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As a representative in the post-lithium-ion batteries (LIBs) landscape, lithium metal batteries (LMBs) exhibit high-energy densities but suffer from low coulombic efficiencies and short cycling lifetimes due to dendrite formation and complex side reactions. Separator modification holds the most promise in overcoming these challenges because it utilizes the original elements of LMBs. In this review, separators designed to address critical issues in LMBs that are fatal to their destiny according to the target electrodes are focused on. On the lithium anode side, functional separators reduce dendrite propagation with a conductive lithiophilic layer and a uniform Li-ion channel or form a stable solid electrolyte interphase layer through the continuous release of active agents. The classification of functional separators solving the degradation stemming from the cathodes, which has often been overlooked, is summarized. Structural deterioration and the resulting leakage from cathode materials are suppressed by acidic impurity scavenging, transition metal ion capture, and polysulfide shuttle effect inhibition from functional separators. Furthermore, flame-retardant separators for preventing LMB safety issues and multifunctional separators are discussed. Further expansion of functional separators can be effectively utilized in other types of batteries, indicating that intensive and extensive research on functional separators is expected to continue in LIBs.
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Next-generation lithium-ion batteries (LIBs) that satisfy the requirements for an electric vehicle energy source should demonstrate high reliability and safety for long-term high-energy-density operation. This inevitably calls for a novel approach to advance major components such as the separator. Herein, a separator is designed and fabricated via application of multilayer functional coating on both sides of a polyethylene separator. The multilayer-coated separator (MCS) has a porous structure that does not interfere with lithium ion diffusion and exhibits superior heat resistance, high electrolyte uptake, and persistent adhesion with the electrode. More importantly, it enables high capacity retention and reduced impedance build up during cycling when used in a coin or pouch cell. These imply its promising application in energy sources requiring long-term stability. Fabrication of the MCS without the use of organic solvents is not only environmentally beneficial but also effective at cost reduction. This approach paves the way for the separator, which has long been considered an inactive major component of LIBs, to become an active contributor to the energy density toward achieving longer cycle stability.
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The demand for safer batteries is growing rapidly due to fire incidents in electronic devices that use Li-ion batteries. Zn-ion batteries are among the most promising candidates to replace Li-ion batteries because they use a water-based electrolyte and are not explosive. However, Zn-ion batteries suffer from persistent corrosion and dendritic crystal formation during the charge-discharge process, which decrease their reversibility and hinder their commercial usage. Extensive research has been conducted to address these issues, but there are significant limitations due to high process and time costs. In this study, the modulation of the Zn-electrolyte interface to overcome these challenges is attempted using acetamide-derived thioacetamide (TAA), a surface modifier used in electroplating. TAA undergoes hydrolysis in an aqueous solution and produces weakly acidic byproducts and sulfide ions. These species are adsorbed onto the Zn metal surface, which induces uniform Zn2+ deposition, facilitates the formation of a stable interfacial layer, and inhibits side reactions due to the reduced water activity. Consequently, the symmetric cell with TAA achieves a low polarization of 50 mV and stable cycling for 700 h at 1 mA cm-2. Additionally, a Zn|V6O13 full cell exhibits electrochemical reversibility, maintaining a capacity retention of 64% over 300 cycles. Therefore, this study offers useful insights into the development of a simple manufacturing process to ensure the competitiveness of Zn-ion batteries for practical applications using functional electrolyte additives.
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Fabrication of physically engineered colloids and their application to the biological fields is emerging importance because of their potential to provide an enhanced performance without altering the chemical properties of biomaterials used. A facile approach is reported to fabricate sub-10-µm-sized PLGA microparticle with small dimples covering the surface by droplet imprinting. Optical and magnetic resonance bioimaging agents are easily co-encapsulated inside the microparticles to obtain a bi-modal imaging agent. Cell internalization efficacy of dimpled particles in DC 2.4 cell is enhanced compared with conventional smooth round-shaped colloids. Our result indicates that morphology-controlled microparticles show promise as a cell labeling with improved cell interaction.
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Materiales Biocompatibles/química , Medios de Contraste/química , Propiedades de SuperficieRESUMEN
Poly(3,4-ethylenedioxythiophene) (PEDOT) has good properties as a conductive polymer such as high conductivity, optical transmittance, and chemical stability, while offering relatively weak physicochemical properties. The main purpose of this paper is to improve physicochemical properties such as solvent resistance and pencil hardness of PEDOT. Carboxyl groups in the poly(MMA-co-MAA) polymer chains can effectively crosslink each other in the presence of aziridine, resulting in physicochemically robust PEDOT/poly(MMA-co-MAA) hybrid conductive films. The electrical conductivity, optical properties, and physicochemical properties of the hybrid conductive film were compared by varying the solid content and poly(MMA-co-MAA) portion in the coating precursor solution. From the results, the transparency and surface resistance of the hybrid film show a tendency to decrease with increasing solid content in the coating precursor. Moreover, solvent resistance and hardness were dramatically enhanced by hybridization of PEDOT and crosslinked poly(MMA-co-MAA) due to curing reactions between carboxyl groups. The chemical composition of 30 wt-% of poly(MMA-co-MAA) (MMA:MAA mole ratio 9:1) and 3 wt-% - 5 wt-% of aziridine yields the best physicochemical properties of poly(MMA-co-MAA)/PEDOT hybrid thin films.
