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Chuang Wei-Tsung,Jeng U-Ser,Sheu Hwo-Shuenn,Hong Po-Da The Polymer Society of Korea 2006 Macromolecular Research Vol.14 No.1
We conducted simultaneous, small-angle, X-ray scattering/differential scanning calorimetry (SAXS/DSC) and simultaneous, wide-angle, X-ray scattering (WAXS)/DSC measurements for a polymer blend of poly($\varepsilon$-caprolactone)/poly(ethylene glycol)(PCL/PEG). The time-dependent SAXS/DSC and WAXS/DSC results, measured while the system was quenched below the melting temperature of PCL from a melting state, revealed the competitive behavior between liquid-liquid phase separation and crystallization in the polymer blend. The time-dependent structural evolution extracted from the SAXS/WAXS/DSC results can be characterized by the following four stages in the PCL crystallization process: the induction (I), nucleation (II), growth (III), and late (IV) stages. The influence of the liquid-liquid phase separation on the crystallization of PCL was also observed by phase-contrast microscope and polarized microscope with 1/4$\lambda$ compensator.
Zhang, Jiliang,Lau, Vincent Wing-hei,Liao, Chang-Zhong,Wong, Kam Wa,Lee, Gi-Hyeok,Zou, Feng,Chang, Chung-Kai,Sheu, Hwo-Shuenn,Kang, Yong-Mook American Chemical Society 2019 Chemistry of materials Vol.31 No.4
<P>Doping is one of the most important ways to tailor the performance of energy materials. However, the crystal structure of doped materials is usually oversimplified as a simple substitution of dopants. Here, we characterized the doped α-Fe<SUB>2</SUB>O<SUB>3</SUB> with different Cu cations using synchrotron X-ray diffraction, X-ray absorption, and X-ray photoelectron spectroscopy, and electrochemically evaluated it as an anode in lithium batteries. The results suggest that doping is not the simple replacement of Fe<SUP>3+</SUP> sites by Cu<SUP>2+</SUP> or Cu<SUP>+</SUP> but induces a complex local structure change, which may be a characteristic of this class of materials. In Cu<SUP>+</SUP>-doped samples, Cu<SUP>+</SUP> not only replaces the Fe<SUP>3+</SUP> site and distorts the FeO<SUB>6</SUB> octahedra, but also gives rise to oxygen vacancies in CuO<SUB>6</SUB> octahedra in the bulk structure and peroxides at the surface, leading to uniform precipitation of Cu as a conductive and buffering agent. These CuO<SUB>6</SUB> octahedra also facilitate homogeneous reactions (electrochemical reduction of Cu<SUP>+</SUP> and Fe<SUP>3+</SUP> together) and the formation of high quality solid-electrolyte interface (SEI) layers. All these factors account for its improved electrochemical performance (discharge capacity of 841(25) mAh/g against 758(21) mAh/g of undoped one, after 80 cycles at 100mA/g). In Cu<SUP>2+</SUP>-doped samples, Cu<SUP>2+</SUP> takes both Fe<SUP>3+</SUP> and empty octahedral interstitial sites, forming linear clusters of three neighboring CuO<SUB>6</SUB> octahedra. Such medium-range phase separation causes electrochemical reduction to metallic Cu before the reduction of Fe<SUP>3+</SUP>, leading to inactive surface Cu that contributes to poor SEI layers and deteriorates its electrochemical performances. The present work allows a better understanding of how doping affects the crystallographic structures and offers insights into how this strategy can be employed to improve electrochemical performance, in contrast to the ambiguity over material properties associated with the commonly accepted model of simple atomic replacement.</P> [FIG OMISSION]</BR>