Facile fabrication of highly flexible,porous PEDOT: PSS/SWCNTs films for thermoelectric applications

High-performance organic composite thermoelectric(TE)materials are considered as a promising alternative for harvesting heat energy.Herein,composite films of poly(3,4-ethyienedioxythiophene):poly(styrene sulfonate)/single-walled carbon nanotubes(PEDOT:PSS/SWCNTs)were fabricated by utilizing a convenient solution mixing method.Thereafter,the as-prepared hybrid films were treated using sulfuric acid(H₂SO₄)to further optimize the TE performance.Film morphological studies revealed that the sulfuric acid treated PEDOT:PSS/SWCNTs composite samples all possessed porous structures.Due to the successful fabrication of highly conductive networks,the porous nano-architecture also exhibited much more excellent TE properties when compared with the dense structure of the pristine samples.For the post-treated sample,a high power factor of 156.43μW·m^-1·K^-2can be achieved by adjusting the content of CNTs,which is approximately 3 orders of magnitude higher than that of the corresponding untreated samples(0.23μW·m^-1·K^-2).Besides,the obtained films also showed excellent mechanical flexibility,owing to the porous nanostructure and the strong p–p interactions between the two components.This work indicates that the H₂SO₄ treatment could be a promising strategy for fabricating highly-flexible and porous PEDOT:PSS/SWCNTs films with high TE performances.     

Donor-acceptor conjugated copolymer with high thermoelectric performance: A case study of the oxidation process within chemical doping

The doping process and thermoelectric properties of donor-acceptor(D-A)type copolymers are investigated with the representative poly([2,6-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophenediyl))(PTB7-Th).The PTB7-Th is doped by Fe Cl;and only polarons are induced in its doped films.The results reveal that the electron-rich donor units within PTB7-Th lose electrons preferentially at the initial stage of the oxidation and then the acceptor units begin to be oxidized at a high doping concentration.The energy levels of polarons and the Fermi level of the doped PTB7-Th remain almost unchange with different doping levels.However,the morphology of the PTB7-Th films could be deteriorated as the doping levels are improved,which is one of the main reasons for the decrease of electrical conductivity at the later stage of doping.The best electrical conductivity and power factor are obtained to be 42.3 S·cm^-1;and 33.9μW·mK^-1,respectively,in the doped PTB7-Th film at room temperature.The power factor is further improved to 38.3μW·mK^-1;at 75℃.This work may provide meaningful experience for development of D-A type thermoelectric copolymers and may further improve the doping efficiency.     

双沟4H-SiC MESFET优化结构的解析模型及性能

优化双沟4H-SiC MESFET结构,通过求解一维和二维泊松方程,建立优化结构的解析模型,分析这种结构的直流和交流特性.结果表明,饱和电流密度的计算结果与实验一致,结构优化后4H-SiC MESFET的饱和电流密度和击穿电压分别为420μA·μm^-1和155 V,明显高于优化前的275μA·μm^-1和141 V;最高输出功率密度为7.4 W·mm^-1,比优化前提高约64%;截止频率和最高振荡频率比优化前略微提高.双沟结构经优化后其交流小信号特性未退化而功率特性获得明显改善.     

Thermoelectric characteristics of flexible reduced graphene oxide/silver selenide nanowire composites prepared by a facile vacuum filtration process

The reduced graphene oxide/silver selenide nanowire (rGO/Ag₂Se NW) composite powders were fabricated via a wet chemical approach, and then flexible rGO/Ag₂Se NW composite film was prepared by a facile vacuum filtration method combined with cold-pressing treatment. A highest power factor of 228.88 μW·m^-1·K^-2 was obtained at 331 K for the cold-pressed rGO/Ag₂Se NW composite film with 0.01 wt% rGO. The rGO/Ag₂Se NW composite film revealed superior flexibility as the power factor retained 94.62% after bending for 500 times with a bending radius of 4 mm, which might be due to the interwoven network structures of Ag₂Se NWs and pliability of rGO as well as nylon membrane. These results demonstrated that the GO/Ag₂Se NW composite film has a potential for preparation of flexible thermoelectric devices.     

