Recent Progress of Two-Dimensional Thermoelectric Materials

Thermoelectric generators have attracted a wide research interest owing to their ability to directly convert heat into electrical power.Moreover,the thermoelectric properties of traditional inorganic and organic materials have been significantly improved over the past few decades.Among these compounds,layered two-dimensional(2D)materials,such as graphene,black phosphorus,transition metal dichalcogenides,IVA–VIA compounds,and MXenes,have generated a large research attention as a group of potentially high-performance thermoelectric materials.Due to their unique electronic,mechanical,thermal,and optoelectronic properties,thermoelectric devices based on such materials can be applied in a variety of applications.Herein,a comprehensive review on the development of 2D materials for thermoelectric applications,as well as theoretical simulations and experimental preparation,is presented.In addition,nanodevice and new applications of 2D thermoelectric materials are also introduced.At last,current challenges are discussed and several prospects in this field are proposed.

Electronic structure engineering in organic thermoelectric materials

Electronic structures, which play a key role in determining electrical and optical properties of π-conjugated organic materials, have attracted tremendous interest. Efficient thermoelectric (TE) conversion of organic materials has rigorous requirements on electronic structures. Recently, the rational design and precise modulation of electronic structures have exhibited great potential in exploring state-of-the-art organic TE materials. This review focuses on the regulation of electronic structures of organic materials toward efficient TE conversion. First, we present the basic knowledge regarding electronic structures and the requirements for efficient TE conversion of organic materials, followed by a brief introduction of commonly used methods for electronic structure characterization. Next, we highlight the key strategies of electronic structure engineering for high-performance organic TE materials. Finally, an overview of the electronic structure engineering of organic TE materials, along with current challenges and future research directions, are provided.

Thermoelectric properties of porous (Bi_(0.15)Sb_(0.85))_2Te_3 thermoelectric materials

In order to obtain thermoelectric materials with high figure of merit, theconcept of Hollow (Vacuum) Quantum Structure or Effect and related thermoelectric materials designwere proposed. To demonstrate the theory, the materials of (Bi_(0.15)Sb_(0.85))_2Te_3 with porousstructure have been fabricated. Their thermoelectric properties and the microstructure wereinvestigated and compared with their density structure. It was found that the porous structure couldimprove their properties greatly.

An Overview of Advanced Chalcogenide Thermoelectric Materials and Their Applications

Thermoelectricity is a strong scientific and technological interest due to its wide application ranging from clean energy producing to photon sensing devices.Recent developments in theoretical studies on the thermoelectric(TE)effects as well as the newly discovered thermoelectric materials provide new opportunities for several applications.Though the scale of production is limited,thermoelectric technology provides an alternative to traditional methods of power generation,heating and cooling systems.TE technologies can be used in power generation,heating and cooling applications.They potentially offer significant energy savings through waste heat recovery and augmented cooling.This article critically discusses the current progress in chalcogenide TE materials and the advantages and limitations associated with the TE technologies.The need for new materials discoveries from the point of view of achieving higher figure-of-merit combined with thermal stabilities in intermediate-and hightemperature Peltier and Seebeck effects applications is also emphasized.Besides,this article aims to evaluate the main features of recently characterized multicomponent chalcogenide ionic compounds with high thermal stabilities as potential TE materials to harvest electric power from high-temperature heat flux via thermoelectricity.

Thermoelectric Properties of N-typer Bi_2Te_3-PbTe Graded Thermoelectric Materials with Different Barriers

In order to investigate the adaptability of thermoelectric materials system with different barriers to functional graded thermoelectric materials, n-type Bi2Te, and PbTe two segments graded thermoelectric materials (GTM) with different barriers were fabricated by conventional hot pressing method. Metals Cu, Al, Fe, Co and Ni were used as barriers between two segments. The effects of different barriers on thermoelectric properties of GTM were investigated. The phase and crystal structures were determined by x-ray diffraction analysis (XRD). The distributions of different compositions were analyzed by electron microprobe analysis (EMA). The thermoelectric properties were measured at 303 K along the direction parallel to the pressing direction. The electric conductivity of samples was measured at 303 K by the four-probe technique. To measure the Seebeck coefficient, heat was applied to the samples, which were placed between two Cu discs. The thermoelectric electromotive force (E) was measured upon applying small temperature differences (DeltaT<275 K) between the both ends of the samples. The Seebeck coefficient of the samples was determined from the E/&UDelta;T.

Thermoelectric properties of p-type Bi-Sb-Te compositionally graded thermoelectric materials with different barriers

In order to find more suitable materials as barriers and to improve the thermoelectric properties, p-type (Bi1-xSbx) 2Te3 (x = 0.85, 0.9) two segments compositionally graded thermoelectric materials (CGTM) with different barriers were fabricated by conventional hot pressure method. Metals Fe, Co, Cu and Al were used as barriers between two segments. The effects of different barriers on thermoelectric properties of CGTM were investigated. The results show that metal Fe is more stable and suitable as the barrier.

