Operando probing and adjusting of the complicated electrode process of multivalent metals at extreme temperature.

Nearly half of the elements in the periodic table are extracted, refined, or plated using electrodeposition in high-temperature melts. However, operando observations and tuning of the electrodeposition process during realistic electrolysis operations are extremely difficult due to severe reaction conditions and complicated electrolytic cell, which makes the improvement of the process very blind and inefficient. Here, we developed a multipurpose operando high-temperature electrochemical instrument that combines operando Raman microspectroscopy analysis, optical microscopy imaging, and a tunable magnetic field. Subsequently, the electrodeposition of Ti-which is a typical polyvalent metal and generally shows a very complex electrode process-was used to verify the stability of the instrument. The complex multistep cathodic process of Ti in the molten salt at 823 K was systematically analyzed by a multidimensional operando analysis strategy involving multiple experimental studies, theoretical calculations, etc. The regulatory effect and its corresponding scale-span mechanism of the magnetic field on the electrodeposition process of Ti were also elucidated, which would be inaccessible with existing experimental techniques and is significant for the real-time and rational optimization of the process. Overall, this work established a powerful and universal methodology for in-depth analysis of high-temperature electrochemistry.

3D-Printed Micro/Nano-Scaled Mechanical Metamaterials: Fundamentals, Technologies, Progress, Applications, and Challenges.

Micro/nano-scaled mechanical metamaterials have attracted extensive attention in various fields attributed to their superior properties benefiting from their rationally designed micro/nano-structures. As one of the most advanced technologies in the 21st century, additive manufacturing (3D printing) opens an easier and faster path for fabricating micro/nano-scaled mechanical metamaterials with complex structures. Here, the size effect of metamaterials at micro/nano scales is introduced first. Then, the additive manufacturing technologies to fabricate mechanical metamaterials at micro/nano scales are introduced. The latest research progress on micro/nano-scaled mechanical metamaterials is also reviewed according to the type of materials. In addition, the structural and functional applications of micro/nano-scaled mechanical metamaterials are further summarized. Finally, the challenges, including advanced 3D printing technologies, novel material development, and innovative structural design, for micro/nano-scaled mechanical metamaterials are discussed, and future perspectives are provided. The review aims to provide insight into the research and development of 3D-printed micro/nano-scaled mechanical metamaterials.

Highly Sensitive Ultrastable Electrochemical Sensor Enabled by Proton-Coupled Electron Transfer.

Electrochemical sensors are critical to artificial intelligence by virtue of capability of mimicking human skin to report sensing signals. But their practical applications are restricted by low sensitivity and limited cycling stability, which result from piezoionic mechanism with insufficient sensing response. Here, we report a highly sensitive ultrastable sensor based on proton-coupled electron transfer, which is different from piezoionic mechanism. The sensor gives a high sensing signal output of 117 mV, which is 16 times higher than that of counterpart device (7 mV). It delivers excellent working stability with performance retention as high as 99.13% over 10 000 bending cycles in air, exceeding that of the best-known sensors reported previously. The flexible sensor displays high sensitivity in detecting real-time signals of human activities with large and subtle deformations, including wrist bending, moving speed, pulse wave and voice vibration. Smart functions, such as braille language and handwriting recognitions, are demonstrated for artificial intelligence.

Electrocatalysis for Continuous Multi-Step Reactions in Quasi-Solid-State Electrolytes Towards High-Energy and Long-Life Aluminum-Sulfur Batteries.

Aluminum-sulfur (Al-S) batteries of ultrahigh energy-to-price ratios are a promising energy storage technology, while they suffer from a large voltage gap and short lifespan. Herein, we propose an electrocatalyst-boosting quasi-solid-state Al-S battery, which involves a sulfur-anchored cobalt/nitrogen co-doped graphene (S@CoNG) positive electrode and an ionic-liquid-impregnated metal-organic framework (IL@MOF) electrolyte. The Co-N4 sites in CoNG continuously catalyze the breaking of Al-Cl and S-S bonds and accelerate the sulfur conversion, endowing the Al-S battery with a shortened voltage gap of 0.43 V and a high discharge voltage plateau of 0.9 V. In the quasi-solid-state IL@MOF electrolytes, the shuttle effect of polysulfides has been inhibited, which stabilizes the reversible sulfur reaction, enabling the Al-S battery to deliver 820 mAh g-1 specific capacity and 78 % capacity retention after 300 cycles. This finding offers novel insights to design Al-S batteries for stable energy storage.

