New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions

作者：Romanenko Konstantin^*; Pringle Jennifer M; O'Dell Luke A; Forsyth Maria

来源：Physical Chemistry Chemical Physics, 2015, 17(29): 18991-19000.

DOI：10.1039/c5cp03294f

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (sigma) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl) phosphonium bis(fluorosulfonyl) imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P(1224)PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, sigma(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, f(m)(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (theta) in porous media, with k(theta) commonly quantified by a power-law dependence that can also be employed to describe sigma(f(m)).

• 出版日期2015