Pilot Scale Hybrid Organic/Inorganic Coatings on a Polyolefin Separator to Enhance Dimensional Stability for Thermally Stable Long-Life Rechargeable Batteries.

The electric vehicle and energy storage markets have grown rapidly in recent years. Thermal runaway caused by malfunctioning Li-ion batteries is an urgent issue with many causes (e.g., mechanical, electrical, and thermal abuse). The most common cause of thermal runaway is the formation of an internal short circuit because of damage to the separator. There has been significant effort to improve the design of separators, but to our knowledge, only inorganic nanoparticle coatings are used in commercial Li-ion batteries. Here, hybrid organic/inorganic coating layers are synthesized in a pilot-scale process that was developed from a crosslinkable polyamide-imide synthesis technique. The fabrication process is optimized to achieve reproducible hybrid organic/inorganic coating layers that are thin (≤4 µm), permeable (≤250 s/100 cc), and thermally stable beyond 150 °C. The hybrid coating layer is applied to mini-18650 Li-ion cells to show that the discharge capacity did not change at low discharge rates, and the retention capacity after 500 cycles was better than that of the reference cells used for comparison. This work demonstrates that a novel hybrid coating layer has the potential to improve the stability of commercial Li-ion batteries.

Designing Materials and Processes for Strong Polyacrylonitrile Precursor Fibers.

Although polyacrylonitrile (PAN)-based carbon fibers have been successfully commercialized owing to their excellent material properties, their actual mechanical performance is still much lower than the theoretical values. Meanwhile, there is a growing demand for the use of superior carbon fibers. As such, many studies have been conducted to improve the mechanical performance of carbon fibers. Among the various approaches, designing a strong precursor fiber with a well-developed microstructure and morphology can constitute the most effective strategy to achieve superior performance. In this review, the efforts used to modulate materials, processing, and additives to deliver strong precursor fibers were thoroughly investigated. Our work demonstrates that the design of materials and processes is a fruitful pathway for the enhancement of the mechanical performance of carbon fibers.

A scalable, ecofriendly, and cost-effective lithium metal protection layer from a Post-it note.

Although there have been many studies addressing the dendrite growth issue of lithium (Li)-metal batteries (LMBs), the Li-metal anode has not yet been implemented in today's rechargeable batteries. There is a need to accelerate the practical use of LMBs by considering their cost-effectiveness, ecofriendliness, and scalability. Herein, a cost-effective and uniform protection layer was developed by simple heat treatment of a Post-it note. The carbonized Post-it protection layer, which consisted of electrochemically active carbon fibers and electrochemically inert CaCO3 particles, significantly contributed to stable plating and stripping behaviors. The resulting protected Li anode exhibited excellent electrochemical performance: extremely low polarization during cycling (<40 mV at a current density of 1 mA cm-2) and long lifespan (5000 cycles at 10 mA cm-2) of the symmetric cell, as well as excellent rate performance at 2C (125 mA h g-1) and long cyclability (cycling retention of 62.6% after 200 cycles) of the LiFePO4‖Li full cell. The paper-derived Li protection layer offer a facile and scalable approach to enhance LMB electrochemical performance.

A Review of Recent Advancements in Electrospun Anode Materials to Improve Rechargeable Lithium Battery Performance.

Although lithium-ion batteries have already had a considerable impact on making our lives smarter, healthier, and cleaner by powering smartphones, wearable devices, and electric vehicles, demands for significant improvement in battery performance have grown with the continuous development of electronic devices. Developing novel anode materials offers one of the most promising routes to meet these demands and to resolve issues present in existing graphite anodes, such as a low theoretical capacity and poor rate capabilities. Significant improvements over current commercial batteries have been identified using the electrospinning process, owing to a simple processing technique and a wide variety of electrospinnable materials. It is important to understand previous work on nanofiber anode materials to establish strategies that encourage the implementation of current technological developments into commercial lithium-ion battery production, and to advance the design of novel nanofiber anode materials that will be used in the next-generation of batteries. This review identifies previous research into electrospun nanofiber anode materials based on the type of electrochemical reactions present and provides insights that can be used to improve conventional lithium-ion battery performances and to pioneer novel manufacturing routes that can successfully produce the next generation of batteries.

A facile route to mechanically robust graphene oxide fibers.

