Nonlinear pyroelectric energy harvesting from relaxor single crystals

Energy harvesting from temperature variations in a Pb(Zn_1/3Nb_2/3)_0.955Ti_0.045O₃ single crystal was studied and evaluated using the Ericsson thermodynamic cycle. The efficiency of this cycle related to Carnot cycle is 100 times higher than direct pyroelectric energy harvesting, and it can be as high as 5.5% for a 10degC temperature variation and 2 kV/mm electric field. The amount of harvested energy for a 60degC temperature variation and 2 kV/mm electric field is 242.7 mJmiddotcm^-3. The influence of ferroelectric phase transitions on the energy harvesting performance is discussed and illustrated with experimental results.     

Energy harvesting based on FE-FE transition in ferroelectric single crystals

The pyroelectric properties of Pb(Zn(1/3)Nb(2/3))(0955)Ti(0.045)O(3) single crystals versus an electric field have been studied for energy harvesting in this paper. Two thermodynamic cycles (Stirling and Ericsson) were used for this purpose. By applying an electric field, a FE-FE transition was induced, abruptly increasing the polarization. This transition minimized the supplied energy and improved the harvested energy. By discharging the single crystal at a higher temperature, a gain of 1100% was obtained with the Stirling cycle at 1 kV/mm (gain is defined as harvested energy divided by supplied energy). The study revealed that Stirling cycles are more interesting for low electric fields. Based on experimental results, simulations were carried out to estimate energy harvesting in high electric fields to evaluate the performances of thin samples (single crystals or oriented thin films). At high electric fields, both cycles gave almost the same energy harvesting, but Ericsson cycles were more appropriate to control the voltage on the sample. The simulation led to a harvested energy of 500 mJ/g for an applied electric field equal to 50 kV/mm. The efficiency with respect to Carnot was raised 20%.     

Pyroelectric properties of Pb0.88Ln0.08Ti0.98Mn0.02O3 (Ln=La, Sm, Eu) ferroelectric ceramic system

In this work, the pyroelectric properties of Pb_0.88Ln_0.08Ti_0.98Mn_0.02O₃ (Ln=La, Sm, Eu) ferroelectric ceramic system are studied. This type of ferroelectric ceramic presents high values of the following characteristics: dielectric constant, Curie temperature, electromechanical anisotropy, and high frequencies of operation, which make them useful for applications such as ultrasonic transducers in biomedical applications. The relationship between dielectric constant and temperature measurements as well as pyroelectric measurements using the technique of Byer and Roundy were performed. Values of the pyroelectric coefficient and figure of merit for infrared detector materials were obtained to use these ceramics in the detection of infrared radiation, laser power measurements, and solar energy technology.     

Enhancement of high temperature thermoelectric properties of intermetallic compounds based on a Skutterudite IrSb3 and a half-Heusler TiNiSb

Phonon glass and electron crystal (PGEC) thermoelectric materials have been expected to be a new class of thermoelectric materials for high temperature applications. Among the efforts to optimize the high temperature thermoelectric properties of various PGEC thermoelectric materials, recent experimental works on the Skutterudite IrSb₃ and half-Heusler TiNiSb intermetallic compounds are presented herein by which the material design concept for high energy conversion efficiency, i.e. a high figure of merit, is suggested. It is revealed that the thermoelectric efficiency of IrSb₃ can be increased by the decrease of lattice thermal conductivity due to the rattling effect of La atoms filled in the structural vacancies of the Skutterudite crystal structure. In the half-Heusler TiNiSn, high temperature thermoelectric properties are improved by Hf substitution to the Ti sites by reducing lattice thermal conductivity and also by Sb doping to increase power factor. It is concluded that the proper alloy designing for controlling crystal structure and carrier concentration could enable these intermetallic compounds to exhibit a high potential for elevated temperature thermoelectric applications.     

