Solid-State NMR Revealing the Impact of Polymer Additives on Li-Ion Motions in Plastic-Crystalline Succinonitrile Electrolytes

To enhance the safety of lithium-ion batteries (LIBs), alternatives to liquid electrolytes are widely studied. One of them is the plastic-crystal succinonitrile (SN) which is able to solvate various Li salts. This system can be further extended by inserting polymers, bringing additional advantages such as higher melting points and the possibility of adjusting thermo-mechanical and electrochemical properties. The plastic-crystalline electrolyte consisting of the Li salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dissolved in SN was extended by adding various thermoplastic polymers, namely, polyacrylonitrile (PAN), poly(ethylene oxide) (PEO), polyethylene carbonate (PEC), and polyvinylpyrrolidone (PVP). Even small amounts (10 wt %) of added polymer to the SN-base were found to impact the Li-ion mobility. Variable temperature investigations on structure and ion dynamics were performed using static and magic angle spinning (MAS) solid-state NMR and various relaxometry measurements. Influence of the Li concentration and the polymers’ functional groups on the structure of SN and the resulting Li-ion mobility was elaborated. Activation energies and jump rates of the Li ions were determined. As a result, the PAN-containing system stands out to be a promising candidate for application in future LIBs as it shows high ion mobility, low activation energy, and a high potential for further modifications. Solid-state NMR turned out to be a reliable method and a good alternative to impedance spectroscopy measurements for investigating ion mobility behavior providing even more information.