Thermoelectric enhancement in triple-doped strontium titanate with multi-scale microstructure

Strontium titanate(SrTiO_3) is a thermoelectric material with large Seebeck coefficient that has potential applications in high-temperature power generators.To simultaneously achieve a low thermal conductivity and high electrical conductivity,polycrystalline SrTiO_3 with a multi-scale architecture was designed by the co-doping with lanthanum,cerium,and niobium.High-quality nano-powders were synthesized via a hydrothermal method.Nano-inclusions and a nano/microsized second phase precipitated during sintering to form mosaic crystal-like and epitaxial-like structures,which decreased the thermal conductivity.Substituting trivalent Ce and/or La with divalent Sr and substituting pentavalent Nb with tetravalent Ti enhanced the electrical conductivity without decreasing the Seebeck coefficient.By optimizing the dopant type and ratio,a low thermal conductivity of 2.77 W·m~(-1)·K~(-1) and high PF of 1.1 mW·m~(-1)·K~(-2) at 1000 K were obtained in the sample co-doped with 5-mol% La,5-mol% Ce,and 5-mol% Nb,which induced a large ZT of 0.38 at 1000 K.     

Ca2+掺杂对CdO多晶热电性能的影响

以CaCO₃作为Ca²⁺源, 利用传统固相烧结法制备了Cd_1-xCa_xO (x=0, 0.01, 0.03, 0.05) 多晶块体样品并研究了Ca²⁺掺杂对CdO高温热电性能的影响. CaCO₃的掺入会导致CdO多晶载流子浓度降低, 使Cd_1-xCa_xO的电阻率ρ和塞贝克系数的绝对值|S|增大、电子热导率κ_e减小. 同时, 在CdO中掺入CaCO₃会引入点缺陷和气孔并可抑制CdO晶粒长大、晶界增多, 从而增加了对声子的散射, 使样品的声子热导率κ_p减小. 由于总热导率的大幅降低, Cd_0.99Ca_0.01O多晶样品在1000 K时的热电优值ZT可达0.42, 比本征CdO提高了约27%, 为迄今n型氧化物热电材料报道的最好结果之一.     

微波低温制备Mg2Si0.4Sn0.6-yBiy热电材料的传输机理

德拜弛豫理论表明, 在频率为2.45 GHz的外加交变电磁场的作用下, 微波对极性分子的极化过程约为10^-10 s, 因此利用微波固相反应可以在短时低温条件下制备出纳米粉体材料. 本文以MgH₂代替Mg粉, 利用微波固相反应在低温下制备了Mg₂Si_0.4Sn_0.6-yBi_y (0 ≤y ≤q 0.03)固溶体, 并结合单带抛物线计算模型对其热电传输机理进行了分析. 研究结果表明: 利用该工艺可以有效抑制Mg的挥发和MgO 的生成, 在400 ℃保温15 min内即可完成MgH₂与Si粉和Sn粉的固相反应, 获得片层间距为100 nm的超细化学计量比产物; 杂质Bi的引入可以有效增加载流子浓度, 并引起晶格畸变, 在晶格畸变和样品特有的纳米片层结构的协同作用下, 声子得到有效散射, 样品具有最低的热导率1.36 W·m^-1·K^-1. 较低的有效掺杂率和复杂的能带结构具有降低能带态密度有效质量和减小载流子弛豫时间的双刃效应, 使得本征激发提前, 在600 K样品取得最大ZT值为0.66.     