Photovoltaic–Pyroelectric Coupled Effect Induced Electricity for Self‐Powered Photodetector System

Ferroelectric materials have demonstrated novel photovoltaic effect to scavenge solar energy. However, most of the ferroelectric materials with wide bandgaps (2.7–4 eV) suffer from low power conversion efficiency of less than 0.5% due to absorbing only 8–20% of solar spectrum. Instead of harvesting solar energy, these ferroelectric materials can be well suited for photodetector applications, especially for sensing near‐UV irradiations. Here, a ferroelectric BaTiO₃ film‐based photodetector is demonstrated that can be operated without using any external power source and a fast sensing of 405 nm light illumination is enabled. As compared with photovoltaic effect, both the responsivity and the specific detectivity of the photodetector can be dramatically enhanced by larger than 260% due to the light‐induced photovoltaic–pyroelectric coupled effect. A self‐powered photodetector array system can be utilized to achieve spatially resolved light intensity detection by recording the output voltage signals as a mapping figure.     

Enhancement of high temperature thermoelectric properties of intermetallic compounds based on a Skutterudite IrSb3 and a half-Heusler TiNiSb

Phonon glass and electron crystal (PGEC) thermoelectric materials have been expected to be a new class of thermoelectric materials for high temperature applications. Among the efforts to optimize the high temperature thermoelectric properties of various PGEC thermoelectric materials, recent experimental works on the Skutterudite IrSb₃ and half-Heusler TiNiSb intermetallic compounds are presented herein by which the material design concept for high energy conversion efficiency, i.e. a high figure of merit, is suggested. It is revealed that the thermoelectric efficiency of IrSb₃ can be increased by the decrease of lattice thermal conductivity due to the rattling effect of La atoms filled in the structural vacancies of the Skutterudite crystal structure. In the half-Heusler TiNiSn, high temperature thermoelectric properties are improved by Hf substitution to the Ti sites by reducing lattice thermal conductivity and also by Sb doping to increase power factor. It is concluded that the proper alloy designing for controlling crystal structure and carrier concentration could enable these intermetallic compounds to exhibit a high potential for elevated temperature thermoelectric applications.     

梯度热电材料的研究进展

热电材料梯度化是在保证各组分单一材料的热电性能的基础上,拓宽其应用温度范围,使各组分材料都能工作在最佳温区,以确保热电材料在一定的工作温度范围内具有较高的ZT值,保证其高的热电转换效率.介绍了热电材料的研究基础及其梯度化设计,对梯度热电材料在国内外的研究进展进行了综述并对未来的研究趋势进行了展望.     

High performance functionally graded and segmented Bi2Te3-based materials for thermoelectric power generation

Bi₂Te₃-based materials possess a figure of merit maximum over a narrow temperature range. When used in a generating mode over a large temperature difference the material operates at a substantially lower overall figure of merit than its maximum value. The conversion efficiency of a thermoelectric generator for low temperature waste heat recovery can be increased by employing functionally graded or segmented materials. In this work functionally graded p-type Bi₂Te₃-based thermoelectric materials have been prepared from melt by the Bridgman method using double doping technique. Segmented n-type thermoelement has been fabricated by joining two Bi₂Te₃-based materials with figure of merit maximum at 270 K and 380 K. The thermoelectric properties of the materials and a thermocouple comprised of p-type functionally graded and n-type segmented materials have been measured over a temperature range 200 K–450 K. The material efficiency of the thermocouple over the temperature gradient 223 K–423 K is estimated to be 10% compared with 8.8% for a standard Bi₂Te₃-based materials.     

Mutual Insight on Ferroelectrics and Hybrid Halide Perovskites: A Platform for Future Multifunctional Energy Conversion

