Stress effect on lattice thermal conductivity of anode material NiNB_(2)O_(6)for lithium-ion batteries

The thermal transport properties of NiNB_(2)O_(6)as anode material for lithium-ion battery and the effect of strain were studied by machine learning interatomic potential combined with Boltzmann transport equation.The results show that the lattice thermal conductivity of NiNB_(2)O_(6)along the three crystal directions[100],[010],and[001]are 0.947 W·m^(-1)·K^(-1),0.727 W·m^(-1)·K^(-1),and 0.465 W·m^(-1)·K^(-1),respectively,indicating the anisotropy of the lattice thermal conductivity of NiNB_(2)O_(6).This anisotropy of the lattice thermal conductivity stems from the significant difference of phonon group velocities in different crystal directions of NiNB_(2)O_(6).When the tensile strain is applied along the[001]crystal direction,the lattice thermal conductivity in all three directions decreases.However,when the compressive strain is applied,the lattice thermal conductivity in the[100]and[010]crystal directions is increased,while the lattice thermal conductivity in the[001]crystal direction is abnormally reduced due to the significant inhibition of compressive strain on the group velocity.These indicate that the anisotropy of thermal conductivity of NiNB_(2)O_(6)can be enhanced by the compressive strain,and reduced by the tensile strain.

Prediction of lattice thermal conductivity with two-stage interpretable machine learning

Thermoelectric and thermal materials are essential in achieving carbon neutrality. However, the high cost of lattice thermal conductivity calculations and the limited applicability of classical physical models have led to the inefficient development of thermoelectric materials. In this study, we proposed a two-stage machine learning framework with physical interpretability incorporating domain knowledge to calculate high/low thermal conductivity rapidly. Specifically, crystal graph convolutional neural network(CGCNN) is constructed to predict the fundamental physical parameters related to lattice thermal conductivity. Based on the above physical parameters, an interpretable machine learning model–sure independence screening and sparsifying operator(SISSO), is trained to predict the lattice thermal conductivity. We have predicted the lattice thermal conductivity of all available materials in the open quantum materials database(OQMD)(https://www.oqmd.org/). The proposed approach guides the next step of searching for materials with ultra-high or ultralow lattice thermal conductivity and promotes the development of new thermal insulation materials and thermoelectric materials.

Two-dimensional square-Au_(2)S monolayer:A promising thermoelectric material with ultralow lattice thermal conductivity and high power factor

The search for new two-dimensional(2 D)harvesting materials that directly convert(waste)heat into electricity has received increasing attention.In this work,thermoelectric(TE)properties of monolayer square-Au_(2)S are accurately predicted using a parameter-free ab initio Boltzmann transport formalism with fully considering the spin–orbit coupling(SOC),electron–phonon interactions(EPIs),and phonon–phonon scattering.It is found that the square-Au_(2)S monolayer is a promising room-temperature TE material with an n-type(p-type)figure of merit ZT=2.2(1.5)and an unexpected high n-type ZT=3.8 can be obtained at 600 K.The excellent TE performance of monolayer square-Au_(2)S can be attributed to the ultralow lattice thermal conductivity originating from the strong anharmonic phonon scattering and high power factor due to the highly dispersive band edges around the Fermi level.Additionally,our analyses demonstrate that the explicit treatments of EPIs and SOC are highly important in predicting the TE properties of monolayer square-Au_(2)S.The present findings will stimulate further the experimental fabrication of monolayer square-Au_(2)S-based TE materials and offer an in-depth insight into the effect of SOC and EPIs on TE transport properties.

Study of lattice thermal conductivity of alpha-zirconium by molecular dynamics simulation

The non-equilibrium molecular dynamics method is adapted to calculate the phonon thermal conductivity of alphazirconium. By exchanging velocities of atoms in different regions, the stable heat flux and the temperature gradient are established to calculate the thermal conductivity. The phonon thermal conductivities under different conditions, such as different heat exchange frequencies, different temperatures, different crystallographic orientations, and crossing grain boundary （GB）, are studied in detail with considering the finite size effect. It turns out that the phonon thermal conductivity decreases with the increase of temperature, and displays anisotropies along different crystallographic orientations. The phonon thermal conductivity in [0001] direction （close-packed plane） is largest, while the values in other two directions of [2īī0] and [01ī0] are relatively close. In the region near GB, there is a sharp temperature drop, and the phonon thermal conductivity is about one-tenth of that of the single crystal at 550 K, suggesting that the GB may act as a thermal barrier in the crystal.

