导电聚合物热电材料研究进展

导电聚合物在室温下具有较高的电导率(σ)、较低的热导率(κ)、柔韧性好、易于合成、原料来源丰富、对环境无污染等优势,是目前最具有热电应用潜力的有机热电材料之一。然而,目前针对导电聚合物作为有机热电材料的相关研究依然处于初级阶段,其在空气气氛中的化学稳定性问题、低的热电优值及尚未完全明确的热电机制一直困扰着研究人员。本文主要针对以上问题,在对前人的研究成果进行综述的基础上对目前有机热电材料所面临的关键问题进行阐述和总结。     

Thermal transporting properties of electrically conductive polyaniline films as organic thermoelectric materials

Thermal transporting properties of electrically conductive polyaniline films were first investigated in wide range of temperatures above room temperature as organic thermoelectric materials. Thermal conductivities of various protonic acid-doped polyaniline films were measured by combination of a laser flash method and a differential scanning calorimeter in relation with electrical conductivity and a kind of dopant. The thermal conductivities thus measured are in the range of conventional organic polymers, indicating that the doped polyaniline films have extremely low thermal conductivities among electrically conductive materials, and have correlation with neither electrical conductivity, nor a kind of dopant. Consequently the polyaniline film, which shows very high electrical conductivity, has comparable thermoelectric figure-of-merit (ZT) with feasible inorganic thermoelectric materials such as iron silicide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Chitosan Bio‐Based Organic–Inorganic Hybrid Aerogel Microspheres

Recently, organic–inorganic hybrid materials have attracted tremendous attention thanks to their outstanding properties, their efficiency, versatility and their promising applications in a broad range of areas at the interface of chemistry and biology. This article deals with a new family of surface‐reactive organic–inorganic hybrid materials built from chitosan microspheres. The gelation of chitosan (a renewable amino carbohydrate obtained by deacetylation of chitin) by pH inversion affords highly dispersed fibrillar networks shaped as self‐standing microspheres. Nanocasting of sol–gel processable monomeric alkoxides inside these natural hydrocolloids and their subsequent CO₂ supercritical drying provide high‐surface‐area organic–inorganic hybrid materials. Examples including chitosan–SiO₂, chitosan–TiO₂, chitosan–redox‐clusters and chitosan–clay‐aerogel microspheres are described and discussed on the basis of their textural and structural properties, thermal and chemical stability and their performance in catalysis and adsorption.     

Electrochemistry of Electrode Materials Containing S−Se Bonds for Rechargeable Batteries

Sulfur (S) and selenium (Se) have been considered as promising high capacity cathode materials for rechargeable batteries. They have differences in their physical properties (e.g., electronic conductivity) but the same number of electrons in their outermost shells, which leads to similarity in their electrochemical behavior in batteries. In recent years, some efforts have been taken to combine them in electrodes in the hope of improved battery performance. The S−Se bonds of these electrode materials lead to unusual properties and intriguing electrochemical behavior, which have attracted increasing interest. In this Minireview, electrode materials containing S−Se bonds are summarized, including inorganic S_xSe_y solid solutions, organic compounds, and organic–inorganic hybrid materials. Our understanding in these materials is still premature, but they have shown unique properties to be electrode materials. We hope this Minireview could provide a new insight into the design, synthesis, and understanding of these materials, which could enable high energy density rechargeable batteries.     

导电高分子及其纳米复合材料的热电性质

与无机热电材料相比, 有机热电材料具有资源丰富、 成本低、 质量轻、 柔韧性好及热导率低等优点, 成为热电研究领域关注的热点. 理论和实验结果表明, 低维化和小尺度化是热电材料研究和开发的发展方向. 本文对低维有机热电材料的合成、 器件组装及热电性质的影响因素等进行简要评述, 并对低维有机热电材料的研究方向进行了讨论.     

Research progress on hybrid organic–inorganic perovskites for photo-applications

Hybrid organic–inorganic perovskite materials have attracted significant attention of most researchers in recently years, which is ascribed to the superior photoelectric properties, such as the suitable band gaps for harvesting sunlight, and exhibit high optical adsorption, high charge-carrier lifetimes and long diffusion lengths. The photodetectors, light-emitting diodes, solar cells and photocatalysts represent the remarkable applications for the hybrid organic–inorganic perovskite materials. Herein, we review the recent progress of hybrid organic–inorganic perovskite-based photodetectors, light-emitting diodes, solar cells and photocatalysts. The challenges and outlook for the hybrid organic–inorganic perovskite-based photodetectors, light-emitting diodes, solar cells and photocatalysts are considered.     

