Junho Ahn

Preparation and characterization of plasticized polymer electrolytes based on the PVdF-HFP copolymer for lithium/sulfur battery

PVdF-TG-LiX polymer electrolytes comprised of polyvinylidene fluoride (PVdF)-hexafluoropropylene (HFP) copolymer, tetra(ethylene glycol) dimethyl ether as plasticizer, LiCF3SO3, LiBF4 and LiPF6 as lithium salt and acetone as solvent have been prepared by solvent casting of slurry that mixed PVdF-HFP copolymer with acetone and salt using a ball-milling technique, which was performed for 2 and 12 h with a ball-to-material ratio of 400:1, and their electrochemical and thermal properties were studied. The ball-milled PVdF-TG-LiX polymer electrolytes have higher ionic conductivity as well as lower glass transition temperature and melting points than the magnetically stirred one. The PVdF-TG-LiPF6 polymer electrolytes prepared by ball-milling, for, 12 h, in particular, resulted in a maximum value in the ionic conductivity, which was 4.99×10−4 S cm−1 at room temperature. The ball-milled PVdF-TG-LiX polymer electrolytes were introduced into Li/S cells with sulfur as cathode and lithium as the anode. The first specific discharge capacities with discharge rate of 0.14 mA cm−2 at room temperature were about 575 and 765 mA h g–cathode−1 for magnetic stirring and 12 h ball milling.

Effect of ball milling on structural and electrochemical properties of (PEO)nLiX (lix = LiCF3SO3 and LiBF4) polymer electrolytes

Polymer electrolytes consisting of poly(ethylene oxide) (PEO) and lithium salts, such as LiCF3SO3 and LiBF4 are prepared by the ballmilling method. This is performed at various times (2, 4, 8, 12 h) with ball:sample ratio of 400:1. The electrochemical and thermal characteristics of the electrolytes are evaluated. The structure and morphology of PEO–LiX polymer electrolyte is changed to amorphous and smaller spherulite texture by ball milling. The ionic conductivity of the PEO–LiX polymer electrolytes increases by about one order of magnitude than that of electrolytes prepared without ball milling. Also, the ball milled electrolytes have remarkably higher ionic conductivity at low temperature. Maximum ionic conductivity is found for the PEO–LiX prepared by ball milling for 12 h, viz. 2:52 � 10 � 4 Sc m � 1 for LiCF3SO3 and 4:99 � 10 � 4 Sc m � 1 for LiBF4 at 90 8C. The first discharge capacity of Li/S cells increases with increasing ball milling time. (PEO)10LiCF3SO3 polymer electrolyte prepared by ball milling show the typical two plateau discharge curves in a Li/S battery. The upper voltage plateau for the polymer electrolyte containing LiBF4 differs markedly from the typical shape.# 2002 Elsevier Science B.V. All rights reserved.

Chiral Supramolecular Gels with Lanthanide Ions: Correlation between Luminescence and Helical Pitch

We report the correlation between the fluorescence intensity and the helical pitch of supramolecular hydrogels with Tb(III) and Eu(III) as well as their inkjet printing patterning as an application. The luminescent gels, which exhibited three different emissions of red, green, and blue, could be prepared without and with Eu(III) and Tb(III). The luminescence intensity of supramolecular gels (gel-Tb and gel-Eu) composed of Tb(III) and Eu(III) was ca. 3-fold larger than that of the sol (1+Tb(III) or 1+Eu(III)), which was attributed to large tilting angles between molecules. By AFM observations, these gels showed well-defined right-handed helical nanofibers formed by coordination bonds in which the helical pitch lengths were strongly dependent on the concentrations of lanthanide ions. In particular, the large luminescence intensity of gel-Tb exhibited a smaller helical pitch length than that of gel-1 due to relatively weak π-π stacking with large tilting angles between molecules. The luminescence intensities were enhanced linearly with increasing concentrations of lanthanide ions. This is the first example of the correlation between the helical pitch length and the luminescence intensity of supramolecular materials. The coordination bonding in supramolecular hydrogels had a strong influence on rheological properties. We also developed a water-compatible inkjet printing system to generate luminescent supramolecular gels on A4-sized paper. The images of a logo and the text were composed of three different emissions and were well-printed on A4 sized paper coated with gel-1.

Reinforcement of a sugar-based bolaamphiphile/functionalized graphene oxide composite gel: rheological and electrochemical properties.

A sugar-based bolaamphiphile/graphene oxide composite hydrogel has been prepared using simple mixing. Unlike the corresponding sugar-based native gel, the composite gel exhibits a fibrillar structure with a 10-20 nm fiber diameter. The composite gel forms an interdigitated bilayer structure incorporating intermolecular hydrogen-bonding interactions. The composite gel formation did not change the beneficial electrical properties of graphene offering the potential for integration of this new material into electronic systems. Interestingly, the mechanical and electrochemical properties of the composite gel are both dramatically enhanced when compared to the native gel, thereby reflecting that the functionalized graphene oxide layers are efficiently intercalated within the composite gel structure.

Sulphur–carbon composites for Li/S batteries

Abstract Structural and electrochemical properties of various types of sulphur–carbon composites were reviewed to propose approaching ways for the development of lithium/sulphur battery with high energy density and good cycle performance. To improve the electrochemical properties of a sulphur cathode, carbon and polymer materials are applied to sulphur composites: multiwalled nanotube (MWNT), graphene, CMK-3 and activated carbon; and polyaniline (PANi), polyacrylonitrile and polythiophene (PTh). These can serve conducting paths and a polysulphide reservoir to enhance the electrical conductivity of the sulphur cathode and effectively prevent dissolution of polysulphides. And the composites are categorised in two parts such as mixed type sulphur composites and embedded type sulphur composites. Among the sulphur–carbon composites, the hollow carbon capsule/S composite prepared by a geometric control and an infusion method of sulphur in sulphur carbon composite electrode, demonstrated the best electrochemical properties.