An insight into the analogies, state‐of‐the‐art technologies, concepts, and prospects under the umbrella of perovskite materials (both inorganic–organic hybrid halide perovskites and ferroelectric perovskites) for future multifunctional energy conversion and storage devices is provided. Often, these are considered entirely different branches of research; however, considering them simultaneously and holistically can provide several new opportunities. Recent advancements have highlighted the potential of hybrid perovskites for high‐efficiency solar cells. The intrinsic polar properties of these materials, including the potential for ferroelectricity, provide additional possibilities for simultaneously exploiting several energy conversion mechanisms such as the piezoelectric, pyroelectric, and thermoelectric effect and electrical energy storage. The presence of these phenomena can support the performance of perovskite solar cells. The energy conversion using these effects (piezo‐, pyro‐, and thermoelectric effect) can also be enhanced by a change in the light intensity. Thus, there lies a range of possibilities for tuning the structural, electronic, optical, and magnetic properties of perovskites to simultaneously harvest energy using more than one mechanism to realize an improved efficiency. This requires a basic understanding of concepts, mechanisms, corresponding material properties, and the underlying physics involved with these effects.     

Interface driven energy filtering of thermoelectric power in spark plasma sintered bi(2)te(2.7)se(0.3) nanoplatelet composites

Control of competing parameters such as thermoelectric (TE) power and electrical and thermal conductivities is essential for the high performance of thermoelectric materials. Bulk-nanocomposite materials have shown a promising improvement in the TE performance due to poor thermal conductivity and charge carrier filtering by interfaces and grain boundaries. Consequently, it has become pressingly important to understand the formation mechanisms, stability of interfaces and grain boundaries along with subsequent effects on the physical properties. We report here the effects of the thermodynamic environment during spark plasma sintering (SPS) on the TE performance of bulk-nanocomposites of chemically synthesized Bi(2)Te(2.7)Se(0.3) nanoplatelets. Four pellets of nanoplatelets powder synthesized in the same batch have been made by SPS at different temperatures of 230, 250, 280, and 350 °C. The X-ray diffraction, transmission electron microscopy, thermoelectric, and thermal transport measurements illustrate that the pellet sintered at 250 °C shows a minimum grain growth and an optimal number of interfaces for efficient TE figure of merit, ZT～0.55. For the high temperature (350 °C) pelletized nanoplatelet composites, the concurrent rise in electrical and thermal conductivities with a deleterious decrease in thermoelectric power have been observed, which results because of the grain growth and rearrangements of the interfaces and grain boundaries. Cross section electron microscopy investigations indeed show significant grain growth. Our study highlights an optimized temperature range for the pelletization of the nanoplatelet composites for TE applications. The results provide a subtle understanding of the grain growth mechanism and the filtering of low energy electrons and phonons with thermoelectric interfaces.     

Chemically doped macroscopic graphene fibers with significantly enhanced thermoelectric properties

Flexible wearable electronics, when combined with outstanding thermoelectric properties, are promising candidates for future energy harvesting systems. Graphene and its macroscopic assemblies (e.g., graphene-based fibers and films) have thus been the subject of numerous studies because of their extraordinary electrical and mechanical properties. However, these assemblies have not been considered suitable for thermoelectric applications owing to their high intrinsic thermal conductivity. In this study, bromine doping is demonstrated to be an effective method for significantly enhancing the thermoelectric properties of graphene fibers. Doping enhances phonon scattering due to the increased defects and thus decreases the thermal conductivity, while the electrical conductivity and Seebeck coefficient are increased by the Fermi level downshift. As a result, the maximum figure of merit is 2.76 × 10^–3, which is approximately four orders of magnitude larger than that of the undoped fibers throughout the temperature range. Moreover, the room temperature power factor is shown to increase up to 624 μW·m^–1·K^–2, which is higher than that of any other material solely composed of carbon nanotubes and graphene. The enhanced thermoelectric properties indicate the promising potential for graphene fibers in wearable energy harvesting systems.

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The influence of a galvanomagnetic stationary vortex current on the magneto-thermoelectric figure of merit of graded inhomogeneous bismuth-antimony alloys

We have studied the influence of a longitudinal graded inhomogeneity in crystals of bismuth-antimony solid solutions on their effective magnetoresistance, which is one of the parameters determining the efficiency (thermoelectric figure of merit) of a thermoelement operating in the presence of a transverse magnetic field. It is shown that, in a thermoelement operating under the action of an external magnetic field, the negative effect of the crystal inhomogeneity caused by the temperature gradient can be compensated for by its graded composition so as to provide for an increase in the thermoelectric figure of merit of the thermoelement.     

