The aim of this work is to study a new composite material anode made of Zn + (NH4)(2)ZnCl4 associated with a MnO2 cathode for proton conductive solid state electrolyte (H-montmorillonite) electrochemical generators. The double salt (NH4)(2)ZnCl4 has been prepared and characterized by X-ray diffraction and differential thermogravimetry. The composition of the anode has been optimized. Generators using such an anode show a specific capacity of about 273 Ah kg(-1) with a high energy to mass ration of about 345 Wh kg(-1) when the relative humidity is at saturation level (RH = 100%) These characteristics depend strongly on both the hydration of the clay and of the double salt. The results of the electrochemical study of such generators as well as the physico-chemical characterization of the anode reaction induced compounds show clearly that the formation of a new phase takes place, and gave us the possibility of proposing a new anodic reaction. (C) 2010 Elsevier B.V. All rights reserved.