Liang Wuu-Jyh, Chen Ying-Pin, Wu Chien-Pang, Kuo Ping-Lin
Fire Protection and Safety Research Center, National Cheng Kung University, Tainan, Taiwan 70101, Republic of China.
J Phys Chem B. 2005 Dec 29;109(51):24311-8. doi: 10.1021/jp051026l.
The chemical-covalent polyether-siloxane hybrids (EDS) doped with various amounts of LiClO4 salt were characterized by FT-IR, DSC, TGA, and solid-state NMR spectra as well as impedance measurements. These observations indicate that different types of complexes by the interactions of Li+ and ClO4- ions are formed within the hybrid host, and the formation of transient cross-links between Li+ ions and ether oxygens results in the increase in T(g) of polyether segments and the decrease in thermal stability of hybrid electrolyte. Initially a cation complexation dominated by the oxirane-cleaved cross-link site and PEO block is present, and after the salt-doped level of O/Li+ = 20, the complexation through the PPO block becomes more prominent. Moreover, a significant degree of ionic association is examined in the polymer-salt complexes at higher salt uptakes. A VTF-like temperature dependence of ionic conductivity is observed in all of the investigated salt concentrations, implying that the diffusion of charge carrier is assisted by the segmental motions of the polymer chains. The behavior of ion transport in these hybrid electrolytes is further correlated with the interactions between ions and polymer host.
通过傅里叶变换红外光谱（FT-IR）、差示扫描量热法（DSC）、热重分析法（TGA）、固态核磁共振光谱以及阻抗测量等手段对掺杂不同量高氯酸锂（LiClO4）盐的化学共价聚醚-硅氧烷杂化材料（EDS）进行了表征。这些观察结果表明，在杂化主体中通过Li+和ClO4-离子的相互作用形成了不同类型的配合物，并且Li+离子与醚氧之间形成的瞬态交联导致聚醚链段的玻璃化转变温度（T(g)）升高，以及杂化电解质的热稳定性降低。最初存在一种以环氧乙烷裂解交联位点和聚环氧乙烷（PEO）嵌段为主导的阳离子络合作用，在盐掺杂水平达到氧/锂（O/Li+）= 20之后，通过聚丙二醇（PPO）嵌段的络合作用变得更加显著。此外，在较高盐吸收量的聚合物-盐配合物中检测到了显著程度的离子缔合。在所有研究的盐浓度下均观察到类似Vogel-Tammann-Fulcher（VTF）的离子电导率温度依赖性，这意味着电荷载流子的扩散受到聚合物链段运动的辅助。这些杂化电解质中的离子传输行为进一步与离子和聚合物主体之间的相互作用相关联。
