Metal-Halogen Interactions Inducing Phase Separation for Self-Healing and Tough Ionogels with Tunable Thermoelectric Performance.

Ionic liquid-based thermoelectric gels become a compelling candidate for thermoelectric power generation and sensing due to their giant thermopower, good thermal stability, high flexibility, and low-cost production. However, the materials reported to date suffer from canonical trade-offs between self-healing ability, stretchability, strength, and ionic conductivity. Herein, a self-healing and tough ionogel (PEO/LiTFSI/EmimCl) with tunable thermoelectric properties by tailoring metal-halogen bonding interactions, is developed. Different affinities between polymer matrix and salts are exploited to induce phase separation, resulting in simultaneous enhancement of ionic conductivity and mechanical strength. Molecular dynamics (MD) simulations and spectroscopic analyses show that Cl- ions impair the lithium-ether oxygen coordination, leading to changes in chain conformation. The migration difference between cations and anions is thus widened and a transition from n-type to p-type thermoelectric ionogels is realized. Furthermore, the dynamic interactions of metal-ligand coordination and hydrogen bonding yield autonomously self-healing capability, large stretchability (2000%), and environment-friendly recyclability. Benefiting from these fascinating properties, the multifunctional PEO-based ionogels are applied in sensors, supercapacitors, and thermoelectric power generation modules. The strategy of tuning solvation dominance to address the trade-offs in thermoelectric ionogels and optimize their macroscopic properties offers new possibilities for the design of advanced ionogels.

Fully inkjet-printed Ag2Se flexible thermoelectric devices for sustainable power generation.

Flexible thermoelectric devices show great promise as sustainable power units for the exponentially increasing self-powered wearable electronics and ultra-widely distributed wireless sensor networks. While exciting proof-of-concept demonstrations have been reported, their large-scale implementation is impeded by unsatisfactory device performance and costly device fabrication techniques. Here, we develop Ag2Se-based thermoelectric films and flexible devices via inkjet printing. Large-area patterned arrays with microscale resolution are obtained in a dimensionally controlled manner by manipulating ink formulations and tuning printing parameters. Printed Ag2Se-based films exhibit (00 l)-textured feature, and an exceptional power factor (1097 µWm-1K-2 at 377 K) is obtained by engineering the film composition and microstructure. Benefiting from high-resolution device integration, fully inkjet-printed Ag2Se-based flexible devices achieve a record-high normalized power (2 µWK-2cm-2) and superior flexibility. Diverse application scenarios are offered by inkjet-printed devices, such as continuous power generation by harvesting thermal energy from the environment or human bodies. Our strategy demonstrates the potential to revolutionize the design and manufacture of multi-scale and complex flexible thermoelectric devices while reducing costs, enabling them to be integrated into emerging electronic systems as sustainable power sources.

Exceptional n-type thermoelectric ionogels enabled by metal coordination and ion-selective association.

Ionic liquid-based ionogels emerge as promising candidates for efficient ionic thermoelectric conversion due to their quasi-solid state, giant thermopower, high flexibility, and good stability. P-type ionogels have shown impressive performance; however, the development of n-type ionogels lags behind. Here, an n-type ionogel consisting of polyethylene oxide (PEO), lithium salt, and ionic liquid is developed. Strong coordination of lithium ion with ether oxygen and the anion-rich clusters generated by ion-preferential association promote rapid transport of the anions and boost Eastman entropy change, resulting in a huge negative ionic Seebeck coefficient (-15 millivolts per kelvin) and a high electrical conductivity (1.86 millisiemens per centimeter) at 50% relative humidity. Moreover, dynamic and reversible interactions among the ternary mixtures endow the ionogel with fast autonomous self-healing capability and green recyclability. All PEO-based ionic thermoelectric modules are fabricated, which exhibits outstanding thermal responses (-80 millivolts per kelvin for three p-n pairs), demonstrating great potential for low-grade energy harvesting and ultrasensitive thermal sensing.

High-efficiency and reliable same-parent thermoelectric modules using Mg3Sb2-based compounds.

