Femtosecond Laser 4D Printing of Light-Driven Intelligent Micromachines

Intelligent micromachines that respond to external light stimuli have a broad range of potential applications, such as microbots, biomedicine, and adaptive optics. However, artificial light-driven intelligent micromachines with a low actuation threshold, rapid responsiveness, and designable and precise 3D transformation capability remain unachievable to date. Here, a single-material and one-step 4D printing strategy are proposed to enable the nanomanufacturing of agile and low-threshold light-driven 3D micromachines with programmable shape-morphing characteristics. The as-developed carbon nanotube-doped composite hydrogel simultaneously enhanced the light absorption, thermal conductivity, and mechanical modulus of the crosslinked network, thus significantly increasing the light sensitivity and response speed of micromachines. Moreover, the structural design and assembly of asymmetric microscale mechanical metamaterial unit cells enable the highly efficient additive nanomanufacturing of 3D shape-morphable micromachines with large dynamic modulation and spatiotemporal controllability. Using this strategy, the world's smallest artificial beating heart with programmable light-stimulus responsiveness for the cardiac cycle is successfully printed. This 4D printing method paves the way for the construction of multifunctional intelligent micromachines for bionics, drug delivery, integrated microsystems, and other fields.     

Biomolecules-Incorporated Metal-Organic Frameworks Gated Light-Sensitive Organic Photoelectrochemical Transistor for Biodetection

Incorporating biomolecules into metal-organic frameworks (MOFs) as exoskeletons to form biomolecules-MOFs biohybrids has attracted great attention as an emerging class of advanced materials. Organic devices have been shown as powerful platforms for next-generation bioelectronics, such as wearable biosensors, tissue engineering constructs, and neural interfaces. Herein, biomolecules-incorporated MOFs as innovative gating module is realized for the first time, which is exemplified by biocatalytic precipitation (BCP)-oriented horseradish peroxidase (HRP)-embedded zeolitic imidazolate framework-90 (HRP@ZIF-90)/CdIn₂S₄ gated organic photoelectrochemical transistor under light illumination. In connection to a sandwich immunocomplexing targeting the model analyte human IgG, the IgG-dependent generation of H₂O₂ and the tandem HRP-triggered BCP reaction can cause the in situ blocking of the pore network of ZIF-90, leading to variant gating effect with corresponding responses of the device. This representative biodetection achieved good analytical performance with a wide linear range and a low detection limit of 100 fg mL⁻¹. In the view of the plentiful biomolecule-MOF complexes and their potential interactions with organic systems, this study provides a proof-of-concept study for the generic development of biomolecules-MOFs-gated electronics and beyond.     

Construction of VS2/VOx Heterostructure via Hydrolysis-Oxidation Coupling Reaction with Superior Sodium Storage Properties

Heterostructure engineering is one of the most promising modification strategies for reinforcing Na⁺ storage of transition metal sulfides. Herein, based on the spontaneous hydrolysis-oxidation coupling reaction of transition metal sulfides in aqueous media, a VO_x layer is induced and formed on the surface of VS₂, realizing tight combination of VS₂ and VO_x at the nanoscale and constructing homologous VS₂/VO_x heterostructure. Benefiting from the built-in electric field at the heterointerfaces, high chemical stability of VO_x, and high electrical conductivity of VS₂, the obtained VS₂/VO_x electrode exhibits superior cycling stability and rate properties. In particular, the VS₂/VO_x anode shows a high capacity of 878.2 mAh g⁻¹ after 200 cycles at 0.2 A g⁻¹. It also exhibits long cycling life (721.6 mAh g⁻¹ capacity retained after 1000 cycles at 2 A g⁻¹) and ultrahigh rate property (up to 654.8 mAh g⁻¹ at 10 A g⁻¹). Density functional theory calculations show that the formation of heterostructures reduces the activation energy for Na⁺ migration and increases the electrical conductivity of the material, which accelerates the ion/electron transfer and improves the reaction kinetics of the VS₂/VO_x electrode.     