Surface contact behavior of functionally graded thermoelectric materials indented by a conducting punch

The contact problem for thermoelectric materials with functionally graded properties is considered.The material properties,such as the electric conductivity,the thermal conductivity,the shear modulus,and the thermal expansion coefficient,vary in an exponential function.Using the Fourier transform technique,the electro-thermoelastic problems are transformed into three sets of singular integral equations which are solved numerically in terms of the unknown normal electric current density,the normal energy flux,and the contact pressure.Meanwhile,the complex homogeneous solutions of the displacement fields caused by the gradient parameters are simplified with the help of Euler’s formula.After addressing the non-linearity excited by thermoelectric effects,the particular solutions of the displacement fields can be assessed.The effects of various combinations of material gradient parameters and thermoelectric loads on the contact behaviors of thermoelectric materials are presented.The results give a deep insight into the contact damage mechanism of functionally graded thermoelectric materials(FGTEMs).

Thermoelectric properties of BiSb_x (x=0.6-0.8) thermoelectric materials fabricated by different processing

In order to improve the thermoelectric properties, hot-pressing sintering andultra high pressure sintering methods were adopted to fabricate BiSb_x. The phase and crystalstructures were determined by X-ray diffraction analysis (XRD). The thermoelectric properties weremeasured at 303 K along the direction parallel to the pressing direction. The electric conductivityof the samples was measured at 303 K by the four-probe technique. To measure the Seebeckcoefficient, heat was applied to the samples placed between two Cu discs. The thermoelectricelectromotive force (E) was measured upon applying small temperature differences (DELTA T<2 deg C)between the both ends of the samples. The Seebeck coefficient of the samples was determined from thevalue of E/DELTA T. The results indicate that the thermoelectric properties of the samplesfabricated by UHPS (ultra high pressure sintering) method are much higher than that by HPS (hotpressing sintering) method and have the highest values at x=0.7.

High-entropy alloys in thermoelectric application:A selective review

Since the superior mechanical,chemical and physical properties of high-entropy alloys(HEAs)were discovered,they have gradually become new emerging candidates for renewable energy applications.This review presents the novel applications of HEAs in thermoelectric energy conversion.Firstly,the basic concepts and structural properties of HEAs are introduced.Then,we discuss a number of promising thermoelectric materials based on HEAs.Finally,the conclusion and outlook are presented.This article presents an advanced understanding of the thermoelectric properties of HEAs,which provides new opportunities for promoting their applications in renewable energy.

Frictional contact analysis of a rigid solid with periodic surface sliding on the thermoelectric material

Understanding and characterizing rough contact and wavy surfaces are essential for developing effective strategies to mitigate wear,optimize lubrication,and enhance the overall performance and durability of mechanical systems.The sliding friction contact problem between a thermoelectric(TE)half-plane and a rigid solid with a periodic wavy surface is the focus of this investigation.To simplify the problem,we utilize mixed boundary conditions,leading to a set of singular integral equations(SIEs)with the Hilbert kernels.The analytical solutions for the energy flux and electric current density are obtained by the variable transform method in the context of the electric and temperature field.The contact problem for the elastic field is transformed into the second-kind SIE and solved by the Jacobi polynomials.Notably,the smoothness of the wavy contact surface ensures that there are no singularities in the surface contact stress,and ensures that it remains free at the contact edge.Based on the plane strain theory of elasticity,the analysis primarily examines the correlation between the applied load and the effective contact area.The distribution of the normal stress on the surface with or without TE loads is discussed in detail for various friction coefficients.Furthermore,the obtained results indicate that the in-plane stress decreases behind the trailing edge,while it increases ahead of the trailing edge when subjected to TE loads.

Heat Conduction in Multilayered Thermoelectric Materials with Multiple Cracks

Multilayer thin-film thermoelectric materials are of technological importance. This paper describes a method to analyze the heat conduction in a multilayered thermoelectric plate containing some non-collinear cracks. The material properties in one layer may be different from those in another even though each layer may still be homogeneous. Using the Fourier integral transforms, the boundary value problem is reduced to a system of general singular integral equations. The model is sufficiently general to account for any number of layers and any number of cracks. As a numerical illustration, the electric flux intensity factor, energy flux intensity factor and thermal flux intensity factor for a three-layer plate specimen with two cracks are presented. The effects of strip width on the electric flux intensity factor and thermal flux intensity factor are studied.

