Synthesis and thermoelectric properties of Rashba semiconductor BiTeBr with intensive texture.

Bismuth tellurohalides with Rashba-type spin splitting exhibit unique Fermi surface topology and are developed as promising thermoelectric materials. However, BiTeBr, which belongs to this class of materials, is rarely investigated in terms of the thermoelectric transport properties. In the study, polycrystalline bulk BiTeBr with intensive texture was synthesized via spark plasma sintering (SPS). Additionally, its thermoelectric properties above room temperature were investigated along both the in-plane and out-plane directions, and they exhibit strong anisotropy. Low sound velocity along two directions is found and contributes to its low lattice thermal conductivity. Polycrystalline BiTeBr exhibits relatively good thermoelectric performance along the in-plane direction, with a maximum dimensionless figure of merit (ZT) of 0.35 at 560 K. Further enhancements of ZT are expected by utilizing systematic optimization strategies.

Structure, Magnetism, and Thermoelectric Properties of Magnesium-Containing Antimonide Zintl Phases Sr14MgSb11 and Eu14MgSb11.

New Mg-containing antimonide Zintl phases, Sr14MgSb11 and Eu14MgSb11, were synthesized from high-temperature solid-state reactions in Ta tubes at 1323 K. Their structures can be viewed as derived from the Ca14AlSb11 structure type, which adopt the tetragonal space group I41/acd (No. 142, Z = 8) with the cell parameters of a = 17.5691(14)/17.3442(11) Å and c = 23.399(4)/22.981(3) Å for the Sr- and Eu-containing compounds, respectively. The corresponding thermoelectric properties were probed, which demonstrated high potential of these compounds as new thermoelectrics for their very low thermal conductivity and moderate Seebeck coefficient. Magnetism studies and theoretical calculations were conducted as well to better understand the structure-and-property correlation of these materials.

A14MgBi11 (A = Ca, Sr, Eu): Magnesium Bismuth Based Zintl Phases as Potential Thermoelectric Materials.

A series of new magnesium bismuth Zintl phases, A14MgBi11 (A = Ca, Sr, Eu), have been synthesized, and their thermoelectric properties were systematically evaluated. These novel phases belong to the well-known Yb14MnSb11 family, whose structure adopts the tetragonal space group I41/acd (No. 142) with cell parameters of a = 17.0470(17)/17.854(2)/17.6660(7) Å and c = 22.665(5)/23.580(6)/23.2446(18) Å for Ca14MgBi11, Sr14MgBi11, and Eu14MgBi11, respectively. Without intentional optimization, these materials exhibit high potential as new thermoelectric candidates. Especially for Sr14MgBi11, a high zT value of 0.72 has been approached at 1073 K. The discovery of these new Zintl series is very interesting, which implies the high possibility of extending the 14-1-11 thermoelectric system to the bismuth analogues in the development of highly efficient thermoelectric materials. Density functional theory (DFT) calculations were incorporated as well to help better understand the properties of these important compounds.

Multiple Converged Conduction Bands in K2Bi8Se13: A Promising Thermoelectric Material with Extremely Low Thermal Conductivity.

We report that K2Bi8Se13 exhibits multiple conduction bands that lie close in energy and can be activated through doping, leading to a highly enhanced Seebeck coefficient and a high power factor with elevated temperature. Meanwhile, the large unit cell, complex low symmetry crystal structure, and nondirectional bonding lead to the very low lattice thermal conductivity of K2Bi8Se13, ranging between 0.42 and 0.20 W m-1 K-1 in the temperature interval 300-873 K. Experimentally, we further support the low thermal conductivity of K2Bi8Se13 using phonon velocity measurements; the results show a low average phonon velocity (1605 ms-1), small Young's modulus (37.1 GPa), large Grüneisen parameter (1.71), and low Debye temperature (154 K). A detailed investigation of the microstructure and defects was carried out using electron diffraction and transmission microscopy which reveal the presence of a K2.5Bi8.5Se14 minor phase intergrown along the side of the K2Bi8Se13 phase. The combination of enhanced power factor and low thermal conductivity results in a high ZT value of ∼1.3 at 873 K in electron doped K2Bi8Se13 material.

Performance improvement of lithium manganese phosphate by controllable morphology tailoring with acid-engaged nano engineering.

