Structure Low Dimensionality and Lone-Pair Stereochemical Activity: the Key to Low Thermal Conductivity in the Pb-Sn-S System.

Recently, metal sulfides have begun to receive attention as potential cost-effective materials for thermoelectric applications beyond optoelectronic and photovoltaic devices. Herein, based on a comparative analysis of the structural and transport properties of 2D PbSnS2 and 1D PbSnS3, we demonstrate that the intrinsic effects that govern the low lattice thermal conductivity (κL) of these sulfides originate from the combination of the low dimensionality of their crystal structures with the stereochemical activity of the lone-pair electrons of cations. The presence of weak bonds in these materials, responsible for phonon scattering, results in inherently low κL of 1.0 W/m K in 1D PbSnS3 and 0.6 W/m K in 2D PbSnS2 at room temperature. However, the nature of the thermal transport is quite distinct. 1D PbSnS3 exhibits a higher thermal conductivity with a crystalline-like peak at low temperatures, while 2D PbSnS2 demonstrates glassy thermal conductivity in the entire temperature range investigated. First-principles density functional theory calculations reveal that the presence of antibonding states below the Fermi level, especially in PbSnS2, contributes to the very low κL. In addition, the calculated phonon dispersions exhibit very soft acoustic phonon branches that give rise to soft lattices and very low speeds of sounds.

Pushing thermal conductivity to its lower limit in crystals with simple structures.

Materials with low thermal conductivity usually have complex crystal structures. Herein we experimentally find that a simple crystal structure material AgTlI2 (I4/mcm) owns an extremely low thermal conductivity of 0.25 W/mK at room temperature. To understand this anomaly, we perform in-depth theoretical studies based on ab initio molecular dynamics simulations and anharmonic lattice dynamics. We find that the unique atomic arrangement and weak chemical bonding provide a permissive environment for strong oscillations of Ag atoms, leading to a considerable rattling behaviour and giant lattice anharmonicity. This feature is also verified by the experimental probability density function refinement of single-crystal diffraction. The particularly strong anharmonicity breaks down the conventional phonon gas model, giving rise to non-negligible wavelike phonon behaviours in AgTlI2 at 300 K. Intriguingly, unlike many strongly anharmonic materials where a small propagative thermal conductivity is often accompanied by a large diffusive thermal conductivity, we find an unusual coexistence of ultralow propagative and diffusive thermal conductivities in AgTlI2 based on the thermal transport unified theory. This study underscores the potential of simple crystal structures in achieving low thermal conductivity and encourages further experimental research to enrich the family of materials with ultralow thermal conductivity.

Amorphous-Like Ultralow Thermal Transport in Crystalline Argyrodite Cu7PS6.

Due to their amorphous-like ultralow lattice thermal conductivity both below and above the superionic phase transition, crystalline Cu- and Ag-based superionic argyrodites have garnered widespread attention as promising thermoelectric materials. However, despite their intriguing properties, quantifying their lattice thermal conductivities and a comprehensive understanding of the microscopic dynamics that drive these extraordinary properties are still lacking. Here, an integrated experimental and theoretical approach is adopted to reveal the presence of Cu-dominated low-energy optical phonons in the Cu-based argyrodite Cu7PS6. These phonons yield strong acoustic-optical phonon scattering through avoided crossing, enabling ultralow lattice thermal conductivity. The Unified Theory of thermal transport is employed to analyze heat conduction and successfully reproduce the experimental amorphous-like ultralow lattice thermal conductivities, ranging from 0.43 to 0.58 W m-1 K-1, in the temperature range of 100-400 K. The study reveals that the amorphous-like ultralow thermal conductivity of Cu7PS6 stems from a significantly dominant wave-like conduction mechanism. Moreover, the simulations elucidate the wave-like thermal transport mainly results from the contribution of Cu-associated low-energy overlapping optical phonons. This study highlights the crucial role of low-energy and overlapping optical modes in facilitating amorphous-like ultralow thermal transport, providing a thorough understanding of the underlying complex dynamics of argyrodites.