Low-cost and environmentally benign selenides as promising thermoelectric materials

Developing high-efficiency materials with earth-abundant and low-toxicity elements has become a popular trend in the field of thermoelectrics.Among these compounds,oxides and sulfides,the lighter,cheaper and green analogies of tellurides,have been extensively investigated and summarized as well defined classes.Nonetheless,the vast family of selenides with better electrical performance,lower thermal conductivity and higher thermoelectric efficiency have not been specially discussed.Here in this review,we present recent advances in binary and multinary selenide thermoelectric materials,covering traditional PbSe,liquid-like Cu_(2)Se,layered SnSe,diamond-like and disordered multinary compounds.The features of selenides are discussed based on both environmental concerns and from the perspective of chemical bonding,transport properties and performance.Emphasis is put on the“compositionstructure-processing-performance”relationship,and some interesting issues are addressed.Finally,challenges for thermoelectric selenides are discussed,and possible optimization strategies are also suggested.

When thermoelectric materials come across with magnetism

Nowadays,thermoelectric materials have attracted a lot of attention as they can directly convert heat into electricity and vice versa.However,while strenuous efforts have been made,those conventional strategies are still inevitably going to meet their performance optimization limits.For this reason,brand new strategies are badly needed to achieve further enhancement.Here,the roles played by magnetism in recent advances of thermoelectric optimization are concluded.Firstly,magnetic thermoelectric materials can just be treated like other normal materials because the use of universal optimization strategies can still get good results.So,it is not a situation which is all or nothing and the tactics of using magnetism for thermoelectric optimization can coexist with other strategies.Besides,through magnetic doping,we can introduce and adjust magnetism in materials for further optimization.Magnetism provides more possibilities in thermoelectric optimization as it can directly influence the spin states in materials.Furthermore,in the form of magnetic secondphase nanoclusters,magnetism can be introduced to thermoelectric materials to conquer the dilemma that the solid solubility of many magnetic ions in thermoelectric materials is too low to have any significant effect on thermoelectric properties.Finally,when exposed to an external magnetic field,topological materials can rely on its unique band structures to optimize.

Machine learning assisted discovering of new M_(2)X_(3)-type thermoelectric materials

Recent years have witnessed a continuous discovering of new thermoelectric materials which has experienced a paradigm shift from try-and-error efforts to experience-based discovering and first-principles calculation. However, both the experiment and first-principles calculation deriving routes to determine a new compound are time and resources consuming. Here, we demonstrated a machine learning approach to discover new M_(2)X_(3)-type thermoelectric materials with only the composition information. According to the classic Bi_(2)Te_(3) material, we constructed an M_(2)X_(3)-type thermoelectric material library with 720 compounds by using isoelectronic substitution, in which only 101 compounds have crystalline structure information in the Inorganic Crystal Structure Database(ICSD) and Materials Project(MP) database. A model based on the random forest(RF) algorithm plus Bayesian optimization was used to explore the underlying principles to determine the crystal structures from the known compounds. The physical properties of constituent elements(such as atomic mass, electronegativity, ionic radius) were used to define the feature of the compounds with a general formula ^(1)M^(2)M^(1)X^(2)X^(3)X(^(1)M +^(2)M:^(1)X +^(2)X+^(3)X = 2:3). The primary goal is to find new thermoelectric materials with the same rhombohedral structure as Bi_(2)Te_(3) by machine learning.The final trained RF model showed a high accuracy of 91% on the prediction of rhombohedral compounds. Finally, we selected four important features to proceed with the polynomial fitting with the prediction results from the RF model and used the acquired polynomial function to make further discoveries outside the pre-defined material library.

Polymer-based thermoelectric materials:A review of power factor improving strategies

Thermoelectric(TE)materials are receiving increasing attention due to their ability to directly converting heat to electricity.They are used to harvest electrical energy from the wasted heat in order to increase the efficiency of global energy.Polymer-based TE materials are particularly fascinating to wearable and mobile devices due to their low density,good flexibility,and low toxicity.This review summarizes the recent breakthroughs and optimization strategies of polymer-based TE materials.Among a large number of different organic TE materials,those with remarkable TE performance are selected and divided into three categories,which are poly(3,4-ethylenedioxythiophene)derivatives,carbon nanotube/conductive polymer composites,and inorganic semiconductive nanomaterial/polymer composites.The effect of components and structures on the power factor are presented and discussed.Finally,some challenges are described and suggestions are provided for preparing the next-generation of polymer-based materials with high TE performance.

