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Abstract To elucidate the gas generation mechanism due to electrolyte decomposition in commercial lithium-ion cells after long cycling, we developed a device which can accurately determine the volume of generated gas in the cell. Experiments on LixC6/Li1−xCoO2 cells using electrolytes such as 1 M LiPF6 in propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) are presented and discussed. In the nominal voltage range (4.2–2.5 V), compositional change due mainly to ester exchange reaction occurs, and gaseous products in the cell are little. Generated gas volume and compositional change in the electrolyte are detected largely in overcharged cells, and we discussed that gas generation due to electrolyte decomposition involves different decomposition reactions in overcharged and overdischarged cells.

Abstract To elucidate the gas generation mechanism due to electrolyte decomposition in commercial lithium-ion cells after long cycling, we developed a device which can accurately determine the volume of generated gas in the cell. Experiments on LixC6/Li1−xCoO2 cells using electrolytes such as 1 M LiPF6 in propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) are presented and discussed. In the nominal voltage range (4.2–2.5 V), compositional change due mainly to ester exchange reaction occurs, and gaseous products in the cell are little. Generated gas volume and compositional change in the electrolyte are detected largely in overcharged cells, and we discussed that gas generation due to electrolyte decomposition involves different decomposition reactions in overcharged and overdischarged cells.

Proton conducting ceramics (PCC) cells are promising energy conversion devices that enable high efficiency energy conversion at lower temperature range, solving the challenge of conventional solid oxide cells (SOCs) due to the high operating temperature. Electrochemical performance and chemical stability of PCC electrolyte has been investigated in recent studies, suggesting that rare-earth doped Ba(Zr,Ce)O3 perovskite-type ceramics are optimal materials exhibiting high proton conductivity and chemical stability during operations. On the contrary, mechanical stability of these PCC electrolyte materials has not been evaluated despite the fact that the mechanical properties are critically important for achieving long-term stable operation as fuel cells or electrolyser cells. For the development of conventional SOCs, mechanical stability during high temperature operation was one of the most significant challenges to deal with, which was attained as a result of detailed studies on in-situ elastic properties of composing materials such as oxygen ion conducting electrolytes and residual stresses. Similarly, for PCC cells, mechanical properties of cells and composing materials have been of significant interest in order to achieve mechanically stable long-term operation, even though PCC cells operate at lower temperature than SOCs. Furthermore, the metal-supported (MS) structure which provides superior mechanical robustness compared to anode-supported (AS) structure is expected to be applied effectively to PCC cells, which are called proton conducting ceramics – metal-supported cells (PCC-MSCs), leading to greater necessity of the mechanical evaluation of the cells and composing materials. Electrolyte is the most crucial component in an electrochemical cell and must be mechanically stable because ion transport and gas tightness made by electrolyte determines electrical performance. However, there has been important concern that larger thermal stresses might be introduced in PCC cells compared to SOCs, resulting from the thermal expansion coefficient (TEC) mismatch between the electrode and electrolyte and from the chemical expansion by the hydration that occurs in a certain temperature range. The PCC electrolyte is highly in need of investigation on in-situ mechanical properties, especially on elastic properties. In this study, elastic properties of electrochemically promising PCC, Y-doped Ba(Zr,Ce)O3 perovskite-type ceramics, were investigated under high temperature conditions. Elastic moduli such as Young’s modulus and Poisson’s ratio were measured by the method that we previously developed for elastic investigation in high temperature conditions using ultrasonic waves. This method enables highly accurate and repetitive examination of elastic properties at high temperatures in materials with poor sinterability including PCC by measuring ultrasonic sound velocities in pellets typically fabricated for electrochemical tests. Pellets of BaZr1-xYxO3-δ (BZY) with different concentrations of doped yttrium, BaZr0.9Y0.1O3-δ (BZY10), BaZr0.85Y0.15O3-δ (BZY15), and BaZr0.8Y0.2O3-δ (BZY20), were fabricated. Additionally, pellets of BaZryCe1-yY0.1O3-δ (BZCY) with different ratio of Ce to Zr, BaZr0.7Ce0.2Y0.1O3-δ (BZCY721) and BaZr0.8Ce0.1Y0.1O3-δ (BZCY811) were fabricated. Powders of PCCs above were consolidated to be thick rounded shape and sintered in air. Each prepared sample was set in an electric furnace in laboratory air atmosphere and sound velocities were measured with the sample slowly heated up to 700 °C and subsequently cooled down to room temperature to calculate elastic moduli at each measuring point. In the first series of heating and cooling measurements for as-sintered samples, hysteresis on elastic moduli in intermediate temperature range was observed. We repeatedly conducted a series of heating and cooling measurements several times, and then the hysteresis was not observed any further. Fig.1 shows final state Young’s modulus of BZCY721, BZCY811, and BZY10 (BZCY901) without hysteresis. Elastic moduli at room temperature have not changed through multiple heating and cooling measurements, and crystal structures and lattice parameters were also confirmed to remain constant by x-ray diffraction (XRD) analysis. The hysteresis found in a specific temperature range suggests that elastic moduli were influenced presumably by a change in defect structure of PCC caused by hydration or defect association of oxygen vacancies and dopants. At room temperature, Young’s modulus decreased with the increment of Ce concentration by 16 % from BZY10 to BZCY721. When materials have the same crystalline structure, Young’s modulus generally decreases as mean atomic volume of the base crystal increases. Because BaCeO3 has larger mean atomic volume than BaZrO3, this observation is qualitatively reasonable. However, in high temperatures, the difference became significant only for BZCY721, Young’s modulus decreased by 30 % from that at room temperature in BZCY721. These results suggest that Ce substitution causes different high temperature dependences. Figure 1

