A Single Component, Single Layer Flexile Foam Evaporator with the Higher Efficiency for Water Generation.

One of the greenest and promising ways to solve the problem of freshwater crisis is surface solar steam generation from seawater. A great number of photothermal materials with multi-component and multi-layered delicate yet complex structures often suffer from either low evaporation rate or high energy loss. Here, we present a single component foam evaporator with steam generation rate of up to 4.32 kg m-2 h-1 under 1 sun irradiation. The evaporator is constructed from an aniline oligomer as a single light-absorbing component, covalent linked with polyethylene glycol to form a monolithic polymer foam. Floating on the seawater, the foam has absorbance of 99.5% over the entire solar spectral range and low thermal conductivity (0.0077 W K-1m-1) that effectively retains heat in the material and at the interface. After 3 months of continuous outdoor natural sunlight irradiation, the evaporator maintains a stable and durable evaporation rate. Moreover, the materials have good mechanical properties (7.48 MPa young's modulus and 57.38% elongation at break) and excellent chemical resistance in 10 common organic solvents and aqueous solutions of pH = 1 to 14. This study provides a new system and strategy for desalination, steam power generation, treatment of polluted water and sewage, etc. This article is protected by copyright. All rights reserved.

3D Printing of Anisotropic Piezoresistive Pressure Sensors for Directional Force Perception.

Anisotropic pressure sensors are gaining increasing attention for next-generation wearable electronics and intelligent infrastructure owing to their sensitivity in identifying different directional forces. 3D printing technologies have unparalleled advantages in the design of anisotropic pressure sensors with customized 3D structures for realizing tunable anisotropy. 3D printing has demonstrated few successes in utilizing piezoelectric nanocomposites for anisotropic recognition. However, 3D-printed anisotropic piezoresistive pressure sensors (PPSs) remain unexplored despite their convenience in saving the poling process. This study pioneers the development of an aqueous printable ink containing waterborne polyurethane elastomer. An anisotropic PPS featuring tailorable flexibility in macroscopic 3D structures and microscopic pore morphologies is created by adopting direct ink writing 3D printing technology. Consequently, the desired directional force perception is achieved by programming the printing schemes. Notably, the printed PPS demonstrated excellent deformability, with a relative sensitivity of 1.22 (kPa* wt. %)-1 over a substantial pressure range (2.8 to 8.1 kPa), approximately fivefold than that of a state-of-the-art carbon-based PPS. This study underscores the versatility of 3D printing in customizing highly sensitive anisotropic pressure sensors for advanced sensing applications that are difficult to achieve using conventional measures.

Iodine Adsorption-Desorption-Induced Structural Transformation and Improved Ag+ Turn-On Luminescent Sensing Performance of a Nonporous Eu(III) Metal-Organic Framework.

Posttreatment of pristine metal-organic frameworks (MOFs) with suitable vapor may be an effective way to regulate their structures and properties but has been less explored. Herein, we report an interesting example in which a crystalline nonporous Eu(III)-MOF was transferred to a porous amorphous MOF (aMOF) via iodine vapor adsorption-desorption posttreatment, and the resulting aMOF showed improved turn-on sensing properties with respect to Ag+ ions. The crystalline Eu-MOF, namely, Eu-IPDA, was assembled from Eu(III) and 4,4'-{4-[4-(1H-imidazol-1-yl)phenyl]pyridine-2,6-diyl}dibenzoic acid (H2IPDA) and exhibited a two-dimensional (2D) coordination network based on one-dimensional secondary building blocks. The close packing of the 2D networks gives rise to a three-dimensional supramolecular framework without any significant pores. Interestingly, the nonporous Eu-IPDA could absorb iodine molecules when Eu-IPDA crystals were placed in iodine vapor at 85 °C, and the adsorption capacity was 1.90 g/g, which is comparable to those of many MOFs with large BET surfaces. The adsorption of iodine is attributed to the strong interactions among the iodine molecule, the carboxy group, and the N-containing group and leads to the amorphization of the framework. After immersion of the iodine-loaded Eu-IPDA in EtOH, approximately 89.7% of the iodine was removed, resulting in a porous amorphous MOF, denoted as a-Eu-IPDA. In addition, the remaining iodine in the a-Eu-IPDA framework causes strong luminescent quenching in the fluorescence emission region of the Eu(III) center when compared with that in Eu-IPDA. The luminescence intensity of a-Eu-IPDA in water suspensions was significantly enhanced when Ag+ ions were added, with a detection limit of 4.76 × 10-6 M, which is 1000 times that of pristine Eu-IPDA. It also showed strong anti-interference ability over many common competitive metal ions and has the potential to sense Ag+ in natural water bodies and traditional Chinese medicine preparations. A mechanistic study showed that the interactions between Ag+ and the absorbed iodine, the carboxylate group, and the N atoms all contribute to the sensing performance of a-Eu-IPDA.

