Barım Gözde, Albayrak Cemal, Yılmaz Ezgi, Dag Ömer
Department of Chemistry, Bilkent University , 06800 Ankara, Turkey.
Langmuir. 2014 Jun 17;30(23):6938-45. doi: 10.1021/la5006105. Epub 2014 Jun 9.
Demand for ionically conducting materials, as membranes and electrodes, is one of the driving forces of current research in chemistry, physics, and engineering. The lithium ion is a key element of these materials, and its assembly into nanostructures and mesophases is important for the membrane and electrode technologies. In this investigation, we show that hydrated lithium salts (such as LiCl·xH2O and LiNO3·xH2O, x is as low as 1.5 and 3.0, respectively) and pluronics (triblock copolymer such as PX where X is 65, 85, 103, and 123) form lyotropic liquid crystalline mesophases (LLCM), denoted as LiY·xH2O-PX-n (Y is Cl(-) or NO3(-), and n is the salt/PX mole ratio). The structure of the mesophase is hexagonal over a broad salt concentration and transforms to a cubic mesophase and then to disordered gel phase with an increasing salt content of the mixtures. The mesophases are unstable at low salt contents and undergo a phase separation into pure pluronics and salt-rich LLCMs. The salt content of the ordered mesophase can be as high as 30 mole ratio for each pluronic, which is a record high for any known salted phases. The mesophases also display high ac ionic conductivities, reaching up to 21 mS/cm at room temperature (RT), and are sensitive to the water content. These mesophases can be useful as ion-conducting membranes and can be used as media for the synthesis of lithium-containing nanoporous materials.
对作为膜和电极的离子导电材料的需求是当前化学、物理和工程研究的驱动力之一。锂离子是这些材料的关键元素,将其组装成纳米结构和中间相对于膜和电极技术很重要。在本研究中,我们表明水合锂盐(如LiCl·xH₂O和LiNO₃·xH₂O,x分别低至1.5和3.0)和普朗尼克(三嵌段共聚物,如X为65、85、103和123的PX)形成溶致液晶中间相(LLCM),表示为LiY·xH₂O - PX - n(Y为Cl⁻或NO₃⁻,n为盐/PX摩尔比)。中间相的结构在很宽的盐浓度范围内为六方相,随着混合物中盐含量的增加转变为立方相,然后转变为无序凝胶相。中间相在低盐含量下不稳定,会相分离成纯普朗尼克和富盐LLCM。对于每种普朗尼克,有序中间相的盐含量可高达30摩尔比,这对于任何已知的盐相来说都是创纪录的高值。这些中间相还表现出高的交流电导率,在室温下高达21 mS/cm,并且对水含量敏感。这些中间相可用作离子导电膜,也可用作合成含锂纳米多孔材料的介质。