Ultrahigh Thermoelectric Performance by Electron and Phonon Critical Scattering in Cu2Se1‐xIx
TL;DR: Iodine-doped Cu2 Se shows a significantly improved thermoelectric performance during phase transitions by electron and phonon critical scattering, leading to a dramatic increase in zT by a factor of 3-7 times culminating in z t values of 2.3 at 400 K.
Abstract: Iodine-doped Cu2 Se shows a significantly improved thermoelectric performance during phase transitions by electron and phonon critical scattering, leading to a dramatic increase in zT by a factor of 3-7 times culminating in zT values of 2.3 at 400 K.
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TL;DR: The mechanisms and strategies for improving thermoelectric efficiency are reviewed and how to report material performance is discussed, as well as how to develop high-performance materials out of nontoxic and earth-abundant elements.
Abstract: BACKGROUND Heat and electricity are two forms of energy that are at opposite ends of a spectrum Heat is ubiquitous, but with low quality, whereas electricity is versatile, but its production is demanding Thermoelectrics offers a simple and environmentally friendly solution for direct heat-to-electricity conversion A thermoelectric (TE) device can directly convert heat emanating from the Sun, radioisotopes, automobiles, industrial sectors, or even the human body to electricity Electricity also can drive a TE device to work as a solid-state heat pump for distributed spot-size refrigeration TE devices are free of moving parts and feasible for miniaturization, run quietly, and do not emit greenhouse gasses The full potential of TE devices may be unleashed by working in tandem with other energy-conversion technologies Thermoelectrics found niche applications in the 20th century, especially where efficiency was of a lower priority than energy availability and reliability Broader (beyond niche) application of thermoelectrics in the 21st century requires developing higher-performance materials The figure of merit, ZT, is the primary measure of material performance Enhancing the ZT requires optimizing the adversely interdependent electrical resistivity, Seebeck coefficient, and thermal conductivity, as a group On the microscopic level, high material performance stems from a delicate concert among trade-offs between phase stability and instability, structural order and disorder, bond covalency and ionicity, band convergence and splitting, itinerant and localized electronic states, and carrier mobility and effective mass ADVANCES Innovative transport mechanisms are the fountain of youth of TE materials research In the past two decades, many potentially paradigm-changing mechanisms were identified, eg, resonant levels, modulation doping, band convergence, classical and quantum size effects, anharmonicity, the Rashba effect, the spin Seebeck effect, and topological states These mechanisms embody the current states of understanding and manipulating the interplay among the charge, lattice, orbital, and spin degrees of freedom in TE materials Many strategies were successfully implemented in a wide range of materials, eg, V2VI3 compounds, VVI compounds, filled skutterudites and clathrates, half-Heusler alloys, diamond-like structured compounds, Zintl phases, oxides and mixed-anion oxides, silicides, transition metal chalcogenides, and organic materials In addition, advanced material synthesis and processing techniques, for example, melt spinning, self-sustaining heating synthesis, and field-assisted sintering, helped reach a much broader phase space where traditional metallurgy and melt-growth recipes fell short Given the ubiquity of heat and the modular aspects of TE devices, these advances ensure that thermoelectrics plays an important role as part of a solutions package to address our global energy needs OUTLOOK The emerging roles of spin and orbital states, new breakthroughs in multiscale defect engineering, and controlled anharmonicity may hold the key to developing next generation TE materials To accelerate exploring the broad phase space of higher multinary compounds, we need a synergy of theory, machine learning, three-dimensional printing, and fast experimental characterizations We expect this synergy to help refine current materials selection and make TE materials research more data driven We also expect increasing efforts to develop high-performance materials out of nontoxic and earth-abundant elements The desire to move away from Freon and other refrigerant-based cooling should shift TE materials research from power generation to solid-state refrigeration International round-robin measurements to cross-check the high ZT values of emerging materials will help identify those that hold the most promise We hope the renewable energy landscape will be reshaped if the recent trend of progress continues into the foreseeable future
1,457 citations
Cites background from "Ultrahigh Thermoelectric Performanc..."
...PbTe (129, 38, 130, 50, 131), PbSe (132, 133), PbS (134, 135, 61); Cu2Se (110, 67, 136, 112), Cu2S (137,...
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...The coupling of a continuous phase transition to charge-carrier transport led to an enhanced a and ZT in Ag-doped Cu2Se (68)....
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...Cu2Se is open-framework structured and a mixed electronic-ionic conductor above ~400 K, and the Cu diffusion channels host multiscale disorder forms that render a phonon-liquid-like behavior (110, 111)....
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...A. A. Olvera et al., Partial indium solubility induces chemical stability and colossal thermoelectric figure of merit in Cu2Se....
