Studies are carried out of morphology, crystal structure, chemical con
tent, thermal and transport properties of Li2SO4-Al2O3 composites prep
ared in two different ways: by thermal decomposition of the precursor
Li2SO4.2Al(OH)(3).mH(2)O at 400 degrees C or by using conventional mix
ing. It is shown that, whatever the preparation technique, if grain si
ze of alumina in composites is small enough (of order of tens nanomete
rs) then after prolonged heating the heterogeneous system Li2SO4-Al2O3
reaches the metastable thermodynamic state - a nanocomposite in which
lithium sulphate is in an unusual epitaxial state. The stabilization
of this state is caused by a strong interface interaction that is lead
ing to the formation of the intermediate thin layer of lithium alumina
te which ''glues'' Li2SO4 and Al2O3 phases providing the contact. The
phase transition temperature of Li2SO4 in composites is 100 degrees lo
wer than in the pure salt. Ionic conductivity of Li2SO4 in the composi
tes smoothly changes at the phase transition, activation energies bein
g 0.40+/-0.05 and 0.66+/-0.01 eV for T>470 degrees C and T<280 degrees
C, respectively. The value of the charge carrier concentration in the
nanocomposites estimated from the frequency dependent conductivity tu
rned out to be comparable with that in glasses and superionic conducto
rs.