Proton conducting ceramics (PCC) cells are promising energy conversion devices that enable high efficiency energy conversion at lower temperature range, solving the challenge of conventional solid oxide cells (SOCs) due to the high operating temperature. Electrochemical performance and chemical stability of PCC electrolyte has been investigated in recent studies, suggesting that rare-earth doped Ba(Zr,Ce)O3 perovskite-type ceramics are optimal materials exhibiting high proton conductivity and chemical stability during operations. On the contrary, mechanical stability of these PCC electrolyte materials has not been evaluated despite the fact that the mechanical properties are critically important for achieving long-term stable operation as fuel cells or electrolyser cells. For the development of conventional SOCs, mechanical stability during high temperature operation was one of the most significant challenges to deal with, which was attained as a result of detailed studies on in-situ elastic properties of composing materials such as oxygen ion conducting electrolytes and residual stresses. Similarly, for PCC cells, mechanical properties of cells and composing materials have been of significant interest in order to achieve mechanically stable long-term operation, even though PCC cells operate at lower temperature than SOCs. Furthermore, the metal-supported (MS) structure which provides superior mechanical robustness compared to anode-supported (AS) structure is expected to be applied effectively to PCC cells, which are called proton conducting ceramics – metal-supported cells (PCC-MSCs), leading to greater necessity of the mechanical evaluation of the cells and composing materials. Electrolyte is the most crucial component in an electrochemical cell and must be mechanically stable because ion transport and gas tightness made by electrolyte determines electrical performance. However, there has been important concern that larger thermal stresses might be introduced in PCC cells compared to SOCs, resulting from the thermal expansion coefficient (TEC) mismatch between the electrode and electrolyte and from the chemical expansion by the hydration that occurs in a certain temperature range. The PCC electrolyte is highly in need of investigation on in-situ mechanical properties, especially on elastic properties. In this study, elastic properties of electrochemically promising PCC, Y-doped Ba(Zr,Ce)O3 perovskite-type ceramics, were investigated under high temperature conditions. Elastic moduli such as Young’s modulus and Poisson’s ratio were measured by the method that we previously developed for elastic investigation in high temperature conditions using ultrasonic waves. This method enables highly accurate and repetitive examination of elastic properties at high temperatures in materials with poor sinterability including PCC by measuring ultrasonic sound velocities in pellets typically fabricated for electrochemical tests. Pellets of BaZr1-xYxO3-δ (BZY) with different concentrations of doped yttrium, BaZr0.9Y0.1O3-δ (BZY10), BaZr0.85Y0.15O3-δ (BZY15), and BaZr0.8Y0.2O3-δ (BZY20), were fabricated. Additionally, pellets of BaZryCe1-yY0.1O3-δ (BZCY) with different ratio of Ce to Zr, BaZr0.7Ce0.2Y0.1O3-δ (BZCY721) and BaZr0.8Ce0.1Y0.1O3-δ (BZCY811) were fabricated. Powders of PCCs above were consolidated to be thick rounded shape and sintered in air. Each prepared sample was set in an electric furnace in laboratory air atmosphere and sound velocities were measured with the sample slowly heated up to 700 °C and subsequently cooled down to room temperature to calculate elastic moduli at each measuring point. In the first series of heating and cooling measurements for as-sintered samples, hysteresis on elastic moduli in intermediate temperature range was observed. We repeatedly conducted a series of heating and cooling measurements several times, and then the hysteresis was not observed any further. Fig.1 shows final state Young’s modulus of BZCY721, BZCY811, and BZY10 (BZCY901) without hysteresis. Elastic moduli at room temperature have not changed through multiple heating and cooling measurements, and crystal structures and lattice parameters were also confirmed to remain constant by x-ray diffraction (XRD) analysis. The hysteresis found in a specific temperature range suggests that elastic moduli were influenced presumably by a change in defect structure of PCC caused by hydration or defect association of oxygen vacancies and dopants. At room temperature, Young’s modulus decreased with the increment of Ce concentration by 16 % from BZY10 to BZCY721. When materials have the same crystalline structure, Young’s modulus generally decreases as mean atomic volume of the base crystal increases. Because BaCeO3 has larger mean atomic volume than BaZrO3, this observation is qualitatively reasonable. However, in high temperatures, the difference became significant only for BZCY721, Young’s modulus decreased by 30 % from that at room temperature in BZCY721. These results suggest that Ce substitution causes different high temperature dependences. Figure 1

