Characterization of the interfacial Li-ion exchange process in a ceramic–polymer composite by solid state NMR

Abstract

Solid-state electrolytes are key for the development of high energy density and safe Li-batteries. A very strong research effort has been made for the development of ceramic-polymer composite solid electrolytes...

Investigating the Interface between Ceramic Particles and Polymer Matrix in Hybrid Electrolytes by Electrochemical Strain Microscopy

“…Combining this information, high friction and a low CRF on the polymer phase and lower friction but higher CRF on the ceramic particle, we verified that the interfacial area with high ESM amplitudes was mostly present on the polymer phase. In agreement with reports from the literature [25,26,31], these findings lead to the major conclusion that, indeed, the transition zone plays an important role in lithium ion transport in PEO 6 −LiTFSI with LLZO:Ta electrolytes. However, the increased ESM amplitude might also reflect the accumulation of lithium ions within this transition zone with a dimension of approximately 20 nm in front of the ceramic particles.…”

“…These results underline the importance of the interaction between ceramic particles and the polymer matrix to increase the overall conductivity. The outstanding influence of interfacial transition zones, reminiscent of the space charge areas between the polymer phase and embedded ceramic particles, as discussed in the literature [29][30][31], are confirmed.…”

“…Recently, based on NMR experiments, Ranque et al suggested that the ion transport between the polymer and ceramic phase is possible also for low (10%) Li 6.55 Ga 0.15 La 3 Zr 2 O 12 content while being, however, comparably slow [31].…”

Unveiling the Cation Exchange Reaction between the NASICON Li1.5Al0.5Ge1.5(PO4)3 Solid Electrolyte and the pyr13TFSI Ionic Liquid

“…The broad peak at 0.5 ppm can be attributed to lithium on the surface/interface of LATP particles based on the previously reported data. 25,27 A significant difference in the ion transport mechanism has been observed for different charging regimes (low current10 μA vs high current100 μA). At low current, the LiTFSI signal increased 12 times in comparison to the signal of the pristine material.…”

2D HETCOR Solid-State NMR Spectroscopy for Multiphase Materials with Mobility Contrast

“…Solid-state nuclear magnetic resonance (NMR) is a powerful tool for the atomic-level characterization of chemical structures and molecular dynamics. − The benefits of multidimensional experiments, to achieve higher chemical resolution and extract more dynamic information, have been well recognized in the last few decades. − Particularly, heteronuclear chemical shift correlation (HETCOR) solid-state NMR experiments have been indispensable and widely employed for the structural studies of polymers, proteins, pharmaceutical compounds, , inorganic materials, and so on. In HETCOR experiments, the establishment of the heteronuclear correlation is usually achieved via cross-polarization (CP) under magic angle spinning (MAS) conditions, relying on the through-space dipolar couplings between different nuclei.…”