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This study demonstrates a novel approach to creating a thin-film electronic device that offers selective or complete disposability only in on-demand conditions while maintaining stable operation reliability during everyday use. The approach involves a transient paper substrate, combined with phase change encapsulation and highly bendable planarization materials, achieved through a simple solution process. The substrate used in this study offers a smooth surface morphology that enables the creation of stable multilayers for thin-film electronic devices. It also exhibits superior waterproof properties, which allows the proof-of-concept organic light-emitting device to function even when submerged in water. Additionally, the substrate provides controlled surface roughness under repeated bending, demonstrating reliable folding stability for 1000 cycles at 10 mm of curvature. Furthermore, a specific component of the electronic device can be selectively made to malfunction through predetermined voltage input, and the entire device can be fully disposed of via Joule-heating-induced combustion.
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Herein we describe a photo-alignment layer of improved azimuthal anchoring energy comparable to conventional rubbing method. In order to address the inherent low anchoring stability of photo-alignment layer, we applied embossing technique to conventional photosensitive polymer film, based on the cinnamoyl photoreactive groups, to introduce physical micro-groove effect for additional anchoring energy. From this, 2.5 × 10â»4 J/m² of azimuthal anchoring energy was achieved, which is considered as synergistic effect from both photoinduced chemical interaction and physical microgroove alignment. In this study, we conducted systematic study on change in anchoring energy as a function of both aspect ratio of embossed pattern and UV exposure dose. We also demonstrated fabrication of sophisticated multi-domain structure of LC cells and discussed theoretical interpretation through LC simulation.
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Cristalización/métodos , Cristales Líquidos/química , Cristales Líquidos/efectos de la radiación , Materiales Manufacturados , Modelos Químicos , Anisotropía , Simulación por Computador , Luz , Ensayo de MaterialesRESUMEN
With the growing interest in suppressing greenhouse gas emissions from fossil fuel combustion, the implementation of electrical energy storage devices for efficiently utilizing renewable energy is expanding worldwide. Zn-ion batteries are attractive for energy storage because of their safety, eco-friendliness, high energy density, and low cost. However, their commercialization is hindered by the poor rechargeability of the zinc anode because of Zn dendrite growth and hydrogen evolution. Herein, we present the application of an artificial layer composed of bimodal BaTiO3 particles on Zn metal to boost the dielectric properties and thus enhance the reversibility of Zn anodes during long-term cycling. The BaTiO3 layer induces electric polarization under external electric fields, causing the Zn ions to move sequentially toward the Zn anode. Moreover, its mechanical characteristics alleviate the volume changes between the BaTiO3 layer and Zn metal. Consequently, Zn dendrite growth is effectively inhibited, and the electrochemical performance is significantly improved in Zn|Zn symmetric cells, resulting in a low overvoltage (39 mV) and stable cycling (800 h) at 1 mA cm-2. Moreover, the Zn-ion full cell using an α-MnO2 cathode exhibits consistent capacity retention up to 380 cycles. This study demonstrates a new strategy to economically and readily suppress dendrite formation by using bimodal dielectric particles as artificial layers to stabilize metal-based batteries.
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Initial reversibility and excellent capacity retention are the key requirements for the success of high-capacity electrode materials in high-performance Li-ion batteries and pose a number of challenges to development. Silicon has been regarded as a promising anode material because of its outstanding theoretical capacity. However, it suffers from colossal volume change and continuous formation of unstable solid electrolyte interphases during lithiation/delithiation processes, which eventually result in low initial Coulombic efficiency (ICE) and severe capacity decay. To circumvent these challenges, a new sandwich Si anode (SiOx /Si/SiOx ) free from prelithiation is designed and fabricated using a combination of P-doping and SiOx layers. This new anode exhibits high conductivity and specific capacity compared to other Si thin-film electrodes. Cells with SiOx /Si/SiOx anodes deliver the highest presently known ICE value among Si thin-film anodes of 90.4% with a charge capacity of 3534 mA h g-1 . In addition, the SiOx layer has sufficient mechanical stability to accommodate the large volume change of the intervening Si layer during charge-discharge cycling, exhibiting high potential for practical applications of Si thin-film anodes.