The mechanical property and microscopic deformation mechanism of nanoparticle-contained graphene foam materials under uniaxial compression.

Nanoparticle-contained graphene foams have found more and more practical applications in recent years, which desperately requires a deep understanding on basic mechanics of this hybrid material. In this paper, the microscopic deformation mechanism and mechanical properties of such a hybrid material under uniaxial compression, that are inevitably encountered in applications and further affect its functions, are systematically studied by the coarse-grained molecular dynamics simulation method. Two major factors of the size and volume fraction of nanoparticles are considered. It is found that the constitutive relation of nanoparticle filled graphene foam materials consists of three parts: the elastic deformation stage, deformation with inner re-organization and the final compaction stage, which is much similar to the experimental measurement of pristine graphene foam materials. Interestingly, both the initial and intermediate modulus of such a hybrid material is significantly affected by the size and volume fraction of nanoparticles, due to their influences on the microstructural evolution. The experimentally observed 'spacer effect' of such a hybrid material is well re-produced and further found to be particle-size sensitive. With the increase of nanoparticle size, the micro deformation mechanism will change from nanoparticles trapped in the graphene sheet, slipping on the graphene sheet, to aggregation outside the graphene sheet. Beyond a critical relative particle size 0.26, the graphene-sheet-dominated deformation mode changes to be a nanoparticle-dominated one. The final microstructure after compression of the hybrid system converges to two stable configurations of the 'sandwiched' and 'randomly-stacked' one. The results should be helpful not only to understand the micro mechanism of such a hybrid material in different applications, but also to the design of advanced composites and devices based on porous materials mixed with particles.

Structural stability and optoelectronic properties of tetragonal MAPbI3 under strain.

In recent years, organic-inorganic hybrid perovskites have attracted wide attention due to their excellent optoelectronic properties in the application of optoelectronic devices. In the manufacturing process of perovskite solar cells, perovskite films inevitably have residual stress caused by non-stoichiometry components and the external load. However, their effects on the structural stability and photovoltaic performance of perovskite solar cells are still not clear. In this work, we investigated the effects of external strain on the structural stability and optoelectronic properties of tetragonal MAPbI3 by using the first-principles calculations. We found that the migration barrier of I- ion increases in the presence of compressive strain and decreases with tensile strain, indicating that the compressive strain can enhance the structural stability of halide perovskites. In addition, the light absorption and electronic properties of MAPbI3 under compressive strain are also improved. The variations of the band gap under triaxial and biaxial strains are consistent within a certain range of strain, resulting from the fact that the band edge positions are mainly influenced by the Pb-I bond in the equatorial plane. Our results provide useful guidance for realizing the commercial applications of MAPbI3-based perovskite solar cells.

Three-dimensional mesostructures as high-temperature growth templates, electronic cellular scaffolds, and self-propelled microrobots.

Recent work demonstrates that processes of stress release in prestrained elastomeric substrates can guide the assembly of sophisticated 3D micro/nanostructures in advanced materials. Reported application examples include soft electronic components, tunable electromagnetic and optical devices, vibrational metrology platforms, and other unusual technologies, each enabled by uniquely engineered 3D architectures. A significant disadvantage of these systems is that the elastomeric substrates, while essential to the assembly process, can impose significant engineering constraints in terms of operating temperatures and levels of dimensional stability; they also prevent the realization of 3D structures in freestanding forms. Here, we introduce concepts in interfacial photopolymerization, nonlinear mechanics, and physical transfer that bypass these limitations. The results enable 3D mesostructures in fully or partially freestanding forms, with additional capabilities in integration onto nearly any class of substrate, from planar, hard inorganic materials to textured, soft biological tissues, all via mechanisms quantitatively described by theoretical modeling. Illustrations of these ideas include their use in 3D structures as frameworks for templated growth of organized lamellae from AgCl-KCl eutectics and of atomic layers of WSe2 from vapor-phase precursors, as open-architecture electronic scaffolds for formation of dorsal root ganglion (DRG) neural networks, and as catalyst supports for propulsive systems in 3D microswimmers with geometrically controlled dynamics. Taken together, these methodologies establish a set of enabling options in 3D micro/nanomanufacturing that lie outside of the scope of existing alternatives.