Olivine-type lithium manganese phosphate (LiMnPO4) has been considered as a promising cathode for next-generation Li-ion batteries. Preparation of high-performance LiMnPO4 still remains a great challenge because of its intrinsically low Li-ion/electronic conductivity. In this work, significant performance enhancement of LiMnPO4 has been realized by a controllable acid-engaged morphology tailoring from large spindles into small plates. We find that acidity plays a critical role in altering the morphology of the LiMnPO4 crystals. We also find that size decrease and plate-like morphology are beneficial for the performance improvement of LiMnPO4. Among the plate-like samples, the one with the smallest size shows the best electrochemical performance. After carbon coating, it can deliver high discharge capacities of 104.0 mAh g(-1) at 10 C and 85.0 mAh g(-1) at 20 C. After 200 cycles at 1 C, it can still maintain a high discharge capacity of 106.4 mAh g(-1), showing attractive applications in high-power and high-energy Li-ion batteries.

Reduced graphene oxide-induced recrystallization of NiS nanorods to nanosheets and the improved Na-storage properties.

Preparation of two-dimensional (2D) graphene-like materials is currently an emerging field in materials science since the discovery of single-atom-thick graphene prepared by mechanical cleavage. In this work, we proposed a new method to prepare 2D NiS, where reduced graphene oxide (rGO) was found to induce the recrystallization of NiS from nanorods to nanosheets in a hydrothermal process. The process and mechanism of recrystallization have been clarified by various characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS). The characterization of ex situ NiS/rGO products by SEM and EDS mapping indicates that the recrystallization of NiS from nanorods to nanosheets is realized actually through an exfoliation process, while the characterization of in situ NiS/rGO products by SEM, TEM, and EDS mapping reveals the exfoliation process. The XPS result demonstrates that hydrothermally assisted chemical bonding occurs between NiS and rGO, which induces the exfoliation of NiS nanorods into nanosheets. The obtained NiS/rGO composite shows promising Na-storage properties.

An Elastic Cross-Linked Binder for Silicon Anodes in Lithium-Ion Batteries with a High Mass Loading.

Due to the urgent demand for lithium-ion batteries (LIBs) with a high energy density, silicon (Si) possessing an ultrahigh capacity has aroused wide attention. However, its practical application is seriously hindered by enormous volume changes of the Si anode during cycling. Developing novel binders suitable for the Si anode has proven to be an effective strategy to improve its electrochemical performance. Herein, we constructed a three-dimensional network binder, in which the polyacrylic acid (PAA) long chains are cross-linked with one kind of amino acid, lysine (Lys). The abundant polar groups in PAA/Lys enable it to tightly adhere to the Si particles via hydrogen bonds, and the cross-linked structure prevents irreversible slipping of the PAA chains upon volume variation of the particles. The Si used was obtained from a sustainable route by recycling photovoltaic waste silicon. With high elasticity and strong adhesion, the PAA/Lys binder can effectively keep the structural integrity of the Si electrode and improve its electrochemical performance. The Si electrode using the PAA/Lys binder exhibits a good cycling stability (1008 mAh g-1 at 2 A g-1 after 250 cycles). Even with a high mass loading of 3.03 mg cm-2, the Si anode can remain stable for 100 cycles at a high fixed areal capacity of 3.03 mAh cm-2. This work gives a practical method to make stable Si electrodes using sustainable Si source and environmentally friendly amino acid-based binders.

High-Performance Stretchable Thermoelectric Generator for Self-Powered Wearable Electronics.

Wearable thermoelectric generators (TEGs), which can convert human body heat to electricity, provide a promising solution for self-powered wearable electronics. However, their power densities still need to be improved aiming at broad practical applications. Here, a stretchable TEG that achieves comfortable wearability and outstanding output performance simultaneously is reported. When worn on the forehead at an ambient temperature of 15 °C, the stretchable TEG exhibits excellent power densities with a maximum value of 13.8 µW cm-2 under the breezeless condition, and even as high as 71.8 µW cm-2 at an air speed of 2 m s-1 , being one of the highest values for wearable TEGs. Furthermore, this study demonstrates that this stretchable TEG can effectively power a commercial light-emitting diode and stably drive an electrocardiogram module in real-time without the assistance of any additional power supply. These results highlight the great potential of these stretchable TEGs for power generation applications.

Opening the Bandgap of Metallic Half-Heuslers via the Introduction of d-d Orbital Interactions.

