Remarkable advances have recently been made in the thermocell array with series or parallel interconnection, however, the output power from the thermocell array is mainly limited by the electrolyte performance of an n-type element. In this work, we investigate iron (II/III) perchlorate electrolytes as a new n-type electrolyte and compared with the ferric/ferrous cyanide electrolyte at its introduction with platinum as the electrodes, which has been the benchmark for thermocells. In comparison, the perchlorate electrolyte (Fe2+/Fe3+) exhibits a high temperature coefficient of redox potential of +1.76 mV/K, which is complementary to the cyanide electrolyte (Fe(CN)63-/Fe(CN)64-) with the temperature coefficient of -1.42 mV/K. The power factor and figure of merit for the electrolyte are higher by 28% and 40%, respectively, than those for the cyanide electrolyte. In terms of device performance, the thermocell using the perchlorate electrolyte provides a power density of 687 mW/m2 that is 45% higher compared to the same device but with the cyanide electrolyte for a small temperature difference of 20 °C. The advent of this high performance n-type electrolyte could open up new ways to achieve substantial advances in p-n thermocells as in p-n thermoelectrics, which has steered the way to the possibility of practical use of thermoelectrics.