Three-Fold Coordination of Copper in Sulfides: A Blockade for Hole Carrier Delocalization but a Driving Force for Ultralow Thermal Conductivity.

Copper-rich sulfides are very promising for energy conversion applications due to their environmental compatibility, cost effectiveness, and earth abundance. Based on a comparative analysis of the structural and transport properties of Cu3BiS3 with those of tetrahedrite (Cu12Sb4S13) and other Cu-rich sulfides, we highlight the role of the cationic coordination types and networks on the electrical and thermal properties. By precession-assisted 3D electron diffraction analysis, we find very high anisotropic thermal vibration of copper attributed to its 3-fold coordination, with an anisotropic atomic displacement parameter up to 0.09 Å2. Density functional theory calculations reveal that these Cu atoms are weakly bonded and give rise to low-energy Einstein-like vibrational modes that strongly scatter heat-carrying acoustic phonons, leading to ultralow thermal conductivity. Importantly, we demonstrate that the 3-fold coordination of copper in Cu3BiS3 and in other copper-rich sulfides constituted of interconnected CuS3 networks causes a hole blockade. This phenomenon hinders the possibility of optimizing the carrier concentration and electronic properties through mixed valency Cu+/Cu2+, differently from tetrahedrite and most other copper-rich chalcogenides, where the main interconnected Cu-S network is built of CuS4 tetrahedra. The comparison with various copper-rich sulfides demonstrates that seeking for frameworks characterized by the coexistence of tetrahedral and 3-fold coordinated copper is very attractive for the discovery of efficient thermoelectric copper-rich sulfides. Considering that lattice vibrations and carrier concentration are key factors for engineering transport phenomena (electronic, phonon, ionic, etc.) in copper-rich chalcogenides for various types of applications, our findings improve the guidelines for the design of materials enabling sustainable energy solutions with wide-ranging applications.

Precursor region with full phonon softening above the charge-density-wave phase transition in 2H-TaSe2.

Research on charge-density-wave (CDW) ordered transition-metal dichalcogenides continues to unravel new states of quantum matter correlated to the intertwined lattice and electronic degrees of freedom. Here, we report an inelastic x-ray scattering investigation of the lattice dynamics of the canonical CDW compound 2H-TaSe2 complemented by angle-resolved photoemission spectroscopy and density functional perturbation theory. Our results rule out the formation of a central-peak without full phonon softening for the CDW transition in 2H-TaSe2 and provide evidence for a novel precursor region above the CDW transition temperature TCDW, which is characterized by an overdamped phonon mode and not detectable in our photoemission experiments. Thus, 2H-TaSe2 exhibits structural before electronic static order and emphasizes the important lattice contribution to CDW transitions. Our ab-initio calculations explain the interplay of electron-phonon coupling and Fermi surface topology triggering the CDW phase transition and predict that the CDW soft phonon mode promotes emergent superconductivity near the pressure-driven CDW quantum critical point.

Effects of traditional Chinese exercises on cardiac rehabilitation in patients with myocardial infarction: a meta-analysis of randomized controlled trials.

