Effect of Molecular Weight on Thermoelectric Performance of P3HT Analogues with 2-Propoxyethyl Side Chains

By replacing hexyl chains in poly(3-hexylthiophene)(P3HT)with 2-propoxyethyls,four poly(3-(2-propoxyethyl)thiophene)(P3POET)homopolymers with comparable polydispersity indexes(PDI)and regioregularities were prepared herein in addition with step increment of about 7 kDa on numberaverage molecular weight(M_(n))from around 11 to 32 kDa(accordingly denoted as P11k,P18k,P25k,and P32k).When doped in film by FeCl_(3)at the optimized conditions,the maximum power factor(PF_(max))increases greatly from 4.3μW·m^(-1)·K^(-2)for P11k to 8.8μW·m^(-1)·K^(-2)for P18k,and further to 9.7μW·m^(-1)·K^(-2)for P25k,followed by a slight decrease to 9.2μW·m^(-1)·K^(-2)for P32k.The close Seebeck coefficients(S)at PF_(max)are observed in these doped polymer films due to their consistent frontier orbital energy levels and Fermi levels.The main contribution to this PF_(max)evolution thus comes from the corresponding conductivities(σ).Theσvariation of the doped films can be rationally correlated with their microstructure evolution.

Diameter-dependent ultra-high thermoelectric performance of ZnO nanowires

Zinc oxide(ZnO)shows great potential in electronics,but its large intrinsic thermal conductivity limits its thermoelectric applications.In this work,we explore the significant carrier transport capacity and diameter-dependent thermoelectric characteristics of wurtzite-ZnO(0001)nanowires based on first-principles and molecular dynamics simulations.Under the synergistic effect of band degeneracy and weak phonon-electron scattering,P-type(ZnO)_(73) nanowires achieve an ultrahigh power factor above 1500μW·cm^(-1)·K^(-2)over a wide temperature range.The lattice thermal conductivity and carrier transport properties of ZnO nanowires exhibit a strong diameter size dependence.When the ZnO nanowire diameter exceeds 12.72A,the carrier transport properties increase significantly,while the thermal conductivity shows a slight increase with the diameter size,resulting in a ZT value of up to 6.4 at 700 K for P-type(ZnO)_(73).For the first time,the size effect is also illustrated by introducing two geometrical configurations of the ZnO nanowires.This work theoretically depicts the size optimization strategy for the thermoelectric conversion of ZnO nanowires.

On-Chip Micro Temperature Controllers Based on Freestanding Thermoelectric Nano Films for Low-Power Electronics

Multidimensional integration and multifunctional com-ponent assembly have been greatly explored in recent years to extend Moore’s Law of modern microelectronics.However,this inevitably exac-erbates the inhomogeneity of temperature distribution in microsystems,making precise temperature control for electronic components extremely challenging.Herein,we report an on-chip micro temperature controller including a pair of thermoelectric legs with a total area of 50×50μm^(2),which are fabricated from dense and flat freestanding Bi2Te3-based ther-moelectric nano films deposited on a newly developed nano graphene oxide membrane substrate.Its tunable equivalent thermal resistance is controlled by electrical currents to achieve energy-efficient temperature control for low-power electronics.A large cooling temperature difference of 44.5 K at 380 K is achieved with a power consumption of only 445μW,resulting in an ultrahigh temperature control capability over 100 K mW^(-1).Moreover,an ultra-fast cooling rate exceeding 2000 K s^(-1) and excellent reliability of up to 1 million cycles are observed.Our proposed on-chip temperature controller is expected to enable further miniaturization and multifunctional integration on a single chip for microelectronics.

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.

