Study on ferrocene derivatives diffusion dynamics in polymer electrolyte by solid-state voltammetry

The diffusion rates of seven ferrocene derivatives have been estimated in polyelectrolyte PEG . LiClO4 by using non-steady-state chronoamperometry. The D-app of ferrocene derivatives increases with temperature, and the dependency of D-app on temperature obeys the Arrhenius equation. The D-app of ferrocene derivatives decreases with increasing size of electroactive species. The Delta D-app values of D-T>Tm and D-T T-m in the polyelectrolyte. On the other hand, the diffusion behaviour of ferrocene derivatives is qualitatively analyzed by using cyclic voltammetry. Copyright (C) 1996 Elsevier Science Ltd

An investigation on ion solvation and ion association in a gel-type solid state polymer electrolyte

Ion salvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)-LiClO4 gel-type polymer electrolytes were investigated. It was found that the fraction of solute existing as single ions (alpha(i)) decreases and that of triple ions (alpha(i)) increases linearly with increasing LiClO4 concentration, while for ion pairs, as the salt concentration increases, its fraction (alpha(p)) increases first and then falls down. The findings can be rationalized by the fact that the ionic conductance of the polymer electrolyte may be mainly contributed by triple ions and higher ionic aggregates with unequal numbers of positive and negative charges in the salt concentration range of practical significance, i.e. in the range of 0.5-1.5 mol/l. The temperature dependence of these fractions was also examined. In the case of tetraethylene glycol as the solvent, alpha(i) and alpha(p) increase as the temperature is raised, but alpha(t) decreases as the temperature increases from 25 degrees C to 85 degrees C. It seems that the increase of alpha(i) and alpha(p) results from the redissociation of triple ions at higher temperature, The same changing trend of those fractions is also observed when PEG(400) is used as the solvent.

SOLID-STATE VOLTAMMETRY OF ELECTROACTIVE SOLUTES IN POLYMER SOLVENTS (PEO) AT ULTRAMICROELECTRODES

This paper describes the electrochemical oxidation and reduction of electroactive solutes which are dissolved in and diffusing through the polymer electrolyte solvent, poly(ethylene oxide) (PEO). The characteristics of electrochemical reactions in polymeric solutions are discussed, including how rigid solvent environments affect mass transport rates, and the transport phenomenon of electroactive species in PEO with bathing gases is explained by using the voltammetric theory of ultramicroelectrodes. The possibility that the microelectrode coated with PEO film can be used as a gas sensor has been discussed.

MICROSTRUCTURE ANALYSIS OF 3 SEGMENTED COPOLYMERS CONTAINING POLYDIMETHYLSILOXANE BY SOLID-STATE HIGH-RESOLUTION NMR

The microstructure of two bicomponent and one tricomponent segmented copolymers, based on polydimethylsiloxane, poly(p-hydroxystyrene) or/and polysulfone, were investigated using an extended Goldman-Shen pulse sequence, proton spin-spin relaxation measurements, and C-13 and Si-29 NMR spectra. The results indicate that there exist four phases with different sizes, components and morphological structure in the segmented copolymers studied in this work, i. e., a rigid-chain phase of very slow motion, a rigid-chain-rich phase of slow motion, a flexible-chain-rich phase of fast motion and a flexible-chain phase of faster motion. The sizes of different domains, calculated from the spin diffusion rates, are about 50-100 angstrom for the flexible-chain-rich phase of fast motion and 200-300 angstrom for the flexible-chain phase of faster motion. The relative quantities of polydimethylsiloxane in the flexible-chain phase of fast motion are slightly different in different kinds of segmented copolymers.

A HIGH-RESOLUTION SOLID-STATE NMR AND DSC STUDY OF MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF POLY(VINYL ALCOHOL)/POLY(N-VINYL-2-PYRROLIDONE) BLENDS

Blends of crystallizable poly(vinyl alcohol) (PVA) with poly(N-vinyl-2-pyrrolidone) (PVPy) were studied by C-13 cross-polarization/magic angle spinning (CP/MAS) n.m.r. and d.s.c. The C-13 CP/MAS spectra show that the blends were miscible on a molecular level over the whole composition range studied, and that the intramolecular hydrogen bonds of PVA were broken and intermolecular hydrogen bonds between PVA and PVPy formed when the two polymers were mixed. The results of a spin-lattice relaxation study indicate that blending of the two polymers reduced the average intermolecular distance and molecular motion of each component, even in the miscible amorphous phase, and that addition of PVPy into PVA has a definite effect on the crystallinity of PVA in the blends over the whole composition range, yet there is still detectable crystallinity even when the PVPy content is as high as 80 wt%. These results are consistent with those obtained from d.s.c. studies.