Thermoelectric performance of XI2 (X = Ge,Sn, Pb) bilayers

We study the thermal and electronic transport properties as well as the thermoelectric (TE) performance of three two-dimensional (2D) XI₂ (X=Ge, Sn, Pb) bilayers using density functional theory and Boltzmann transport theory. We compared the lattice thermal conductivity, electrical conductivity, Seebeck coefficient, and dimensionless figure of merit (ZT) for the XI₂ monolayers and bilayers. Our results show that the lattice thermal conductivity at room temperature for the bilayers is as low as ~1.1 W·m^{-1·K-1-1.7 W}·m^{-1·K-1, which is about 1.6 times as large as the monolayers for all the three materials. Electronic structure calculations show that all the} XI₂ bilayers are indirect-gap semiconductors with the band gap values between 1.84 eV and 1.96 eV at PBE level, which is similar as the corresponding monolayers. The calculated results of ZT show that the bilayer structures display much less direction-dependent TE efficiency and have much larger n-type ZT values compared with the monolayers. The dramatic difference between the monolayer and bilayer indicates that the inter-layer interaction plays an important role in the TE performance of XI₂, which provides the tunability on their TE characteristics.     

聚乙烯单链量子热输运的同位素效应

高分子导热材料的有效调控受到了日益广泛的关注.应用密度泛函理论(DFT)、中央插入延展(central insertion scheme,CIS)方法及非平衡格林函数(NEGF)理论,对包含432个原子、长18.533 nm的聚乙烯单链量子热输运的同位素效应进行了研究.计算结果表明,室温下长100 nm的纯12C聚乙烯单链的热导率理论上限高达314.1 W·m~(-1)·K~(-1);对于~(12)C聚乙烯单链,其他条件一定时,~(14)C掺杂引起的热导同位素效应比~(13)C更为显著;室温下纯~(12)C聚乙烯单链中~(14)C掺杂原子百分数为50%时同位素效应最显著,此时平均热导比未掺杂时下降了51%.这对探索聚乙烯材料热输运的同位素影响机理具有十分积极的意义.     

Highly flexible and excellent performance continuous carbon nanotube fibrous thermoelectric modules for diversified applications

A highly flexible and continuous fibrous thermoelectric (TE) module with high-performance has been fabricated based on an ultra-long single-walled carbon nanotube fiber, which effectively avoids the drawbacks of traditional inorganic TE based modules. The maximum output power density of a 1-cm long fibrous TE module with 8 p-n pairs can reach to 3436 μW·cm^-2, the power per unit weight to 2034 μW·g^-1, at a steady-state temperature difference of 50 K. The continuous fibrous TE module is used to detect temperature change of a single point, which exhibits a good responsiveness and excellent stability. Because of its adjustability in length, the flexible fibrous TE module can satisfy the transformation of the temperature difference between two distant heat sources into electrical energy. Based on the signal of the as-fabricated TE module, a multi-region recognizer has been designed and demonstrated. The highly flexible and continuous fibrous TE module with excellent performance shows a great potential in diversified applications of TE generation, temperature detection, and position identification.     

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.     

In situ formed FeS2@CoS cathode for long cycling life lithium-ion battery

Pyrite FeS₂ exhibits an ultrahigh energy density (1671 W·h·kg^-1, for the reaction of FeS₂+4Li=Fe+2Li₂S) in secondary lithium-ion batteries, but its poor cycling stability, huge volume expansion, the shuttle effect of polysulfides, and slow kinetic properties limit its practical application. In this work, we synthesize a composite structure material CoS on FeS₂ surface (FeS_x@CoS, 1 < x ≤ 2) by using a cobalt-containing MOF to improve its cycle stability. It is found that CoS inhibits the side reactions and adsorbs polysulfides. As a result, the modified FeS₂ shows a higher discharge capacity of 577 mA·h·g^-1 (919 W·h·kg^-1) after 60 cycles than 484 mA·h·g^-1 (778 W·h·kg^-1) of bare pyrite FeS₂. This efficient strategy provides a valuable step toward the realization of high cycling stability FeS₂ cathode materials for secondary lithium-ion batteries and enriches the basic understanding of the influence of FeS₂ interfacial stability on its electrochemical performances.     