Harness High-Temperature Thermal Energy via Elastic Thermoelectric Aerogels

Despite notable progress in thermoelectric(TE)materials and devices,developing TE aerogels with high-temperature resistance,superior TE performance and excellent elasticity to enable self-powered high-temperature monitoring/warning in industrial and wearable applications remains a great challenge.Herein,a highly elastic,flame-retardant and high-temperature-resistant TE aerogel,made of poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate)/single-walled carbon nanotube(PEDOT:PSS/SWCNT)composites,has been fabricated,displaying attractive compression-induced power factor enhancement.The as-fabricated sensors with the aerogel can achieve accurately pressure stimuli detection and wide temperature range monitoring.Subsequently,a flexible TE generator is assembled,consisting of 25 aerogels connected in series,capable of delivering a maximum output power of 400μW when subjected to a temperature difference of 300 K.This demonstrates its outstanding high-temperature heat harvesting capability and promising application prospects for real-time temperature monitoring on industrial high-temperature pipelines.Moreover,the designed self-powered wearable sensing glove can realize precise wide-range temperature detection,high-temperature warning and accurate recognition of human hand gestures.The aerogel-based intelligent wearable sensing system developed for firefighters demonstrates the desired self-powered and highly sensitive high-temperature fire warning capability.Benefitting from these desirable properties,the elastic and high-temperature-resistant aerogels present various promising applications including self-powered high-temperature monitoring,industrial overheat warning,waste heat energy recycling and even wearable healthcare.

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.

Investigating the Potential of Quasi-One-Dimensional Organic Crystals of TTT(TCNQ)2 for Thermoelectric Applications

The purpose of this paper is to present the results of investigations on quasi-one-dimensional organic crystals of tetrathiotetracene-tetracyanoquinodi- methane (TTT(TCNQ)2) from the prospective of thermoelectric applications. The calculations were performed after analytical expressions, obtained in the frame of a physical model, more detailed than the model presented earlier by authors. The main Hamiltonian of the model includes the electronic and phonon part, electron-phonon interactions and the impurity scattering term. In order to estimate the electric charge transport between the molecular chains, the physical model was upgraded to the so-called three-dimen- sional (3D) physical model. Numeric computations were performed to determine the electrical conductivity, Seebeck coefficient, thermal conductivity, thermoelectric power factor and thermoelectric figure-of-merit as a function on charge carrier concentrations, temperatures and impurity concentrations. A detailed analysis of charge-lattice interaction, consisting of the exploration of the Peierls structural transition in TCNQ molecular chains of TTT(TCNQ)2 was performed. As result, the critical transition temperature was determined. The dispersion of renormalized phonons was examined in detail.

Thermoelectric generators and their applications:Progress,challenges,and future prospects

Our community currently deals with issues such as rising electricity costs,pollution,and global warming.Scientists work to improve energy harvesting-based power generators in order to reduce their impacts.The Seebeck effect has been used to illustrate the capacity of thermoelectric generators(TEGs)to directly convert thermal energy to electrical energy.They are also ecologically beneficial since they do not include chemical products,function quietly because they lack mechanical structures and/or moving components,and may be built using different fabrication technologies such as three-dimentional(3D)printing,silicon technology,and screen printing,etc.TEGs are also position-independent and have a long operational lifetime.TEGs can be integrated into bulk and flexible devices.This review gives further investigation of TEGs,beginning with a full discussion of their operating principle,kinds,materials utilized,figure of merit,and improvement approaches,which include various thermoelectric material arrangements and utilised technologies.This paper also discusses the use of TEGs in a variety of disciplines such as automobile and biomedical.

Ion–Electron Coupling Enables Ionic Thermoelectric Material with New Operation Mode and High Energy Density

Ionic thermoelectrics(i-TE) possesses great potential in powering distributed electronics because it can generate thermopower up to tens of millivolts per Kelvin. However,as ions cannot enter external circuit, the utilization of i-TE is currently based on capacitive charge/discharge, which results in discontinuous working mode and low energy density. Here,we introduce an ion–electron thermoelectric synergistic(IETS)effect by utilizing an ion–electron conductor. Electrons/holes can drift under the electric field generated by thermodiffusion of ions, thus converting the ionic current into electrical current that can pass through the external circuit. Due to the IETS effect, i-TE is able to operate continuously for over 3000 min.Moreover, our i-TE exhibits a thermopower of 32.7 mV K^(-1) and an energy density of 553.9 J m^(-2), which is more than 6.9 times of the highest reported value. Consequently, direct powering of electronics is achieved with i-TE. This work provides a novel strategy for the design of high-performance i-TE materials.