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A pixel isolated liquid crystal display was fabricated by polarization-selective anisotropic photoreaction of a prepolymer containing a cinnamate oligomer. The cinnamate oligomer was mainly distributed on the surface region of a UV-cured polymer wall. Anisotropic photo-dimerization of cinnamate moiety was achieved by polarized UV exposure. It was found that the polymer walls containing cinnamate dimers formed by polarized UV exposure showed ordered orientation of LC molecules at the boundary of the polymer walls resulting in electro-optic performance improvement.
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Cinamatos/química , Cristalización/métodos , Presentación de Datos , Cristales Líquidos/química , Polímeros/química , Refractometría/métodos , Cinamatos/efectos de la radiación , Luz , Cristales Líquidos/efectos de la radiación , Polímeros/efectos de la radiación , Rayos UltravioletaRESUMEN
A Polymeric mirror from 1D photonic crystal exhibiting full specular reflection is applied on the exterior of the counter electrode of a dye-sensitized solar cells (DSSCs). Reflection of exiting light from the cell allows for the reuse of the light and thereby significantly increases the efficiency of the DSSCs (from 8.07% to 8.85%). Furthermore, it is also found to be effective even with incorporation of an internal scattering layer, which is widely used within a TiO2 anode layer for enhancing light trapping in DSSCs (from 9.17% to 9.53%).
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As an alternative to the rubbing method, the photoalignment method has been extensively developed for liquid crystal displays owing to its various advantages including the absence of any contamination problems, feasibility of multi-domain structure formation, and low temperature processing capability. However, cinnamate-based photo-reactive materials that are widely used in photoalignment suffer from several limitations including low pretilt angle and limited control of tilted-up direction of the liquid crystals compared to that of the rubbing process. In this work, we demonstrate a simple and convenient method to generate the pretilt angle, compared to that achieved via the rubbing method, by means of a simple directional peel-off process using a photo-reactive cinnamate oligomer having flexible molecular chain.
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Cinamatos/química , Cinamatos/efectos de la radiación , Presentación de Datos , Cristales Líquidos/química , Cristales Líquidos/efectos de la radiación , Fotoquímica/métodos , Refractometría/instrumentación , Diseño Asistido por Computadora , Diseño de Equipo , Análisis de Falla de Equipo , LuzRESUMEN
One of the challenges in developing Lithium anodes for Lithium ion batteries (LIB) is controlling the formation of Li dendrites during cycling of the battery. Nanostructuring and nanopatterning of electrodes shows a promising way to suppress the growth of Li dendrites. However, in order to control this behavior, a fundamental understanding of the effect of nanopatterning on the electro-mechanical properties of Li metal is necessary. In this paper, we have investigated the mechanical and wear properties of Li metal using Atomic Force Microscopy (AFM) in an airtight cell. By using different load regimes, we determined the mechanical properties of Li metal. We show that as a result of nanopatterning, Li metal surface underwent work hardening due to residual compressive stress. The presence of such stresses can help to improve cycle lifetime of LIBs with Li anodes and obtain very high energy densities.
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A synthesized graft polymer is used as a biodegradable polymer for an in situ gel-forming injectable implant system. The amphiphilic character of the polymer in the graft structure lowered the viscosity of the polymer solution, which enabled easy injection. A micro-sized gel can be obtained with this system, which has not been found for previous in situ gel-forming systems with poly[(D,L-lactide)-co-glycolide] copolymer. In addition, a protein particle embedded gel exhibits good in vitro drug release performance as a result of the enhanced stability and shorter diffusion length.
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Implantes Absorbibles , Preparaciones de Acción Retardada , Sistemas de Liberación de Medicamentos/métodos , Ácido Láctico/química , Ácido Poliglicólico/química , Polímeros/química , Microscopía Electrónica de Rastreo , Copolímero de Ácido Poliláctico-Ácido Poliglicólico , Factores de Tiempo , ViscosidadRESUMEN
Dopamine, which can be electrochemically oxidized to polydopamine on cathode surface, was introduced as an electrolyte additive for high-voltage lithium-ion batteries (LIBs). The addition of 0.1 wt % dopamine to the electrolyte led to the formation of a polydopamine-containing layer on the cathode, thereby resulting in suppression of the oxidative decomposition of the electrolyte during high-voltage operation (up to 4.5 V) of a LiNi1/3Co1/3Mn1/3O2/artificial graphite cell. The addition of dopamine to the electrolyte improved the capacity retention of the cell from 136 to 147 mAh g(-1) after 100 cycles at a rate of 1 C and a cutoff voltage of 4.5 V, while the cycle performance and rate capability with a cutoff voltage of 4.3 V were comparable to those of the cell without dopamine. Further evidence of the positive impact of dopamine on high-voltage LIBs was the lower DC-IRs and AC impedances, as well as the retention of the cathode morphology even after operation at 4.5 V.