Achieving high carrier mobility and low lattice thermal conductivity in GeTe-based alloys by cationic/anionic co-doping

TheⅣ-Ⅵcompound GeTe is considered as a promising alternative to the toxic PbTe for high-efficiency mid-temperature thermoelectric applications.However,pristine GeTe suffers from a high concentration of Ge vacancies,resulting in an excessively high hole concentration(>1×10^(21)cm^(-3)),which greatly limits its thermoelectric enhancement.To address this issue,CuBiTe_(2)alloying is introduced to increase the formation energy of Ge vacancies in GeTe,thereby inhibiting the high carrier concentration.The carrier scattering caused by the electronegativity difference between different elements is suppressed due to the similar electronegativity of Cu and Ge atoms.A relatively high hole mobility is obtained,which ultimately leads to a high power factor.Additionally,by introducing Se as an alloying element at the anionic site in GeTe,dense point defects with mass/strainfield fluctuations are induced.This contributes to the strengthening of phonon scattering,thereby reducing the lattice thermal conductivity from 1.44 W·m^(-1)·K^(-1)for pristine GeTe to 0.28 W·m^(-1)·K^(-1)for Ge_(0.95)Cu_(0.05)Bi_(0.05)Te_(0.9)Se_(0.15)compound at 623 K.

Screening outstanding mechanical properties and low lattice thermal conductivity using global attention graph neural network

Mechanical and thermal properties of materials are extremely important for various engineering and scientific fields such as energy conversion and energy storage.However,the characterization of these properties via high throughput screening at the quantum level,although highly accurate,is inefficient and very time-and resource-consuming.In contrast,prediction at the classical level is highly efficient but less accurate.We deploy scalable global attention graph neural network for accurate prediction of mechanical properties which bridge the gap between the accuracy at the quantum level and efficiency at the classical level.Using 10,158 elastic constants as training data,we trained the models on 5 mechanical properties,namely bulk modulus,shear modulus,Young’s modulus,Poisson’s ratio,and hardness.With the trained model,we predicted 775,947 data in search of materials with ultrahigh hardness.We further verify the recommended ultrahigh hardness materials by high precision first principles calculations,and we finally identify 20 structures with extreme hardness close to diamond,the hardest material in nature.Among those,two super hard materials are completely new and have not been reported in literature so far.We further recommend potential materials from bulk modulus prediction to search low lattice thermal conductivity,and we verify the thermal conductivity of 338 structures with first principles.Our results demonstrate that one can find materials with extreme mechanical properties recommended by graph neural network and low thermal conductivity material from bulk modulus prediction with minimal first principles calculations of the structures(only 0.04%)in the large-scale materials pool.

Grain boundaries induce significant decrease in lattice thermal conductivity of CdTe

Semiconductors are promising in photoelectric and thermoelectric devices, for which the thermal transport properties are of particular interest. However, they have not been fully understood, especially when crystalline imperfections are present. Here, using cadmium telluride (CdTe) as an example, we illustrate how grain boundaries (GBs) affect the thermal transport properties of semiconductors. We develop a machine-learning force field from density functional theory calculations for predicting the lattice thermal conductivity (LTC) via equilibrium molecular dynamics simulations. The LTC of crystalline CdTe decreases with the relationship of κL~1/T in the simulation temperature range of 300 – 900 K, in which the isotropic LTC decreases from 3.34 to 0.23 W/ (m⋅K) due to the enhanced anharmonicity. More important, after introducing GBs, the LTC is suppressed in all directions, especially in the direction normal to the GB planes. More severe LTC suppression occurs in CdTe with Σ9 GB than that with Σ3 GB at 300 K, decreasing by 92.8% and 61.4% along the direction normal to the GB planes compared to the isotropic LTC of the crystalline CdTe, respectively. The decreased LTC is consistent with the weaker bonding near GB planes and lower shear modulus of the defective material. The analyses of the phonon dispersion curves, vibrational density of states, and phonon participation ratio indicate that the decreased LTC mainly arises from phonon scattering at GBs. Overall, our work highlights that GBs can greatly influence the LTC of semiconductors, thus providing a promising approach for thermal property design.