Morphable 3D mesostructures and microelectronic devices by multistable buckling mechanics.

Three-dimensional (3D) structures capable of reversible transformations in their geometrical layouts have important applications across a broad range of areas. Most morphable 3D systems rely on concepts inspired by origami/kirigami or techniques of 3D printing with responsive materials. The development of schemes that can simultaneously apply across a wide range of size scales and with classes of advanced materials found in state-of-the-art microsystem technologies remains challenging. Here, we introduce a set of concepts for morphable 3D mesostructures in diverse materials and fully formed planar devices spanning length scales from micrometres to millimetres. The approaches rely on elastomer platforms deformed in different time sequences to elastically alter the 3D geometries of supported mesostructures via nonlinear mechanical buckling. Over 20 examples have been experimentally and theoretically investigated, including mesostructures that can be reshaped between different geometries as well as those that can morph into three or more distinct states. An adaptive radiofrequency circuit and a concealable electromagnetic device provide examples of functionally reconfigurable microelectronic devices.

Temperature Rise Associated with Adiabatic Shear Band: Causality Clarified.

One of the most important issues related to adiabatic shear failure is the correlation among temperature elevation, adiabatic shear band (ASB) formation and the loss of load capacity of the material. Our experimental results show direct evidence that ASB forms several microseconds after stress collapse and temperature rise reaches its maximum about 30 µs after ASB formation. This observation indicates that temperature rise cannot be the cause of ASB. Rather, it might be the result of adiabatic shear localization. As such, the traditional well-accepted thermal-softening mechanism of ASB needs to be reconsidered.

A finite deformation theory of desolvation and swelling in partially photo-cross-linked polymer networks for 3D/4D printing applications.

Photopolymerization is a process strongly dependent on the light field in the resin. This typically results in a non-uniformly crosslinked network where some parts of the network are fully cross-linked while other parts are partially crosslinked. The partially crosslinked part could exhibit a high volume expansion upon swelling and a high volume shrinkage upon desolvation. Through control over the light field in the photopolymer resin, this feature has been used to create solvent responsive shape changing structures as well as 3D/4D printed smart devices, showing promising application potential. In this paper, we develop a finite deformation theory to consider the nonuniform crosslink density of the network and the interaction between different species inside the network. The mechanical properties of the network are correlated with the reaction process and the existence of residual uncrosslinked monomers is included in the partially crosslinked network. The efficiency of the theory is proved by the finite element simulations of two special applications of the partially crosslinked network.

Mechanics of shape distortion of DLP 3D printed structures during UV post-curing.

Digital light processing (DLP) three-dimensional (3D) printing technology has advantages of fast printing speed and high printing precision. It can print objects with small and complex geometrical features and has been widely used in jewelry manufacturing and dentistry. In DLP printing, it is common to use post-treatment with UV light irradiation to improve the final mechanical properties. However, it was found that the UV post-curing process can lead to shape distortion and thus reduction of dimension accuracy. In this paper, we combined photopolymerization reaction kinetics and Euler-Bernoulli beam theory to study UV post-curing induced shape distortion of thin structures prepared by DLP 3D printing. Experiments were conducted to characterize the evolution of mechanical behavior of printed samples during the post-printing process, which was correlated to printing parameters (printing time of single-layer, height of single-layer and printing UV intensity), post-curing UV light intensity and the thickness of the strip. Moreover, post-curing induced distortion was used for the fabrication of 3D structures.

Reflection phase dispersion editing generates wideband invisible acoustic Huygens's metasurface.

Acoustic metasurfaces show non-traditional abilities in wave manipulation and provide alternate mechanisms for information communication and invisibility technology. However, most of the mechanisms remain narrow band (relative bandwidth ∼5%), and a wideband trait is essential for engineering applications. For example, controllable effective material properties-reflection or transmission phase-has barely been realized in wideband because the intrinsic dispersion relation is not always editable. In this paper, wideband reflection phase editing is realized, and wideband invisibility of a phase preserved Huygens's metasurface on a flat background is achieved with anomalous reflection. This metasurface is built with proposed unsymmetrical twin Helmholtz resonators which reach a predefined dispersion relation target value. The total instantaneous acoustic fields show nearly identical carpeting effects in a consecutive band with relative bandwidth 52.1% (from 5400 to 9200 Hz) in simulation and experiment.