Excellent mechanical, electrical, and thermal properties of graphene have been achieved at the macroscale by assembling individual graphene or graphene oxide (GO) particles. Wet-spinning is an efficient and well-established process that can provide GO assemblies in fiber form. The coagulation bath in the wet-spinning process has rarely been considered for the design of mechanically robust GO fibers (GOFs). In this study, locating the amidation reaction in the coagulation bath yielded mechanically improved GOFs. The imides 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide were used to form covalent amide bonds between GO flakes and chitosan, thereby reinforcing the GOFs. Evidence and effects of the amidation reaction were systematically examined. The tensile strength and breaking strain of the GOFs improved by 41.6% and 75.2%, respectively, and the toughness almost doubled because of the optimized crosslinking reaction. Our work demonstrated that using a coagulation bath is a facile way to enhance the mechanical properties of GOFs.

Dendrite Suppression Membranes for Rechargeable Zinc Batteries.

Aqueous batteries with zinc metal anodes are promising alternatives to Li-ion batteries for grid storage because of their abundance and benefits in cost, safety, and nontoxicity. However, short cyclability due to zinc dendrite growth remains a major obstacle. Here, we report a cross-linked polyacrylonitrile (PAN)-based cation exchange membrane that is low cost and mechanically robust. Li2S3 reacts with PAN, simultaneously leading to cross-linking and formation of sulfur-containing functional groups. Hydrolysis of the membrane results in the formation of a membrane that achieves preferred cation transport and homogeneous ionic flux distribution. The separator is thin (30 µm-thick), almost 9 times stronger than hydrated Nafion, and made of low-cost materials. The membrane separator enables exceptionally long cyclability (>350 cycles) of Zn/Zn symmetric cells with low polarization and effective dendrite suppression. Our work demonstrates that the design of new separators is a fruitful pathway to enhancing the cyclability of aqueous batteries.

Recent Progress in Coaxial Electrospinning: New Parameters, Various Structures, and Wide Applications.

Electrospinning, a common method for synthesizing 1D nanostructures, has contributed to developments in the electrical, electrochemical, biomedical, and environmental fields. Recently, a coaxial electrospinning process has been used to fabricate new nanostructures with advanced performance, but intricate and delicate process conditions hinder reproducibility and mass production. Herein, recent progress in new emerging parameters for successful coaxial electrospinning, and the various nanostructures and critical application areas resulting from these activities. Relationships between the new parameters and final product characteristics are described, new possibilities for nanostructures achievable via coaxial electrospinning are identified, and new research directions with a view to future applications are suggested.

Suppressing Lithium Dendrite Growth with a Single-Component Coating.

A single-component coating was formed on lithium (Li) metal in a lithium iodide/organic carbonate [dimethyl carbonate (DMC) and ethylene carbonate (EC)] electrolyte. LiI chemically reacts with DMC to form lithium methyl carbonate (LMC), which precipitates and forms the chemically homogeneous coating layer on the Li surface. This coating layer is shown to enable dendrite-free Li cycling in a symmetric Li∥Li cell even at a current density of 3 mA cm-2. Adding EC to DMC modulates the formation of LMC, resulting in a stable coating layer that is essential for long-term Li cycling stability. Furthermore, the coating can enable dendrite-free cycling after being transferred to common LiPF6/carbonate electrolytes, which are compatible with metal oxide cathodes.

Redox-Triggered Coloration Mechanism of Electrically Tunable Colloidal Photonic Crystals.

Electrically tunable colloidal photonic crystals (ETPCs) have been investigated because of several merits such as easy color tunability, no discoloration, and clear color. The coloration mechanism of ETPCs has been explained in terms of only the electric field. Herein, we report on a new mechanism: electric field plus redox reaction. Specifically, the coloration behavior of ETPCs was investigated under electrically conductive or insulated conditions using current-voltage, cyclic voltammetry, and zeta potential measurements, as well as scanning electron microscopy. Electrophoretic movement of ETPC particles toward the positive electrode was caused by the electric field due to the particles' negative surface charge. At the positive electrode, ETPC particles lost their electrons and formed a colloidal crystal structure. Finally, an ETPC transparent tube device was constructed to demonstrate the coloration mechanism.

The synergistic effect of inert oxide and metal fluoride dual coatings on advanced cathode materials for lithium ion battery applications.