Half-Heusler compounds with semiconducting behavior have been developed as high-performance thermoelectric materials for power generation. Many half-Heusler compounds also exhibit metallic behavior without a bandgap and thus inferior thermoelectric performance. Here, taking metallic half-Heusler MgNiSb as an example, a bandgap opening strategy is proposed by introducing the d-d orbital interactions, which enables the opening of the bandgap and the improvement of the thermoelectric performance. The width of the bandgap can be engineered by tuning the strength of the d-d orbital interactions. The conduction type and the carrier density can also be modulated in the Mg1- x Tix NiSb system. Both improved n-type and p-type thermoelectric properties are realized, which are much higher than that of the metallic MgNiSb. The proposed bandgap opening strategy can be employed to design and develop new half-Heusler semiconductors for functional and energy applications.

Achieving metal-like malleability and ductility in Ag2Te1-x S x inorganic thermoelectric semiconductors with high mobility.

Inorganic semiconductor Ag2Te1-x S x has been recently found to exhibit unexpected plastic deformation with compressive strain up to 30%. However, the origin of the abnormal plasticity and how to simultaneously achieve superb ductility and high mobility are still elusive. Here, we demonstrate that crystalline/amorphous Ag2Te1-x S x (x = 0.3, 0.4, and 0.5) composites can exhibit excellent compressive strain up to 70% if the monoclinic Ag2Te phase, which commonly exists in the matrix, is eliminated. Significantly, an ultra-high tensile elongation reaching 107.3% was found in Ag2Te0.7S0.3, which is the highest one yet reported in the system and even surpasses those achieved in some metals and high-entropy alloys. Moreover, high mobility of above 1000 cm2 V-1 s-1 at room temperature and good thermoelectric performance are simultaneously maintained. A modified Ashby plot with ductility factor versus carrier mobility is thereby proposed to highlight the potential of solid materials for applications in flexible/wearable electronics.

High-Power-Density Wearable Thermoelectric Generators for Human Body Heat Harvesting.

Wearable thermoelectrics has attracted significant interest in recent years. Among them, rigid-structure thermoelectric generators (TEGs) were seldomly employed for wearable applications, although those exhibit significant advantages of high device output performance and impact resistance. Here, we report a type of rigid wearable TEGs (w-TEGs) without ceramic substrates made using a simple cutting-and-bonding method. Owing to the small contact area, the w-TEGs comprising 48-n/p-pairs can be well attached to the human body. The lack of ceramic substrates leaves more space in the height direction, which benefits the wearability in practical applications and high power density. We demonstrated that increasing the height of w-TEGs from 1.38 to 3.14 mm significantly improves the power density by a factor of 10. As a result, the maximum power densities of 7.9 µW cm-2 and 43.6 µW cm-2 for the w-TEGs were realized under the breezeless condition and a wind speed for normal walking, respectively. This work provides a feasible design solution for rigid-structure free-substrate w-TEGs with very high power density, which will speed up the research of wearable thermoelectrics.

Graphene sheet/porous NiO hybrid film for supercapacitor applications.

We report the preparation of a nickel-foam-supported graphene sheet/porous NiO hybrid film by the combination of electrophoretic deposition and chemical-bath deposition. The obtained graphene-sheet film of about 19 layers was used as the nanoscale substrate for the formation of a highly porous NiO film made up of interconnected NiO flakes with a thickness of 10-20 nm. The graphene sheet/porous NiO hybrid film exhibits excellent pseudocapacitive behavior with pseudocapacitances of 400 and 324 F g(-1) at 2 and 40 A g(-1), respectively, which is higher than those of the porous NiO film (279 and 188 F g(-1) at 2 and 40 A g(-1)). The enhancement of the pseudocapacitive properties is due to reinforcement of the electrochemical activity of the graphene-sheet film.

Mo-Fe/NbFeSb Thermoelectric Junctions: Anti-Thermal Aging Interface and Low Contact Resistivity.

In recent years, high-performance half-Heusler compounds have been developed as promising thermoelectric materials for power generation. Aiming at practical device applications, one key step is to seek suitable metal electrodes so that low interfacial resistivity is guaranteed under long-term thermal aging. In the previous work, the fresh Mo/Nb0.8Ti0.2FeSb junction was found exhibiting low contact resistivity below 1 µΩ cm2; however, it increased by tens of times under long-term thermal aging, mainly originating from the formation of the high-resistivity FeSb2 phase and the appearance of cracks. Here, the Mo-Fe electrodes are employed to build the junctions with Nb0.8Ti0.2FeSb. The interfacial behavior and contact resistance in these junctions were investigated both before and after the thermal aging. Interestingly, no obvious formation of FeSb2 phase and cracks were observed. As a result, the contact resistivity was below ∼1 µΩ cm2 after 15 days' thermal aging, indicating better connection reliability and lower contact resistivity compared to the Mo/Nb0.8Ti0.2FeSb junction. These findings highlight the applicability of Mo-Fe electrodes and pave the way for NbFeSb-based half-Heusler thermoelectric materials for device applications.

