Polymeric Nanofibers with Ultrahigh Piezoelectricity <i>via</i> Self-Orientation of Nanocrystals

Piezoelectricity in macromolecule polymers has been gaining immense attention, particularly for applications in biocompatible, implantable, and flexible electronic devices. This paper introduces core–shell-structured piezoelectric polyvinylidene fluoride (PVDF) nanofibers chemically wrapped by graphene oxide (GO) lamellae (PVDF/GO nanofibers), in which the polar β-phase nanocrystals are formed and uniaxially self-oriented by the synergistic effect of mechanical stretching, high-voltage alignment, and chemical interactions. The β-phase orientation of the PVDF/GO nanofibers along their axes is observed at atomic scale through high resolution transmission electron microscopy, and the β-phase content is found to be 88.5%. The piezoelectric properties of the PVDF/GO nanofibers are investigated in terms of piezoresponse mapping, local hysteresis loops, and polarization reversal by advanced piezoresponse force microscopy. The PVDF/GO nanofibers show a desirable out-of-plane piezoelectric constant (<i>d</i>₃₃) of −93.75 pm V^–1 (at 1.0 wt % GO addition), which is 426% higher than that of the conventional pure PVDF nanofibers. The mechanism behind this dramatic enhancement in piezoelectricity is elucidated by three-dimensional molecular modeling

Ultrathin Coaxial Fiber Supercapacitors Achieving High Energy and Power Densities

Fiber-based supercapacitors have attracted significant interests because of their potential applications in wearable electronics. Although much progress has been made in recent years, the energy and power densities, mechanical strength, and flexibility of such devices are still in need of improvement for practical applications. Here, we demonstrate an ultrathin microcoaxial fiber supercapacitor (μCFSC) with high energy and power densities (2.7 mW h/cm³ and 13 W/cm³), as well as excellent mechanical properties. The prototype with the smallest reported overall diameter (∼13 μm) is fabricated by successive coating of functional layers onto a single micro-carbon-fiber via a scalable process. Combining the simulation results via the electrochemical model, we attribute the high performance to the well-controlled thin coatings that make full use of the electrode materials and minimize the ion transport path between electrodes. Moreover, the μCFSC features high bending flexibility and large tensile strength (more than 1 GPa), which make it promising as a building block for various flexible energy storage applications

Biomimetic, Flexible, and Self-Healable Printed Silver Electrode by Spontaneous Self-Layering Phenomenon of a Gelatin Scaffold

Organic–inorganic hybrid layer-by-layer (LBL) composite structures can not only increase the strength and ductility of materials but also well disperse nanomaterials for better-conducting pathways. Here, we discovered the self-assembly process of an organic and silver (Ag) LBL hybrid structure having excellent sustainability during the long-term bending cycle. During the assembly process, the organic and Ag hybrid structure can be self-assembled into a layered structure. Unlike other conventional LBL fabrication processes, we applied the hydrogel scaffold of a biological polymer, which can spontaneously phase separate into an LBL structure in a water/alcohol solvent system. This new hydrogel-based Ag LBL patterns can successfully be printed on a flexible polyimide film without nozzle-clogging problem. Although these Ag LBL patterns cracked during the bending cycle, carbonized organic compounds between the Ag layers help to self-heal within few minutes at a low temperature (<80 °C). On the basis of our new hydrogel-based Ag ink, we could fabricate a fully printed reliable microscale flexible heater. We expect that our self-layering phenomenon can expand to the broad research field of flexible electronics in the near future