Dielectric properties and spatial distribution of polarization of ceramic + polymer composite sensors

Thin films ceramic + polymer composite sensors with mixed connectivities possess high values of piezo- and pyroelectric coefficients and the formability and flexibility which are not attainable in a single-phase ferroelectric material, i. e., an electroceramic or a polymer. The efficiency and the piezo- and pyroelectric figure of merit (FOM) are influenced by the temperature dependence of the dielectric properties and the nature of the spatial distribution of polarization of the composite material. We report the results of a study of dielectric properties of calcium – modified lead titanate (PTCa) and a polar copolymer, polyvinylidene fluoride and trifluoroethylene P(VDF-TrFE) and PTCa and epoxy in a wide frequency range. Each of the two composites was fabricated with two different volume fractions of the constituent phases. Furthermore, the spatial distribution of polarization was determined by the laser intensity modulation method (LIMM) for each composite sensor in order to assess the polarization distribution of the sensors. These results are also reported in this work. Received: 6 November 2000 / Reviewed and accepted: 7 November 2000     

Promising and Eco-Friendly Cu2X-Based Thermoelectric Materials: Progress and Applications

Due to the nature of their liquid-like behavior and high dimensionless figure of merit, Cu₂X (X = Te, Se, and S)-based thermoelectric materials have attracted extensive attention. The superionicity and Cu disorder at the high temperature can dramatically affect the electronic structure of Cu₂X and in turn result in temperature-dependent carrier-transport properties. Here, the effective strategies in enhancing the thermoelectric performance of Cu₂X-based thermoelectric materials are summarized, in which the proper optimization of carrier concentration and minimization of the lattice thermal conductivity are the main focus. Then, the stabilities, mechanical properties, and module assembly of Cu₂X-based thermoelectric materials are investigated. Finally, the future directions for further improving the energy conversion efficiency of Cu₂X-based thermoelectric materials are highlighted.     

Single crystal PMN-PT/epoxy 1-3 composite for energy-harvesting application

One key parameter in using electroactive materials to harvest electric energy from mechanical sources is the energy conversion efficiency. Recently, it was shown that, in the relaxor ferroelectric PMN-PT single crystals, a very high longitudinal electromechanical coupling factor (>90%) can be obtained. This paper investigates energy harvesting using 1-3 composites of PMN-PT single crystals in a soft epoxy matrix. It is shown that 1-3 composites enable the single crystals operating in the longitudinal mode to achieve high efficiency for energy harvesting, and the soft-polymer, matrix-supported single-crystal rods maintain high mechanical integrity under different external loads. For comparison, 1-3 composites with piezoceramic PZT also are investigated in energy-harvesting applications, and the results show that the high coupling factor of single crystal PMN-PT 1-3 composites leads to much higher electric energy output for similar mechanical energy input. The harvested energy density of 1-3 composite with single crystal (22.1 mW/cm3 under a stress of 40.4 MPa) is about twice of that harvested with PZT ceramic 1-3 composite (12 mW/cm3 under a stress of 39 MPa). At a higher stress level, the harvested-energy density of 1-3 PMN-PT single crystal composite can reach 96 mW/cm3.     

热电材料的第一性原理高通量研究

热电材料是一种新型能量转换材料, 在温差发电或通电制冷等领域具有广泛应用。热电优值ZT值是衡量热电材料能量转换效率的关键参数, ZT值要求热电材料具有优异的电输运性能及较低的热导率。传统第一性原理热电材料研究往往关注少量样本下的电热输运性质理解与优化, 很难得到系统性的规律, 也不利于新体系的设计优化。材料基因组计划力求通过大数据、高通量手段去加速材料设计与发现, 具有广阔的发展前景。在热电材料研究领域, 第一性原理高通量计算也将在新材料预测与性能优化等方面起到越来越重要的作用。另一方面, 高通量研究也带来了新的挑战, 譬如电热输运性质的高通量算法发展、大数据分析手段等等, 这些方面的问题决定了高通量方法在材料应用中的效率与准确性。本文综述了热电材料中现有的电热输运性质高通量计算方法, 介绍了这些方法具体的应用案例, 并对高通量与热电材料结合的未来发展趋势进行了展望。     