3D Printing Architecting ß-PVDF Reservoirs for Preferential ZnO Epitaxial Growth Toward Advanced Piezoelectric Energy Harvesting.

For polyvinylidene fluoride (PVDF) based piezoelectric composites, epitaxial growth of ZnO nanorods (ZnO-nr) piezoceramic layer on PVDF is an effective way to improve their piezoelectric performance. However, the crystal nucleus of ZnO featuring polar surfaces that cannot be directly attached to hydrophobic PVDF with low surface energy. Herein, direct ink writing (DIW) 3D printing is employed for the first time to create ß-PVDF reservoirs with significantly enhanced surface energy, facilitating the attachment and epitaxial growth of ZnO-nr. The printed ß-PVDF reservoirs designed with programmed macro-pores and abundant inner micropores, enable a higher loading of ZnO-nr by more than one magnitude, thereby boosting the electro-mechanical response. The resulting PVDF/ZnO core-shell piezoelectric energy harvester (PEH) delivers an output voltage of 33.2 V, as well as an unprecedentedly high relative output voltage of 2.76 V/wt.%, which is 2.63 times that of the state-of-the-art 3D-printed PVDF/piezoceramics PEHs. Furthermore, it can differentiate subtle human motions whereas hybrid PEHs cannot distinct. This work demonstrates that the DIW 3D printing approach offers a simple and convenient design idea for creating high performance PEHs.

Self-Healable, Self-Adhesive and Degradable MXene-Based Multifunctional Hydrogel for Flexible Epidermal Sensors.

Conductive hydrogels have garnered significant interest in the realm of wearable flexible sensors due to their close resemblance to human tissue, wearability, and precise signal acquisition capabilities. However, the concurrent attainment of an epidermal hydrogel sensor incorporating reliable self-healing capabilities, biodegradability, robust adhesiveness, and the ability to precisely capture subtle electrophysiological signals poses a daunting and intricate challenge. Herein, an innovative MXene-based composite hydrogel (PBM hydrogel) with exceptional self-healing, self-adhesive, and versatile functionality is engineered through the integration of conductive MXene nanosheets into a well-structured poly(vinyl alcohol) (PVA) and bacterial cellulose (BC) hydrogel three-dimensional (3D) network, utilizing multiple dynamic cross-linking synergistic repeated freeze-thaw strategy. The hydrogel harnesses the presence of dynamically reversible borax ester bonds and multiple hydrogen bonds between its constituents, endowing it with rapid self-healing efficiency (97.8%) and formidable self-adhesive capability. The assembled PBM hydrogel epidermal sensor possesses a rapid response time (10 ms) and exhibits versatility in detecting diverse external stimuli and human movements such as vocalization, handwriting, joint motion, Morse code signals, and even monitoring infusion status. Additionally, the PBM hydrogel sensor offers the added advantage of swift degradation in phosphate-buffered saline solution (within a span of 56 days) and H2O2 solution (in just 53 min), maintaining an eco-friendly profile devoid of any environmental pollution. This work lays the groundwork for possible uses in electronic skins, interactions between humans and machines, and the monitoring of individualized healthcare.

Topological Engineering Electrodes with Ultrafast Oxygen Transport for Super-Power Sodium-Oxygen Batteries.

