High Thermoelectric Performance in Rhombohedral GeSe-LiBiTe2.

GeSe, an analogue of SnSe, shows promise in exhibiting exceptional thermoelectric performance in the Pnma phase. The constraints on its dopability, however, pose challenges in attaining optimal carrier concentrations and improving ZT values. This study demonstrates a crystal structure evolution strategy for achieving highly doped samples and promising ZTs in GeSe via LiBiTe2 alloying. A rhombohedral phase (R3m) can be stabilized in the GeSe-LiBiTe2 system, further evolving into a cubic (Fm3̅m) phase with a rising temperature. The band structures of GeSe-LiBiTe2 in the rhombohedral and cubic phases feature a similar multiple-valley energy-converged valence band of L and Σ bands. The observed high carrier concentration (∼1020 cm-3) reflects the effective convergence of these bands, enabling a high density-of-states effective mass and an enhanced power factor. Moreover, a very low lattice thermal conductivity of 0.6-0.5 W m-1 K-1 from 300 to 723 K is achieved in 0.9GeSe-0.1LiBiTe2, approaching the amorphous limit value. This remarkably low lattice thermal conductivity is related to phonon scattering from point defects, planar vacancies, and ferroelectric instability-induced low-energy Einstein oscillators. Finally, a maximum ZT value of 1.1 to 1.3 at 723 K is obtained, with a high average ZT value of over 0.8 (400-723 K) in 0.9GeSe-0.1LiBiTe2 samples. This study establishes a viable route for tailoring crystal structures to significantly improve the performance of GeSe-related compounds.

Engineering High Voltage Aqueous Aluminum-Ion Batteries.

The energy transition to renewables necessitates innovative storage solutions beyond the capacities of lithium-ion batteries. Aluminum-ion batteries (AIBs), particularly their aqueous variants (AAIBs), have emerged as potential successors due to their abundant resources, electrochemical advantages, and eco-friendliness. However, they grapple with achieving their theoretical voltage potential, often yielding less than expected. This perspective article provides a comprehensive examination of the voltage challenges faced by AAIBs, attributing gaps to factors such as the aluminum reduction potential, hydrogen evolution reaction, and aluminum's inherent passivation. Through a critical exploration of methodologies, strategies, such as underpotential deposition, alloying, interface enhancements, tailored electrolyte compositions, and advanced cathode design, are proposed. This piece seeks to guide researchers in harnessing the full potential of AAIBs in the global energy storage landscape.

Tuning Main Group Element-based Metal-Organic Framework to Boost Electrocatalytic Nitrogen Reduction Under Ambient Conditions.

Main group element-based materials are emerging catalysts for ammonia (NH3 ) production via a sustainable electrochemical nitrogen reduction reaction (N2 RR) pathway under ambient conditions. However, their N2 RR performances are less explored due to the limited active behavior and unclear mechanism. Here, an aluminum-based defective metal-organic framework (MOF), aluminum-fumarate (Al-Fum), is investigated. As a proof of concept, the pristine Al-Fum MOF is synthesized by the solvothermal reaction process, and the defect engineering method namely solvent-assisted linker exchange, is applied to create the defective Al sites. The defective Al sites play an important role in ensuring the N2 RR activity for defective Al-Fum. It is found that only the defective Al-Fum enables stable and effective electrochemical N2 RR, in terms of the highest production rate of 53.9 µg(NH3 ) h-1 mgcat -1 (in 0.4 m K2 SO4 ) and the Faradaic efficiency of 73.8% (in 0.1 m K2 SO4 ) at -0.15 V vs reversible hydrogen electrode) under ambient conditions. Density functional theory calculations confirm that the N2 activation can be achieved on the defective Al sites. Such sites also allow the subsequent protonation process via the alternating associative mechanism. This defect characteristic gives the main group Al-based MOFs the ability to serve as promising electrocatalysts for N2 RR and other attractive applications.

Bio-Polyethylene and Polyethylene Biocomposites: An Alternative toward a Sustainable Future.