Objective: Traditional Chinese exercises (TCE) are excellent cardiac rehabilitation (CR) training that can effectively improve cardiorespiratory fitness. However, there is no published meta-analysis of TCE on CR in patients with myocardial infarction (MI). Therefore, this study aimed to provide a comprehensive evaluation from multiple perspectives. Methods: This meta-analysis is based on the Cochrane Handbook of Systematic Reviews. Eight databases were searched from the date of database construction to March 15, 2023. Two investigators independently screened the literature and assessed their quality. The meta-analysis was performed with RevMan5.4 software. Results: A total of 21 articles involving 1,890 patients were included. N-terminal pro-brain natriuretic peptide (NT-proBNP) in the TCE group were lower than the control group (MD = -96.34, 95%CI: -140.69 ∼-51.98, P < 0.00001, I2 = 96%), the left ventricular ejection fraction (LVEF) in the TCE group was higher than the control group (MD = 4.58, 95%CI: 3.28-5.88, P < 0.00001, I2 = 79%), the left ventricular end diastolic dimension (LVDD) in TCE group was lower than the control group (MD = -3.83, 95%CI: -5.27 ∼-2.38, P < 0.00001, I2 = 94%), the left ventricular end systolic diameter (LVESD) in TCE group was lower than the control group (MD = -2.17, 95%CI: -4.10 ∼-0.24, P < 0.00001, I2 = 96%), The 6-minute walk test (6MWT) in the TCE group was higher than the control group (MD = 69.60, 95%CI: 34.59-104.60, P < 0.00001, I2 = 99%), the oxygen uptake (VO2) in the TCE group was higher than the control group (MD = 4.38, 95%CI: 2.25-6.51, P < 0.00001, I2 = 94%), the 36-item short form survey (SF-36) in the TCE group was higher than the control group (MD = 13.34, 95%CI: 9.25-17.42, P = 0.008, I2 = 75%), the Hamilton Anxiety Scale (HAMA) in the TCE group was lower than the control group (MD = -4.34, 95%CI: -5.18 ∼-3.50, P = 1.00, I2 = 0%), the Hamilton Depression Scale (HAMD) in the TCE group was lower than the control group (MD = -3.48, 95%CI: -5.35 ∼-1.61, P = 0.0002, I2 = 88%), the incidence of major adverse cardiac events (MACEs) in the TCE group was lower than the control group (RR = 0.31, 95%CI: 0.20-0.47, P = 0.52, I2 = 0%). Subgroup analysis revealed differences in TCE types could be a potential source of heterogeneity. Conclusion: MI patients who used TCE have not only notable improvements in cardiopulmonary function, physical function, quality of life, and emotions but also reduced the incidence of MACEs. Tai Chi might be more efficient than Ba Duan Jin. Systematic Review Registration: https://www.crd.york.ac.uk/PROSPERO/, identifier CRD42023408675.

Soft Phonon Mode Triggering Fast Ag Diffusion in Superionic Argyrodite Ag8 GeSe6.

The structural coexistence of dual rigid and mobile sublattices in superionic Argyrodites yields ultralow lattice thermal conductivity along with decent electrical and ionic conductivities and therefore attracts intense interest for batteries, fuel cells, and thermoelectric applications. However, a comprehensive understanding of their underlying lattice and diffusive dynamics in terms of the interplay between phonons and mobile ions is missing. Herein, inelastic neutron scattering is employed to unravel that phonon softening on heating to Tc ≈ 350 K triggers fast Ag diffusion in the canonical superionic Argyrodite Ag8 GeSe6 . Ab initio molecular dynamics simulations reproduce the experimental neutron scattering signals and identify the partially ultrafast Ag diffusion with a large diffusion coefficient of 10-4 cm-2 s-1 . The study illustrates the microscopic interconnection between soft phonons and mobile ions and provides a paradigm for an intertwined interaction of the lattice and diffusive dynamics in superionic materials.

Ultrafast Time-resolved Polarization-dependent Investigations on the Dynamics in the A ˜ 2 B2 State of NO2 Molecules.

We perform time-resolved polarization-dependent study on ultrafast dynamics in the A ˜ 2 B2 state of NO2 . A linearly-polarized 400 nm femtosecond laser is used to resonantly pump NO2 to its first excited state A ˜ 2 B2 , and the time-dependent ionic yields produced via strong field ionization at 800 nm are measured under different laser polarizations. The yield ratios measured with the lasers perpendicular and parallel to each other first decrease and then increases as the wave packet evolves on the excited state, with a minimum ratio at 180 fs delay time, which can be attributed to the evolution time in the A ˜ 2 B2 state. The behavior of the time-resolved ionization in elliptically polarized laser field is also investigated and discussed.

Clustered piperidinium-functionalized poly(terphenylene) anion exchange membranes with well-developed conductive nanochannels.