The effects of redox potential and electric charge on the rate of electron-transfer reaction by a two-electron process were investigated. For electron donors, beta-NADH, beta-NADPH and alpha-NADH were used; they have similar structures but different charges and different redox potentials. For electron acceptors, the following 5-ethylphenazine derivatives were used: 1-(3-carboxypropyloxy)-5-ethylphenazine, 1-(3-ethoxycarbonylpropyloxy)-5-ethylphenazine, and 1-[N-(2-aminoethyl)carbamoylpropyloxy]-5-ethylphenazine. They have similar structures and different charges. Using these donors and acceptors, the potential and the charge effects were estimated separately. In the potential effect, a linear free energy relationship was observed for the change in the redox potential of the donor with a Brønsted slope of about unity. On the other hand, the slope for the change in the potential of the acceptor was about 0.5. These results show that the potential effect due to electron donors is different from that due to electron acceptors. A linear relationship was also observed between activation free energy and electrostatic force (or potential). The redox potential effect and the electrostatic effect are independent and additive. New theory for the mechanism of electron-transfer reactions is needed to explain these results.

The effects of redox potential and electric charge on the rate of electron-transfer reaction by a two-electron process were investigated. For electron donors, beta-NADH, beta-NADPH and alpha-NADH were used; they have similar structures but different charges and different redox potentials. For electron acceptors, the following 5-ethylphenazine derivatives were used: 1-(3-carboxypropyloxy)-5-ethylphenazine, 1-(3-ethoxycarbonylpropyloxy)-5-ethylphenazine, and 1-[N-(2-aminoethyl)carbamoylpropyloxy]-5-ethylphenazine. They have similar structures and different charges. Using these donors and acceptors, the potential and the charge effects were estimated separately. In the potential effect, a linear free energy relationship was observed for the change in the redox potential of the donor with a Brønsted slope of about unity. On the other hand, the slope for the change in the potential of the acceptor was about 0.5. These results show that the potential effect due to electron donors is different from that due to electron acceptors. A linear relationship was also observed between activation free energy and electrostatic force (or potential). The redox potential effect and the electrostatic effect are independent and additive. New theory for the mechanism of electron-transfer reactions is needed to explain these results.