Strong anharmonicity-assisted low lattice thermal conductivities and high thermoelectric performance in double-anion Mo_(2)AB_(2)(A=S,Se,Te;B=Cl,Br,I)semiconductors

The thermoelectric properties of layered Mo_(2)AB_(2)(A=S,Se,Te;B=Cl,Br,I)materials are systematically investigated by first-principles approach.Soft transverse acoustic modes and direct Mo d–Mo d couplings give rise to strong anharmonicities and low lattice thermal conductivities.The double anions with distinctly different electronegativities of Mo_(2)AB_(2)monolayers can reduce the correlation between electron transport and phonon scattering,and further benefit much to their good thermoelectric properties.Thermoelectric properties of these Mo_(2)AB_(2)monolayers exhibit obvious anisotropies due to the direction-dependent chemical bondings and transport properties.Furthermore,their thermoelectric properties strongly depend on carrier type(n-type or p-type),carrier concentration and temperature.It is found that n-type Mo_(2)AB_(2)monolayers can be excellent thermoelectric materials with high electric conductivity,σ,and figures of merit,ZT.Choosing the types of A and B anions of Mo_(2)AB_(2)is an effective strategy to optimize their thermoelectric performance.These results provide rigorous understanding on thermoelectric properties of double-anions compounds and important guidance for achieving high thermoelectric performance in multi-anion compounds.

Highly sensitive tuning of lattice thermal conductivity of graphenelike borophene by fluorination and chlorination

Boron-based 2D materials are of current interest.However,graphene-like geometry is unstable for B due to the electron deficiency,which can be stabilized by introducing H,F and Cl.Here,using density functional theory combined with phonon Boltzmann transport equation,we perform systematic studies on how the functionalization changes the lattice thermal conductivity(LTC).We find that when going from hydrogenation to fluorination and chlorination,the LTC along zigzag direction changes from 367.6 to 211.3 and 43.0 W/(rrvK),while the corresponding values in armchair direction are 279.6,198.9,and 41.6 W/(m·K),respectively.These huge differences imply the sensitivity of LTC to functionalization,which can be attributed to the enhanced anharmonicity as revealed by analyzing group velocity,Gruneisen parameter,anharmonic scattering rates,and three-phonon scattering space.

From thermal conductive to thermal insulating:Effect of carbon vacancy content on lattice thermal conductivity of ZrC_(x)

Lattice thermal conductivities of zirconium carbide(ZrC_(x),x=1,0.75 and 0.5)ceramics with different carbon vacancy concentrations were calculated using a combination of first-principles calculations and the Debye-Callaway model.The Gruneisen parameters,Debye temperatures,and phonon group velocities were deduced from phonon dispersions of ZrC_(x) determined using first-principles calculations.In addition,the effects of average atomic mass,grain size,average atomic volume and Zr isotopes on the lattice thermal conductivities of ZrC_(x) were analyzed using phonon scattering models.The lattice thermal conductivity decreased as temperature increased for ZrC,ZrC_(0.75) and ZrC_(0.5)(Zr2 C),and decreased as carbon vacancy concentration increased.Intriguingly,ZrC_(x) can be tailored from a thermal conducting material for ZrC with high lattice thermal conductivity to a thermal insulating material for ZrC_(0.5) with low lattice thermal conductivity.Thus,it opens a window to tune the thermal properties of ZrC_(x) by controlling the carbon vacancy content.