A hot-pressed PLZT under DC bias for field-stabilized pyroelectric detector applications

 The temperature dependence of the pyroelectric response of a hot-pressed PLZT (lead lanthanide zirconate titanate) (9.5/65/35) under a modest dc electric bias field has been investigated in an assessment of the performance of this material for applications in small-area pyroelectric devices. A strong pyroelectric response has been induced in the material at and above its transition temperature by the application of an electric field. The electrical resistivity, relative dielectic constant, loss tangent, ferroelectic hysteresis, and pyroelectric coefficients are reported. The material shows a very high figure of merit for a dielectric bolometer application that is competitive with existing relaxor ferroelectric materials such as Pb(Mg_1/3Nb_2/3)O₃ (PMN) and Pb(Sc_1/2Ta_1/2)O₃ (PST). Received: 21 March 1997 / Accepted: 6 May 1997     

Thermal imaging using organic films

Advances in the synthesis of non-centrosymmetric molecules coupled with the recently acquired ability to incorporate them into stable three-dimensional arrays with a high degree of order, hold out exciting possibilities for the development of high quality, low cost organic materials for a variety of applications.

In this paper we review the efforts that have been made in engineering molecules so as to optimize their pyroelectric properties. Results are presented for three classes of organic material: (i) spin cast films of vinylidene fluoride- trifluoroethylene copolymer, (ii) ferroelectric liquid crystal polymers encapsulated in thin cells and (iii) organic superlattices assembled using the Langmuir-Blodgett (LB) technique.

When consideration is given to a figure of merit for a commercial device such as a thermal imager rather than to a single physical material parameter, LB films are shown to be the most attractive of the three options. In this paper we list their several advantages including reasonable pyroelectric coefficients, low dielectric loss, low piezoelectric activity and the ability to fabricate films of the required optimum thickness.     

Pyroelectric nanogenerators for harvesting thermoelectric energy

Harvesting thermoelectric energy mainly relies on the Seebeck effect that utilizes a temperature difference between two ends of the device for driving the diffusion of charge carriers. However, in an environment that the temperature is spatially uniform without a gradient, the pyroelectric effect has to be the choice, which is based on the spontaneous polarization in certain anisotropic solids due to a time-dependent temperature variation. Using this effect, we experimentally demonstrate the first application of pyroelectric ZnO nanowire arrays for converting heat energy into electricity. The coupling of the pyroelectric and semiconducting properties in ZnO creates a polarization electric field and charge separation along the ZnO nanowire as a result of the time-dependent change in temperature. The fabricated nanogenerator has a good stability, and the characteristic coefficient of heat flow conversion into electricity is estimated to be ～0.05-0.08 Vm(2)/W. Our study has the potential of using pyroelectric nanowires to convert wasted energy into electricity for powering nanodevices.     

Si含量对反应烧结SiC陶瓷热电性能的影响

采用可控溶渗反应烧结法制备了致密SiC陶瓷，研究了不同Si含量对反应烧结SiC陶瓷热电性能的影响。经研究发现，反应烧结SiC陶瓷中Si的存在使SiC陶瓷的电阻率急剧下降，大大改善了SiC陶瓷的电学性能；同时Si也改变了SiC陶瓷塞贝克系数随温度的变化趋势，即没有添加Si元素的SiC陶瓷的塞贝克系数随温度的升高逐渐增大，而添加Si元素的SiC陶瓷的塞贝克系数随温度的升高逐渐减小；总的来看，随着Si含量的增加，SiC陶瓷的塞贝克系数扣电导率不断增大，因此Sic陶瓷的功率因子不断提高，而且随着温度的升高，Si含量对SiC陶瓷热电优值的影响越来越明显，当含量为15％时，材料的热电优值是SiC烧结体的30倍。