Quantifying oxygen distortions in lithium-rich transition-metal-oxide cathodes using ABF STEM.

Lithium-rich cathodes can store excess charge beyond the transition metal redox capacity by participation of oxygen in reversible anionic redox reactions. Although these processes are crucial for achieving high energy densities, their structural origins are not yet fully understood. Here, we explore the use of annular bright-field (ABF) imaging in scanning transmission electron microscopy (STEM) to measure oxygen distortions in charged Li1.2Ni0.2Mn0.6O2. We show that ABF STEM data can provide positional accuracies below 20 pm but this is restricted to cases where no specimen mistilt is present, and only for a range of thicknesses above 3.5 nm. The reliability of these measurements is compromised even when the experimental and post-processing designs are optimised for accuracy and precision, indicating that extreme care must be taken when attempting to quantify distortions in these materials.

Ionic conductivity in crystalline polymer electrolytes.

Polymer electrolytes are the subject of intensive study, in part because of their potential use as the electrolyte in all-solid-state rechargeable lithium batteries. These materials are formed by dissolving a salt (for example LiI) in a solid host polymer such as poly(ethylene oxide) (refs 2, 3, 4, 5, 6), and may be prepared as both crystalline and amorphous phases. Conductivity in polymer electrolytes has long been viewed as confined to the amorphous phase above the glass transition temperature, Tg, where polymer chain motion creates a dynamic, disordered environment that plays a critical role in facilitating ion transport. Here we show that, in contrast to this prevailing view, ionic conductivity in the static, ordered environment of the crystalline phase can be greater than that in the equivalent amorphous material above Tg. Moreover, we demonstrate that ion transport in crystalline polymer electrolytes can be dominated by the cations, whereas both ions are generally mobile in the amorphous phase. Restriction of mobility to the lithium cation is advantageous for battery applications. The realization that order can promote ion transport in polymers is interesting in the context of electronically conducting polymers, where crystallinity favours electron transport.

Temperature dependence of the electrical resistance of sound and carious teeth.

Temperature variations are expected to influence measurement error in electrical resistance of teeth. It was the aim of this study to determine the changes in electrical behavior of extracted human teeth due to temperature changes in the range of room temperature to intra-oral temperature. Nine extracted teeth were selected, and the occlusal or an approximal surface was chosen for measurement. Carious involvement of the surfaces ranged from sound to cavitated. Electrical impedance spectroscopy sweeps in a frequency range of about 100 kHz to 10 Hz were completed at selected temperatures between 22 degrees C and 40 degrees C. After fitting the data to equivalent circuits that yielded parameter values for components of the equivalent circuit, we calculated the dc bulk resistance (Rh). The temperature dependence of Rb of the surfaces with different carious involvement was very similar, and the mean drop of Rb from 20 to 35 degrees C was 45% (SD 2%). It was concluded that the electrical resistance of sound and carious tooth surfaces is inversely related to temperature.

Impedance spectroscopy of teeth with and without approximal caries lesions--an in vitro study.

Caries diagnosis by the measurement of electrical resistance is hampered by polarization effects when dc or single-low-frequency ac currents are used. Electrical impedance spectroscopy, measuring impedance over a large range of frequencies, will provide more detailed information about the electrical characteristics of teeth. It was the aim of this study (a) to characterize the complex impedance behavior of whole extracted teeth, measured at the approximal surface, and (b) to identify parameters of the complex impedance behavior of the teeth which would be useful in distinguishing between degrees of carious involvement. Thirty-nine extracted premolar teeth with 59 unrestored and undamaged (excepting caries) approximal surfaces were selected. The tooth surfaces were divided into three groups according to their macroscopic appearance: sound (group S, n = 16), white- or brown-spot lesion present (group L, n = 33), or cavitated (group C, n = 10). The teeth were inserted into a jig which allowed for counter-electrode contact via a conducting gel. The working electrode consisted of a carbonated fiber material. Electrical impedance measurements were performed over a maximum range of about 1 MHz to 0.1 Hz. We analyzed electrical impedance data by fitting equivalent circuits. Fit was evaluated numerically and visually. The complex impedance spectra divided naturally into three groups which corresponded almost perfectly with the classifications of S,L, and C. The groups differed most in the dc resistance (Rdc), as calculated from the impedance parameters. Mean Rdc for groups S, L, and C were 68 M omega, 5.9 M omega, and 321 k omega, respectively. These means were significantly different from each other (log-transformed data, ANOVA, p < 0.001; Tukey multiple comparisons, p < 0.001). It is concluded that the in vitro performance of electrical impedance spectroscopy in differentiating among sound, non-cavitated carious, and cavitated approximal tooth surfaces is excellent.

Detection of dental decay and its extent using a.c. impedance spectroscopy.

Dental caries (decay), the most prevalent of diseases, represents a health problem of immense proportions. It principally affects posterior (back) teeth on occlusal (biting) and approximal (adjacent contacting) surfaces. Caries starts as a subsurface demineralization of enamel, may progress to the underlying dentine and, eventually, to cavitation of the surface. Accurate diagnosis before cavitation would permit targeted preventive treatment, thereby significantly improving dental health and reducing the need for expensive drilling and filling. Inaccessibility of caries initiation sites and recent changes in lesion morphology contribute to the relatively poor accuracy of conventional diagnostic methods. Among alternative techniques, measurements of electrical resistance have shown the most promise. Here we describe a new experimental technique that demonstrates an outstanding 100% correlation between a.c. impedance measurements of whole teeth and the actual extent of approximal caries in vitro. Only relatively minor modifications should be required to transfer the technique to in vivo applications.

Crystal Structure of the Polymer Electrolyte Poly(ethylene oxide)3:LiCF3SO3.

Ionically conducting polymers (polymer electrolytes) are under intensive investigation because they form the basis of all solid-state lithium batteries, fuel cells, and electrochromic display devices, as well as being highly novel electrolytes. Little is known about the structures of the many crystalline complexes that form between poly(ethylene oxide) and a wide range of salts. The crystal structure is reported of the archetypal polymer electrolyte poly(ethylene oxide)(3):LiCF(3)SO(3), which has been determined from powder x-ray diffraction data. The poly(ethylene oxide) (PEO) chain adopts a helical conformation parallel to the crystallographic b axis. The Li(+) cation is coordinated by five oxygen atoms-three ether oxygens and one from each of two adjacent CF(3)SO(3)(-) groups. Each CF(3)SO(3)(-) in turn bridges two Li(+) ions to form chains running parallel to and intertwined with the PEO chain. There are no interchain links between PEO chains, and the electrolyte can be regarded as an infinite columnar coordination complex.