Anion exchange membrane fuel cells (AEMFCs) attract considerable attention owing to their high-power density and potential utilization of cheap non-noble metal catalysts. However, anion exchange membranes (AEMs) still face the problems of low conductivity, poor dimensional and chemical stability. To address these issues, AEMs with clustered piperidinium groups and ether-bond-free poly(terphenylene) backbone (3QPAP-x, x = 0.3, 0.4, and 0.5) were designed. Transmission electron microscope results show that the clustered ionic groups are responsible for fabricating well-developed conductive nanochannels and restraining the swelling behavior of the membranes. 3QPAP-0.4 and 3QPAP-0.5 AEMs exhibit higher conductivity (117.5 mS cm-1, 80 °C) and lower swelling ratio than that of commercial FAA-3-50 (80.4 mS cm-1, 80 °C). The conductivity of 3QPAP-0.5 only decreased by 10.4% after treating with 1 M NaOH at 80 °C for 720 h. The Hofmann elimination degradation of the cationic groups is restrained by the long flexible alkyl chain between cations. Based on the high performance of 3QPAP-0.5, an H2-O2-type AEMFC reaches 291.2 mW cm-2 (60 °C), which demonstrates that the as-prepared AEMs are promising for application in fuel cells.

Synergistic Effect of Bismuth and Indium Codoping for High Thermoelectric Performance of Melt Spinning SnTe Alloys.

In this work, a nonequilibrium melt spinning (MS) technology combined with hot pressing was adopted for rapid synthesizing of SnTe compounds in less than 1 h. The refined microstructure generated by MS significantly decreases the lattice thermal conductivity. Compared to the pristine SnTe sample prepared by traditional melting and long-term annealing, the melt-spun one reveals a 15% lower thermal conductivity of ∼6.8 W/m K at room temperature and a 10% higher zT of ∼0.65 at 900 K. To further improve the electrical transport properties of the SnTe system, elements of Bi and In are introduced. It was found that Bi and In codoping can enhance Seebeck coefficients in a broad temperature range via optimizing carrier density and introducing resonant states. Point defects and nanoparticles introduced by Bi and In codoping remarkably enhanced phonon scattering and decreased lattice thermal conductivities. Finally, a significant enhancement on the thermoelectric performance was achieved: a peak zT of 1.26 at 900 K and an average zT of ∼0.48 over the temperature range of 300-900 K are obtained in Sn0.9675Bi0.03In0.0025Te. This work demonstrates that MS combined with appropriate doping could be an effective strategy to improve the thermoelectric performance of SnTe-related samples.

High-Temperature Structural and Thermoelectric Study of Argyrodite Ag8GeSe6.

Argyrodites with a general chemical formula of A8BX6 (A = Cu, Ag; B = Si, Ge, Sn; and X = S, Se, and Te) are known for the intimate interplay among mobile ions, electrons, and phonons, which yields rich material physics and materials chemistry phenomena. In particular, the coexistence of fast ionic conduction and promising thermoelectric performance in Ag8GeTe6, Ag8SnSe6, Ag8SiTe6, Ag8SiSe6, and Cu8GeSe6 at high temperatures ushered us to their chemical neighbor Ag8GeSe6, whose high-temperature crystal structure and thermoelectric properties are not yet reported. In this work, we have employed a growth-from-the-melt technique followed by hot pressing to prepare polycrystalline Ag8GeSe6 samples, on which the crystal structure, micro-morphology, compositional analysis, UV-vis absorption, specific heat, speed of sound, and thermoelectric properties were characterized as a function of the Se-deficiency ratio and temperature. We found that (i) the crystal structure of Ag8GeSe6 evolved from orthorhombic at room temperature to face center cubic above 410 K, with a region of phase separations in between; (ii) like other argyrodite 816 phases, Ag8GeSe6 exhibited ultralow thermal conductivities over a wide temperature range as the phonon mean free path was down to the order of interatomic spacing; and (iii) varying Se deficiency effectively optimized the carrier concentration and power factor, a figure of merit zT value ∼0.55 was achieved at 923 K in Ag8GeSe5.88. These results not only fill a knowledge gap of Ag8GeSe6 but also contribute to a comprehensive understanding of 816 phase argyrodites at large.