4.7 Article

High performance polymer electrolyte membrane with efficient proton pathway over a wide humidity range and effective cross-linking network

Journal

REACTIVE & FUNCTIONAL POLYMERS
Volume 161, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.reactfunctpolym.2021.104854

Keywords

High-temperature proton exchange membranes; Polybenzimidazole; Covalent cross-linking; Zirconium 3-sulfopropyl phosphonate; Proton conductivity

Funding

  1. National Natural Science Foundation of China [21776167, 21276148]
  2. Natural Science Foundation of Shandong Province, China [ZR2019QB012, 2019ZBXC411]
  3. State Key Laboratory of Chemical Engineering (Tianjin University) [SKLChE14B01]

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The mPBI-TGDDM/ZrSP polymer electrolyte membranes with high proton conductivity are prepared by covalent cross-linking and doping with ZrSP, showing great potential for direct methanol fuel cells.
It is vital to constructing long-term proton transfer channels with sufficient conduction sites in proton exchange membranes. The mPBI-TGDDM/ZrSP polymer electrolyte membranes are prepared by covalent cross-linking with tetrafunctional N,N,N?,N?-tetraglycidy-4,4?- diaminodiphenyl-methane (TGDDM) and doping with the zirconium 3-sulfopropyl phosphonate (ZrSP). The new high-temperature proton conductor ZrSP contains sulfonic acid groups and phosphonic acid groups. TGDDM has high functionality which efficiently enhanced the dimensional stability, mechanical properties, and oxidative resistance of the membranes under low cross-linking degrees (5%?10%). The low cross-linking degree and good mechanical stability also allow high doping levels of ZrSP and consequently high proton conductivity. At 100% relative humidity (RH), 50% RH and 0 RH, the proton conductivity of mPBI-TGDDM(5%)/ZrSP(50%) membrane is 0.127, 0.078 and 0.0186 S cm-1 at 180 ?C, respectively. A large number of sulfonic and phosphonic acid groups in the membrane can establish an efficient proton pathway over a wide humidity range. High cross-linking will decrease the conductivity, and high doping will increase the conductivity, thus affecting the performance of the fuel cells. The mPBI-TGDDM/ZrSP membranes exhibited good methanol resistance and good membrane selectivity and thus the membranes have great application potential in direct methanol fuel cells (DMFCs).

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