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A highly adhesive and thermally stable copolyimide (P84) that is soluble in organic solvents is newly applied to silicon (Si) anodes for high energy density lithium-ion batteries. The Si anodes with the P84 binder deliver not only a little higher initial discharge capacity (2392 mAh g(-1)), but also fairly improved Coulombic efficiency (71.2%) compared with the Si anode using conventional polyvinylidene fluoride binder (2148 mAh g(-1) and 61.2%, respectively), even though P84 is reduced irreversibly during the first charging process. This reduction behavior of P84 was systematically confirmed by cyclic voltammetry and Fourier-transform infrared analysis in attenuated total reflection mode of the Si anodes at differently charged voltages. The Si anode with P84 also shows ultrastable long-term cycle performance of 1313 mAh g(-1) after 300 cycles at 1.2 A g(-1) and 25 °C. From the morphological analysis on the basis of scanning electron microscopy and optical images and of the electrode adhesion properties determined by surface and interfacial cutting analysis system and peel tests, it was found that the P84 binder functions well and maintains the mechanical integrity of Si anodes during hundreds of cycles. As a result, when the loading level of the Si anode is increased from 0.2 to 0.6 mg cm(-2), which is a commercially acceptable level, the Si anode could deliver 647 mAh g(-1) until the 300th cycle, which is still two times higher than the theoretical capacity of graphite at 372 mAh g(-1).
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Engineering surface morphology as in honeycomb-structured planar films is of great importance for providing new potential application and improved performance in biomedical fields. We demonstrate potential new applications for the uniform biocompatible golf-ball-shaped microparticles that resembles 3D feature of honeycomb-structured film. Dimple size controllable golf-ball-shaped microparticles were fabricated by microfluidic device. Surface dimples not only can act as picoliter beaker but also enhance cell adhesion without any chemical modification of the surface.
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Ácido Láctico/química , Ácido Láctico/farmacología , Microesferas , Tamaño de la Partícula , Ácido Poliglicólico/química , Ácido Poliglicólico/farmacología , Adhesión Celular/efectos de los fármacos , Línea Celular Tumoral , Cristalización , Células HEK293 , Humanos , Microscopía Electrónica de Rastreo , Copolímero de Ácido Poliláctico-Ácido Poliglicólico , Cloruro de Sodio/química , Propiedades de SuperficieRESUMEN
A flexible hybrid anode from graphite and thin film silicon is realized by the concept of a 3D sandwich current collector by the combination of micro-contact printing and RF magnetron sputtering. Flexible lithium-ion batteries with a new hybrid anode demonstrate not only enhanced specific capacity but also improved rate capability compared to that of a conventional graphite anode under bending deformation.
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We report the fabrication of a flexible and binder-free metal fibril mat-supported Si anode (Si@SFM) by a simple process. The fabricated Si@SFM anode showed a high discharge capacity, â¼3000 mAh g(-1) at a current rate of 300 mA g(-1), and exhibited stable capacity retention, 90% at a 1 C rate (2000 mA g(-1)) after 200 cycles. The rate capability of the electrode was still high even when both the charge and the discharge current rates were markedly increased at the same time (1234 mAh g(-1) for charge-discharge time of â¼12 min). Moreover, owing to its mechanical flexibility, the Si@SFM can be adopted as a key component of flexible lithium-ion batteries (LIBs). After cell packaging, the rechargeable flexible battery under bending stress showed only a little capacity fading (86% of initial capacity) at 1000 mA g(-1) over 150 cycles. These results suggest that the Si@SFM electrode is readily suitable for use in rechargeable flexible LIBs.
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Mesoporous silicon nanofibers (m-SiNFs) have been fabricated using a simple and scalable method via electrospinning and reduction with magnesium. The prepared m-SiNFs have a unique structure in which clusters of the primary Si nanoparticles interconnect to form a secondary three-dimensional mesoporous structure. Although only a few nanosized primary Si particles lead to faster electronic and Li(+) ion diffusion compared to tens of nanosized Si, the secondary nanofiber structure (a few micrometers in length) results in the uniform distribution of the nanoparticles, allowing for the easy fabrication of electrodes. Moreover, these m-SiNFs exhibit impressive electrochemical characteristics when used as the anode materials in lithium ion batteries (LIBs). These include a high reversible capacity of 2846.7 mAh g(-1) at a current density of 0.1 A g(-1), a stable capacity retention of 89.4% at a 1 C rate (2 A g(-1)) for 100 cycles, and a rate capability of 1214.0 mAh g(-1) (at 18 C rate for a discharge time of â¼3 min).