RESUMEN
We report rheology and structural studies of poly(lactide)-poly(ethylene oxide)-poly(lactide) (PLA-PEO-PLA) triblock copolymer gels with various ratios of l-lactide and d-lactide in the PLA blocks. These materials form associative micellar gels in water, and previous work has shown that stereoregular triblocks with a l/d ratio of 100/0 form much stiffer gels than triblocks with a 50/50 l/d ratio. Our systems display an unexpected maximum in the storage modulus, G', of the hydrogels at intermediate l/d ratio. The impact of stereochemistry on the rheology is very striking; gels with an l/d ratio of 85/15 have storage moduli that are â¼1-2 orders of magnitude higher than hydrogels with l/d ratios of 100/0. No stereocomplexation is observed in the gels, although PLLA crystals are found for gels with l/d ratios of 95/5 and 90/10, and SANS results show a decrease in the intermicellar spacing for intermediate l/d ratios. We expect the dominant contribution to the elasticity of the gels to be intermicellar bridging chains and attribute the rheology to a competition between an increase in the time for PLA endblocks to pull out of micelles as the l/d ratio is increased and PLLA crystallization occurs, and a decrease in the number of bridging chains for micelles with crystalline PLA domains, as formation of bridges may be hindered by crowded crystalline PLA domains. These results provide a new strategy for controlling the rheology of PLA-based hydrogels for potential applications in biomaterials, as well as fundamental insights into how intermicellar interactions can be tuned via stereochemistry.
Asunto(s)
Dioxanos/química , Fenómenos Mecánicos , Nanoestructuras/química , Poliésteres/química , Polietilenglicoles/química , Reología , Geles , EstereoisomerismoRESUMEN
Lithium (Li) metal serving as an anode has the potential to double or triple stored energies in rechargeable Li batteries. However, they typically have short cycling lifetimes due to parasitic reactions between the Li metal and electrolyte. It is critically required to develop early fault-detection methods for different failure mechanisms and quick lifetime-prediction methods to ensure rapid development. Prior efforts to determine the dominant failure mechanisms have typically required destructive cell disassembly. In this study, non-destructive diagnostic method based on rest voltages and coulombic efficiency are used to easily distinguish the different failure mechanisms-from loss of Li inventory, electrolyte depletion, and increased cell impedance-which are deeply understood and well validated by experiments and modeling. Using this new diagnostic method, the maximum lifetime of a Li metal cell can be quickly predicted from tests of corresponding anode-free cells, which is important for the screenings of electrolytes, anode stabilization, optimization of operating conditions, and rational battery design.
RESUMEN
Although the determination of site occupancies is often a major goal in Rietveld refinement studies, the accurate refinement of site occupancies is exceptionally challenging due to many correlations and systematic errors that have a hidden impact on the final refined occupancy parameters. Through the comparison of results independently obtained from neutron and synchrotron powder diffraction, improved approaches capable of detecting occupancy defects with an exceptional sensitivity of 0.1% (absolute) in the class of layered NMC (Li[NixMnyCoz]O2) Li-ion battery cathode materials have been developed. A new method of visualizing the diffraction parameter space associated with crystallographic site scattering power through the use of f* diagrams is described, and this method is broadly applicable to ternary compounds. The f* diagrams allow the global minimum fit to be easily identified and also permit a robust determination of the number and types of occupancy defects within a structure. Through a comparison of neutron and X-ray diffraction results, a systematic error in the synchrotron results was identified using f* diagrams for a series of NMC compounds. Using neutron diffraction data as a reference, this error was shown to specifically result from problems associated with the neutral oxygen X-ray atomic form factor and could be eliminated by using the ionic O2- form factor for this anion while retaining the neutral form factors for cationic species. The f* diagram method offers a new opportunity to experimentally assess the quality of atomic form factors through powder diffraction studies on chemically related multi-component compounds.