Advances in organic thermoelectric materials and devices for smart applications

Organic thermoelectric(OTE)materials have been considered to be promising candidates for large area and low‐cost wearable devices owing to their tailorable molecular structure,intrinsic flexibility,and prominent solution processability.More importantly,OTE materials offer direct energy conversion from the human body,solid‐state cooling at low electric consumption,and diversified functions.Herein,we summarize recent developments of OTE materials and devices for smart applications.We first review the fundamentals of OTE materials from the viewpoint of thermoelectric performance,mechanical properties and bionic functions.Second,we describe OTE devices in flexible generators,photothermoelectric detectors,self‐powered sensors,and ultra‐thin cooling elements.Finally,we present the challenges and perspectives on OTE materials as well as devices in wearable electronics and fascinating applications in the Internet of Things.

Editorial for rare metals, special issue on advanced thermoelectric materials

As a clean energy technology to combat the global energy dilemma and the environmental problems, thermoelectrics that enable a direct conversion between heat and electricity have attracted increasing attention in recent decades. This solid-state, vibrationless technology has long been used for powering the spacecrafts of several deep-space missions and has limited commercial use in niche market, but these are now actively considered for a variety of new applications, such as the conversion of automobile exhaust heat into electricity. Meanwhile, materials research flourishes with the knowledge that significantly improves the thermoelectric efficiency for even more applications. This motivates Rare Metals to have a special issue focusing on thermoelectrics.

Planar Zintl-phase high-temperature thermoelectric materials XCuSb(X=Ca,Sr,Ba)with low lattice thermal conductivity

A recent discovery of high-performance Mg_(3)Sb_(2) has ignited tremendous research activities in searching for novel Zintl-phase compounds as promising thermoelectric materials.Herein,a series of planar Zintl-phase XCuSb(X=Ca,Sr,Ba)thermoelectric materials are developed by vacuum induction melting.All these compounds exhibit high carrier mobilities and intrinsic low lattice thermal conductivities(below 1 W·m^(−1)·K^(−1) at 1010 K),resulting in peak p-type zT values of 0.14,0.30,and 0.48 for CaCuSb,SrCuSb,and BaCuSb,respectively.By using BaCuSb as a prototypical example,the origins of low lattice thermal conductivity are attributed to the strong interlayer vibrational anharmonicity of Cu–Sb honeycomb sublattice.Moreover,the first-principles calculations reveal that n-type BaCuSb can achieve superior thermoelectric performance with the peak zT beyond 1.1 because of larger conducting band degeneracy.This work sheds light on the high-temperature thermoelectric potential of planar Zintl compounds,thereby stimulating intense interest in the investigation of this unexplored material family for higher zT values.

Accurate and explainable machine learning for the power factors of diamond-like thermoelectric materials

The application of machine learning(ML)-based methods to the study of thermoelectric(TE)materials is promising.Although conventional ML algorithms can achieve high prediction performance,their lack of interpretability severely obstructs researchers from extracting material-oriented insights from ML models.In this work,high ML-based prediction performance was achieved with respect to TE power factors(PFs),and the results were well understood by the SHapley Additive exPlanations(SHAP),a method to identify the correlations between targets and descriptors.We designed a robust PF prediction model for diamond-like compounds via a stacking technique,and the model achieved a coefficient of determination value above 0.95 on the test set.From the SHAP analysis,the PFs were negatively correlated with electronegativity and positively correlated with the descriptor“volume per atom”based on the previously reported dataset.TE domain knowledge was adopted to understand these correlations.This work shows that ML models can achieve high accuracy while exhibiting good interpretability,making them useful for materials scientists.

Magnesium-based energy materials: Progress, challenges, and perspectives

Magnesium-based energy materials, which combine promising energy-related functional properties with low cost, environmental compatibility and high availability, have been regarded as fascinating candidates for sustainable energy conversion and storage. In this review,we provide a timely summary on the recent progress in three types of important Mg-based energy materials, based on the fundamental strategies of composition and structure engineering. With regard to Mg-based materials for batteries, we systematically review and analyze different material systems, structure regulation strategies as well as the relevant performance in Mg-ion batteries(MIBs) and Mg-air batteries(MABs), covering cathodes, electrolytes, anodes for MIBs, and anodes for MABs;as to Mg-based hydrogen storage materials, we discuss how catalyst adding, composite, alloying and nanostructuring improve the kinetic and thermodynamic properties of de/hydrogenation reactions, and in particular, the impacts of composition and structure modification on hydrogen absorption/dissociation processes and free energy modification mechanism are focused;regarding Mg-based thermoelectric materials, the relations between composition/structure and electrical/thermal transport properties of Mg_(3)X_(2)(X = Sb, Bi), Mg_(2)X(X = Si, Ge, Sn) and Mg Ag Sb-based materials, together with the representative research progress of each material system, are summarized and discussed. Finally, by pointing out remaining challenges and providing possible solutions, this review aims to shed light on the directions and perspectives for practical applications of magnesium-based energy materials in the future.