Controlling the Activation Energy for Single-Ion Diffusion through a Hybrid Polyelectrolyte Matrix by Manipulating the Central Coordinate Semimetal Atom.

The diffusion of lithium ions decoupled from a solid polymer electrolyte matrix is the key for high-energy electrochemical devices with the safety needed for commercial use. This Letter reports how the ion mobility in a single-phase hybrid polyelectrolyte (SPHP) matrix can be tuned by changing an inorganic coordinating atom from silicon (Si) to germanium (Ge). Nuclear Magnetic Resonance (NMR) results show that the lithium ion activation barrier in the polyelectrolyte with Si can be modulated from 0.26 eV to the unprecedented value of 0.12 eV in the polyelectrolyte with Ge. Density functional theory is used to show that the electronic structures of both polymers are very different, although their chemical structures are very similar, except for the coordinating atom. This simple chemical substitution route will certainly increase the interest in these polymers for applications in electrochemical devices.