Polyethylene (PE), a highly prevalent non-biodegradable polymer in the field of plastics, presents a waste management issue. To alleviate this issue, bio-based PE (bio-PE), derived from renewable resources like corn and sugarcane, offers an environmentally friendly alternative. This review discusses various production methods of bio-PE, including fermentation, gasification, and catalytic conversion of biomass. Interestingly, the bio-PE production volumes and market are expanding due to the growing environmental concerns and regulatory pressures. Additionally, the production of PE and bio-PE biocomposites using agricultural waste as filler materials, highlights the growing demand for sustainable alternatives to conventional plastics. According to previous studies, addition of ≈50% defibrillated corn and abaca fibers into bio-PE matrix and a compatibilizer, results in the highest Young's modulus of 4.61 and 5.81 GPa, respectively. These biocomposites have potential applications in automotive, building construction, and furniture industries. Moreover, the advancement made in abiotic and biotic degradation of PE and PE biocomposites is elucidated to address their environmental impacts. Finally, the paper concludes with insights into the opportunities, challenges, and future perspectives in the sustainable production and utilization of PE and bio-PE biocomposites. In summary, production of PE and bio-PE biocomposites can contribute to a cleaner and sustainable future.

Discordant Distortion in Cubic GeMnTe2 and High Thermoelectric Properties of GeMnTe2-x%SbTe.

GeMnTe2 adopts a cubic rock salt structure and is a promising mid-temperature thermoelectric material. The pair distribution function analysis of neutron total scattering data, however, indicates that GeMnTe2 is locally distorted from the ideal rock salt structure with Ge2+ cations being discordant and displaced ∼0.3 Å off the octahedron center. By alloying GeMnTe2 with SbTe, the carrier concentration can be tuned in GeMnTe2-x%SbTe (x = 15.1), leading to converged multiple broad valence bands and a high Seebeck coefficient of >200 µV K-1 from 300 to 823 K. The system exhibits a large density-of-state effective mass of >10 me and a high weighted mobility of 80 cm2 V-1 s-1, leading to a power factor of 15 µWcm-1 K-2 at 823 K. The composition GeMnTe2-15.1%SbTe exhibits very low lattice thermal conductivity of ∼0.5 Wm-1 K-1 at 823 K, attributed to the combination of off-centering cations in the rock salt structure, Ge/Mn positional disorder, dislocations, and abundant Ge-rich and Mn-rich nanoparticles. A ZT value of ∼1.5 can be achieved for GeMnTe2-15.1%SbTe with a ZTave of 0.96 in the temperature range of 400-823 K.

Integration of Metal-Organic Frameworks and Metals: Synergy for Electrocatalysis.

Electrocatalysis is a highly promising technology widely used in clean energy conversion. There is a continuing need to develop advanced electrocatalysts to catalyze the critical electrochemical reactions. Integrating metal active species, including various metal nanostructures (NSs) and atomically dispersed metal sites (ADMSs), into metal-organic frameworks (MOFs) leads to the formation of promising heterogeneous electrocatalysts that take advantage of both components. Among them, MOFs can provide support and protection for the active sites on guest metals, and the resulting host-guest interactions can synergistically enhance the electrocatalytic performance. In this review, three key concerns on MOF-metal heterogeneous electrocatalysts regarding the catalytic sites, conductivity, and catalytic stability are first presented. Then, rational integration strategies of MOFs and metals, including the integration of metal NSs via surface anchoring, space confining, and MOF coating, as well as the integration of ADMSs either with the metal nodes/linkers or within the pores of MOFs, along with their recent progress on synergistic cooperation for specific electrochemical reactions are summarized. Finally, current challenges and possible solutions in applying these increasingly concerned electrocatalysts are also provided.

Ammonia Electrosynthesis with a Stable Metal-Free 2D Silicon Phosphide Catalyst.