Stable cycling of Prussian blue/Zn battery in a nonflammable aqueous/organic hybrid electrolyte.

Although rechargeable aqueous batteries are attracting increasing attention in recent years due to high safety, low cost, high power density and environmental friendliness, the aqueous batteries suffer from limited cycle life due to a narrow electrochemical window of the aqueous electrolytes, severe side reaction and instability of electrode materials in aqueous electrolytes. In this work, we propose a hybrid aqueous electrolyte with a mixed solvent of water and acetonitrile (ACN), which exhibits a wide electrochemical window, high ionic conductivity, and nonflammability. An aqueous battery with an iron hexacyanoferrate (FeHCF) cathode, Zn anode and H2O/ACN hybrid electrolyte shows a high capacity of 69.1 mA h g-1 at 10C (89.5% relative to that at 1C) and an extremely long cycle life with 51.4% capacity retention after 19 000 cycles at 10C. The excellent cycling performance of the aqueous FeHCF/Zn batteries can be attributed to the reduced water activity and extended electrochemical window because of the strong hydrogen-bonding interaction between ACN and H2O. Besides, the large particle size and good crystallization of FeHCF can inhibit its dissolution in the aqueous electrolyte which further improves cycling performance. This work will shed light on the design of safe aqueous batteries for applications in large-scale energy storage.

Demonstration of valley anisotropy utilized to enhance the thermoelectric power factor.

Valley anisotropy is a favorable electronic structure feature that could be utilized for good thermoelectric performance. Here, taking advantage of the single anisotropic Fermi pocket in p-type Mg3Sb2, a feasible strategy utilizing the valley anisotropy to enhance the thermoelectric power factor is demonstrated by synergistic studies on both single crystals and textured polycrystalline samples. Compared to the heavy-band direction, a higher carrier mobility by a factor of 3 is observed along the light-band direction, while the Seebeck coefficient remains similar. Together with lower lattice thermal conductivity, an increased room-temperature zT by a factor of 3.6 is found. Moreover, the first-principles calculations of 66 isostructural Zintl phase compounds are conducted and 9 of them are screened out displaying a pz-orbital-dominated valence band, similar to Mg3Sb2. In this work, we experimentally demonstrate that valley anisotropy is an effective strategy for the enhancement of thermoelectric performance in materials with anisotropic Fermi pockets.

Medium Entropy-Enabled High Performance Cubic GeTe Thermoelectrics.

The configurational entropy is an emerging descriptor in the functional materials genome. In thermoelectric materials, the configurational entropy helps tune the delicate trade-off between carrier mobility and lattice thermal conductivity, as well as the structural phase transition, if any. Taking GeTe as an example, low-entropy GeTe generally have high carrier mobility and distinguished zT > 2, but the rhombohedral-cubic phase transition restricts the applications. In contrast, despite cubic structure and ultralow lattice thermal conductivity, the degraded carrier mobility leads to a low zT in high-entropy GeTe. Herein, medium-entropy alloying is implemented to suppress the phase transition and achieve the cubic GeTe with ultralow lattice thermal conductivity yet decent carrier mobility. In addition, co-alloying of (Mn, Pb, Sb, Cd) facilitates multivalence bands convergence and band flattening, thereby yielding good Seebeck coefficients and compensating for decreased carrier mobility. For the first time, a state-of-the-art zT of 2.1 at 873 K and average zT ave of 1.3 between 300 and 873 K are attained in cubic phased Ge0.63Mn0.15Pb0.1Sb0.06Cd0.06Te. Moreover, a record-high Vickers hardness of 270 is attained. These results not only promote GeTe materials for practical applications, but also present a breakthrough in the burgeoning field of entropy engineering.

High-Performance Mg3Sb2-x Bi x Thermoelectrics: Progress and Perspective.

