果表明,少量的Ga掺杂(x=0.01)可以有效提高空穴浓度,抑制本征激发,改善样品的电输运性能.掺Ga样品在625 K时功率因子达到最大值10μW/cm·K~2,比未掺Ga的Cu_(2.95)SbSe_4样品提高了约一倍.但是随着Ga掺杂浓度的进一步提高,缺陷对载流子的散射增强,同时载流子有效质量增大,导致载流子迁移率急剧下降.因此Ga含量增加反而使样品的电性能恶化.在热输运方面,Ga掺杂可以有效降低双极扩散对热导率的贡献,同时掺杂引入的点缺陷对高频声子有较强的散射作用,因此高温区的热导率明显降低.最终该体系在664 K时获得最大ZT值0.53,比未掺Ga的样品提高了近50%.     

Enhanced thermoelectric performance of spark plasma sintered copper-deficient nanostructured copper selenide

We report the thermoelectric properties of nanostructured Cu-deficient Cu₂Se, which was synthesized by high energy ball milling followed by spark plasma sintering. Our method obtained a significant enhancement in the thermoelectric figure of merit (ZT), i.e., ~1.4 at 973 K, which was ~30% higher than its bulk counterpart. This enhancement in the thermoelectric performance was due mainly to a significant reduction in the lattice thermal conductivity, which was attributed to enhanced phonon scattering at various length scales by nanoscale defects as well as abundant nanograin boundaries. The nanoscale defects were characterized by transmission electron microscopy of the nanostructured Cu_2−xSe samples, which formed the basis of the ZT enhancement.     

Resonant enhancement in nanostructured thermoelectric performance via electronic thermal conductivity engineering

The use of an asymmetric broadening in the transport distribution, a characteristic of resonant structures, is proposed as a route to engineer a decrease in electronic thermal conductivity thereby enhancing the electronic figure of merit in nanostructured thermoelectrics. Using toy models, we first demonstrate that a decrease in thermal conductivity resulting from such an asymmetric broadening may indeed lead to an electronic figure of merit well in excess of 1000 in an idealized situation and in excess of 10 in a realistic situation. We then substantiate with realistic resonant structures designed using graphene nano-ribbons by employing a tight binding framework with edge correction that match density functional theory calculations under the local density approximation. The calculated figure of merit exceeding 10 in such realistic structures further reinforces the concept and sets a promising direction to use nano-ribbon structures to engineer a favorable decrease in the electronic thermal conductivity.     

Control of ferromagnetism via electron doping in In2O3:Cr

Carrier-induced ferromagnetism in wide-gap transparent conductive oxides has been widely discussed and debated, leading to confusion and skepticism regarding whether dilute magnetic oxides exist at all. We show from density-functional calculations within a band-gap corrected approach that ferromagnetic Cr-Cr coupling can be switched on and off via electron doping in the wide-gap transparent n-type conductive oxide In2O3. We show that (i) Cr does not produce in In2O3 any free electrons and renders the system an insulating paramagnet. (ii) Extrinsic n-type doping of In2O3:Cr via Sn produces free electrons, whose concentration is controllable via the oxygen partial pressure. Such additional carriers stabilize a strong long-range Cr-Cr ferromagnetic coupling.     

制备工艺对p型碲化铋基合金热电性能的影响

利用区熔法、机械合金化、放电等离子烧结(SPS)技术、热压法等多种工艺制备了p型碲化铋基热电材料.在300—500K的温度范围内测量了各热电性能参数，包括电导率(σ)、塞贝克系数(α)和热导率(κ)，研究了制备工艺对热电性能的影响.结果表明，所制备的块体材料与同组成区熔晶体相比，性能优值ZT均有不同程度的提高.其中，利用区熔法结合SPS技术可获得热电性能最佳的块体材料，其ZT值达1.15. 关键词： 碲化铋 放电等离子烧结 区熔法 热电性能     

Improving the thermoelectric properties of thick Sb2Te3 film via Cu doping and annealing deposited by DC magnetron sputtering using a mosaic target

Thick Cu-doped Sb₂Te₃ films were deposited on flexible substrate by DC magnetron sputtering from a mosaic Cu–Sb₂Te₃ target. The Cu-doped Sb₂Te₃ films were vacuum annealed to improve their thermoelectric properties. Density functional theory was used to clarify the internal mechanism of the Cu doped into the Sb₂Te₃ system. The results showed that Cu substitution on a Sb site induced electronic states or impurity peaks of Sb₂Te₃ at a valence band maximum. The carrier concentration of the Cu-doped Sb₂Te₃ films increased as the Cu-doped concentration increased. However, the crystallite size and Seebeck coefficient of the Cu-doped Sb₂Te₃ films decreased as the Cu-doped concentration increased. Post-annealing treatment improved the microstructure and thermoelectric properties of the Cu-doped Sb₂Te₃ films. The maximum electrical conductivity and power factor values of 754.20 S/cm at 50 °C and 1.56 10⁻³ W/mK² at 100 °C were obtained in the annealed film with a Cu-doped concentration of 3 at%.     

Enhanced electrochemical properties of LiMnPO4/C via doping with Cu

Li_0.98Cu_0.01MnPO₄/C composite cathode materials for lithium ion battery are synthesized by sol-gel method followed by heat treatment in the air. Field-emission scanning electron microscopy measurements show that both firing temperature and carbon content affect the morphology of the end products. X-ray powder diffraction analysis indicates that the samples are olivine-structured. The galvanostatic charge?Cdischarge results show that the optimal firing temperature registers 500°C and that the electrochemical performances of Li_0.98Cu_0.01MnPO₄/C are improved by elevating its carbon amount. The cyclic ability and rate performances of LiMnPO₄ are greatly improved by doping Cu.