Metal-free 2D phosphorus-based materials are emerging catalysts for ammonia (NH3 ) production through a sustainable electrochemical nitrogen reduction reaction route under ambient conditions. However, their efficiency and stability remain challenging due to the surface oxidization. Herein, a stable phosphorus-based electrocatalyst, silicon phosphide (SiP), is explored. Density functional theory calculations certify that the N2 activation can be realized on the zigzag Si sites with a dimeric end-on coordinated mode. Such sites also allow the subsequent protonation process via the alternating associative mechanism. As the proof-of-concept demonstration, both the crystalline and amorphous SiP nanosheets (denoted as C-SiP NSs and A-SiP NSs, respectively) are obtained through ultrasonic exfoliation processes, but only the crystalline one enables effective and stable electrocatalytic nitrogen reduction reaction, in terms of an NH3 yield rate of 16.12 µg h-1  mgcat. -1 and a Faradaic efficiency of 22.48% at -0.3 V versus reversible hydrogen electrode. The resistance to oxidization plays the decisive role in guaranteeing the NH3 electrosynthesis activity for C-SiP NSs. This surface stability endows C-SiP NSs with the capability to serve as appealing electrocatalysts for nitrogen reduction reactions and other promising applications.

High-performance thermoelectrics and challenges for practical devices.

Thermoelectric materials can be potentially employed in solid-state devices that harvest waste heat and convert it to electrical power, thereby improving the efficiency of fuel utilization. The spectacular increases in the efficiencies of these materials achieved over the past decade have raised expectations regarding the use of thermoelectric generators in various energy saving and energy management applications, especially at mid to high temperature (400-900 °C). However, several important issues that prevent successful thermoelectric generator commercialization remain unresolved, in good part because of the lack of a research roadmap.

N-Type Thermoelectric AgBiPbS3 with Nanoprecipitates and Low Thermal Conductivity.

Thermoelectric sulfide materials are of particular interest due to the earth-abundant and cost-effective nature of sulfur. Here, we report a new n-type degenerate semiconductor sulfide, AgBiPbS3, which adopts a Fm3̅m structure with a narrow band gap of ∼0.32 eV. Despite the homogeneous distribution of elements at the scale of micrometer, Ag2S nanoprecipitates with dimensions of several nanometers were detected throughout the matrix. AgBiPbS3 exhibits a low room-temperature lattice thermal conductivity of 0.88 W m-1 K-1, owing to the intrinsic low lattice thermal conductivity of Ag2S and the effective scattering of phonons at nanoprecipitate boundaries. Moreover, compared to AgBiS2, AgBiPbS3 demonstrates a significantly improved weighted mobility of >16 cm2 V-1 s-1 at 300 K, leading to an enhanced PF of 1.6 µW cm-1 K-2 at 300 K. The superior electrical transport in AgBiPbS3 can be attributed to the high valley degeneracy of the L point (the conduction band minimum), which is contributed by the Pb s and Pb p orbitals. Further, Ga doping is found to be effective in modulating the Fermi levels of AgBiPbS3, leading to further enhancement of PF with a PFave of 2.7 µW cm-1 K-2 in the temperature range of 300-823 K. Consequently, a relatively high ZTave of 0.22 and a peak ZT of ∼0.4 at 823 K have been achieved in 3% Ga-doped AgBiPbS3, highlighting the potential of AgBiPbS3 as an n-type thermoelectric sulfide.

[Research and Practice of Vehicle-mounted Mobile CT Based on Emergency Medical Rescue].

OBJECTIVE: In order to solve the problem of inadequate CT screening ability in emergency medical rescue in remote mountainous areas, high-altitude areas, other public health events and sudden natural disasters, a vehicle-mounted mobile CT suitable for emergency medical rescue is studied. METHODS: A vehicle chassis system suitable for long-distance transportation and a cabin system suitable for epidemic prevention and control was designed. A domestic 32-slice CT with small volume, light weight and high stability was selected to design a vehicle-mounted mobile CT suitable for emergency medical rescue. RESULTS: The high-performance vehicle-mounted mobile CT can provide rapid support, and provide large-scale screening, emergency medical rescue, a supplement to daily CT scanning in peacetime and wartime. CONCLUSIONS: The vehicle CT has high stability, fast scanning speed and high social and economic value.

Thermoelectric Performance of the 2D Bi2Si2Te6 Semiconductor.