Thermoelectric modules can convert waste heat directly into useful electricity, providing a clean and sustainable way to use fossil energy more efficiently. Mg3Sb2-based alloys have recently attracted considerable interest from the thermoelectric community due to their nontoxic nature, abundance of constituent elements and excellent mechanical and thermoelectric properties. However, robust modules based on Mg3Sb2 have progressed less rapidly. Here, we develop multiple-pair thermoelectric modules consisting of both n-type and p-type Mg3Sb2-based alloys. Thermoelectric legs based on the same parent fit into each other in terms of thermomechanical properties, facilitating module fabrication and ensuring low thermal stress. By adopting a suitable diffusion barrier layer and developing a new joining technique, an integrated all-Mg3Sb2-based module demonstrates a high efficiency of 7.5% at a temperature difference of 380 K, exceeding the state-of-the-art same-parent thermoelectric modules. Moreover, the efficiency remains stable during 150 thermal cycling shocks (∼225 h), demonstrating excellent module reliability.

Mixed-phase WO3 Cocatalysts on Hierarchical Si-based Photocathode for Efficient Photoelectrochemical Li Extraction.

Photoelectrochemical lithium (Li) extraction can be expected to provide a useful recycle of Li+ from waste Li-containing battery, but the process is limited by the photocathodes with poor Li+ absorption and low yield rate. Here, we have designed a hierarchical silicon (Si)-based photocathode with mixed-phase tungsten oxide (WO3 ) cocatalysts for photoelectrochemical Li extraction under 1 sun illumination, achieving a high Li yield rate of ≈223.0 µg cm-2 h-1 and an excellent faradaic efficiency of 91.9 % at 0.0817 V versus Li0/+ redox couple. The WO3 cocatalysts with the mixture of amorphous and crystalline phase accelerates the Li+ insertion and precipitation and enriches the concentration of Li+ at the photocathode surface. This robust photoelectrochemical Li extraction system provides a new insight on designing green and efficient route for cyclic utilization of Li resources in the sustainable energy field.

Photoelectrochemical N2 -to-NH3 Fixation with High Efficiency and Rates via Optimized Si-Based System at Positive Potential versus Li0/.

As a widely used commodity chemical, ammonia is critical for producing nitrogen-containing fertilizers and serving as the promising zero-carbon energy carrier. Photoelectrochemical nitrogen reduction reaction (PEC NRR) can provide a solar-powered green and sustainable route for synthesis of ammonia (NH3 ). Herein, an optimum PEC system is reported with an Si-based hierarchically-structured PdCu/TiO2 /Si photocathode and well-thought-out trifluoroethanol as the proton source for lithium-mediated PEC NRR, achieving a record high NH3 yield of 43.09 µg cm-2 h-1 and an excellent faradaic efficiency of 46.15% under 0.12 MPa O2 and 3.88 MPa N2 at 0.07 V versus lithium(0/+) redox couple (vs Li0/+ ). PEC measurements coupled with operando characterization reveal that the PdCu/TiO2 /Si photocathode under N2 pressures facilitate the reduction of N2 to form lithium nitride (Li3 N), which reacts with active protons to produce NH3 while releasing the Li+ to reinitiate the cycle of the PEC NRR. The Li-mediated PEC NRR process is further enhanced by introducing small amount of O2 or CO2 under pressure by accelerating the decomposition of Li3 N. For the first time, this work provides mechanistic understanding of the lithium-mediated PEC NRR process and opens new avenues for efficient solar-powered green conversion of N2 -to-NH3 .

Boundary-oriented Network for Automatic Breast Tumor Segmentation in Ultrasound Images.

Breast cancer is considered as the most prevalent cancer. Using ultrasound images is a momentous clinical diagnosis method to locate breast tumors. However, accurate segmentation of breast tumors remains an open problem due to ultrasound artifacts, low contrast, and complicated tumor shapes in ultrasound images. To address this issue, we proposed a boundary-oriented network (BO-Net) for boosting breast tumor segmentation in ultrasound images. The BO-Net boosts tumor segmentation performance from two perspectives. Firstly, a boundary-oriented module (BOM) was designed to capture the weak boundaries of breast tumors by learning additional breast tumor boundary maps. Second, we focus on enhanced feature extraction, which takes advantage of the Atrous Spatial Pyramid Pooling (ASPP) module and Squeeze-and-Excitation (SE) block to obtain multi-scale and efficient feature information. We evaluate our network on two public datasets: Dataset B and BUSI. For the Dataset B, our network achieves 0.8685 in Dice, 0.7846 in Jaccard, 0.8604 in Precision, 0.9078 in Recall, and 0.9928 in Specificity. For the BUSI dataset, our network achieves 0.7954 in Dice, 0.7033 in Jaccard, 0.8275 in Precision, 0.8251 in Recall, and 0.9814 in Specificity. Experimental results show that BO-Net outperforms the state-of-the-art segmentation methods for breast tumor segmentation in ultrasound images. It demonstrates that focusing on boundary and feature enhancement creates more efficient and robust breast tumor segmentation.