Water-resistant organic thermoelectric generator with >10μW output

Flexible p–n thermoelectric generator(TEG)technology has rapidly advanced with power enhancement and size reduction.To achieve a stable power supply and highly efficient energy conversion,absolute chemical stability of n-type materials is essential to ensuring large temperature differences between device terminals and ambient stability.With the aim of improving the long-term stability of the n-type operation of carbon nanotubes(CNTs)in air and water,this study uses cationic surfactants,such as octylene-1,8-bis(dimethyldodecylammonium bromide)(12-8-12),a gemini surfactant,to stabilize the nanotubes in a coating,which retains the n-doped state for more than 28 days after exposure to air and water in experiments.TEGs with 10 p-n units of 12-8-12/CNT(n-type)and sodium dodecylbenzene sulfonate/CNT(p-type)layers are manufactured,and their water stability is evaluated.The initial maximum output of 16.1μW(75 K temperature difference)is retained after water immersion for 40 days without using a sealant to prevent TEG module degradation.The excellent stability of these CNT-based TEGs makes them suitable for underwater applications,such as battery-free health monitoring and information gathering systems,and facilitates the development of soft electronics.

Waste Heat Recovery from a Drier Receiver of an A/C Unit Using Thermoelectric Generators

Thermoelectric generators(TEGs)are considered promising devices for waste heat recovery from various systems.The Seebeck effect can be utilized to generate power using the residual heat emitted by the filter dryer receiver(FDR)of an air conditioning(A/C)system,which would otherwise go to waste.The study aims to build a set of thermoelectric generators(TEG)to collect the waste heat of the FDR and generate low-power electricity.A novel electrical circuit with two transformers is designed and fabricated to produce a more stable voltage for operation and charging.The thermoelectric generator(TEGs)was installed on the FDR of the A/C unit.The test showed that climate conditions have a significant impact on the output power generated from the system.The results showed that the peak voltage recorded in the current study is 5.2 V per day(wet,cold,and wind weather)with an output power of 0.2 W.These values are acceptable for powering the load and charging a single battery with 3.5 V as the voltage increases battery 0.1 V/20 min charge.A case study of operating the emergency signs in a building was considered.The current heat recovery system is deemed to be easily installed and can be connected to a network of TEGs to produce more power.

Ga intercalation in van der Waals layers for advancing p-type Bi_(2)Te_(3)-based thermoelectrics

Tetradymite-structured chalcogenides,such as Bi_(2)Te_(3) and Sb_(2)Te_(3),are quasi-two-dimensional(2D)layered compounds,which are significant thermoelectric materials applied near room temperature.The intercalation of guest species in van der Waals(vdW)gap implemented for tunning properties has attracted much attention in recent years.We attempt to insert Ga atoms in the vdW gap between the Te layers in p-type Bi_(0.3)Sb_(1.7)Te_(3)(BST)for further improving thermoelectrics.The vdW-related defects(including extrinsic interstitial and intrinsic defects)induced by Ga intercalation can not only modulate the carrier concentration but also enhance the texture,thereby yielding excellent electrical properties,which are reflected in the power factor PF~4.43 mW·m^(-1)·K^(-2).Furthermore,the intercalation of Ga produces multi-scale lattice imperfections such as point defects,Te precipitations,and nanopores,realizing the low lattice thermal conductivity in BST-Ga samples.Ultimately,a peak zT~1.1 at 373 K is achieved in the BST-1%Ga sample and greatly improved by~22%compared to the pristine BST.The weak bonding of vdW interlayer interaction can boost the synergistic effect for advancing BST-based or other layered thermoelectrics.

Efficient thermal management and all-season energy harvesting using adaptive radiative cooling and a thermoelectric power generator

Passive daytime radiative cooling(PDRC) is useful for thermal management because it allows an object to emit terrestrial heat into space without the use of additional energy.To produce sub-ambient temperatures under direct sunlight,PDRC materials are designed to reduce their absorption of solar energy and to enhance their long-wavelength infrared(LWIR) emissivity.In recent years,many photonic structures and polymer composites have been studied to improve the cooling system of buildings.However,in cold weather(i.e. during winter in cold climates),buildings need to be kept warm rather than cooled due to heat loss.To overcome this limitation,temperature-responsive radiative cooling is a promising alternative.In the present study,adaptive radiative cooling(ARC) film fabricated from a polydimethylsiloxane/hollow SiO_(2) microsphere/thermochromic pigment composite was investigated.We found that the ARC film absorbed solar radiation under cold conditions while exhibiting radiative cooling at ambient temperatures above 40℃.Thus,in outdoor experiments,the ARC film achieved sub-ambient temperatures and had a theoretical cooling power of 63.2 W/m~2 in hot weather.We also demonstrated that radiative cooling with an energy harvesting system could be used to improve the energy management of buildings,with the thermoelectric module continuously generating output power using the ARC film.Therefore,we believe that our proposed ARC film can be employed for efficient thermal management of buildings and all-season energy harvesting in the near future.