ADP ribosylation is considered one of the important covalent modifications of cellular proteins catalyzed by ADP ribosyltransferase, which transfers ADP ribose moiety of NAD to an acceptor protein. Because a growing body of evidence has suggested significant biological roles for mono-ADP ribosylations in transmembrane signal transduction and other cell metabolism, how alcohol intake alters them is of interest. Cholera toxin and pertussis toxin have been widely used as probes to investigate the roles of GTP-binding proteins (G-proteins) in the transduction of hormonal and sensory signals. We first tested effects of long-term alcohol intake on these toxin-catalyzed ADP ribosylations of G-proteins in rat liver plasma membranes. Treatment of rat liver plasma membrane with [32P]NAD and thiol-preactivated cholera toxin resulted in the labeling of a 44-kD band, most likely an α-subunit of the stimulatory GTP-binding protein, the extent of which was much greater in alcohol-fed rats than in pair-fed controls. Analogous experiments with pertussis toxin also demonstrated enhancement of toxin-catalyzed ADP ribosylation of the inhibitory GTP-binding protein after long-term alcohol intake. More interesting was that long-term alcohol intake remarkably stimulated endogenous mono-ADP ribosylation of a 58-kD protein in a GTP-dependent manner. In vitro, ethanol (50 mmol/L) or a single load of ethanol (3 gm/kg) did not stimulate the reaction. Thus long-term alcohol intake stimulated both toxin-catalyzed and endogenous mono-ADP ribosylations of proteins in rat liver plasma membranes. Pursuit of alcohol interaction with mono-ADP ribosylation may provide an interesting approach to the study of alcohol's effects on the liver. (HEPATOLOGY 1993;18:870-873).

ADP ribosylation is considered one of the important covalent modifications of cellular proteins catalyzed by ADP ribosyltransferase, which transfers ADP ribose moiety of NAD to an acceptor protein. Because a growing body of evidence has suggested significant biological roles for mono-ADP ribosylations in transmembrane signal transduction and other cell metabolism, how alcohol intake alters them is of interest. Cholera toxin and pertussis toxin have been widely used as probes to investigate the roles of GTP-binding proteins (G-proteins) in the transduction of hormonal and sensory signals. We first tested effects of long-term alcohol intake on these toxin-catalyzed ADP ribosylations of G-proteins in rat liver plasma membranes. Treatment of rat liver plasma membrane with [32P]NAD and thiol-preactivated cholera toxin resulted in the labeling of a 44-kD band, most likely an α-subunit of the stimulatory GTP-binding protein, the extent of which was much greater in alcohol-fed rats than in pair-fed controls. Analogous experiments with pertussis toxin also demonstrated enhancement of toxin-catalyzed ADP ribosylation of the inhibitory GTP-binding protein after long-term alcohol intake. More interesting was that long-term alcohol intake remarkably stimulated endogenous mono-ADP ribosylation of a 58-kD protein in a GTP-dependent manner. In vitro, ethanol (50 mmol/L) or a single load of ethanol (3 gm/kg) did not stimulate the reaction. Thus long-term alcohol intake stimulated both toxin-catalyzed and endogenous mono-ADP ribosylations of proteins in rat liver plasma membranes. Pursuit of alcohol interaction with mono-ADP ribosylation may provide an interesting approach to the study of alcohol's effects on the liver. (HEPATOLOGY 1993;18:870-873).

The current study was carried out with particular emphasis on the association between phonetic function tests and alterations in the appearance of the hypopharyngeal and laryngeal mucosa, such as capillary dilatation, edema, and vocal fold injection after alcohol intake. The results demonstrated the occurrence of previously unrecognized pathophysiological changes associated with synchronous phonetic functions in the vocal pathway after alcohol intake. Serum ethanol and aldehyde concentration levels were evaluated hourly for 2.5 h after ingestion of alcohol. When an electronystagmogram showed the typical pattern of alcohol intake, the study was initiated. Occasionally, rhinography was performed on subjects complaining of a stuffy nose after alcohol intake.