Point Defect Engineering Boosting the Thermoelectric Properties of Layered 122 Zintl Compounds

The layered 122 Zintl compounds have become an intriguing class of thermoelectric materials due to the promising electronic transport properties and inherently low thermal conductivity, showing the typical characteristics of "phonon-glass electron-crystal". Owing to the unprecedented performance tunability, the thermoelectric properties of the layered-structure compounds are completive with some traditional thermoelectric materials. Point defects involving vacancy, aliovalent doping and equivalent alloying atoms have been introduced to further enhance the thermoelectric properties. This review emphasizes the effects of various point defects on the thermoelectric parameters, and provides perspective on the strategies for increasing the thermoelectric figure of merit zT, which are believed to be applicable for improving the thermoelectric properties of many other compounds.     

聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸盐热电性能的 提升策略研究进展

近十年,有机聚合物及其复合热电材料与柔性器件取得了显著进展,在废热回收利用、可穿戴电子学、软体机器人和物联网等领域有广泛的应用.其中,聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)是迄今研究最多也是性能最高的聚合物体系.本文对近年来有关PEDOT:PSS热电性能有效提升主要策略的文献报道进行了总结.首先,从PEDOT:PSS的二次掺杂/去掺杂、酸或碱处理和离子液体处理方面等,重点论述了掺杂/去掺杂策略的研究进展;然后,分别从改善聚集态结构、构筑PEDOT微纳米结构和与碳纳米材料复合等3个方面,重点介绍了采用此3种策略提升PEDOT:PSS热电性能的研究进展;最后,对该领域进行总结,提出了开展进一步研究的建议,并对其未来发展前景进行展望.     

Effect of variation of metal and non-metal elements on various properties of rare-earth-based inverse perovskites Gd3XY (X = Ga,In and Y = B,N)

Ferromagnetic rare-earth-based inverse perovskites Gd₃AlX (X = B, N) are studied using hybrid functionals in the framework of density functional theory. Different exchange correlation potentials are employed to analyze the structural parameters and geometry of the materials. The spin polarization and band structure explain the metallic behavior of these materials with high values of magnetic moment. The calculated elastic constants specify all materials are ordered perovskite compounds, among which Gd₃GaB, Gd₃GaN, Gd₃InN are brittle in nature while as Gd₃InB is ductile in nature. The quasi-harmonic Debye model was used to predict the thermodynamic properties of the material. The analysis of thermoelectric properties viz. Seebeck coefficient, electronic and thermal conductivities at higher temperature has been carried out. To check the optoelectronic response of the material various optical properties have been calculated up to 14 eV photon energy range. The competent thermoelectric and optoelectronic properties with high value of magnetic moment and ductile character suggests the application in thermoelectric and electro-optic devices.     

ZnO纳米线基MWNTs/PVDF复合热电材料的制备及特性研究

将不同比例的多壁碳管(MWNTs)与聚偏二氟乙烯(PVDF)聚合物混合后,喷涂于n型ZnO半导体纳米线阵列上,制备了一种新型ZnO纳米线基MWNTs/PVDF热电复合材料.与以往采用价格昂贵的p型与n型单壁碳纳米管(SWNTs)与聚合物混合制备的复合热电材料特性相比,这种新型热电复合材料在降低制造成本的同时,利用分散于聚合物中MWNTs的一维电子传输特性及形成的大量界面势垒,加上ZnO半导体纳米线具有的较高载流子密度与迁移率,提高了复合热电材料中电子的输运特性,增加了材料对声子的散射强度.测试发现,在一定的温度梯度下,随着MWNTs添加质量百分比的增加,热电材料的温差电动势和电导率也随之增加,但其Seebeck系数变化量不大.研究表明,这种热电材料有望替代采用p型与n型SWNTs构建的SWNTs/PVDF复合热电材料.研究结果对开发超轻、无毒、廉价、可应用于各种微纳电子领域的新型电源具有重要的参考价值.     

Optoelectronic structure and related transport properties of BiCuSeO-based oxychalcogenides: First principle calculations

Recent experiments have revealed that the p-type BiCuSeO-based oxychalcogenides compounds exhibit a high thermoelectric figures of merit due to their very low lattice thermal conductivities and moderate Seebeck coefficient in the medium temperature range. In the present work, we reported on the optoelectronic and thermoelectric properties using the full potential linear augmented plane wave method and modified Becke-Johnson potential with spin-orbit coupling. The properties show that the BiCuSeO-based oxychalcogenides exhibit a semiconductor behavior with band gap values of 0.51, 0.45 and 0.41 eV for BiCuSO, BiCuSeO, and BiCuTeO, respectively. Due to their prominent role for thermoelectric applications, we combined Boltzmann transport theory to DFT results to compute the transport properties, mainly electronic conductivity, thermal conductivity, Seebeck coefficient and power factor. The present results show the dominance of BiCuTeO for thermoelectric application compared to the BiCuSO and BiCuSeO.     