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...PbTe (129, 38, 130, 50, 131), PbSe (132, 133), PbS (134, 135, 61); Cu2Se (110, 67, 136, 112), Cu2S (137, 138); SnSe (97, 100–102), Mg3Sb2 (139), SiGe (140–142), BiCuSeO (143, 144), Bi2Te3 (58, 122, 49), Cu(In,Ga)Te2 (145,45, 146),CoSb3 (11, 147, 148), InSb (149, 150), andhalf-Heuslercompounds (151, 152, 107). benchmark material Bi2Te3 as an example, doping Sb on the Bi site and Se on the Te site led to high p-type and n-type performance, respectively....
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TL;DR: This review aims to comprehensively summarize the state-of-the-art strategies for the realization of high-performance thermoelectric materials and devices by establishing the links between synthesis, structural characteristics, properties, underlying chemistry and physics.
Abstract: The long-standing popularity of thermoelectric materials has contributed to the creation of various thermoelectric devices and stimulated the development of strategies to improve their thermoelectric performance. In this review, we aim to comprehensively summarize the state-of-the-art strategies for the realization of high-performance thermoelectric materials and devices by establishing the links between synthesis, structural characteristics, properties, underlying chemistry and physics, including structural design (point defects, dislocations, interfaces, inclusions, and pores), multidimensional design (quantum dots/wires, nanoparticles, nanowires, nano- or microbelts, few-layered nanosheets, nano- or microplates, thin films, single crystals, and polycrystalline bulks), and advanced device design (thermoelectric modules, miniature generators and coolers, and flexible thermoelectric generators). The outline of each strategy starts with a concise presentation of their fundamentals and carefully selected examples. In the end, we point out the controversies, challenges, and outlooks toward the future development of thermoelectric materials and devices. Overall, this review will serve to help materials scientists, chemists, and physicists, particularly students and young researchers, in selecting suitable strategies for the improvement of thermoelectrics and potentially other relevant energy conversion technologies.
951 citations
TL;DR: In this article, a review of thermoelectric properties, applications and parameter relationships is presented, including modifications of electronic band structures and band convergence to enhance Seebeck coefficients; nanostructuring and all-scale hierarchical architecturing to reduce the lattice thermal conductivity.
866 citations
Cites background from "Ultrahigh Thermoelectric Performanc..."
...ZT of the current bulk thermoelectric materials as a function of year: the le before 1990s, Bi2Te3, PbTe and SiGe; the middle part elucidates that the ZTs were [20], nanoþamorphous-Bi2Te3 [21], nano-SiGe [22], nanostructural PbS [23]) a modulation doping (SiGe) [25,26]; the right part shows the high performance rea recently and characterized by low-cost, earth-abundant, and low thermal conductiv [31], Cu2S systems [32,33], SnS [34,35], Cu2Se systems [17,19,36,37], Half-Heus developed for nearly 200 years since the observation of the Seebeck effect in 1821, the development can be divided into three generations according to ZT values [5]....
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TL;DR: This review captures the synthesis, assembly, properties, and applications of copper chalcogenide NCs, which have achieved significant research interest in the last decade due to their compositional and structural versatility.
Abstract: This review captures the synthesis, assembly, properties, and applications of copper chalcogenide NCs, which have achieved significant research interest in the last decade due to their compositional and structural versatility. The outstanding functional properties of these materials stems from the relationship between their band structure and defect concentration, including charge carrier concentration and electronic conductivity character, which consequently affects their optoelectronic, optical, and plasmonic properties. This, combined with several metastable crystal phases and stoichiometries and the low energy of formation of defects, makes the reproducible synthesis of these materials, with tunable parameters, remarkable. Further to this, the review captures the progress of the hierarchical assembly of these NCs, which bridges the link between their discrete and collective properties. Their ubiquitous application set has cross-cut energy conversion (photovoltaics, photocatalysis, thermoelectrics), en...
636 citations
TL;DR: A new type of high performance thermoelectric material Cu_( 2-x)S composed of non-toxic and earth-abundant elements Cu and S is reported, which has lower thermal conductivity and more strikingly reduced specific heat compared to the heavier Cu_(2)Se.
Abstract: A new type of high performance thermoelectric material Cu_(2-x)S composed of non-toxic and earth-abundant elements Cu and S is reported Cu_(2-x)S surprisingly has lower thermal conductivity and more strikingly reduced specific heat compared to the heavier Cu_(2)Se, leading to an increased zT to 17
596 citations
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TL;DR: A new era of complex thermoelectric materials is approaching because of modern synthesis and characterization techniques, particularly for nanoscale materials, and the strategies used to improve the thermopower and reduce the thermal conductivity are reviewed.