High-responsivity solar-blind photodetector based on MOCVD-grown Si-doped β-Ga_2O_3 thin film

Si-doped β-Ga_2O_3 films are fabricated through metal-organic chemical vapor deposition(MOCVD). Solar-blind ultraviolet(UV) photodetector(PD) based on the films is fabricated by standard photolithography, and the photodetection properties are investigated. The results show that the photocurrent increases to 11.2 m A under 200 μW·cm-2254 nm illumination and ±20 V bias, leading to photo-responsivity as high as 788 A·W~(-1). The Si-doped β-Ga_2O_3-based PD is promised to perform solar-blind photodetection with high performance.     

高能电子辐射下聚四氟乙烯深层充电特性

介质深层充放电现象是诱发航天器异常故障的重要因素之一.分析了高能电子辐射下介质内部电荷沉积、能量沉积特性和电导特性,考虑了真空与介质界面电荷对电场分布的影响,建立了介质二维深层充电的物理模型,并基于有限元方法实现了数值计算.计算了高能电子辐射下聚四氟乙烯的深层充电特性.结果表明:真空环境下,介质的表面存在较弱的反向电场,随着介质深度增大,电场减小至零,随后逐渐增大,最大值出现在靠近接地附近,但在接地点,电场存在小幅降低.分析了不同辐射时间下(1 h,1 d,10 d和30 d),介质内部最大电位和最大电场的时空演变特性.随着辐射时间的增加,最大电位由-128V增加至-7.9×104V,最大电场由2.83×105V·m-1增加至1.76×108V·m-1.讨论了入射电子束流密度对最大电场的影响,典型空间电子环境(1×10-10A·m-2)下,电子辐照10 d时,介质内部最大电场为2.95×106V·m-1.而恶劣空间电子环境(2×10-8A·m-2)下,电子辐射42 h,介质内部最大电场即达到108V·m-1,超过材料击穿阈值(约为108V·m-1),极易发生放电现象.该物理模型和数值方法可以作为航天器复杂部件多维电场仿真的研究基础.     

Anisotropic thermoelectric transport properties in polycrystalline SnSe_2

It is reported that SnSe_2 consisting of the same elements as SnSe, is a new promising thermoelectric material with advantageous layered structure. In this work, the thermoelectric performance of polycrystalline SnSe_2 is improved through introducing SnSe phase and electron doping(Cl doped in Se sites). The anisotropic transport properties of SnSe_2 are investigated. A great reduction of the thermal conductivity is achieved in SnSe_2 through introducing SnSe phase, which mainly results from the strong SnSe_2–SnSe inter-phase scattering. Then the carrier concentration is optimized via Cl doping, leading to a great enhancement of the electrical transport properties, thus an extraordinary power factor of ～5.12 μW·cm~(-1)·K~(-2) is achieved along the direction parallel to the spark plasma sintering(SPS) pressure direction( P). Through the comprehensive consideration on the anisotropic thermoelectric transport properties, an enhanced figure of merit ZT is attained and reaches to ～ 0.6 at 773 K in SnSe_2-2% SnSe after 5% Cl doping along the P direction, which is much higher than ～ 0.13 and ～ 0.09 obtained in SnSe_2-2% SnSe and pristine SnSe_2 samples, respectively.     

Synthesis and thermoelectric properties of Bi-doped SnSe thin films

Bi doped n-type SnSe thin films were prepared by chemical vapor deposition (CVD) and their structure and thermoelectric properties were studied. The x-ray diffraction patterns, x-ray photoelectron spectroscopy, and microscopic images show that the prepared SnSe thin films were composed of pure SnSe crystals. The Seebeck coefficients of the Bi-doped SnSe were greatly improved compared to that of undoped SnSe thin films. Specifically, Sn_0.99Bi_0.01Se thin film exhibited a Seebeck coefficient of -905.8μV·K^-1 at 600 K, much higher than 285.5 μV·K^-1 of undoped SnSe thin film. Further first-principles calculations reveal that the enhancement of the thermoelectric properties can be explained mainly by the Fermi level lifting and the carrier pockets increasing near the Fermi level due to Bi doping in the SnSe samples. Our results suggest the potentials of the Bi-doped SnSe thin films in thermoelectric applications.     

