The preparation and characterization of two new families of lithium-co
nducting solid-state electrolytes is reported. Both systems are silica
(SiO2) - polyethyleneglycol (PEG(n)) hybrid materials with (type I) o
r without (type II) covalent organic-inorganic chemical bonds. Their e
lectrical conductivity has been studied by complex impedance spectrosc
opy between 20 degrees C and 100 degrees C in the frequency range 1 Hz
to 10 MHz as a function of the polymer chain length (200 < n < 1900),
polymer concentration and lithium concentration (4 < [O]/[Li] < 80) T
he highest room-temperature ionic conductivity (sigma congruent to 6 x
10(-2) S cm(-1)) has been found for type II material for ratios [O]/[
Li] = 15 and PEG(300)/TEOS = 1.0. The effect of the chain length on th
e polymer mobility has been studied by nuclear magnetic resonance by m
easuring the Li+ line widths and the spin-lattice relaxation time T-1
between -100 degrees C and + 100 degrees C. The bonded chain mobility
increases with the chain length ( type II) while the opposite occurs w
ith unbonded chain material (type I). Both types of materials present
high ionic conductivity at room temperature and are adequate as Li+-co
nducting electrolyte in all solid-state electrochemical devices.