Early proton-exchange membrane technology was developed in the early 1960s by Leonard Niedrach and Thomas Grubb, chemists working for the General Electric Company. Significant government resources were devoted to the study and development of these membranes for use in NASAs Project Gemini spaceflight program. A number of technical problems led NASA to forego the use of proton-exchange membrane fuel cells in favor of batteries as a lower capacity but more reliable alternative for Gemini missions 1-4. An improved generation of General Electrics PEM fuel cell was used in all subsequent Gemini missions, but was abandoned for the subsequent Apollo missions. The fluorinated ionomer Nafion, which is today the most widely utilized proton-exchange membrane material, was developed by DuPont plastics chemist Walther Grot. Grot also demonstrated its usefulness as an electrochemical separator membrane.
In 2014, Andre Geim of the University of Manchester published initial results on atom thick monolayers of graphene and boron nitride which allowed only protons to pass through the material, making them a potential replacement for fluorinated ionomers as a PEM material.