Hierarchical structure-property relationships in graft-type fluorinated polymer electrolyte membranes using small- and ultrasmall-angle X-ray scattering analysis

Tran Duy, T.*; Sawada, Shinichi; Hasegawa, Shin; Yoshimura, Kimio; Oba, Yojiro*; Onuma, Masato*; Katsumura, Yosuke*; Maekawa, Yasunari

The hierarchical structures of graft-type ETFE-based polymer electrolyte membranes (ETFE-PEMs) were investigated using small- and ultrasmall-angle X-ray cattering experiments. The ETFE-PEMs with IECs 2.4 mmol/g possessed conducting graft domains around lamellar crystals, with a d-spacing of 21.8-29.1 nm, and oriented crystallites with short and long correlation distances of 218-320 and 903-1124 nm, respectively. The membranes with IECs 2.7 mmol/g showed a new phase of crystallite network domains with a d-range of 225-256 nm, indicating a phase transition from oriented crystallite to crystallite network structures in the IEC range of 2.4-2.7 mmol/g. Noted that for the ETFE-PEMs with high IECs higher conductivity at 30% RH and compatible tensile strengths at 100% RH and 80 C, compared with Nafion, originated from the well-interconnected ion channels around the crystallites and the remaining lamellar crystals and crystallites, respectively.