Enhancing durability of polymer electrolyte membrane using cation size selective agents

Radical species generated during proton exchange membrane fuel cell operation considerably limit the achievable durability, particularly for heavy-duty vehicle applications. A promising solution to the problem is the incorporation of radical scavenger additives such as cerium which mitigates chemical attacks on the membrane. However, these additives migrate during fuel cell operation causing a loss in durability and performance due to detrimental interaction with various components of the fuel cell. Here, we study cation size selective agents as a means to immobilize cerium within perfluorosulfonic acid (PFSA) membranes. We synthesized an organometallic complex of cerium with 15-Crown-5 and investigated the effectiveness of this complex to immobilize cerium. Over 300% increase in cerium retention and an 80% increase in chemical durability were observed owing to the stabilization effect of crown ethers on cerium. Migration under a potential gradient can be eliminated while the complex also contributes to the enhancement in cerium radical scavenging activity. Current challenges with the proposed solution are highlighted and future work is discussed. [Display omitted] •Crown ethers eliminated cerium migration driven by potential gradients.•15-Crown-5 is the best size for cerium complexation in PFSAs.•15-Crown-5 can increase Ce3+ retention in an acid environment by over 300%.•Crown ethers can enhance the radical scavenging abilities of cerium itself.•Durability enhancement of 80% was achieved by the use of 15-Crown-5 in Nafion.