TPV系统热辐射发电模块数值分析

建立TPV系统热辐射发电模块的数理模型,通过数值模拟获得SiC辐射器分别配合GaSb和Si电池所构成的TPV系统的输出伏安特性曲线;以GaSb电池为例,分别分析SiC辐射器温度和电池温度对系统性能的影响,得出如下结论:辐射器温度升高,系统输出电能密度迅速增大,电池效率稳步提高,辐射器温度从1400 K升至1900 K,系统输出电能密度从0.67 W·cm^-2增至5.43 W·cm^-2,电池效率从16.3%上升到24.8%;电池温度升高导致系统性能下降,电池温度每升高10 K,系统输出电能密度减少约0.15 W·cm^-2,电池效率也大幅下降.最后讨论与GaSb匹配的一种选择性辐射器的辐射能量分布情况,与SiC辐射器相比,选择性辐射器可以显著减少辐射能量中的不可用部分,从而有效提高系统的性能与稳定性.     

势能模型对石墨烯导热性质分子动力学模拟的影响

针对常用的Tersoff势、Rebo势和Airebo势,系统性地分析势能模型对分子动力学模拟计算石墨烯色散关系、声子态密度、群速度和热导率的影响. 结果表明：Rebo势和Airebo势描述的声子色散关系接近实验值,Airebo势对应的声子态密度与第一性原理计算的结果较为符合,Rebo势和Airebo势计算的Γ点处声子群速度高于Tersoff势. 采用Airebo势得到石墨烯热导率约为1 150 W·（m·K）^-1,与实验值相近. 综合各种影响,相比于Tersoff势和Rebo势,Airebo势能模型更适合计算石墨烯的导热性质.     

等离子体密度对激光拉曼放大机理的影响

等离子体中的背向拉曼散射机理可以用来产生超短超强的激光脉冲. 本文采用粒子模拟方法模拟研究了等离子体密度对激光拉曼放大过程的影响. 研究发现, 过低的等离子体密度会导致等离子体波提前波破而降低能量转换效率; 而过高的等离子体密度又会导致其他不稳定性的快速增长, 限制作用距离和输出能量. 因此, 拉曼放大机理的最佳等离子体密度应处于等离子体波破的密度阈值附近, 可以获得最高的能量转换效率和能量输出. 另外, 空间频谱分析显示放大激光的强度饱和主要来自于自相位调制不稳定性的发展. 利用10¹³ W·cm^-2的抽运激光脉冲, 模拟证实拉曼放大机理可有效地将种子激光的强度从10¹³ W·cm^-2 放大到10¹⁷ W·cm^-2, 脉宽压缩到40 fs, 且能量转换效率达到58%.     

Dense pair plasma generation by two laser pulses colliding in a cylinder channel

An all-optical scheme for high-density pair plasmas generation is proposed by two laser pulses colliding in a cylinder channel. Two dimensional particle-in-cell simulations show that, when the first laser pulse propagates in the cylinder,electrons are extracted out of the cylinder inner wall and accelerated to high energies. These energetic electrons later run into the second counter-propagating laser pulse, radiating a large amount of high-energy gamma photons via the Compton back-scattering process. The emitted gamma photons then collide with the second laser pulse to initiate the Breit–Wheeler process for pairs production. Due to the strong self-generated fields in the cylinder, positrons are confined in the channel to form dense pair plasmas. Totally, the maximum density of pair plasmas can be 4.60 × 10~(27)m~(-3), for lasers with an intensity of 4×10~(22)W·cm~(-2). Both the positron yield and density are tunable by changing the cylinder radius and the laser parameters. The generated dense pair plasmas can further facilitate investigations related to astrophysics and particle physics.