text: In the 1970s–80s, it was realized that nanosized systems may affect ionic conductivity, opening a new field of nanoionics. In 1973, it was reported that ionic conductivity of lithium iodide (LiI) crystals could be increased 50 times by adding to it a fine powder of ‘’insulating’’ material (alumina). This effect was reproduced in the 1980s in Ag- and Tl-halides doped with alumina nanoparticles. Similarly, addition of insulating nanoparticles helped increase the conductivity of ionic polymers. These unexpected results were explained by charge separation at the matrix-nanoparticle interface that provided additional conductive channels to the matrix, and the small size of the filler particles was required to increase the area of this interface. Similar charge-separation effects were observed for grain boundaries in crystalline ionic conductors.