Flexible thin broadband microwave absorber based on a pyramidal periodic structure of lossy composite.

Microwave absorber with broadband absorption and thin thickness is one of the main research interests in this field. A flexible ultrathin and broadband microwave absorber comprising multiwall carbon nanotubes, spherical carbonyl iron, and silicone rubber is fabricated in a newly proposed pyramidal spatial periodic structure (SPS). The SPS with equivalent thickness of 3.73 mm covers the -10 dB and -15 dB absorption bandwidth in the frequency range 2-40 GHz and 10-40 GHz, respectively. The excellent absorption performance is achieved by concentration and dissipation of the electromagnetic field inside different parts of the magnetic-dielectric lossy protrusions in different frequency ranges.

3D printing of complex origami assemblages for reconfigurable structures.

Origami engineering principles have recently been applied to a wide range of applications, including soft robots, stretchable electronics, and mechanical metamaterials. In order to achieve the 3D nature of engineered structures (e.g. load-bearing capacity) and capture the desired kinematics (e.g., foldability), many origami-inspired engineering designs are assembled from smaller parts and often require binding agents or additional elements for connection. Attempts at direct fabrication of 3D origami structures have been limited by available fabrication technologies and materials. Here, we propose a new method to directly 3D print origami assemblages (that mimic the behavior of their paper counterparts) with acceptable strength and load-bearing capacity for engineering applications. Our approach introduces hinge-panel elements, where the hinge regions are designed with finite thickness and length. The geometrical design of these hinge-panels, informed by both experimental and theoretical analysis, provides the desired mechanical behavior. In order to ensure foldability and repeatability, a novel photocurable elastomer system is developed and the designs are fabricated using digital light processing-based 3D printing technology. Various origami assemblages are produced to demonstrate the design flexibility and fabrication efficiency offered by our 3D printing method for origami structures with enhanced load bearing capacity and selective deformation modes.

High-Speed 3D Printing of High-Performance Thermosetting Polymers via Two-Stage Curing.

Design and direct fabrication of high-performance thermosets and composites via 3D printing are highly desirable in engineering applications. Most 3D printed thermosetting polymers to date suffer from poor mechanical properties and low printing speed. Here, a novel ink for high-speed 3D printing of high-performance epoxy thermosets via a two-stage curing approach is presented. The ink containing photocurable resin and thermally curable epoxy resin is used for the digital light processing (DLP) 3D printing. After printing, the part is thermally cured at elevated temperature to yield an interpenetrating polymer network epoxy composite, whose mechanical properties are comparable to engineering epoxy. The printing speed is accelerated by the continuous liquid interface production assisted DLP 3D printing method, achieving a printing speed as high as 216 mm h-1 . It is also demonstrated that 3D printing structural electronics can be achieved by combining the 3D printed epoxy composites with infilled silver ink in the hollow channels. The new 3D printing method via two-stage curing combines the attributes of outstanding printing speed, high resolution, low volume shrinkage, and excellent mechanical properties, and provides a new avenue to fabricate 3D thermosetting composites with excellent mechanical properties and high efficiency toward high-performance and functional applications.

Non-Doped Deep Blue and Doped White Electroluminescence Devices Based on Phenanthroimidazole Derivative.

A novel deep-blue emitter PhImPOTD based on phenathroimidazole was synthesized, which is incorporated by an electron-donating dibenzothiophene unit and electron-withdrawing phenanthroimidazole and diphenylphosphine oxide moieties. Furthermore, the weak π-π stacking and intermolecular aggregation render the photoluminescence quantum yield is as high as 0.34 in the solid state. Non-doped organic light emitting diodes (OLEDs) based on PhImPOTD emitter exhibits a low turn-on voltage of 3.6 V, a favorable efficiency of 1.13 cd A-1 and a deep blue emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.15, 0.08). The CIE is very close to the NTSC (National Television Standards Committe) blue standard (CIE: 0.14, 0.08). PhImPOTD is also utilized as blue emitter and the host for a yellow emitter (PO-01) to fabricate white organic light-emitting diodes (WOLEDs). This gives a forward-viewing maximum CE of 4.83 cd A-1 and CIE coordinates of (0.32, 0.32) at the luminance of 1000 cd m-2. Moreover, the single-carrier devices unambiguously demonstrate that typical bipolar-dominant characteristics of PhImPOTD. This work demonstrates not only that the phenanthroimidazole unit is an excellent building block to construct deep blue emission materials, but also the introduction of a diphenylphosphine oxide deprotonation substituent is an efficient tactic for harvesting deep-blue emitting devices.