Interfacial behavior of a thermoelectric film bonded to a graded substrate

To improve the thermoelectric converting performance in applications such as power generation,reutilization of heat energy,refrigeration,and ultrasensitive sensors in scramjet engines,a thermoelectric film/substrate system is widely designed and applied,whose interfacial behavior dominates the strength and service life of thermoelectric devices.Herein,a theoretical model of a thermoelectric film bonded to a graded substrate is proposed.The interfacial shear stress,the normal stress in the thermoelectric film,and the stress intensity factors affected by various material and geometric parameters are comprehensively studied.It is found that adjusting the inhomogeneity parameter of the graded substrate,thermal conductivity,and current density of the thermoelectric film can reduce the risk of interfacial failure of the thermoelectric film/graded substrate system.Selecting a stiffer and thicker thermoelectric film is advantageous to the reliability of the thermoelectric film/graded substrate system.The results should be of great guiding significance for the present and upcoming applications of thermoelectric materials in various fields.

Effect of Polyaniline/manganese Dioxide Composite on the Thermoelectric Effect of Cement-based Materials

To enhance the thermoelectric effect of cement-based materials,conductive polyaniline(PANI)modified MnO_(2)powder was synthesized and used as a thermoelectric component in the cement composites.The nanostructured PANI was deposited on the surface of the nanorod-shapedα-MnO_(2)particle and the weight ratio of PANI to MnO_(2)was 22.3:77.7 in the composite.The synthesized PANI/MnO_(2)composite was nanostructured according to the SEM image.The test results of the thermoelectric properties proved that the PANI/MnO_(2)composite was effective as the Seebeck coefficient and electrical conductivity values of the cement composites with PANI/MnO_(2)inside were 3-4 orders of magnitude higher than those of pure cement paste and the thermal conductivity values of these cement samples were similar.The obtained maximum figure of merit(ZT)value(2.75×10^(-3))was much larger than that of conductive materials reinforced cement-based composites.The thermoelectric effect of cement composites is mainly enhanced by the increased Seebeck coefficient and electrical conductivity in this work.

Effect of Surfactants on the Thermoelectric Performance of Double-Walled Carbon Nanotubes

Thermoelectrics are a promising solution to the recovery of some of the 60%of the worldwide energy wasted as heat.However,their conversion efficiency is low and the best performing materials are brittle,toxic,and made of expensive ceramics.The challenge in developing better performing materials is in disrupting the electrical vs thermal conductivity correlation,to achieve low thermal conductivity simultaneously with a high electrical conductivity.Carbon nanotubes allow for the decoupling of the electronic density of states from the phonon density of states and this paper shows that flexible,thin films of double-walled carbon nanotube(DWCNT)can form effective n-and p-doped semiconductors that can achieve a combined Seebeck coefficient of 157.6µV K^(−1),the highest reported for a single DWCNT device to date.This is achieved through selected surfactant doping,whose role is correlated with the length of the hydrocarbon chain of the hydrophobic tail group of the surfactant’s molecules.CNTs functionalized with Triton X-405 show the highest output power consisting of a single junction of p-and n-type thermoelectric elements,reaching as high as 67 nW for a 45 K temperature gradient.Thus enabling flexible,cheaper,and more efficient thermoelectric generators through the use of functionalized CNTs.

Optimization of thermoelectric properties in elemental tellurium via high pressure

High pressure and high temperature(HPHT)technology,as an extreme physical condition,plays an important role in regulating the properties of materials,having the advantages of enhancing doping efficiency,refining grain size,and manufacturing defects,therefore it is quite necessary to study the effectiveness on tuning thermoelectric properties.Elemental telluride,a potential candidate for thermoelectric materials,has the poor doping efficiency and high resistivity,which become an obstacle for practical applications.Here,we report the realization of a dual optimization of electrical behaviors and thermal conductivity through HPHT method combining with the introduction of black phosphorus.The results show the maximum zT of 0.65 and an average zT of 0.42(300 K–610 K),which are increased by 55%and 68%in the synthesis pressure regulation system,respectively.This study clarifies that the HPHT method has significant advantages in modulating the thermoelectric parameters,providing a reference for seeking high performance thermoelectric materials.