Sodium-oxygen battery has attracted tremendous interest due to its extraordinary theoretical specific energy (1605 Wh kg-1 NaO2) and appealing element abundance. However, definite mechanistic factors governing efficient oxygen diffusion and consumption inside electrolyte-flooded air cathodes remain elusive thus precluding a true gas diffusion electrode capable of high discharge current (i.e., several mA cm-2) and superior output power. Herein, 3D-printing technology is adopted to create gas channels with tailored channel size and structure to demystify the diffusion-limited oxygen delivery process. It is revealed that as the clogging discharging products increase, large channel size, and interconnected channel structure are essential to guaranteeing fast O2 diffusion. Moreover, to further encourage O2 diffusion, a bio-inspired breathable cathode with progressively branching channels that balances between O2 passage and reaction is 3D printed. This elaborated 3D electrode allows a sodium-oxygen cell to deliver an impressive discharging current density of up to 4 mA cm-2 and an output power of 8.4 mW cm-2, giving rise to an outstanding capacity of 18.4 mAh cm-2. The unraveled mystery of oxygen delivery enabled by 3D printing points to a valuable roadmap for the rational design of metal-air batteries toward practical applications.

Phase-Stabilized Crystal Etching to Unlock An Oxygen-Vacancy-Rich Potassium Vanadate For Ultra-Fast Zn Storage.

Despite holding the advantages of high theoretical capacity and low cost, the practical application of layered-structured potassium vanadates in zinc ion batteries (ZIBs) has been staggered by the sluggish ion diffusion, low intrinsic electronic conductivity, and unstable crystal structure. Herein, for the first time, a phase stabilized crystal etching strategy is proposed to innovate an oxygen-vacancy-rich K0.486 V2 O5 nanorod composite (Ov-KVO@rGO) as a high-performance ZIB cathode. The in situ ascorbic acid assisted crystal etching process introduces abundant oxygen-vacancies into the K0.486 V2 O5 lattices, not only elaborately expanding the lattice spacing for faster ion diffusion and more active sites due to the weakened interlayer electrostatic interaction, but also enhancing the electronic conductivity by accumulating electrons around the vacancies, which is also evidenced by density functional theory calculations. Meanwhile, the encapsulating rGO layer ably stabilizes the K0.486 V2 O5 crystal phase otherwise is hard to endure subject to such a harsh chemical etching. As a result, the optimized Ov-KVO@rGO electrode delivers record-high rate capabilities with 462 and 272.39 mAh g-1 at 0.2 and 10 A g-1 , respectively, outperforming all previously reported potassium vanadate cathodes and most other vanadium-based materials. This work highlights a significant advancement of layer-structured vanadium based-materials towards practical application in ZIBs.

Customizing Three-Dimensional Elastic Barium Titanate Sponge for Intelligent Piezoelectric Sensing.

Piezoelectric energy harvesters (PEHs) with porous structures, such as piezoelectric elastic sponges, exhibit high force-to-electricity conversion efficiencies owing to their excellent compression recovery properties. However, conventional preparation methods are limited to producing bulk-form sponge-like PEHs and fail to create more elaborate three-dimensional (3D) structures that could enhance conversion efficiency. Herein, we invent a composite ink consisting of waterborne polyurethane (WPU), barium titanate (BTO), and cellulose nanofibers (CNFs) that is suitable for direct ink writing (DIW) 3D printing. This ink, when coupled with freeze-drying, allows the customization of piezoelectric sponges with functional 3D structures. The printed lattice sponge exhibits remarkable compression recovery of 70% and a notably high relative sensitivity of 9.83 mV/kPa*wt % (where *wt % denotes the BTO content) across a wide pressure range of 2.98-37 kPa, which is approximately three times broader than those of other composite piezoelectric pressure sensors based on BTO or piezoceramic (PZT) materials. Furthermore, a customized 3D piezoelectric sponge with a "boomerang" configuration is utilized as an anisotropic bending sensor on the wrist for intelligently monitoring the stroke posture and programming scientific training for table tennis players. This study highlights a versatile strategy for constructing elastic sponges with high piezoelectricity and designing 3D PEH functional structures that can be applied to flexible self-powered intelligent sensing systems.

Ultrathick GeP Anode To Balance the Extreme Load and Compliance for High Areal Capacity Flexible Sodium-Ion Batteries.