Bi2Si2Te6, a 2D compound, is a direct band gap semiconductor with an optical band gap of ∼0.25 eV, and is a promising thermoelectric material. Single-phase Bi2Si2Te6 is prepared by a scalable ball-milling and annealing process, and the highly densified polycrystalline samples are prepared by spark plasma sintering. Bi2Si2Te6 shows a p-type semiconductor transport behavior and exhibits an intrinsically low lattice thermal conductivity of ∼0.48 W m-1 K-1 (cross-plane) at 573 K. The first-principles density functional theory calculations indicate that such low lattice thermal conductivity is derived from the interactions between acoustic phonons and low-lying optical phonons, local vibrations of Bi, the low Debye temperature, and strong anharmonicity result from the unique 2D crystal structure and metavalent bonding of Bi2Si2Te6. The Bi2Si2Te6 exhibits an optimal figure of merit ZT of ∼0.51 at 623 K, which can be further enhanced by the substitution of Bi with Pb. Pb doping leads to a large increase in power factor S2σ, from ∼3.9 µW cm-1 K-2 of Bi2Si2Te6 to ∼8.0 µW cm-1 K-2 of Bi1.98Pb0.02Si2Te6 at 773 K, owing to the increase in carrier concentration. Moreover, Pb doping induces a further reduction in the lattice thermal conductivity to ∼0.38 W m-1 K-1 (cross-plane) at 623 K in Bi1.98Pb0.02Si2Te6, due to strengthened point defect (PbBi') scattering. The simultaneous optimization of the power factor and lattice thermal conductivity achieves a peak ZT of ∼0.90 at 723 K and a high average ZT of ∼0.66 at 400-773 K in Bi1.98Pb0.02Si2Te6.

Reversible Al Metal Anodes Enabled by Amorphization for Aqueous Aluminum Batteries.

Aqueous aluminum metal batteries (AMBs) are regarded as one of the most sustainable energy storage systems among post-lithium-ion candidates, which is attributable to their highest theoretical volumetric capacity, inherent safe operation, and low cost. Yet, the development of aqueous AMBs is plagued by the incapable aluminum plating in an aqueous solution and severe parasitic reactions, which results in the limited discharge voltage, thus making the development of aqueous AMBs unsuccessful so far. Here, we demonstrate that amorphization is an effective strategy to tackle these critical issues of a metallic Al anode by shifting the reduction potential for Al deposition. The amorphous aluminum (a-Al) interfacial layer is triggered by an in situ lithium-ion alloying/dealloying process on a metallic Al substrate with low strength. Unveiled by experimental and theoretical investigations, the amorphous structure greatly lowers the Al nucleation energy barrier, which forces the Al deposition competitive to the electron-stealing hydrogen evolution reaction (HER). Simultaneously, the inhibited HER mitigates the passivation, promoting interfacial ion transfer kinetics and enabling steady aluminum plating/stripping for 800 h in the symmetric cell. The resultant multiple full cells using Al@a-Al anodes deliver approximately a 0.6 V increase in the discharge voltage plateau compared to that of bare Al-based cells, which far outperform all reported aqueous AMBs. In both symmetric cells and full cells, the excellent electrochemical performances are achieved in a noncorrosive, low-cost, and fluorine-free Al2(SO4)3 electrolyte, which is ecofriendly and can be easily adapted for sustainable large-scale applications. This work brings an intriguing picture of the design of metallic anodes for reversible and high-voltage AMBs.

Valence Disproportionation of GeS in the PbS Matrix Forms Pb5Ge5S12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance.

Converting waste heat into useful electricity using solid-state thermoelectrics has a potential for enormous global energy savings. Lead chalcogenides are among the most prominent thermoelectric materials, whose performance decreases with an increase in chalcogen amounts (e.g., PbTe > PbSe > PbS). Herein, we demonstrate the simultaneous optimization of the electrical and thermal transport properties of PbS-based compounds by alloying with GeS. The addition of GeS triggers a complex cascade of beneficial events as follows: Ge2+ substitution in Pb2+ and discordant off-center behavior; formation of Pb5Ge5S12 as stable second-phase inclusions through valence disproportionation of Ge2+ to Ge0 and Ge4+. PbS and Pb5Ge5S12 exhibit good conduction band energy alignment that preserves the high electron mobility; the formation of Pb5Ge5S12 increases the electron carrier concentration by introducing S vacancies. Sb doping as the electron donor produces a large power factor and low lattice thermal conductivity (κlat) of ∼0.61 W m-1 K-1. The highest performance was obtained for the 14% GeS-alloyed samples, which exhibited an increased room-temperature electron mobility of ∼121 cm2 V-1 s-1 for 3 × 1019 cm-3 carrier density and a ZT of 1.32 at 923 K. This is ∼55% greater than the corresponding Sb-doped PbS sample and is one of the highest reported for the n-type PbS system. Moreover, the average ZT (ZTavg) of ∼0.76 from 400 to 923 K is the highest for PbS-based systems.