A Materials Perspective on Direct Recycling of Lithium-Ion Batteries: Principles,Challenges and Opportunities

As the dominant means of energy storage technology today, the widespread deployment of lithium-ion batteries (LIBs) would inevitably generate countless spent batteries at their end of life. From the perspectives of environmental protection and resource sustainability, recycling is a necessary strategy to manage end-of-life LIBs. Compared with traditional hydrometallurgical and pyrometallurgical recycling methods, the emerging direct recycling technology, rejuvenating spent electrode materials via a non-destructive way, has attracted rising attention due to its energy efficient processes along with increased economic return and reduced CO₂ footprint. This review investigates the state-of-the-art direct recycling technologies based on effective relithiation through solid-state, aqueous, eutectic solution and ionic liquid mediums and thoroughly discusses the underlying regeneration mechanism of each method regarding different battery chemistries. It is concluded that direct regeneration can be a more energy-efficient, cost-effective, and sustainable way to recycle spent LIBs compared with traditional approaches. Additionally, it is also identified that the direct recycling technology is still in its infancy with several fundamental and technological hurdles such as efficient separation, binder removal and electrolyte recovery. In addressing these remaining challenges, this review proposes an outlook on potential technical avenues to accelerate the development of direct recycling toward industrial applications.     

Ultra-Stable and Sensitive Ultraviolet Photodetectors Based on Monocrystalline Perovskite Thin Films

The detection of ultraviolet (UV) radiation with effective performance and robust stability is essential to practical applications. Metal halide single-crystal perovskites (ABX₃) are promising next-generation materials for UV detection. The device performance of all-inorganic CsPbCl₃ photodetectors (PDs) is still limited by inner imperfection of crystals grown in solution. Here wafer-scale single-crystal CsPbCl₃ thin films are successfully grown by vapor-phase epitaxy method, and the as-constructed PDs under UV light illumination exhibit an ultralow dark current of 7.18 pA, ultrahigh ON/OFF ratio of ≈5.22 × 10⁵, competitive responsivity of 32.8 A W⁻¹, external quantum efficiency of 10867% and specific detectivity of 4.22 × 10¹² Jones. More importantly, they feature superb long-term stability toward moisture and oxygen within twenty-one months, good temperature tolerances at low and high temperatures. The ability of the photodetector arrays for excellent UV light imaging is further demonstrated.     

C-Shaped Cartilage Development Using Wharton's Jelly-Derived Hydrogels to Assemble a Highly Biomimetic Neotrachea for use in Circumferential Tracheal Reconstruction

A highly biomimetic neotrachea with C-shaped cartilage rings has promising clinical applications in the treatment of circumferential tracheal defects (CTDs) owing to its structure and physiological function. However, to date, most fabricated tracheal cartilages are O-shaped. In this study, finite element analysis demonstrates C-shaped cartilage rings that exhibit better compliance than O-shaped. Hydrogel is developed using methacryloyl-modified decellularized Wharton's jelly matrix (DWJMA) for the regeneration of C-shaped cartilage rings. This novel hydrogel possesses adjustable physicochemical properties and favorable cytocompatibility. When loaded with chondrocytes, DWJMA hydrogels support the optimal cartilage regeneration both in vitro and in vivo. More importantly, a highly biomimetic neotrachea simultaneously simulating the structural and physiological properties of the normal trachea is regenerated via modular assembly of several individual C-shaped cartilage rings. The results demonstrate the highly biomimetic neotrachea have better patency (88.6 ± 6.1% vs 74.4 ± 9.4%, p < 0.05), improve the survival rate, alleviate weight loss and mucoid impaction, than its O-shaped counterpart when used for the treatment of CTDs in a rabbit model. Therefore, this study proposes a novel hydrogel for the regeneration of C-shaped cartilage and provides new insights into the treatment of CTDs using a highly biomimetic neotrachea with C-shaped cartilage rings.     

Spring-Like Ammonium Salt Assisting Stress Release for Low-Temperature Deposited FAPbI3 Films Toward Flexible Photovoltaic Application

The substrates of conventional flexible perovskite solar cells (FPSCs) are thermoplastic polymer material polyethylene naphthalate (PEN), which will deform during high temperature annealing process. In addition, lead iodide (PbI₂) permanently formed and the substrate undergoes reversible deformation from 20 °C to 200 °C and back to 20 °C. Therefore, to balance the substrate supporting capacity and the crystalline quality of narrow band gap α-phase formamidinium lead iodide (α-FAPbI₃), an annealing process of 120 °C for 30 minutes is determined. Additionally, there will also be a large number of gaps and lattice strain at the perovskite grain boundaries during the annealing process as the FAPbI₃ phase transition is accompanied by much lattice shrinkage. As a result, 1,6-hexanediammonium diiodide (HADI) is chosen to passivate the defects and release the stress of perovskite film. Therefore, a recorded 1.4% extended stretch rate of the flexible film is attained. Finally, the champion PCE of 21.14% under AM 1.5G and 31.52% under 1062 lux is achieved after HADI treatment, accompanied by a better long-term and mechanical stability. This study provides annealing process optimization and stress relief strategies for the further development of narrow band gap FPSCs.     