Abstract: Thermoelectric materials, which can generate electricity from waste heat or be used as solid-state Peltier coolers, could play an important role in a global sustainable energy solution. Such a development is contingent on identifying materials with higher thermoelectric efficiency than available at present, which is a challenge owing to the conflicting combination of material traits that are required. Nevertheless, because of modern synthesis and characterization techniques, particularly for nanoscale materials, a new era of complex thermoelectric materials is approaching. We review recent advances in the field, highlighting the strategies used to improve the thermopower and reduce the thermal conductivity.
8,999 citations
Book•
01 Jan 1940
TL;DR: The Fermi Glass and the Anderson Transition as discussed by the authorsermi glass and Anderson transition have been studied in the context of non-crystalline Semiconductors, such as tetrahedrally-bonded semiconductors.
Abstract: 1. Introduction 2. Theory of Electrons in a Non-Crystalline Medium 3. Phonons and Polarons 4. The Fermi Glass and the Anderson Transition 5. Liquid Metals and Semimetals 6. Non-Crystalline Semiconductors 7. Tetrahedrally-Bonded Semiconductors - Amorphous Germanium and Silicon 8. Aresnic and Other Three-Fold Co-ordinated Materials 9. Chalcogenide and Other Glasses 10. Selenium, Tellurium, and their Alloys
8,188 citations
TL;DR: Th thin-film thermoelectric materials are reported that demonstrate a significant enhancement in ZT at 300 K, compared to state-of-the-art bulk Bi2Te3 alloys, and the combination of performance, power density and speed achieved in these materials will lead to diverse technological applications.
Abstract: Thermoelectric materials are of interest for applications as heat pumps and power generators. The performance of thermoelectric devices is quantified by a figure of merit, ZT, where Z is a measure of a material's thermoelectric properties and T is the absolute temperature. A material with a figure of merit of around unity was first reported over four decades ago, but since then-despite investigation of various approaches-there has been only modest progress in finding materials with enhanced ZT values at room temperature. Here we report thin-film thermoelectric materials that demonstrate a significant enhancement in ZT at 300 K, compared to state-of-the-art bulk Bi2Te3 alloys. This amounts to a maximum observed factor of approximately 2.4 for our p-type Bi2Te3/Sb2Te3 superlattice devices. The enhancement is achieved by controlling the transport of phonons and electrons in the superlattices. Preliminary devices exhibit significant cooling (32 K at around room temperature) and the potential to pump a heat flux of up to 700 W cm-2; the localized cooling and heating occurs some 23,000 times faster than in bulk devices. We anticipate that the combination of performance, power density and speed achieved in these materials will lead to diverse technological applications: for example, in thermochemistry-on-a-chip, DNA microarrays, fibre-optic switches and microelectrothermal systems.
4,921 citations
TL;DR: Thermoelectric materials are solid-state energy converters whose combination of thermal, electrical, and semiconductor properties allows them to be used to convert waste heat into electricity or electrical power directly into cooling and heating.
Abstract: Thermoelectric materials are solid-state energy converters whose combination of thermal, electrical, and semiconducting properties allows them to be used to convert waste heat into electricity or electrical power directly into cooling and heating. These materials can be competitive with fluid-based systems, such as two-phase air-conditioning compressors or heat pumps, or used in smaller-scale applications such as in automobile seats, night-vision systems, and electrical-enclosure cooling. More widespread use of thermoelectrics requires not only improving the intrinsic energy-conversion efficiency of the materials but also implementing recent advancements in system architecture. These principles are illustrated with several proven and potential applications of thermoelectrics.
4,700 citations
TL;DR: Electrical transport measurements, coupled with microstructure studies and modeling, show that the ZT improvement is the result of low thermal conductivity caused by the increased phonon scattering by grain boundaries and defects, which makes these materials useful for cooling and power generation.
Abstract: The dimensionless thermoelectric figure of merit (ZT) in bismuth antimony telluride (BiSbTe) bulk alloys has remained around 1 for more than 50 years. We show that a peak ZT of 1.4 at 100°C can be achieved in a p-type nanocrystalline BiSbTe bulk alloy. These nanocrystalline bulk materials were made by hot pressing nanopowders that were ball-milled from crystalline ingots under inert conditions. Electrical transport measurements, coupled with microstructure studies and modeling, show that the ZT improvement is the result of low thermal conductivity caused by the increased phonon scattering by grain boundaries and defects. More importantly, ZT is about 1.2 at room temperature and 0.8 at 250°C, which makes these materials useful for cooling and power generation. Cooling devices that use these materials have produced high-temperature differences of 86°, 106°, and 119°C with hot-side temperatures set at 50°, 100°, and 150°C, respectively. This discovery sets the stage for use of a new nanocomposite approach in developing high-performance low-cost bulk thermoelectric materials.
4,695 citations