Promoting the Water-Reduction Kinetics and Alkali Tolerance of MoNi4 Nanocrystals via a Mo2 TiC2 Tx Induced Built-In Electric Field.

Mo-Ni alloy-based electrocatalysts are regarded as promising candidates for the hydrogen evolution reaction (HER), despite their vulnerable stability in alkaline solution that hampers further application. Herein, Mo2 TiC2 Tx MXene, is employed as a support for MoNi4 alloy nanocrystals (NCs) to fabricate a unique nanoflower-like MoNi4 -MXn electrocatalyst. A remarkably strong built-in electric field is established at the interface of two components, which facilitates the electron transfer from Mo2 TiC2 Tx to MoNi4 . Due to the accumulation of electrons at the MoNi4 sites, the adsorption of the catalytic intermediates and ionic species on MoNi4 is affected consequently. As a result, the MoNi4 -MX10 nanohybrid exhibits the lowest overpotential, even lower than 10% Pt/C catalyst at the current density of 10 mA cm-2 in 1 m KOH solution (122.19 vs 129.07 mV, respectively). Furthermore, a lower Tafel slope of 55.88 mV dec-1 is reported as compared to that of the 10% Pt/C (65.64 mV dec-1 ). Additionally, the MoNi4 -MX10 catalyst also displays extraordinary chemical stability in alkaline solution, with an activity loss of only 0.15% per hour over 300 h of operation. This reflects the great potential of using MXene-based interfacial engineering for the synthesis of a highly efficient and stable electrocatalyst.

Rechargeable Aqueous Aluminum-Ion Battery: Progress and Outlook.

The high cost and scarcity of lithium resources have prompted researchers to seek alternatives to lithium-ion batteries. Among emerging "Beyond Lithium" batteries, rechargeable aluminum-ion batteries (AIBs) are yet another attractive electrochemical storage device due to their high specific capacity and the abundance of aluminum. Although the current electrochemical performance of nonaqueous AIBs is better than aqueous AIBs (AAIBs), AAIBs have recently gained attention due to their low cost and enhanced safety. Extensive efforts are devoted to developing AAIBs in the last few years. Yet, it is still challenging to achieve stable electrodes with good electrochemical performance and electrolytes without side reactions. This review summarizes the recent progress in the exploration of anode and cathode materials and the selection of electrolytes of AAIBs. Lastly, the main challenges and future research outlook of high-performance AAIBs are also presented.

In Situ Synthesis and Microfabrication of High Entropy Alloy and Oxide Compounds by Femtosecond Laser Direct Writing under Ambient Conditions.

Synthesis and coating of multi-metal oxides (MMOs) and alloys on conductive substrates are indispensable to electrochemical applications, yet demand multiple, resource-intensive, and time-consuming processes. Herein, an alternative approach to the synthesis and coating of alloys and MMOs by femtosecond laser direct writing (FsLDW) is reported. A solution-based precursor ink is deposited and dried on the substrate and illuminated by a femtosecond laser. During the illumination, dried precursor ink is transformed to MMO/alloys and is simultaneously bonded to the substrate. The formulation of the alloy and MMO precursor ink for laser processing is universally applicable to a large family of oxides and alloys. The process is conducted at room temperature and in an open atmosphere. To demonstrate, a large family of 57 MMOs and alloys are synthesized from a group of 13 elements. As a proof of concept, Ni0.24 Co0.23 Cu0.24 Fe0.15 Cr0.14 high entropy alloy synthesized on stainless-steel foil by FsLDW is used for the oxygen evolution reaction, which achieves a current density of 10 mA cm-2 at a significantly low overpotential of 213 mV. Further, FsLDW can also achieve microfabrication of alloys/MMO with feature sizes down to 20 µm.