The ever-growing application of miniaturized electric devices calls for the manufacturing of energy storage systems with a high areal energy density. Thick electrode design is a promising strategy to acquire high areal energy density by enhancing active mass loading and minimizing inactive components. However, the sluggish reaction kinetics and poor electrode mechanical stability that are accompanied by the increased electrode thickness remain unsolved problems. Herein, for the first time, we propose a novel chemical cross-linking strategy to fabricate GeP thick electrodes with adjustable electrode thicknesses and active mass loadings for high areal capacity sodium-ion batteries (SIBs). The chemical cross-linking between carboxylic multiwalled carbon nanotubes (CNTs) and pyrolysis cellulose nanofibers (CNFs) forms a 3D network that encloses GeP nanoparticles, which guarantees fast charge transfer, efficient stress relief, and alleviated volume expansion/shrinkage of the electrode. The hierarchical porous structure generates numerous interconnected channels for unfettered Na+ diffusion, ensuring uncompromised reaction kinetics as the electrode thickness increases. As a result, the ultrathick 1031 µm GeP@C-CNTs-CNFs electrode featuring a mass loading of 18.3 mg cm-2 delivers an ultrahigh areal capacity of 10.58 mAh cm-2 accompanied by superior cycling stability, which outperforms all reported Ge-based electrodes (generally below 1.5 mAh cm-2). This work sheds insightful light on designing high areal capacity flexible thick electrodes for the applications of miniaturized electric devices.

SLS 3D Printing To Fabricate Poly(vinyl alcohol)/Hydroxyapatite Bioactive Composite Porous Scaffolds and Their Bone Defect Repair Property.

Poly(vinyl alcohol) (PVA) exhibits a wide range of potential applications in the biomedical field due to its favorable mechanical properties and biocompatibility. However, few studies have been carried out on selective laser sintering (SLS) of PVA due to its poor thermal processability. In this study, in order to impart PVA powder the excellent thermal processability, the molecular complexation technology was performed to destroy the strong hydrogen bonds in PVA and thus significantly reduced the PVA melting point and crystallinity to 190.9 °C and 27.9%, respectively. The modified PVA (MPVA) was then compounded with hydroxyapatite (HA) to prepare PVA/HA composite powders suitable for SLS 3D printing. The final SLS 3D-printed MPVA/HA composite porous scaffolds show high precision and interconnected pores with a porosity as high as 68.3%. The in vitro cell culture experiments revealed that the sintered composite scaffolds could significantly promote the adhesion and proliferation of osteoblasts and facilitate bone regeneration, and the quantitative real-time polymerase chain reaction results further demonstrate that the printed MPVA/20HA scaffold could significantly enhance the expression levels of both early osteogenic-specific marker of alkaline phosphatase stain and runt-related transcription factor 2. Meanwhile, in in vivo experiments, it is encouragingly found that the resultant MPVA/20HA SLS 3D-printed part has an obvious effect on promoting the growth of new bone tissue as well as a better bone regeneration capability. This work could provide a promising strategy for fabrication of PVA scaffolds through SLS 3D printing, exhibiting a great potential for clinical applications in bone tissue engineering.

Direct Ink Writing 3D Printing for High-Performance Electrochemical Energy Storage Devices: A Minireview.

Despite tremendous efforts that have been dedicated to high-performance electrochemical energy storage devices (EESDs), traditional electrode fabrication processes still face the daunting challenge of limited energy/power density or compromised mechanical compliance. 3D thick electrodes can maximize the utilization of z-axis space to enhance the energy density of EESDs but still suffer from limitations in terms of poor mechanical stability and sluggish electron/ion transport. Direct ink writing (DIW), an eminent branch of 3D printing technology, has gained popularity in the manufacture of 3D electrodes with intricately designed architectures and rationally regulated porosity, promoting a triple boost in areal mass loading, ion diffusion kinetics, and mechanical flexibility. This focus review highlights the fundamentals of printable inks and typical configurations of 3D-printed devices. In particular, preparation strategies for high-performance and multifunctional 3D-printed EESDs are systemically discussed and classified according to performance evaluation metrics such as high areal energy density, high power density, high volumetric energy density, and mechanical flexibility. Challenges and prospects for the fabrication of high-performance 3D-printed EESDs are outlined, aiming to provide valuable insights into this thriving field.

Porous amorphous metal-organic frameworks based on heterotopic triangular ligands for iodine and high-capacity dye adsorption.