Influence of Ni nanoparticle addition and spark plasma sintering on the TiNiSn–Ni system: Structure,microstructure, and thermoelectric properties

The electronic and thermal properties of thermoelectric materials are highly dependent on their microstructure and therefore on the preparation conditions, including the initial synthesis and, if applicable, densification of the obtained powders. Introduction of secondary phases on the nano- and/or microscale is widely used to improve the thermoelectric figure of merit by reduction of the thermal conductivity. In order to understand the effect of the preparation technique on structure and properties, we have studied the thermoelectric properties of the well-known half-Heusler TiNiSn with addition of a small amount of nickel nanoparticles. The different parameters are the initial synthesis (levitation melting and microwave heating), the amount of nickel nanoparticles added and the exact pressing profile using spark plasma sintering. The resulting materials have been characterized by synchrotron X-ray diffraction and microprobe measurements and their thermoelectric properties are investigated. We found the lowest (lattice) thermal conductivity in samples with full-Heusler TiNi₂Sn and Ni₃Sn₄ as secondary phases.     

Potential of Chevrel phases for thermoelectric applications

A low lattice thermal conductivity is one of the requirements to achieve high thermoelectric figures of merit. Several low thermal conductivity materials were identified and developed over the past few years at the Jet Propulsion Laboratory (JPL), including filled skutterudites and Zn₄Sb₃-based materials. A study of the mechanisms responsible for the high phonon scattering rates in these compounds has demonstrated that materials with structures that can accommodate additional atoms in their lattice are likely to possess low lattice thermal conductivity values. Chevrel phases (Mo₆Se₈-type) are just such materials and are currently being investigated at JPL for thermoelectric applications. The crystal structures of the Chevrel phases present cavities which can greatly vary in size and can contain a large variety of atoms ranging from large ones such as Pb to small ones such as Cu. In these materials, small inserted atoms usually show large thermal parameters which indicate that they move around and can significantly scatter the phonons. The electronic and thermal properties of these materials can potentially be controlled by a careful selection of the filling element(s). We have synthesized (Cu, Cu/Fe, Ti)_xMo₆Se₈ samples and report in this paper on their thermoelectric properties. Approaches to optimize the properties of these materials for thermoelectric applications are discussed. Solid State Sciences, 1293-2558/99/7-8/© 1999 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.     

Automated search for new thermoelectric materials: the case of LiZnSb

An automated band structure calculation based on the inorganic crystal structure database and the augmented plane wave method for electronic structure calculations is presented. Using a rigid band approach and semiclassic Boltzmann theory the band structures are analyzed and a large number of compounds are screened for potential interesting thermoelectric properties. We thereby propose LiZnSb as a potential new thermoelectric material. The k-space structure of the lowest conduction band of LiZnSb is analyzed in detail, and excellent thermoelectric properties are expected for this material. Furthermore the lattice dynamics are calculated, and anisotropic lattice thermal conduction is predicted.     

Advances in organic–inorganic hybrid sorbents for the extraction of organic and inorganic pollutants in different types of food and environmental samples

The efficiency of the extraction and removal of pollutants from food and the environment has been an important issue in analytical science. By incorporating inorganic species into an organic matrix, a new material known as an organic–inorganic hybrid material is formed. As it possesses high selectivity, permeability, and mechanical and chemical stabilities, organic–inorganic hybrid materials constitute an emerging research field and have become popular to serve as sorbents in various separaton science methods. Here, we review recent significant advances in analytical solid‐phase extraction employing organic–inorganic composite/nanocomposite sorbents for the extraction of organic and inorganic pollutants from various types of food and environmental matrices. The physicochemical characteristics, extraction properties, and analytical performances of sorbents are discussed; including morphology and surface characteristics, types of functional groups, interaction mechanism, selectivity and sensitivity, accuracy, and regeneration abilities. Organic–inorganic hybrid sorbents combined with extraction techniques are highly promising for sample preparation of various food and environmental matrixes with analytes at trace levels.     

Investigation of structural,magneto‐electronic,and thermoelectric response of ductile SnAlO3 from high‐throughput DFT calculations

Successfully optimized calculations for the stability of SnAlO₃ perovskite in its paramagnetic phase and various structural parameters have been figured out in this study. Structural stability and ductile character is reflected from the calculated elastic constants and mechanical properties. Moreover, the melting temperature of the present material has also been calculated. We have discussed in detail, the ground state electronic band structure and paramagnetic character. In addition, the Boltzmann's transport theory has been employed to obtain the Seebeck, electrical and thermal conductivity coefficients so as to manifest the thermoelectric response of the material. Remarkably, the observed high electrical conductivity in inclusion of metallicity and paramagnetic nature is a characteristic of perovskite type electrode materials. The above discussed material properties suggest the possible application of this compound as an efficient electrode material.     