Gradient Variation Oxygen-Content Vanadium-Oxygen Composite Films with Enhanced Crystallinity and Excellent Durability for Smart Windows.

Vanadium dioxide (VO2)-based smart windows show excellent promise for energy-saving and have been extensively researched. However, for the glass industry-compatible magnetron sputtering process, VO2 films are difficult to obtain and have homogeneous crystalline state, leaving them lacking the ideal solar modulation (ΔTsol) and sensitivity (narrow hysteresis loop). More importantly, the instability of VO2 hinders its commercialization. Multilayer structures have been repeatedly investigated to solve these problems. Unfortunately, the mediocre thermochromic properties as well as the complex and expensive manufacturing steps still hinder its commercialization. In this work, we prepared gradient variation oxygen-content vanadium-oxygen composite films (V2O3/VO2/V2O5, VOgv) with enhanced crystallinity and excellent durability by one-step continuous sputtering. According to optical measurements, the ΔTsol of the VOgv films was significantly increased by 145% (from 6.85 to 16.80%) compared to VO2 films, and the width of the hysteresis loop was reduced by 67% (from 19.34 to 6.36 °C), while the VOgv films exhibited a wider preparation window. The accelerated tests have shown that the film has an equivalent service life of approximately 20 years. We exploited the intrinsic similarity in properties of homologous compounds of vanadium oxide and simplified the preparation process, which is supposed to break the existing application bottlenecks and increase the commercializing possibility of VO2-based thermochromic smart windows.

Tailoring Intermolecular Interactions Towards High-Performance Thermoelectric Ionogels at Low Humidity.

Development of ionic thermoelectric (iTE) materials is of immense interest for efficient heat-to-electricity conversion due to their giant ionic Seebeck coefficient (Si ), but challenges remain in terms of relatively small Si at low humidity, poor stretchability, and ambiguous interaction mechanism in ionogels. Herein, a novel ionogel is reported consisting of polyethylene oxide (PEO), polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and 1-ethyl-3-methylimidazolium acetate (Emim:OAC). By delicately designing the interactions between ions and polymers, the migration of anions is restricted due to their strong binding with the hydroxyl groups of polymers, while the transport of cations is facilitated through segmental motions due to the increased amorphous regions, thereby leading to enlarged diffusion difference between the cations and anions. Moreover, the plasticizing effect of P123 and Emim:OAC can increase the elongation at break. As a consequence, the ionogel exhibits excellent properties including high Si (18 mV K-1 at relative humidity of 60%), good ionic conductivity (1.1 mS cm-1 ), superior stretchability (787%), and high stability (over 80% retention after 600 h). These findings show a promising strategy to obtain multifunctional iTE materials by engineering the intermolecular interactions and demonstrate the great potential of ionogels for harvesting low-grade heat in human-comfortable humidity environments.

Tuning the Electron Localization of Gold Enables the Control of Nitrogen-to-Ammonia Fixation.

The (photo)electrochemical N2 reduction reaction (NRR) provides a favorable avenue for the production of NH3 using renewable energy in mild operating conditions. Understanding and building an efficient catalyst with high NH3 selectivity represents an area of intense interest for the early stages of development for NRR. Herein, we introduce a CoOx layer to tune the local electronic structure of Au nanoparticles with positive valence sites for boosting conversion of N2 to NH3 . The catalysts, possessing high average oxidation states (ca. 40 %), achieve a high NH3 yield rate of 15.1 µg cm-2 h-1 and a good faradic efficiency of 19 % at -0.5 V versus reversible hydrogen electrode. Experimental results and simulations reveal that the ability to tune the oxidation state of Au enables the control of N2 adsorption and the concomitant energy barrier of NRR. Altering the Au oxidation state provides a unique strategy for control of NRR in the production of valuable NH3 .

Self-Template Synthesis of Nanoporous VO2-Based Films: Localized Surface Plasmon Resonance and Enhanced Optical Performance for Solar Glazing Application.

