Cuerva Cristián, Caro-Campos Irene, Cano Mercedes, Rodríguez-Castellón Enrique, Kuhn Alois, García-Alvarado Flaviano, Schmidt Rainer
Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain.
Departamento de Química Inorgánica, Facultad de Ciencias, Instituto Interuniversitario de Investigación en Biorrefinerías I3B, Universidad de Málaga, 29071 Málaga, Spain.
ACS Appl Mater Interfaces. 2025 Jul 30;17(30):42915-42924. doi: 10.1021/acsami.5c00209. Epub 2025 Jun 12.
Liquid crystalline electrolytes are emerging as a promising class of functional materials for energy storage applications. They offer the ability to operate under anhydrous conditions without the presence of acids or flammable solvents, allowing high operating temperatures. Herein, the liquid crystalline phase of a bispyrazolate Pd(II) metallomesogen is used as a platform for Li-ion conduction, taking advantage of the existence of nanochannels in the hexagonal columnar mesophase. Li-doped liquid crystal composites have been prepared with different lithium content, and their mesomorphic properties and ionic conductivities were studied. It was found that the intercalation of lithium ions between molecules does not hinder the formation of the mesophase but rather extends the temperature range in which it is stable due to the existence of ion-dipole interactions between the lithium ions and the uncoordinated N-pyrazolic atoms, leading to lower melting and higher clearing temperatures. High Li-ion conductivity was found in the solid and liquid crystalline phases by complex impedance spectroscopy. The optimally doped composite with an 8:2 (metallomesogen:LiTFSI) molar ratio reaches conductivity values as high as 1.89 × 10 Ω cm. The work presented is expected to pave the way for a promising class of liquid crystalline Li-ion electrolytes based on metallomesogens.
液晶电解质正成为一类用于储能应用的有前途的功能材料。它们能够在无水条件下、不存在酸或易燃溶剂的情况下运行，从而允许较高的工作温度。在此，双吡唑钯（II）金属介晶的液晶相被用作锂离子传导的平台，利用六方柱状中间相纳米通道的存在。制备了具有不同锂含量的锂掺杂液晶复合材料，并研究了它们的介晶性质和离子电导率。发现锂离子在分子间的嵌入并不阻碍中间相的形成，而是由于锂离子与未配位的N-吡唑原子之间存在离子-偶极相互作用，扩展了中间相稳定的温度范围，导致较低的熔点和较高的清亮点温度。通过复阻抗谱在固相和液晶相中发现了高锂离子电导率。摩尔比为8:2（金属介晶：LiTFSI）的最佳掺杂复合材料的电导率高达1.89×10Ω·cm。所展示的工作有望为基于金属介晶的一类有前途的液晶锂离子电解质铺平道路。