Transfer and Dynamic Inversion of Coassembled Supramolecular Chirality through 2D-Sheet to Rolled-Up Tubular Structure

Transfer and inversion of supramolecular chirality from chiral calix[4]arene analogs (3D and 3L) with an alanine moiety to an achiral bipyridine derivative (1) with glycine moieties in a coassembled hydrogel are demonstrated. Molecular chirality of 3D and 3L could transfer supramolecular chirality to an achiral bipyridine derivative 1. Moreover, addition of 0.6 equiv of 3D or 3L to 1 induced supramolecular chirality inversion of 1. More interestingly, the 2D-sheet structure of the coassembled hydrogels formed with 0.2 equiv of 3D or 3L changed to a rolled-up tubular structure in the presence of 0.6 equiv of 3D or 3L. The chirality inversion and morphology change are mainly mediated by intermolecular hydrogen-bonding interactions between the achiral and chiral molecules, which might be induced by reorientations of the assembled molecules, confirmed by density functional theory calculations.

Electrochemical properties of magnesium electrolyte with organic solvent

Three kinds of electrolytes are investigated to find out the proper electrolyte for magnesium battery. Propylene carbonate electrolyte using magnesium salt of Mg(ClO4)2 shows a higher ionic conductivity than that of dimethyl carbonate and tri(ethyleneglycol dimethyl)ether (TRGDME) but low decomposition potential. The TRGDME electrolyte with 0.5?M Mg(ClO4)2 has a higher ionic conductivity of 6 ? 10?4 ?S?cm?1 than that of dimethyl carbonate, but the decomposition voltage of the electrolyte is over 3.0?V which can be used for Mg/S cell.

Electrochemical and interfacial properties of (PEO)10LiCF3SO3−Al2O3 nanocomposite polymer electrolytes using ball milling

Electrochemical and interfacial properties of (PEO)10LiCF3SO3−Al2O3 composite polymer electrolytes (CPEs) prepared by either ball milling or stirring are reported. Ball milling was introduced into a slurry preparative technique utilizing PEO, lithium salt and Al2O3 powder ranging from 5 to 15 wt.%. The ionic conductivity was increased by ball milling over a range of temperatures. In particular, a significant increase at low temperature below the melting point of crystalline PEO was observed. Interfacial stability between lithium electrode and CPE was significantly improved by the addition of alumina as well as by ball milling. The electrochemical stability window produced by (PEO)10LiCF3SO3−Al2O3 ball milling was higher than that of stirring, which was about 4.4 V. Charge/discharge performance of Li/CPE/S cells with (PEO)10LiCF3SO3−Al2O3-12 hr ball milling was superior to that of a pristine polymer electrolyte due to the low interface resistance and high ionic conductivity.

Retracted Article: Spatially resolved mechanical properties of photo-responsive azobenzene-based supramolecular gels

The viscoelastic and stiffness properties of azobenzene-based supramolecular gels have been investigated by rheometry and AFM. Interestingly, the viscoelastic properties of cis-isomers were 8–10 fold enhanced in comparison to the trans-isomer, which was a unique phenomenon. More interestingly, Youngs modulus of gels increased linearly with time of UV irradiation. The stiffness of gels was finely controlled in the spatial micro-scale environment. The improved mechanical strength was attributed to electrostatic interaction with the production of radicals of the gelators.

Non-peptidic guanidinium-functionalized silica nanoparticles as selective mitochondria-targeting drug nanocarriers

We report on the design and fabrication of a Fe3O4 core-mesoporous silica nanoparticle shell (Fe3O4@MSNs)-based mitochondria-targeting drug nanocarrier. A guanidinium derivative (GA) was conjugated onto the Fe3O4@MSNs as the mitochondria-targeting ligand. The fabrication of the Fe3O4@MSNs and their functionalization with GA were carried out by the sol-gel polymerization of alkoxysilane groups. Doxorubicin (DOX), an anti-cancer drug, was loaded into the pores of a GA-attached Fe3O4@MSNs due to both its anti-cancer properties and to allow for the fluorescent visualization of the nanocarriers. The selective and efficient mitochondria-targeting ability of a DOX-loaded GA-Fe3O4@MSNs (DOX/GA-Fe3O4@MSNs) was demonstrated by a co-localization study, transmission electron microscopy, and a fluorometric analysis on isolated mitochondria. It was found that the DOX/GA-Fe3O4@MSNs selectively accumulated into mitochondria within only five minutes; to the best of our knowledge, this is the shortest accumulation time reported for mitochondria targeting systems. Moreover, 2.6 times higher amount of DOX was accumulated in mitochondria by DOX/GA-Fe3O4@MSNs than by DOX/TPP-Fe3O4@MSNs. A cell viability assay indicated that the DOX/GA-Fe3O4@MSNs have high cytotoxicity to cancer cells, whereas the GA-Fe3O4@MSNs without DOX are non-cytotoxic; this indicates that the DOX/GA-Fe3O4@MSNs have great potential for use as biocompatible and effective mitochondria-targeting nanocarriers for cancer therapy.