Poly(tetrafluoroethylene) (Teflon) has been selected as the self-template structural material in the preparation of VO2 films using a reactive magnetron sputtering method and post-annealing process. VO2 films with spontaneous random nanoporous structures growing on quartz glasses have been deliberately established via bottom-up processing through this novel and facile approach. The nanoporous VO2 films exhibit an excellent optical performance based on the localized surface plasmon resonance, with ultrahigh luminous transmittance ( Tlum-L) up to 78.0% and the promoted solar modulation ability (Δ Tsol) of 14.1%. Meanwhile, the ingenious microstructure of the film provides an antireflection function from multiple perspectives on visible light and indicates the potential of the windshield on vehicles for smart solar modulation. The nanoporous films expand the practical application of thermochromic VO2 to a fire-new field, breaking the optical performance envelope of the single-layer dense VO2 film away, and offering a universal method to prepare homogeneous nanoporous structures for thin films.

Room-Temperature Synthesis of Inorganic-Organic Hybrid Coated VO2 Nanoparticles for Enhanced Durability and Flexible Temperature-Responsive Near-Infrared Modulator Application.

Vanadium dioxide is one kind of desirable infrared modulator for sensors because of its remarkable temperature-responsive infrared modulation ability via autogeneic metal-insulator transition. However, the detriments of poor chemical stability and narrow scope of extensive-researched application (e.g., smart windows) restrict its mass production. Here, we propose a VO2@MgF2@PDA inorganic-organic hybrid coated architecture for greatly enhancing the optical durability more than 13 times in contrast to pristine VO2 and the transmittance difference between room and high temperature changed within 20% (decreasing from 25 to 20.1%) at λ = 1200 nm after the ageing time of 1000 h at constant temperature (60 °C) and relative humidity (90%). Furthermore, based on the as-synthesized durability-enhanced nanoparticles, we fabricated a flexible sensor for temperature-field fluorescence imaging by integrating the VO2-based near-infrared modulator with the upconversion fluorescence material. Additionally, the formation mechanism of VO2@MgF2 core-shell nanoparticles was studied in detail. The inorganic-organic combination strategy paves a new way for improving the stability of nanoparticles, and the use of VO2-based flexible temperature-fluorescence sensors is a promising technique for remote and swift temperature-field distribution imaging on complicated and campulitropal surfaces.

Organic-inorganic hybrid optical foils with strong visible reflection, excellent near infrared-shielding ability and high transparency.

Research on functional flexible films has recently been attracting widespread attention especially with regards to foils, which can be designed artificially on the basis of the practical requirements. In this work, a foil with high visible reflection and a strong near infrared shielding efficiency was prepared by a simple wet chemical method. In the process of making this kind of optical foil, emulsion polymerization was first introduced to synthesize polymer opals, which were further compressed between two pieces of polyethylene terephthalate (PET) foil under polymer melting temperature to obtain a photonic crystal film with a strong reflection in the visible region to block blue rays. The following step was to coat a layer of the inorganic nano paint, which was synthesized by dispersing Cs-doped WO3 (CWO) nanoparticles homogenously into organic resin on the surface of the PET to achieve a high near infrared shielding ability. The final composite foil exhibited unique optical properties such as high visible reflectance (23.9%) to block blue rays, and excellent near infrared shielding efficiency (98.0%), meanwhile it still maintained a high transparency meaning that this foil could potentially be applied in energy-saving window films. To sum up, this study provides new insight into devising flexible hybrid films with novel optical properties, which could be further extended to prepare other optical films for potential use in automobile, architectural and other decorative fields.

Fast Fabrication of a Stable Perovskite Solar Cell with an Ultrathin Effective Novel Inorganic Hole Transport Layer.

With the aim of fabricating simple, reproducible, and scalable perovskite solar cells (PSCs) with least time consumption, a novel CoOx hole transport layer (HTL) was first proposed and introduced in this work. The CoOx HTL thickness was minimized to about 10 nm with complete coverage on the FTO substrate (F-doped SnO2) by direct current magnetron sputtering. The ultrathin HTL could minimize the incident light loss caused by cobalt ion absorption and reduce the carrier transport loss by shortening the transport path. Copper was incorporated into the CoOx lattice to address the low conductivity of the CoOx film and the energy-level mismatch between CoOx and the perovskite material. On the basis of cobalt-copper binary oxide (Co1-yCuyOx), the highest power conversion efficiency (PCE) of about 10% was achieved, which was acceptable for mass production. Moreover, the deposition of such Co1-yCuyOx films takes only 2 min without size limitation of substrates. A well-functioned device based on the Co1-yCuyOx HTL could hence be fabricated within 100 min. Excellent stability was demonstrated as well, with over 90% of the initial PCE remaining after being stored in a dark and humid environment (relative humidity 60%) for 12 days.