The effect of Al2O3/LiF dual coatings on the electrochemical performance of over-lithiated layered oxide (OLO) has been investigated. A uniform coating of Al2O3 and LiF is obtained on the surface of the layered pristine material. The OLO with a dual Al2O3/LiF coating with a ratio of 1 : 1.5 exhibits excellent electrochemical performance. An initial discharge capacity of 265.66 mA h g(-1) is obtained at a C-rate of 0.1C. This capacity is approximately 15 mA h g(-1) higher than that of pristine OLO. The capacity retention (92.8% at the 50th cycle) is also comparable to that of pristine OLO (91.4% at the 50th cycle). Coating the cathode with a dual layer comprising Al2O3 and LiF leads to improved charging and discharging kinetics, and prevents direct contact between the cathode and the electrolyte.

Silicon/Carbon Nanotube/BaTiO3 Nanocomposite Anode: Evidence for Enhanced Lithium-Ion Mobility Induced by the Local Piezoelectric Potential.

We report on the synergetic effects of silicon (Si) and BaTiO3 (BTO) for applications as the anode of Li-ion batteries. The large expansion of Si during lithiation was exploited as an energy source via piezoelectric BTO nanoparticles. Si and BTO nanoparticles were dispersed in a matrix consisting of multiwalled carbon nanotubes (CNTs) using a high-energy ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the BTO, which can be poled, so that a piezoelectric potential is generated. We found that this local piezoelectric potential can improve the electrochemical performance of the Si/CNT/BTO nanocomposite anodes. Experimental measurements and simulation results support the increased mobility of Li-ions due to the local piezoelectric potential.

Fabrication of double-tubular carbon nanofibers using quadruple coaxial electrospinning.

This work reports the fabrication of double-tubular (or tube-in-tube) carbon nanofibers (CNFs). Tetra-layered nanofibers were manufactured using coaxial electrospinning with a concentric quadruple cylindrical nozzle system. Subsequent heat treatment eroded the first and third layers and converted the second and fourth layers into the carbonized structure, resulting in double-tubular CNFs. The morphologies and microstructures of the two tubes in the CNFs were investigated, revealing that the outer layer possessed denser and higher quality carbon crystals due to the coaxial electrospinning mechanism. Nanoparticles were readily incorporated between the two tubes in the double-tubular CNFs, providing a method for developing new multi-functional one dimensional materials.

New electrospinning nozzle to reduce jet instability and its application to manufacture of multi-layered nanofibers.

A new nozzle system for the efficient production of multi-layered nanofibers through electrospinning is reported. Developed a decade ago, the commonly used coaxial nozzle system consisting of two concentric cylindrical needles has remained unchanged, despite recent advances in multi-layered, multi-functional nanofibers. Here, we demonstrate a core-cut nozzle system, in which the exit pipe of the core nozzle is removed such that the core fluid can form an envelope inside the shell solution. This configuration effectively improves the coaxial electrospinning behavior of two fluids and significantly reduces the jet instability, which was proved by finite element simulation. The proposed electrospinning nozzle system was then used to fabricate bi- and tri-layered carbon nanofibers.

Flutter-driven triboelectrification for harvesting wind energy.

Technologies to harvest electrical energy from wind have vast potentials because wind is one of the cleanest and most sustainable energy sources that nature provides. Here we propose a flutter-driven triboelectric generator that uses contact electrification caused by the self-sustained oscillation of flags. We study the coupled interaction between a fluttering flexible flag and a rigid plate. In doing so, we find three distinct contact modes: single, double and chaotic. The flutter-driven triboelectric generator having small dimensions of 7.5 × 5 cm at wind speed of 15 ms(-1) exhibits high-electrical performances: an instantaneous output voltage of 200 V and a current of 60 µA with a high frequency of 158 Hz, giving an average power density of approximately 0.86 mW. The flutter-driven triboelectric generation is a promising technology to drive electric devices in the outdoor environments in a sustainable manner.

Directly drawn poly(3-hexylthiophene) field-effect transistors by electrohydrodynamic jet printing: improving performance with surface modification.

In this study, direct micropatterning lines of poly(3-hexylthiophene) (P3HT) without any polymer binder were prepared by electrohydrodynamic jet printing to form organic field-effect transistors (OFETs). We controlled the dielectric surface by introducing self-assembled monolayers and polymer thin films to investigate the effect of surface modifications on the characteristics of printed P3HT lines and electrical performances of the OFETs. The morphology of the printed P3HT lines depended on the surface energy and type of substrate. The resulting OFETs exhibited high performance on octadecyltrichlorosilane-modified substrates, which was comparable to that of other printed P3HT OFETs. In order to realize the commercialization of the OFETs, we also fabricated a large-area transistor array, including 100 OFETs and low-operating-voltage flexible OFETs.