Cavitation-Induced Stiffness Reductions in Quantum Dot–Polymer Nanocomposites

The elastic stiffness of two polymer nanocomposite systems is investigated. The nanoscale fillers comprise cadmium selenide (CdSe, ∼4 nm) and cadmium selenide/cadmium sulfide (CdSe/CdS, ∼13 nm) quantum dots (QDs). The QDs are embedded within an electrospun structural block copolymer, poly­(styrene-ethylene-butylene-styrene) (SEBS). Tensile testing shows a monotonic decrease in the tensile Young’s modulus with increasing partially phase-separated QD concentration; this is to be compared to corresponding nanocomposites reinforced with nanorod (NR) and tetrapod (TP)-SEBS nanocomposites which show a monotonic increase with particle loading. While most studies to date emphasize the increase in Young’s modulus in polymer nanocomposites at higher reinforcement loadings, few focus on the tunability of the modulus from <i>reductions</i> in stiffness. The present work reveals up to an ∼80% reduction in tensile Young’s modulus with the addition of 5 vol % of QDs to electrospun SEBS. In this study, we sought mechanistic insight into this reduction in composite stiffness using a 2D lattice spring model. Simulation results reveal that the stiffness decrease with the addition of QD reinforcements is likely due to cavitation in the polymer in the vicinity of the QD aggregates arising from polymer debonding under tension. We anticipate that this study, performed with a commonly used structural rubber, may find use in designing polymer–matrix nanocomposite fibers with specific Young’s moduli for applications requiring a tunable lower stiffness material

Cu₂Te Incorporation-Induced High Average Thermoelectric Performance in <i>p</i>‑Type Bi₂Te₃ Alloys

p-Type (Bi, Sb)2Te3 alloys are attractive materials for near-room-temperature thermoelectric applications due to their high atomic masses and large spin–orbit interactions. However, their narrow band gaps originating from spin–orbit interactions lead to bipolar excitation, thereby limiting average thermoelectrics within a local temperature region (300–400 K). Here, we introduce Cu2Te into the Bi0.3Sb1.7Te3 (BST) lattice to implement high thermoelectrics over a wide temperature range. The carrier concentration is synergistically modulated via Cu substitution and the evolution of intrinsic point defects (antisites and vacancies). Furthermore, the chain effect caused by Cu2Te incorporation in BST is reflected in the improvement of the weighted mobility μW, thereby enhancing the power factor in the whole temperature range. Extrinsic and intrinsic defects due to the incorporation of Cu2Te lead to a significant reduction in the lattice thermal conductivity κL, which is further demonstrated by Raman spectroscopy. Combining κL and μW, the quantity factor B increases from 0.5 to 1 with increasing Cu2Te content due to not only the reduction of κL but also a significant improvement in electrical properties. Eventually, a peak figure of merit (zT) of ∼1.15 at 423 K is achieved in BST-Cu2Te samples, and an average figure of merit (zTave) of ∼1.12 (350–500 K) surpasses other excellent p-type Bi2Te3-based thermoelectrics. Such a synergistic effect can facilitate near-room-temperature thermoelectric applications of Bi2Te3-based alloys and provide chances for the technology space in thermoelectrics

Encapsulation of Perovskite Nanocrystals into Macroscale Polymer Matrices: Enhanced Stability and Polarization

Lead halide perovskites hold promise for photonic devices, due to their superior optoelectronic properties. However, their use is limited by poor stability and toxicity. We demonstrate enhanced water and light stability of high-surface-area colloidal perovskite nanocrystals by encapsulation of colloidal CsPbBr₃ quantum dots into matched hydrophobic macroscale polymeric matrices. This is achieved by mixing the quantum dots with presynthesized high-molecular-weight polymers. We monitor the photoluminescence quantum yield of the perovskite–polymer nanocomposite films under water-soaking for the first time, finding no change even after >4 months of continuous immersion in water. Furthermore, photostability is greatly enhanced in the macroscale polymer-encapsulated nanocrystal perovskites, which sustain >10¹⁰ absorption events per quantum dot prior to photodegradation, a significant threshold for potential device use. Control of the quantum dot shape in these thin-film polymer composite enables color tunability via strong quantum-confinement in nanoplates and significant room temperature polarized emission from perovskite nanowires. Not only does the high-molecular-weight polymer protect the perovskites from the environment but also no escaped lead was detected in water that was in contact with the encapsulated perovskites for months. Our ligand-passivated perovskite-macroscale polymer composites provide a robust platform for diverse photonic applications

Self-Assembly of Silver Nanowire Ring Structures Driven by the Compressive Force of a Liquid Droplet