Intercalative Motifs-Induced Space Confinement and Bonding Covalency Enhancement Enable Ultrafast and Large Sodium Storage

Alloying-type metal sulfides with high theoretical capacities are promising anodes for sodium-ion batteries, but suffer from sluggish sodiation kinetics and huge volume expansion. Introducing intercalative motifs into alloying-type metal sulfides is an efficient strategy to solve the above issues. Herein, robust intercalative In S motifs are grafted to high-capacity layered Bi₂S₃ to form a cation-disordered (BiIn)₂S₃, synergistically realizing high-rate and large-capacity sodium storage. The In S motif with strong bonding serves as a space-confinement unit to buffer the volume expansion, maintaining superior structural stability. Moreover, the grafted high-metallicity Indium increases the bonding covalency of Bi S, realizing controllable reconstruction of Bi S bond during cycling to effectively prevent the migration and aggregation of atomic Bi. The novel (BiIn)₂S₃ anode delivers a high capacity of 537 mAh g⁻¹ at 0.4 C and a superior high-rate stability of 247 mAh g⁻¹ at 40 C over 10000 cycles. Further in situ and ex situ characterizations reveal the in-depth reaction mechanism and the breakage and formation of reversible Bi S bonds. The proposed space confinement and bonding covalency enhancement strategy via grafting intercalative motifs can be conducive to developing novel high-rate and large-capacity anodes.     

A Sensing and Stretchable Polymer-Dispersed Liquid Crystal Device Based on Spiderweb-Inspired Silver Nanowires-Micromesh Transparent Electrode

Polymer-dispersed liquid crystal (PDLC) devices are truly promising optical modulators for information display, smart window as well as intelligent photoelectronic applications due to their fast switching, large optical modulation as well as cost-effectiveness. However, realizing highly soft PDLC devices with sensing function remains a grand challenge because of the intrinsic brittleness of traditional transparent conductive electrodes. Here, inspired by spiderweb configuration, a novel type of silver nanowires (AgNWs) micromesh-based stretchable transparent conductive electrodes (STCEs) is developed to support the realization of soft PDLC device. Benefiting from the embedding design of AgNWs micromesh in polydimethylsiloxane (PDMS), the STCEs can maintain excellent electrical conductivity and transparency even in various extreme conditions such as bending, folding, twisting, stretching as well as multiple chemical corrosion. Further, STCEs with the embedded AgNWs micromesh endow the assembled PDLC device with excellent photoelectrical properties including rapid switching speed (<1 s), large optical modulation (69% at 600 nm), as well as robust mechanical stability (bending over 1000 cycles and stretching to 40%). Moreover, the device displays the pressure sensing function with high sensitivity in response to pressure stimulus. It is conceivable that AgNWs micromesh transparent electrodes will shape the next generation of related soft smart electronics.     

Durable Integrated K-Metal Anode with Enhanced Mass Transport through Potassiphilic Porous Interconnected Mediator

K-metal batteries have become one of the promising candidates for the large-scale energy storage owing to the virtually inexhaustible and widely potassium resources. The uneven K⁺ deposition and dendrite growth on the anode causes the batteries prematurely failure to limit the further application. An integrated K-metal anode is constructed by cold-rolling K metal with a potassiphilic porous interconnected mediator. Based on the experimental results and theoretical calculations, it demonstrates that the potassiphilic porous interconnected mediator boosts the mass transportation of K-metal anode by the K affinity enhancement, which decreases the concentration polarization and makes a dendrite-free K-metal anode interface. The interconnected porous structure mitigates the internal stress generated during repetitive deposition/stripping, enabling minimized the generation of electrode collapse. As a result, a durable K-metal anode with excellent cycling ability of exceed 1, 000 h at 1 mA cm⁻²/1 mAh cm⁻² and lower polarization voltage in carbonate electrolyte is obtained. This proposed integrated anode with fast K⁺ kinetics fabricated by a repeated cold rolling and folding process provides a new avenue for constructing a high-performance dendrites-free anode for K-metal batteries.