Se-alloying reducing lattice thermal conductivity of Ge_(0.95)Bi_(0.05)Te

High lattice thermal conductivity of intrinsic GeTe limits the wide application of GeTe-based thermoelectrics.Recently,the optimization of GeTe-based thermoelectric materials has been focusing on reducing lattice thermal conductivity via strengthening phonon scattering.In this study,we systematically studied thermoelectric properties of Se-alloyed Ge_(0.95) Bi_(0.05) Te via theoretical calculations,structural characterizations,and performance evaluations.Our results indicate that Se-alloying can induce dense point defects with mass/strain-field fluctuations and correspondingly enhance point defect phonon scattering of the Ge_(0.95) Bi_(0.05) Te matrix.Se-alloying might also change chemical bonding strength to introduce resonant states in the base frequency of Ge_(0.95) Bi_(0.05) Te matrix,which can strengthen Umklapp phonon scattering.Finally,a decreased lattice thermal conductivity from∼1.02 W m^(−1) K^(−1) to∼0.65 W m^(−1) K^(−1) at 723 K is obtained in Ge_(0.95) Bi_(0.05) Te_(1-x) Se_(x) pellets with increasing the Se content from 0 to 0.3.A peak figure of merit of∼1.6 at 723 K is achieved in Ge_(0.95) Bi_(0.05) Te_(0.7) Se_(0.3) pellet,which is∼77%higher than that of pristine GeTe.This study extends the understanding on the thermoelectric performance of GeTe.

Lattice Thermal Conductivity of Boron Nitride Nanoribbon from Molecular Dynamics Simulation

The lattice thermal conductivity of boron nitride nanoribbon（BNNR） is calculated by using equilibrium molecular dynamics（EMD） simulation method. The Green–Kubo relation derived from linear response theory is used to acquire the thermal conductivity from heat current auto-correlation function（HCACF）. HCACF of the selected BNNR system shows a tendency of a very fast decay and then be followed by a very slow decay process,finally,approaching zero approximately within 3 ps. The convergence of lattice thermal conductivity demonstrates that the thermal conductivity of BNNR can be simulated by EMD simulation using several thousands of atoms with periodic boundary conditions. The results show that BNNR exhibit lower thermal conductivity than that of boron nitride（BN） monolayer,which indicates that phonons boundary scatting significantly suppresses the phonons transport in BNNR. Vacancies in BNNR greatly affect the lattice thermal conductivity,in detail,only 1% concentration of vacancies in BNNR induce a 60% reduction of the lattice thermal conductivity at room temperature.

Nanotwinning induced decreased lattice thermal conductivity of high temperature thermoelectric boron subphosphide (B12P2) from deep learning potential simulations

Boron subphosphide(B_(12)P_(2))is a promising high temperature thermoelectric material due to its good thermal stability,and chemical inertness.However,the thermal properties of B_(12)P_(2) have not been well revealed so far.Here,we first develop a deep learning potential for B_(12)P_(2) based on quantum mechanical calculations.Then the isotropic lattice thermal conductivity(LTC)of crystalline B_(12)P_(2) is predicted to be 39.70±4.38 W/m⋅K from molecular dynamics simulations using this deep learning potential.The LTC exhibits the relationship ofκL~1/T in the temperature range of 300~1500 K.More important,a twin boundary strategy is proposed to reduce the LTC of B_(12)P_(2).In nanotwinned B_(12)P_(2),the phonon transport in all directions is significantly suppressed by twin boundaries(TBs)with the isotropic LTC of 15.85±2.70 W/m⋅K,especially in the direction normal to the TB plane.The decrease of vibrational density of states and phonon participation ratio due to TBs’phonon scattering is the main reason of the low LTC in nanotwinned B_(12)P_(2).In addition,the elastic moduli(B and G)of B_(12)P_(2) crystal decrease by less than 7%after inducing TBs,which suggests that the mechanical properties are not significantly affected by TBs.Overall,this work enriches our understanding of the thermal properties of B_(12)P_(2) and offers a promising approach,i.e.,introducing TBs,to design high-performance thermoelectric materials.