The research on amorphous metal-organic frameworks (aMOFs) is still in its infancy, and designing and constructing aMOFs with functional pores remains a challenge. Two aMOFs based on Co(II) and heterotopic triangular ligands with large conjugated aromatic planes, namely aMOF-1 and aMOF-2, were constructed and characterized by IR, XPS, EA, ICP, XANS and so on. aMOF-1 possesses mesopores, whereas aMOF-2 possesses micropores. The porosity, conjugated aromatic plane and uncoordinated N atoms in the framework allow these aMOFs to adsorb iodine and dyes. The iodine adsorption capacity of aMOF-1 is 3.3 g per g, which is higher than that of aMOF-2 (0.56 g per g), mainly due to the expansion or swelling of aMOF-1 after iodine adsorption. The uptake of cationic dyes by aMOF-2 showed more rapid kinetics and a higher removal rate than that by aMOF-1, mainly due to the difference in the porosity and surface charge. Although the surface charges of aMOF-1 and aMOF-2 are negative, both of them showed significantly faster adsorption kinetics toward anionic dyes, among which methyl orange (MO) and Congo red (CR) can be removed in 5 min. This occurs possibly because the quick adsorption of Na+ ions alters the surface charge of the framework and promotes dye uptake. The adsorption capacities of aMOF-1 for MO and CR reached 921 and 2417 mg g-1, respectively. The correlation data for aMOF-2 are 1042 and 1625 mg g-1, respectively. All adsorption capacities are among the highest compared to many cMOFs. Adsorption in mixed dye solution is found to be charge-dependent, kinetic-dependent, and synergetic in these systems. The porosity, surface charge regulation during adsorption, weak interactions and multiple adsorption processes contribute to the dye adsorption performance.

Electrospinning of Highly Bi-Oriented Flexible Piezoelectric Nanofibers for Anisotropic-Responsive Intelligent Sensing.

Flexible piezoelectric energy harvesters (PEHs) have gained substantial attention owing to their wearability, breathability, and sustainable self-powered supply. However, existing film PEHs cannot identify forces in different bending directions, limiting their applications in wearable electronics and artificial intelligence. This study constructs a fabric PEH for the first time by introducing piezoelectric anisotropic BaTi2 O5 nanorods (BT2-nr) into piezoelectric polyvinylidene fluoride (PVDF) nanofibers with a bi-oriented architecture, in which BT2-nr uniformly aligns in the PVDF nanofiber during electrospinning. The dual-orientation feature endows the flexible PEH with anisotropy, which can sensitively identify the forces at different bending directions (e.g., bent vertically, parallelly, or twisted by 45° along the fiber orientations). Simultaneously, the composite PVDF/BT2 PEH containing 15 wt.% BT2-nr delivers an optimal piezoelectric output of 31.2 V with a high sensitivity of 5.22 V N-1 . The developed anisotropic PEH can be used as a self-powered pressure sensor for multimodal intelligent biomonitoring of human movement. This study provides a feasible strategy for fabricating self-powered flexible PEHs with high electromechanical conversion efficiency and multifunctionality for wearable piezoelectric pressure sensors.

Simulation Guided Coaxial Electrospinning of Polyvinylidene Fluoride Hollow Fibers with Tailored Piezoelectric Performance.

Electrospun polyvinylidene fluoride (PVDF) piezoelectric fibers have high potential applicability in mechanical energy harvesting and self-powered sensing owing to their high electromechanical coupling capabilities. Strategies for tailoring fiber morphology have been the primary focus for realizing enhanced piezoelectric output. However, the relationship between piezoelectric performance and fiber structure remains unclear. This study fabricates PVDF hollow fibers through coaxial electrospinning, whose wall thickness can be tuned by changing the internal solution concentration. Simulation analysis demonstrates an increased effective deformation of the hollow fiber as enlarging inner diameter, resulting in enhanced piezoelectric output, which is in excellent agreement with the experimental results. This study is the first to unravel the influence mechanism of morphology regulation of a PVDF hollow fiber on its piezoelectric performance from both simulation and experimental aspects. The optimal PVDF hollow fiber piezoelectric energy harvester (PEH) delivers a piezoelectric output voltage of 32.6 V, ≈3 times that of the solid PVDF fiber PEH. Furthermore, the electrical output of hollow fiber PEH can be stably stored in secondary energy storage systems to power microelectronics. This study highlights an efficient approach for reconciling the simulation and tailoring the fiber PEH morphology for enhanced performances for future self-powered systems.