Since the first successful implementation of n-type doping, low-cost Mg3Sb2-x Bi x alloys have been rapidly developed as excellent thermoelectric materials in recent years. An average figure of merit zT above unity over the temperature range 300-700 K makes this new system become a promising alternative to the commercially used n-type Bi2Te3-x Se x alloys for either refrigeration or low-grade heat power generation near room temperature. In this review, with the structure-property-application relationship as the mainline, we first discuss how the crystallographic, electronic, and phononic structures lay the foundation of the high thermoelectric performance. Then, optimization strategies, including the physical aspects of band engineering with Sb/Bi alloying and carrier scattering mechanism with grain boundary modification and the chemical aspects of Mg defects and aliovalent doping, are extensively reviewed. Mainstream directions targeting the improvement of zT near room temperature are outlined. Finally, device applications and related engineering issues are discussed. We hope this review could help to promote the understanding and future developments of low-cost Mg3Sb2-x Bi x alloys for practical thermoelectric applications.

Trace fluorinated-carbon-nanotube-induced lithium dendrite elimination for high-performance lithium-oxygen cells.

Lithium metal has attracted considerable attention due to its ultrahigh theoretical capacity. Nevertheless, issues such as dendritic Li formation and instability of the Li metal/electrolyte interface still restrain its practical applications. In this work, we design a Li composite anode with fluorinated carbon nanotubes (FCNT) fabricated by a simple melting-soaking method. It was found that trace amounts of added FCNT (only 1.6 wt%) lead to a significant chemical/electrochemical stability of metallic Li. The obtained Li/FCNT composite electrode (LFCNT) exhibits much better stability in open air and electrolyte than bare Li. The LFCNT enables uniform plating/stripping of metallic Li, preventing the dendrite formation during repeated cycling. In situ optical microscopy observations confirm dendrite-free Li deposition with the mechanism clarified by density functional theory calculations. Compared with bare Li, the LFCNT shows a considerable improvement in rate capability, voltage hysteresis and cycle performance, sustaining stable cycling at a high current density of 3 mA cm-2 or a capacity up to 5 mA h cm-2. Li-O2 cells with a LFCNT anode exhibit a long life of 135 cycles at a capacity of 1000 mA h g-1, which is six-fold than that with the bare Li anode.

Tuning Optimum Temperature Range of Bi2 Te3 -Based Thermoelectric Materials by Defect Engineering.

Bi2 Te3 -based solid solutions, which have been widely used as thermoelectric (TE) materials for the room temperature TE refrigeration, are also the potential candidates for the power generators with medium and low-temperature heat sources. Therefore, depending on the applications, Bi2 Te3 -based materials are expected to exhibit excellent TE properties in different temperature ranges. Manipulating the point defects in Bi2 Te3 -based materials is an effective and important method to realize this purpose. In this review, we focus on how to optimize the TE properties of Bi2 Te3 -based TE materials in different temperature ranges by defect engineering. Our calculation results of two-band model revel that tuning the carrier concentration and band gap, which is easily realized by defects engineering, can obtain better TE properties at different temperatures. Then, the typical paradigms about optimizing the TE properties at different temperatures for n-type and p-type Bi2 Te3 -based ZM ingots and polycrystals are discussed in the perspective of defects engineering. This review can provide the guidance to improve the TE properties of Bi2 Te3 -based materials at different temperatures by defects engineering.

Revealing the Intrinsic Electronic Structure of 3D Half-Heusler Thermoelectric Materials by Angle-Resolved Photoemission Spectroscopy.

Accurate determination of the intrinsic electronic structure of thermoelectric materials is a prerequisite for utilizing an electronic band engineering strategy to improve their thermoelectric performance. Herein, with high-resolution angle-resolved photoemission spectroscopy (ARPES), the intrinsic electronic structure of the 3D half-Heusler thermoelectric material ZrNiSn is revealed. An unexpectedly large intrinsic bandgap is directly observed by ARPES and is further confirmed by electrical and optical measurements and first-principles calculations. Moreover, a large anisotropic conduction band with an anisotropic factor of 6 is identified by ARPES and attributed to be one of the most important reasons leading to the high thermoelectric performance of ZrNiSn. These successful findings rely on the grown high-quality single crystals, which have fewer Ni interstitial defects and negligible in-gap states on the electronic structure. This work demonstrates a realistic paradigm to investigate the electronic structure of 3D solid materials by using ARPES and provides new insights into the intrinsic electronic structure of the half-Heusler system benefiting further optimization of thermoelectric performance.