In a nanowire dispersed in liquid droplets, the interplay between the surface tension of the liquid and the elasticity of the nanowire determines the final morphology of the bent or buckled nanowire. Here, we investigate the fabrication of a silver nanowire ring generated as the nanowire encapsulated inside of fine droplets. We used a hybrid aerodynamic and electrostatic atomization method to ensure the generation of droplets with scalable size in the necessary regime for ring formation. We analytically calculate the compressive force of the droplet driven by surface tension as the key mechanism for the self-assembly of ring structures. Thus, for potential large-scale manufacturing, the droplet size provides a convenient parameter to control the realization of ring structures from nanowires

High Stability Induced by the TiN/Ti Interlayer in Three-Dimensional Si/Ge Nanorod Arrays as Anode in Micro Lithium Ion Battery

Three-dimensional (3D) Si/Ge-based micro/nano batteries are promising lab-on-chip power supply sources because of the good process compatibility with integrated circuits and Micro/Nano-Electro-Mechanical System technologies. In this work, the effective interlayer of TiN/Ti thin films were introduced to coat around the 3D Si nanorod (NR) arrays before the amorphous Ge layer deposition as anode in micro/nano lithium ion batteries, thus the superior cycling stability was realized by reason for the restriction of Si activation in this unique 3D matchlike Si/TiN/Ti/Ge NR array electrode. Moreover, the volume expansion properties after the repeated lithium-ion insertion/extraction were experimentally investigated to evidence the superior stability of this unique multilayered Si composite electrode. The demonstration of this wafer-scale, cost-effective, and Si-compatible fabrication for anodes in Li-ion micro/nano batteries provides new routes to configurate more efficient 3D energy storage systems for micro/nano smart semiconductor devices

ZIF‑8 Cooperating in TiN/Ti/Si Nanorods as Efficient Anodes in Micro-Lithium-Ion-Batteries

Zeolite imidazolate framework-8 (ZIF-8) nanoparticles embedded in TiN/Ti/Si nanorod (NR) arrays without pyrolysis have shown increased energy storage capacity as anodes for lithium ion batteries (LIBs). A high capacity of 1650 μAh cm^–2 has been achieved in this ZIF-8 composited multilayered electrode, which is ∼100 times higher than the plain electrodes made of only silicon NR. According to the electrochemical impedance spectroscopy (EIS) and ¹H nuclear magnetic resonance (NMR) characterizations, the improved diffusion of lithium ions in ZIF-8 and boosted electron/Li⁺ transfer by the ZIF-8/TiN/Ti multilayer coating are proposed to be responsible for the enhanced energy storage ability. The first-principles calculations further indicate the favorable accessibility of lithium with appropriate size to diffuse in the open pores of ZIF-8. This work broadens the application of ZIF-8 to silicon-based LIBs electrodes without the pyrolysis and provides design guidelines for other metal–organic frameworks/Si composite electrodes

Mechanisms of Local Stress Sensing in Multifunctional Polymer Films Using Fluorescent Tetrapod Nanocrystals

Nanoscale stress-sensing can be used across fields ranging from detection of incipient cracks in structural mechanics to monitoring forces in biological tissues. We demonstrate how tetrapod quantum dots (tQDs) embedded in block copolymers act as sensors of tensile/compressive stress. Remarkably, tQDs can detect their own composite dispersion and mechanical properties with a switch in optomechanical response when tQDs are in direct contact. Using experimental characterizations, atomistic simulations and finite-element analyses, we show that under tensile stress, densely packed tQDs exhibit a photoluminescence peak shifted to higher energies (“blue-shift”) due to volumetric compressive stress in their core; loosely packed tQDs exhibit a peak shifted to lower energies (“red-shift”) from tensile stress in the core. The stress shifts result from the tQD’s unique branched morphology in which the CdS arms act as antennas that amplify the stress in the CdSe core. Our nanocomposites exhibit excellent cyclability and scalability with no degraded properties of the host polymer. Colloidal tQDs allow sensing in many materials to potentially enable autoresponsive, smart structural nanocomposites that self-predict impending fracture