Desolvation Induced Origami of Photocurable Polymers by Digit Light Processing.

Self-folding origami is of great interest in current research on functional materials and structures, but there is still a challenge to develop a simple method to create freestanding, reversible, and complex origami structures. This communication provides a feasible solution to this challenge by developing a method based on the digit light processing technique and desolvation-induced self-folding. In this new method, flat polymer sheets can be cured by a light field from a commercial projector with varying intensity, and the self-folding process is triggered by desolvation in water. Folded origami structures can be recovered once immersed in the swelling medium. The self-folding process is investigated both experimentally and theoretically. Diverse 3D origami shapes are demonstrated. This method can be used for responsive actuators and the fabrication of 3D electronic devices.

Revealing the role of thiocyanate anion in layered hybrid halide perovskite (CH3NH3)2Pb(SCN)2I2.

The effect of the SCN- ion on the structural, electronic, optical, and mechanical properties of the layered (MA)2Pb(SCN)2I2 (MA=CH3NH3+) perovskite is investigated by using first-principles calculations. Our results suggest that the introduction of SCN- ions at the apical positions gives rise to shorter Pb-S bond lengths, more distorted octahedra, and more hydrogen bonds, which have important effects on the electronic, optical, mechanical, and piezoelectric properties in (MA)2Pb(SCN)2I2. Furthermore, a strong relativistic Rashba splitting is induced due to the breaking of the inversion symmetry, which helps to suppress the carrier recombination and enhance the carrier lifetime. The analysis of mechanical properties reveals that the incorporation of SCN- ions is beneficial to strengthen Young's modulus of the perovskite materials and it enhances the piezoelectric properties. Our investigation suggests that doping SCN- ions into the perovskite materials could be a promising strategy to improve the stability and mechanical properties of organic-inorganic hybrid halide perovskite compounds.

Effects of oxygen on light activation in covalent adaptable network polymers.

Light activated polymers are a novel group of active materials that deform when irradiated with light at specific wavelengths. This paper focuses on the understanding and evaluation of light activated covalent adaptable networks formed by radical polymerization reactions, which have potential applications as novel actuators, surface patterning, and light-induced bending and folding. In these polymer networks, free radicals are generated upon light irradiation and lead to evolution of the polymer network structure through bond exchange reactions. It is well known that oxygen is an important inhibitor in radical-based chemistry as oxygen reacts with free radicals and renders them as inactive species towards further propagation and reaction. However, it is unclear how radical depletion by oxygen may affect the light-induced actuation. This paper studies the effects of oxygen on both stress relaxation and bending actuation. Light induced stress relaxation experiments are conducted in an environmental chamber where the concentration of oxygen is controlled by the nitrogen flow. A constitutive model that considers oxygen diffusion, radical termination due to oxygen, and the polymer network evolution is developed and used to study the stress relaxation and bending, and the model predictions agree well with experiments. Parametric studies are conducted to identify the situations where the effects of oxygen are negligible and other conditions where they must be considered.

Bioinspired Double-Broadband Switchable Microwave Absorbing Grid Structures with Inflatable Kresling Origami Actuators.

Tunable radar stealth structures are critical components for future military equipment because of their potential to further enhance the design space and performance. Some previous investigations have utilized simple origami structures as the basic adjusting components but failed to achieve the desired broadband microwave absorbing characteristic. Herein, a novel double-broadband switchable microwave absorbing grid structure has been developed with the actuators of inflatable Kresling origami structures. Geometric constraints are derived to endow a bistable feature with this origami configuration, and the stable states are switched by adjusting the internal pressure. An ultra-broadband microwave absorbing structure is proposed with a couple of complementary microwave stealth bands, and optimized by a particle swarm optimization algorithm. The superior electromagnetic performance results from the mode switch activating different absorbing components at corresponding frequencies. A digital adjusting strategy is applied, which effectively achieves a continuously adjusting effect. Further investigations show that the proposed structure possesses superior robustness. In addition, minimal interactions are found between adjacent grid units, and the electromagnetic performance is mainly related to the duty ratio of the units in different states. They have enhanced the microwave absorbing performance of grid structures through a tunable design, a provided a feasible paradigm for other tunable absorbers.