Numerical Predictions of the Effective Thermal Conductivity of the Rigid Polyurethane Foam

A reconstruction method is proposed for the polyurethane foam and then a complete numerical method is developed to predict the effective thermal conductivity of the polyurethane foam. The finite volume method is applied to solve the 2D heterogeneous pure conduction. The lattice Boltzmann method is adopted to solve the 1D homogenous radiative transfer equation rather than Rosseland approximation equation. The lattice Boltzmann method is then adopted to solve 1D homogeneous conduction-radiation energy transport equation considering the combined effect of conduction and radiation. To validate the accuracy of the present method, the hot disk method is adopted to measure the effective thermal conductivity of the polyurethane foams at different temperature. The numerical results agree well with the experimental data. Then, the influences of temperature, porosity and cell size on the effective thermal conductivity of the polyurethane foam are investigated. The results show that the effective thermal conductivity of the polyurethane foams increases with temperature; and the effective thermal conductivity of the polyurethane foams decreases with increasing porosity while increases with the cell size.

Phonon transport properties of Janus Pb_(2)XAs(X=P,Sb,and Bi)monolayers:A DFT study

Grasping the underlying mechanisms behind the low lattice thermal conductivity of materials is essential for the efficient design and development of high-performance thermoelectric materials and thermal barrier coating materials.In this paper,we present a first-principles calculations of the phonon transport properties of Janus Pb_(2)PAs and Pb_(2)SbAs monolayers.Both materials possess low lattice thermal conductivity,at least two orders of magnitude lower than graphene and h-BN.The room temperature thermal conductivity of Pb_(2)SbAs(0.91 W/m K)is only a quarter of that of Pb_(2)PAs(3.88 W/m K).We analyze in depth the bonding,lattice dynamics,and phonon mode level information of these materials.Ultimately,it is determined that the synergistic effect of low group velocity due to weak bonding and strong phonon anharmonicity is the fundamental cause of the intrinsic low thermal conductivity in these Janus structures.Relative regular residual analysis further indicates that the four-phonon processes are limited in Pb_(2)PAs and Pb_(2)SbAs,and the three-phonon scattering is sufficient to describe their anharmonicity.In this study,the thermal transport properties of Janus Pb_(2)PAs and Pb_(2)SbAs monolayers are illuminated based on fundamental physical mechanisms,and the low lattice thermal conductivity endows them with the potential applications in the field of thermal barriers and thermoelectrics.

Phonon engineering significantly reducing thermal conductivity of thermoelectric materials: a review

Lattice thermal conductivity, κL, is a fundamental parameter for evaluating the performance of thermoelectric materials. However, the predicted value of κL based on the Debye dispersion model is often overestimated compared with the experimentally determined value.Many researchers have attempted to modify the theoretical model and have sought more reliable results. In this review,the recent progress in the study of phonon dispersion models is summarized and we propose that the lattice thermal conductivity can be most accurately determined by using the modified sinusoidal phonon dispersion model.Moreover, experimental methods that have the potential to reduce a thermoelectric material's κLare reviewed, for example, methods that generate standing waves or anharmonic lattice vibrations. A high concentration of standing waves and anharmonic lattice vibrations can effectively suppress excessive κL. Finally, this review presents the challenges of sinusoidal phonon dispersion when applied to real materials, which are often complicated and therefore time-consuming, especially when dealing with material defects.

Realizing Cd and Ag codoping in p-type Mg_(3)Sb_(2)toward high thermoelectric performance

Mg_(3)Sb_(2)has attracted intensive attention as a typical Zintl-type thermoelectric material.Despite the exceptional thermoelectric performance in n-type Mg_(3)Sb_(2),the dimensionless figure of merit(zT)of p-type Mg_(3)Sb_(2)remains lower than 1,which is mainly attributed to its inferior electrical properties.Herein,we synergistically optimize the thermoelectric properties of p-type Mg_(3)Sb_(2)materials via codoping of Cd and Ag,which were synthesized by high-energy ball milling combined with hot pressing.It is found that Cd doping not only increases the carrier mobility of p-type Mg_(3)Sb_(2),but also diminishes its thermal conductivity(κ_(tot)),with Mg_(2.85)Cd_(0.5)Sb_(2)achieving a lowκtot value of∼0.67 W m^(−1)K^(−1)at room temperature.Further Ag doping elevates the carrier concentration,so that the power factor is optimized over the entire temperature range.Eventually,a peak zT of∼0.75 at 773 K and an excellent average zT of∼0.41 over 300−773 K are obtained in Mg_(2.82)Ag_(0.03)Cd_(0.5)Sb_(2),which are∼240%and∼490%higher than those of pristine Mg_(3.4)Sb_(2),respectively.This study provides an effective pathway to synergistically improve the thermoelectric performance of p-type Mg_(3)Sb_(2)by codoping Cd and Ag,which is beneficial to the future applications of Mg_(3)Sb_(2)-based thermoelectric materials.