HIGH-TEMPERATURE SUPERCONDUCTOR, YBA2CU3O7-X AS ALL-SOLID-STATE LITHIUM CELL

The utility of the high-temperature superconductor, YBa2Cu3O7-x as the cathode material for an all-solid-state lithium cell has been examined. The capacity of YBa2Cu3O7-x is 223 mA h g-1 and the discharge efficiency is > 92%. Measurements of a.c. impedance show that the charge-transfer resistance at the interface of the electrolyte/cathode is very low and increases with the depth-of-discharge of the battery. Studies using X-ray photoelectron spectroscopy (XPS) reveal that the cathode becomes doped with Li+ ions as the cell discharges.

A HIGH-RESOLUTION SOLID-STATE NMR-STUDY OF THE MISCIBILITY, MORPHOLOGY, AND TOUGHENING MECHANISM OF POLYSTYRENE WITH POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

An extended Goldman-Shen pulse sequence was used to observe indirectly the proton spin diffusion in the blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxides) (PPO). The results indicate that the average distance between PS and PPO is less than 5 angstrom in the intimately mixed phase, but there are heterogeneous domains on a 100-angstrom scale. The data of spin relaxation of carbons, T1(C), for homopolymers and their blends suggest that there is a strong pi-pi electron conjugation interaction between the aromatic rings of PS and those of PPO, while the aromatic rings of PPO drive the aromatic rings of PS to move cooperatively. It is the cooperative motion that markedly improves the impact strength of PS.

AN ALL-SOLID-STATE LITHIUM POLYANILINE RECHARGEABLE CELL

The performance of an all-solid-state cell having a lithium negative electrode, a modified polyethylene oxide (PEO)-epoxy resin (ER) electrolyte, and a polyaniline (PAn) positive electrode has been studied using cyclic voltammetry, charge/discharge cycling, and polarization curves at various temperatures. The redox reaction of the PAn electrode at the PAn/modifed PEO-ER interface exhibits good reversibility. At 50-80-degrees-C, the Li/PEO-ER-LiClO4/PAn cell shows more than 40 charge/discharge cycles, 90% charge/discharge efficiency, and 54 W h kg-1 discharge energy density (on PAn weight basis) at 50-mu-A between 2 and 4 V. The polarization performance of the battery improves steadily with increase in temperature.

In situ solid state NMR observation of the methanol-to-hydrocarbons (MTH) process over nanosized and microsized HZSM-5 zeolites

The formation of surface alkoxy species on nanosized HZSM-5 and microsized HZSM-5, after exposure to methanol and subsequent conversion to olefins, has been investigated by in situ solid state NMR. Compared to microsized HZSM-5 zeolite, the nanosized HZSM-5 zeolite was found to exhibit a higher affinity for trapping methanol species. Activation of the adsorbed methanol species resulted in the formation of various surface alkoxy species with different rigid characters, including the carboxylate-like surface species, as evidenced by deconvolution of the related spectra. The present results support the existence of the so-called carbon-pool in the conversion of methanol, which serves as the reaction precursor not only for the coupling of the species to form olefins, but also for uncontrolled polymerization to give coke on the surface. The nanosized HZSM-5 shows a distinct resistance to the formation of carbonaceous deposits on the surface.

A high-resolution solid-state NMR study on nano-structured HZSM-5 zeolite

Variations in the structure and acidity properties of HZSM-5 zeolites with reduction in crystal sizes down to nanoscale (less than 100 nm) have been investigated by XRD, TEM and solid-state NMR with a system capable of in situ sample pretreatment. As evidenced by a combination of Al-27 MAS NMR, Si-29 MAS, CP/MAS NMR and H-1 MAS NMR techniques, the downsize of the zeolite crystal leads to an obvious line broadening of the Al-27, Si-29 MAS NMR spectrum, an increasing of the silanol concentration on the external surface, and a pronounced alteration of the acidity distribution between the external and internal surfaces of the zeolite. In a HZSM-5 zeolite with an average size at about 70 nm, the nonacidic hydroxyl groups (silanols) are about 14% with respect to the total amount of Si, while only 4% of such hydroxyl groups exist in the same kind of zeolite at 1000 nm crystal size. The result of H-1 MAS NMR obtained using Fluorinert(R) FC-43 (perfluorotributyl amine) as a probe molecule demonstrates that most of the silanols are located on the external surface of the zeolite. Moreover, the concentration of Bronsted acid sites on the external surface of the nano-structured zeolite appears to be distinctly higher than that of the microsized zeolite.