Enhanced electrical property of Ni-doped CoOx hole transport layer for inverted perovskite solar cells.

Ultrathin Ni doped CoOx films were prepared by direct current co-sputtering at room temperature as inorganic hole transport materials for inverted perovskite solar cells. P-type doping was designed to adjust the valence band position of CoOx to match the that of CH3NH3PbI3, which would effectively eliminate the interface barrier. Moreover, the hole extraction ability would be enhanced and the power conversion efficiency of the devices hence increased from 3.68% to 9.60%. The optimized performance was also accompanied by decent stability as a result of its intrinsic stability.

Achieving High Current Density of Perovskite Solar Cells by Modulating the Dominated Facets of Room-Temperature DC Magnetron Sputtered TiO2 Electron Extraction Layer.

The short circuit current density of perovskite solar cell (PSC) was boosted by modulating the dominated plane facets of TiO2 electron transport layer (ETL). Under optimized condition, TiO2 with dominant {001} facets showed (i) low incident light loss, (ii) highly smooth surface and excellent wettability for precursor solution, (iii) efficient electron extraction, and (iv) high conductivity in perovskite photovoltaic application. A current density of 24.19 mA cm-2 was achieved as a value near the maximum limit. The power conversion efficiency was improved to 17.25%, which was the record value of PSCs with DC magnetron sputtered carrier transport layer. What is more, the room-temperature process had a great significance for the cost reduction and flexible application of PSCs.

Mesostructured perovskite solar cells based on highly ordered TiO2 network scaffold via anodization of Ti thin film.

An anodized TiO2 interconnected network was fabricated and utilized as a mesoporous scaffold and electron transporter in perovskite solar cells. By modifying the synthesis parameters, the morphological features of the interconnected TiO2 nanostructures can be widely tuned and precisely controlled. The functional properties of the anodized TiO2 network are found to be severely influenced by morphology as well as the extent of oxidation. The device with the optimized TiO2 network exhibits superior electron extraction and transferability, resulting in conspicuous enhancement of the photocurrent and power conversion efficiency (PCE). This work proposes a promising and facile method for improving the performance of perovskite solar cells.

One step spray-coated TiO2 electron-transport layers for decent perovskite solar cells on large and flexible substrates.

Spray-coating as a facile and quantitative method was introduced to prepare thin and continuous TiO2 compact layers on different substrates for perovskite solar cells. The as-prepared film is highly transparent and smooth, which is of significance in perovskite solar cells to decrease incident light loss and facilitate the film cast and electric contact. The compact TiO2 layer shows excellent performance when coated with perovskite and assembled into a device. Since it provides unlimited substrate size, patterning function and the TiO2 used for spray-coating is well crystallized, this method has huge potential for mass production and great adaptability for a variety of applications.

Composite Film of Vanadium Dioxide Nanoparticles and Ionic Liquid-Nickel-Chlorine Complexes with Excellent Visible Thermochromic Performance.

Vanadium dioxide (VO2), as a typical thermochromic material used in smart windows, is always limited by its weaker solar regulation efficiency (ΔTsol) and lower luminous transmittance (Tlum). Except for common approaches such as doping, coating, and special structure, compositing is another effective method. The macroscopic thermochromic (from colorless to blue) ionic liquid-nickel-chlorine (IL-Ni-Cl) complexes are selected in this paper to be combined with VO2 nanoparticles forming a composite film. This novel scheme demonstrates outstanding optical properties: ΔTsol = 26.45% and Tlum,l = 66.44%, Tlum,h = 43.93%. Besides, the addition of the IL-Ni-Cl complexes endows the film with an obvious color change from light brown to dark green as temperature rises. This splendid visible thermochromic performance makes the composite film superior in function exhibiting and application of smart windows.

Sonographic diagnosis of complete uterine inversion: an unusual case.

Complete puerperal uterine inversion is an uncommon but potentially life-threatening obstetric emergency. It generally occurs as an obstetrical complication in the postpartum period and can present in acute, subacute, and chronic forms depending on the time interval after delivery. Maternal mortality has been reported to be as high as 15%, mainly because of life associated threatening blood loss and shock. Early diagnosis and treatment are essential, but diagnosis of this is not simple. This is a report of unusual case of complete uterine inversion diagnosed by accurate ultrasound leading to prompt potentially life-saving treatment.