Dynamic carrier transports and low thermal conductivity in n-type layered InSe thermoelectrics

Semiconductor InSe with wide bandgap and layered crystal structure is expected to be a promising thermoelectric material,and its excellent plasticity brings great potential applications in flexible and wearable thermoelectric devices.To advance its thermoelectric performance,this work systematically investigates the carrier and phonon transport properties in n-type InSe.It is found that InSe compound presents an exceptional dynamic carrier transport property due to the amphoteric indium(In+and In^(3+)),which contributes to favorable temperature-dependent increasing carrier concentration.More importantly,with S alloying in InSe,the carrier concentration can be further enhanced from∼3.2×10^(13) cm–3 in InSe to∼4.8×10^(15) cm^(-3) in InSe_(0.97)S_(0.03) at 300 K,because S(χP∼2.58)with larger Pauling electronegativity than Se(χP∼2.55)can induce more In3+state to increase carrier concentration in matrix.This boosted dynamic carrier transport property benefits an obviously enhanced power factor.Additionally,InSe compound presents intrinsically low thermal conductivity∼1.6 W m^(-1) K^(-1) at 300 K due to low-symmetry crystal structure and strong anharmonicity.This work indicates that the special dynamic carrier transport property and intrinsically low thermal conductivity in InSe make it as a worthexpecting thermoelectric material.

Advances in thermoelectric(GeTe)_(x)(AgSbTe_(2))_(100-x)

The(GeTe)_(x)(AgSbTe_(2))_(100-x)alloys,also called TAGS-x in short,have long been demonstrated as a promising candidate for thermoelectric applications with successful services as the p-type leg in radioisotope thermoelectric generators for space missions.This largely stems from the complex band structure for a superior electronic performance and strong anharmonicity for a low lattice thermal conductivity.Utilization of the proven strategies including carrier concentration optimization,band and defects engineering,an extraordinary thermoelectric figure of merit,zT,has been achieved in TAGS-based alloys.Here,crystal structure,band structure,microstructure,synthesis techniques and thermoelectric transport properties of TAGS-based alloys,as well as successful strategies for manipulating the thermoelectric performance,are surveyed with opportunities for further advancements.These strategies involved are believed to be in principle applicable for advancing many other thermoelectrics.

Thermoelectric properties of orthorhombic silicon allotrope Si(oP32)from first-principles calculations

The diamond-like cubic silicon(d-Si)is widely used in modern electronics and solar cell industries.However,it is not an optimal candidate for thermoelectric application due to its high lattice thermal conductivity.Si(oP32)is a recently predicted orthorhombic silicon allotrope,whose total energy is close to that of d-Si.Using first-principles calculations and Boltzmann transport theory,we systematically investigate the thermoelectric properties of Si(oP32).The lower phonon thermal conductivity and higher power factor are obtained in Si(oP32)than those in diamond silicon.The low phonon thermal conductivity(33.77 W/mK at 300 K)is mainly due to the reduction of the phonon group velocity and enhancement of phonon-phonon scattering(including scattering phase space and strength).Meanwhile,the results also show that the thermoelectric performance along the zz lattice direction is better than that along the xx and yy lattice directions,and the figure of merit(700 K)along the zz lattice direction could approach to 2.45 and 1.75 for p-type and n-type Si(oP32),respectively.The values are much higher than those of d-Si(about 0.06))and Si24(0.6),indicating that the Si(oP32)is a promising candidate for thermoelectric applications.Our theoretical studies shed light on the thermoelectric properties of Si(oP32)and could stimulate further experimental studies.