3D Printing of Electron/Ion-Flux Dual-Gradient Anodes for Dendrite-Free Zinc Batteries.

3D porous Zn-metal anodes have aroused widespread interest for Zn-ion batteries (ZIBs). Nevertheless, the notorious "top-growth" dendrites caused by the intrinsic top-concentrated ions and randomly distributed electrons may ultimately trigger a cell failure. Herein, an electron/ion-flux dual-gradient 3D porous Zn anode is reported for dendrite-free ZIBs by adopting 3D printing technology. The 3D-printed Zn anode with layer-by-layer bottom-up attenuating Ag nanoparticles (3DP-BU@Zn) establishes dual-gradient electron/ion fluxes, i.e., an internal bottom-up gradient electron flux created by bottom-rich conductive Ag nanoparticles, and a gradient ion flux resulting from zincophilic Ag nanoparticles which pump ions toward the bottom. Meanwhile, the 3D-printing-enabled hierarchical porous structure and continuously conducting network endow unimpeded electron transfer and ion diffusion among the electrode, dominating a bottom-preferential Zn deposition behavior. As a result, the 3DP-BU@Zn symmetrical cell affords highly reversible Zn plating/stripping with an extremely small voltage hysteresis of 17.7 mV and a superior lifespan over 630 h at 1 mA cm-2 and 1 mAh cm-2 . Meanwhile, the 3DP-BU@Zn//VO2 full cell exhibits remarkable cyclic stability over 500 cycles. This unique dual-gradient strategy sheds light on the roadmap for the next-generation safe and durable Zn-metal batteries.

Densifiable Ink Extrusion for Roll-To-Roll Fiber Lithium-Ion Batteries with Ultra-High Linear and Volumetric Energy Densities.

Conventional bulky and rigid planar architecting power systems are difficult to satisfy the growing demand for wearable applications. 1D fiber batteries bearing appealing features of miniaturization, adaptability, and weavability represent a promising solution, yet challenges remain pertaining to energy density and scalability. Herein, an ingenious densifiable functional ink is invented to fabricate scalable, flexible, and high-mass-loading fiber lithium-ion batteries (LIBs) by adopting a fast ink-extrusion technology. In the formulated ink, pyrrole-modified reduced graphene oxide is elaborately introduced and exerts multiple influences; it not only assembles carbon nanotubes and poly(vinylidene fluoride-co-hexafluoropropylene) to compose a sturdy, conductive, and agglomeration-free 3D network that realizes an ultra-high content (75 wt%) of the active materials and endows the electrode excellent flexibility but also serves as a capillary densification inducer, encouraging an extremely large linear mass loading (1.01 mg cm-1 per fiber) and packing density (782.1 mg cm-3 ). As a result, the assembled fiber LIBs deliver impressive linear and volumetric energy densities with superb mechanical compliance, demonstrating the best performance among all the reported extruded fiber batteries. This work highlights a highly effective and facile approach to fabricate high-performance fiber energy storage devices for future practical wearable applications.

3D printing of fast kinetics reconciled ultra-thick cathodes for high areal energy density aqueous Li-Zn hybrid battery.

The limitation of areal energy density of rechargeable aqueous hybrid batteries (RAHBs) has been a significant longstanding problem that impedes the application of RAHBs in miniaturized energy storage. Constructing thick electrodes with optimized geometrical properties is a promising strategy for achieving high areal energy density, but the sluggish ion/electron transfer and poor mechanical stability, as well as the increased electrode thickness, itself present well-known problems. In this work, a 3D printing technique is introduced to construct an ultra-thick lithium iron phosphate (LFP)/carboxylated carbon nanotube (CNT)/carboxyl terminated cellulose nanofiber (CNF) composite electrode with uncompromised reaction kinetics for high areal energy density Li-Zn RAHBs. The uniformly dispersed CNTs and CNFs form continuous interconnected 3D networks that encapsulate LFP nanoparticles, guaranteeing fast electron transfer and efficient stress relief as the electrode thickness increases. Additionally, multistage ion diffusion channels generated from the hierarchical porous structure assure accelerated ion diffusion. As a result, LFP/Zn hybrid pouch cells assembled with 3D printed electrodes deliver a well-retained reversible gravimetric capacity of about 143.5 mAh g-1 at 0.5 C as the electrode thickness increases from 0.52 to 1.56 mm, and establish a record-high areal energy density of 5.25 mWh cm-2 with an impressive utilization of active material up to 30 mg cm-2 for an ultra-thick (2.08 mm) electrode, which outperforms almost all reported zinc-based hybrid-ion and single-ion batteries. This work opens up exciting prospects for developing high areal energy density energy storage devices using 3D printing.

