NOVEL POLYMER-IN-CERAMIC ELECTROLYTES. ION-TRANSPORT PHENOMENA

Solid electrolytes could revolutionize battery and supercapacitor technology because of their nontoxicity, stability during operation and enhanced safety. The major limitation of solid electrolytes is their low ionic conductivity at room temperature, and intricate ion transport complicated by grain-boundary phenomena.

We have developed, and present here, novel polymer-in-ceramic composite electrolytes with high ion-conduction properties, prepared by electrophoretic deposition. Nanoparticles of LiAlO₂, Li₁₀SnP₂S₁₂, and some ion-conducting glasses were used as ceramic matrices. Polyethyleneimine (PEI) and polyethylene oxide (PEO) were tested as binders and lithium-ion-conducting mediums. Our recently developed simplified Poisson-Boltzmann model reveals that the adsorption of PEI on the surface of ceramic particles increases zeta potential, repulsion forces between the particles and their deposition rate. The electrophoretic deposition of PEO and nanoceramic powders occurs from the individual entities. We have succeeded in depositing films containing 5 to 40% PEO which are homogeneous in composition and uniform in thickness. XRD and DSC tests showed that the crystallinity of the polymer confined in the pores of ceramics, is suppressed. This was expected to improve the ionic conductivity of composite electrolytes saturated with LiI salt. However, on the basis of AC-impedance, NMR and high-resolution X-ray tomography data, we suggest that the high ionic conductivity (0.5mS/cm) and low activation energy (2.3kJ/mole) are brought about by the parallel-to-the-current-path grain boundaries between the excess of LiI and ceramic nanoparticles, and not by the confined-in-ceramic polymer. It is obvious that the nanoarchitecturing of ordered, fast-ion-conduction paths and the elimination of perpendicular blocking grain boundaries will reduce the effect of high-resistant grains.