Lithium Self-Diffusion in a Polymer Electrolyte for Solid-State Batteries: ToF-SIMS/ssNMR Correlative Characterization and Modeling Based on Lithium Isotopic Labeling.

Manufacturers aim to commercialize efficient and safe batteries by finding new strategies. Solid-state electrolytes can be seen as an opportunity to develop batteries with a high energy density. They allow the use of lithium foil as the anode, increasing the energy density. Also, they are composed of nonflammable materials making them safer than liquid electrolytes. However, to enhance the electrochemical performances of forthcoming solid-state lithium metal batteries, phenomena governing ionic conductivity have yet to be mastered in such devices. Lithium isotopic tracing was successfully used in previous works to further understand lithium ion transport mechanisms in batteries. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 6/7 Li high-resolution solid-state nuclear magnetic resonance (ssNMR) spectroscopy are two complementary techniques probing local and global scale, respectively. Both techniques can distinguish lithium isotopes. Here, four polymer membranes were elaborated with the same lithium concentration, but with various isotopic enrichments from 7.6 to 95.4% of 6 Li. The selected material was a poly(ethylene oxide) (PEO) membrane containing lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) as lithium salt. They are widely studied in the lithium battery field. First, reliable ToF-SIMS and ssNMR methodologies were validated in light of the converging results. They led to accurate determination of lithium isotopic abundance of polymer membranes with a 1 or a 2% uncertainty, respectively. Then, the developed methodologies were applied to characterize lithium self-diffusion in a polymer membrane. Furthermore, numerical simulations based on a two-dimensional diffusion model compared with ToF-SIMS analyses allowed us to extract a lithium self-diffusion coefficient of 1.6 × 10 -12 m 2 ·s -1 at 60 °C, which complements other published values. The robust methodologies described in this work can be extended to various applications and materials. They stand as powerful strategies to better understand lithium ionic transport, especially in multiphase materials, for example, in hybrid solid-state electrolytes.