Bilayer MSe_(2)(M=Zr,Hf,Mo,W)performance as a hopeful thermoelectric materials

Significant advancements in nanoscale material efficiency optimization have made it feasible to substantially adjust the thermoelectric transport characteristics of materials.Motivated by the prediction and enhanced understanding of the behavi-or of two-dimensional(2D)bilayers(BL)of zirconium diselenide(ZrSe_(2)),hafnium diselenide(HfSe_(2)),molybdenum diselenide(MoSe_(2)),and tungsten diselenide(WSe_(2)),we investigated the thermoelectric transport properties using information generated from experimental measurements to provide inputs to work with the functions of these materials and to determine the critical factor in the trade-off between thermoelectric materials.Based on the Boltzmann transport equation(BTE)and Barden-Shockley deformation potential(DP)theory,we carried out a series of investigative calculations related to the thermoelectric properties and characterization of these materials.The calculated dimensionless figure of merit(ZT)values of 2DBL-MSe_(2)(M=Zr,Hf,Mo,W)at room temperature were 3.007,3.611,1.287,and 1.353,respectively,with convenient electronic densities.In ad-dition,the power factor is not critical in the trade-off between thermoelectric materials but it can indicate a good thermoelec-tric performance.Thus,the overall thermal conductivity and power factor must be considered to determine the preference of thermoelectric materials.

Advancing thermoelectrics by suppressing deep-level defects in Pb-doped AgCrSe_(2) alloys

AgCrSe2-based compounds have attracted much attention as an environmentally friendly thermoelectric material in recent years due to the intriguing liquid-like properties.However,the ultra-low carrier concentration and the high Ag_(Cr)deep-level defects limit the overall thermoelectric performance.Here,we successfully introduced Pb into Ag-deficient Ag_(0.97)CrSe_(2) alloys to tune the carrier concentration across a broad temperature range.The Pb^(2+) as an acceptor dopant preferentially occupies Cr sites,boosting the hole carrier concentration to 1.77×10^(19) cm^(-3) at room temperature.Furthermore,the Pb strongly inhibits the creation of intrinsic Ag_(Cr) defects,weakens the increased thermal excited ionization with the increasing temperature and slowed the rising trend of the carrier concentration.The designed carrier concentration matches the theoretically predicted optimized one over the entire temperature range,leading to a remarkable enhancement in power factor,especially the maximum power factor of ~500 μW·m^(-1)·K^(-2) at 750 K is superior to most previous results.Additionally,the abundant point defects promote phonon scattering,thus reducing the lattice thermal conductivity.As a result,the maximum figure of merit zT(~0.51 at 750 K) is achieved in Ag_(0.97)Cr_(0.995)Pb_(0.005)Se_(2).This work confirms the feasibility of manipulating deep-level defects to achieve temperature-dependent optimal carrier concentration and provides a valuable guidance for other thermoelectric materials.

Adaptive genetic algorithm-based design of gamma-graphyne nanoribbon incorporating diamond-shaped segment with high thermoelectric conversion efficiency

The gamma-graphyne nanoribbons(γ-GYNRs) incorporating diamond-shaped segment(DSSs) with excellent thermoelectric properties are systematically investigated by combining nonequilibrium Green’s functions with adaptive genetic algorithm. Our calculations show that the adaptive genetic algorithm is efficient and accurate in the process of identifying structures with excellent thermoelectric performance. In multiple rounds, an average of 476 candidates(only 2.88% of all16512 candidate structures) are calculated to obtain the structures with extremely high thermoelectric conversion efficiency.The room temperature thermoelectric figure of merit(ZT) of the optimal γ-GYNR incorporating DSSs is 1.622, which is about 5.4 times higher than that of pristine γ-GYNR(length 23.693 nm and width 2.660 nm). The significant improvement of thermoelectric performance of the optimal γ-GYNR is mainly attributed to the maximum balance of inhibition of thermal conductance(proactive effect) and reduction of thermal power factor(side effect). Moreover, through exploration of the main variables affecting the genetic algorithm, it is revealed that the efficiency of the genetic algorithm can be improved by optimizing the initial population gene pool, selecting a higher individual retention rate and a lower mutation rate. The results presented in this paper validate the effectiveness of genetic algorithm in accelerating the exploration of γ-GYNRs with high thermoelectric conversion efficiency, and could provide a new development solution for carbon-based thermoelectric materials.