Thinking Like a Chemist: Intuition in Thermoelectric Materials

The coupled transport properties required to create an efficient thermoelectric material necessitates a thorough understanding of the relationship between the chemistry and physics in a solid. We approach thermoelectric material design using the chemical intuition provided by molecular orbital diagrams, tight binding theory, and a classic understanding of bond strength. Concepts such as electronegativity, band width, orbital overlap, bond energy, and bond length are used to explain trends in electronic properties such as the magnitude and temperature dependence of band gap, carrier effective mass, and band degeneracy and convergence. The lattice thermal conductivity is discussed in relation to the crystal structure and bond strength, with emphasis on the importance of bond length. We provide an overview of how symmetry and bonding strength affect electron and phonon transport in solids, and how altering these properties may be used in strategies to improve thermoelectric performance.     

Chemical synthesis of hybrid materials based on PAni and PEDOT with polyoxometalates for electrochemical supercapacitors

Hybrid organic–inorganic materials based on conjugated polymers constitute state-of-the-art compounds with recognized technological implications. In the area of energy conversion, production and storage devices, these materials have been applied as electrodes for batteries, supercapacitors, fuel cells or solar cells, among others. Their importance relies on the wide variety of organic and inorganic counterparts that these hybrids can be made of. The properties from each part can be tailored in order to contribute to a final desired characteristic or the combined properties from both. The unique combination of useful properties found in these materials include electronic conductivity (e⁻ or h⁺), ionic transport, reversible electroactivity, electrooptical properties typical of semiconductors as well as electrochromic, pH- and composition-dependent properties, all of them to add to their polymeric nature. This is an excellent basis for the design of hybrid materials in which either of these properties or their combinations work to enhance or combine with those of a myriad inorganic phases with electronic, magnetic, photochemical, electrochemical, optical or catalytic properties. A large variety of functional hybrid materials can thus be designed and fabricated in which multifunctionality can be easily built to address specific technological needs. In this work we present our most recent results on new synthesis methodology developed for the chemical synthesis of the hybrid PAni/PMo12 and their application as electrochemical supercapacitors. We also report the synthesis of a new hybrid material of PEDOT/PMo12 synthesized for the first time by chemical methods and applied also in electrochemical supercapacitors. Initial results shows capacitance values as high as 168 F/g for the hybrid PAni/PMo12 and about 130 F/g for the hybrid PEDOT/PMo12.     

2D inorganic nanosheet-based hybrid photocatalysts: Design,applications, and perspectives

Highly anisotropic 2D nanosheets of inorganic solids with nanometer-level thickness attract a great deal of research activity because of their unique merits in exploring novel high performance photocatalysts applicable for environmental purification and production of renewable clean energy. The 2D inorganic nanosheets possess many valuable properties such as tailorable band structures and chemical compositions, large surface areas, well-defined defect-free surface structure, and tunable electrical conductivities. Due to these unique advantages of 2D inorganic nanosheets, these materials can be used as promising building blocks for hybrid-type photocatalysts with optimized band structures, expanded surface areas, improved charge separation behaviors, and enhanced reaction kinetics. Of prime importance is that unusually strong electronic coupling can occur between very thin 2D inorganic nanosheets and hybridized nanospecies, leading to the synergistic optimization of electronic and optical properties, and thus the remarkable enhancement of photocatalytic activity. Depending on the type of component nanosheets, diverse examples of inorganic nanosheet-based photocatalysts are presented along with the in-depth discussion about critical roles of inorganic nanosheet in these hybrid photocatalysts. Future perspectives in the researches for 2D inorganic nanosheet-based photocatalysts are discussed to offer useful directions for designing and synthesizing novel high performance photocatalysts applicable for renewable energy production and environmental purification.     

聚酰亚胺无机纳米杂化材料

聚酰亚胺(PI)作为一种功能材料，具有良好的介电性、优良力学性能，已被广泛应用于航空航天及微电子领域，但其明显的吸水性和热膨胀性限制了其在高温和精密状态下的应用。无机纳米材料具有很低的热膨胀系数和较低的吸水性，非常适合于对PI的改性。本文阐述了PI纳米杂化材料的制备方法。概要介绍了PI纳米杂化材料的类型、特点、性能及应用领域，并对这类材料的发展前景进行了综述。