Novel multi-layered 1-D nanostructure exhibiting the theoretical capacity of silicon for a super-enhanced lithium-ion battery.

Silicon/carbon (Si/C) nanocomposites have recently received much attention as Li-ion battery negative electrodes due to their mutual synergetic effects in capacity and mechanical integrity. The contribution of Si to the total capacity of the Si/C nanocomposites determines their structural efficiency. Herein, we report on a multi-layered, one-dimensional nanostructure that exhibits the theoretical specific capacity of Si in the nanocomposite. Concentrically tri-layered, compartmentalized, C-core/Si-medium/C-shell nanofibers were fabricated by triple coaxial electrospinning. The pulverization of Si was accommodated inside the C-shell, whereas the conductive pathway of the Li-ions and electrons was provided by the C-core, which was proven by ex situ Raman spectroscopy. The compartmentalized Si in between the C-core and C-shell led to excellent specific capacity at a high current rate (>820 mA h g(-1) at 12000 mA g(-1)) and the realization of the theoretical specific capacity of the Li15Si4 phase of Si nanoparticles (3627 mA h g(-1)). The electrochemical characterization and inductively coupled plasma-atomic emission spectrometry provided direct evidence of full participation of Si in the electrochemical reactions.

Highly stretchable resistive pressure sensors using a conductive elastomeric composite on a micropyramid array.

A stretchable resistive pressure sensor is achieved by coating a compressible substrate with a highly stretchable electrode. The substrate contains an array of microscale pyramidal features, and the electrode comprises a polymer composite. When the pressure-induced geometrical change experienced by the electrode is maximized at 40% elongation, a sensitivity of 10.3 kPa(-1) is achieved.

Effects of substrate on piezoelectricity of electrospun poly(vinylidene fluoride)-nanofiber-based energy generators.

We report the effects of various substrates and substrate thicknesses on electrospun poly(vinylidene fluoride) (PVDF)-nanofiber-based energy harvesters. The electrospun PVDF nanofibers showed an average diameter of 84.6 ± 23.5 nm. A high relative ß-phase fraction (85.2%) was achieved by applying high voltage during electrospinning. The prepared PVDF nanofibers thus generated considerable piezoelectric potential in accordance with the sound-driven mechanical vibrations of the substrates. Slide glass, poly(ethylene terephthalate), poly(ethylene naphthalate), and paper substrates were used to investigate the effects of the intrinsic and extrinsic substrate properties on the piezoelectricity of the energy harvesters. The thinnest paper substrate (66 µm) with a moderate Young's modulus showed the highest voltage output (0.4885 V). We used high-performance 76, 66, and 33 µm thick papers to determine the effect of paper thickness on the output voltage. The thinnest paper substrate resulted in the highest voltage output (0.7781 V), and the numerical analyses of the sound-driven mechanical deformation strongly support the hypothesis that substrate thickness has a considerable effect on piezoelectric performance.

Moisture condensation behavior of hierarchically carbon nanotube-grafted carbon nanofibers.

Hierarchical micro/nanosurfaces with nanoscale roughness on microscale uneven substrates have been the subject of much recent research interest because of phenomena such as superhydrophobicity. However, an understanding of the effect of the difference in the scale of the hierarchical entities, i.e., nanoscale roughness on microscale uneven substrates as opposed to nanoscale roughness on (a larger) nanoscale uneven surface, is still lacking. In this study, we investigated the effect of the difference in scale between the nano- and microscale features. We fabricated carbon nanotube-grafted carbon nanofibers (CNFs) by dispersing a catalyst precursor in poly (acrylonitrile) (PAN) solution, electrospinning the PAN/catalyst precursor solution, carbonization of electrospun PAN nanofibers, and direct growth of carbon nanotubes (CNTs) on the CNFs. We investigated the relationships between the catalyst concentrations, the size of catalyst nanoparticles on CNFs, and the sizes of CNFs and CNTs. Interestingly, the hydrophobic behavior of micro/nano and nano/nano hierarchical surfaces with water droplets was similar; however a significant difference in the water condensation behavior was observed. Water condensed into smaller droplets on the nano/nano hierarchical surface, causing it to dry much faster.

SnO2@TiO2 double-shell nanotubes for a lithium ion battery anode with excellent high rate cyclability.

SnO2@TiO2 double-shell nanotubes have been facilely synthesized by atomic layer deposition (ALD) using electrospun PAN nanofibers as templates. The double-shell nanotubes exhibited excellent high rate cyclability for lithium ion batteries. The retention of hollow structures during cycling was demonstrated.