Efficient and Selective CO2 Reduction to Formate on Pd-Doped Pb3 (CO3 )2 (OH)2 : Dynamic Catalyst Reconstruction and Accelerated CO2 Protonation.

Exploring catalyst reconstruction under the electrochemical condition is critical to understanding the catalyst structure-activity relationship as well as to design effective electrocatalysts. Herein, a PbF2 nanocluster is synthesized and its self-reconstruction under the CO2 reduction condition is investigated. F- leaching, CO2 -saturated environment, and application of a cathodic potential induce self-reconstruction of PbF2 to Pb3 (CO3 )2 (OH)2 , which effectively catalyze the CO2 reduction to formate. The in situ formed Pb3 (CO3 )2 (OH)2 discloses >80% formate Faradaic efficiencies (FEs) across a broad range of potentials and achieves a maximum formate FE of ≈90.1% at -1.2 V versus reversible hydrogen electrode (RHE). Kinetic studies show that the CO2 reduction reaction (CO2 RR) on the Pb3 (CO3 )2 (OH)2 is rate-limited at the CO2 protonation step, in which proton is supplied by bicarbonate (HCO3 - ) in the electrolyte. To improve the CO2 RR kinetics, the Pb3 (CO3 )2 (OH)2 is further doped with Pd (4 wt%) to enhance its HCO3 - adsorption, which leads to accelerated protonation of CO2 . Therefore, the Pd-Pb3 (CO3 )2 (OH)2 (4 wt%) reveals higher formate FEs of >90% from -0.8 to -1.2 V versus RHE and reaches a maximum formate FE of 96.5% at -1.2 V versus RHE with a current density of ≈13 mA cm-2 .

Special Issue: Next Generation Metal-Ion Batteries.

Recently, rechargeable metal-ion batteries have been the research focus for their long cycle life and high energy density. In this special issue, we collected 30 researcch and review papers that cover the research progress of electrode materials, separators, and electrolytes in various advanced metal-ion and other energy storage devices.

Defect engineering in thermoelectric materials: what have we learned?

Thermoelectric energy conversion is an all solid-state technology that relies on exceptional semiconductor materials that are generally optimized through sophisticated strategies involving the engineering of defects in their structure. In this review, we summarize the recent advances of defect engineering to improve the thermoelectric (TE) performance and mechanical properties of inorganic materials. First, we introduce the various types of defects categorized by dimensionality, i.e. point defects (vacancies, interstitials, and antisites), dislocations, planar defects (twin boundaries, stacking faults and grain boundaries), and volume defects (precipitation and voids). Next, we discuss the advanced methods for characterizing defects in TE materials. Subsequently, we elaborate on the influences of defect engineering on the electrical and thermal transport properties as well as mechanical performance of TE materials. In the end, we discuss the outlook for the future development of defect engineering to further advance the TE field.

Cubic AgMnSbTe3 Semiconductor with a High Thermoelectric Performance.

The reaction of MnTe with AgSbTe2 in an equimolar ratio (ATMS) provides a new semiconductor, AgMnSbTe3. AgMnSbTe3 crystallizes in an average rock-salt NaCl structure with Ag, Mn, and Sb cations statistically occupying the Na sites. AgMnSbTe3 is a p-type semiconductor with a narrow optical band gap of ∼0.36 eV. A pair distribution function analysis indicates that local distortions are associated with the location of the Ag atoms in the lattice. Density functional theory calculations suggest a specific electronic band structure with multi-peak valence band maxima prone to energy convergence. In addition, Ag2Te nanograins precipitate at grain boundaries of AgMnSbTe3. The energy offset of the valence band edge between AgMnSbTe3 and Ag2Te is ∼0.05 eV, which implies that Ag2Te precipitates exhibit a negligible effect on the hole transmission. As a result, ATMS exhibits a high power factor of ∼12.2 µW cm-1 K-2 at 823 K, ultralow lattice thermal conductivity of ∼0.34 W m-1 K-1 (823 K), high peak ZT of ∼1.46 at 823 K, and high average ZT of ∼0.87 in the temperature range of 400-823 K.