Thin-film batteries based on zinc/manganese dioxide chemistry with gel ZnCl2 electrolyte were manufactured as single (1.5 V) and double (3.0 V) cells from electrodes printed on paper substrates covered with different polymeric insulating coatings. Their properties were evaluated by means of electrochemical impedance spectroscopy and chronopotentiometry. Best performing cells achieved capacities in the range of 3 mAh cm−2 during discharge with 100 μA current, corresponding approximately to C/100 discharge rate. The influence of the cell elements on the overvoltage was examined and suggestions for the optimization of their performance were postulated. In particular, it was observed that limitations in the delivered power were governed by the poor conductivity of the carbon current collector. An optimized cell was built and showed a 4-fold improvement in the power delivered at 1 mA.