Mechano-Regulable and Healable Silk-Based Materials for Adaptive Applications.

Mechanically adaptive materials responsive to environmental stimuli through changing mechanical properties are highly attractive in intelligent devices. However, it is hard to regulate the mechanical properties of most mechanically adaptive materials in a facile way. Moreover, it remains a challenge to achieve mechano-regulable materials with mechanical properties ranging from high strength to extreme toughness. Here, inspired by the reversible nanofibril network structure of skeletal muscle to achieve muscle strength regulation, we present a mechano-regulable biopolymeric silk fibroin (SF) composite through regulating dynamic metal-ligand coordination bonds by using water molecules as competitive regulators. Efficient interfacial hydrogen bonds between tannic acid-tungsten disulfide nanohybrids and the SF matrix endow the composite with high mechanical strength and self-healing ability. The resulting composite exhibits 837-fold change in Young's modulus (5.77 ± 0.61 GPa to 6.89 ± 0.64 MPa) after water vapor triggering, high mechanical properties (72.5 ± 6.3 MPa), and excellent self-healing efficiency (nearly 100%). The proof-of-concept ultraconformable iontronic skin and smart actuators are demonstrated, thereby providing a direction for future self-adaptive smart device applications.

3D Printing-Enabled In-Situ Orientation of BaTi2O5 Nanorods in ß-PVDF for High-Efficiency Piezoelectric Energy Harvesters.

Piezoelectric energy harvesters (PEHs) with a three-dimensional (3D) structure are arousing increasing interest because of the ability to efficiently convert mechanical energy into electricity catering for self-powered systems. Among them, 3D PEHs composed of 1-3-type piezoelectric composites which exploit one-dimensional (1D) piezoceramic fillers rather than conventional powders are particularly attractive. However, an issue involving the orientation of the 1D fillers to utilize the piezoelectric effect renders the 3D structural design for high-efficiency energy conversion more challenging. Herein, for the first time, we introduce the fused deposition modeling (FDM) 3D printing to the flexible construction of poly(vinylidene fluoride) (PVDF)-based 3D PEHs by incorporating 1D BaTi2O5 (BT2) nanorods as piezoelectric fillers. The shearing force generated by FDM successfully realizes the in situ uniform orientation of BT2 nanorods in the PVDF (98% ß crystals) matrix along the nozzle extrusion direction. Besides, by coupling 3D printing with the appealing piezoelectric anisotropy feature of BT2 nanorods, the 3D PEH is able to generate different piezoelectric responses to the same applied external force from X, Y, and Z directions. Furthermore, an optimized 3D conical array structure is constructed to amplify the effective deformation of the PEH to enhance its piezoelectric output. As expected, customized PEH can continuously power commercial electronic devices and monitor various human motions, indicating 3D printing as a multifunctional strategy to fabricate 3D PEHs with 1-3-type piezoelectric composite materials for self-powering microelectronic applications.

Surface-Adaptive Capillarity Enabling Densified 3D Printing for Ultra-High Areal and Volumetric Energy Density Supercapacitors.

Endowing supercapacitors with higher energy density is of great practical significance but remains extremely challenging. In this work, an innovative densified 3D printing enabled by a surface-adaptive capillarity strategy is proposed for the first time. The printable ink formulated with pyrrole surface-modified reduced graphene oxide renders the printed electrodes excellent surface tension regulability to the subsequent capillary densification, creating an intensely condensed electrode with well-maintained structural integrity. Furthermore, simultaneous in situ nitrogen doping and hierarchical micro-meso porosity are readily realized upon post-carbonization, encouraging enhanced capacitance and fast reaction dynamics. As a result, the printed symmetric supercapacitor delivers a double leap in areal and volumetric energy densities in both aqueous and organic electrolytes, a rarely achieved yet gravely desired attribute for 3D printed energy storage devices.