Development of Hydrophilic Oxide/Polymer Composite Membranes for Polymer Electrolyte Fuel Cells Operating at Wide Temperature Range

Abstract

Toward the wide-spread use of heavy-duty vehicles (HDVs) operated by polymer electrolyte fuel cells (PEFCs) should approach the higher temperature around 120oC besides normal temperature (60-80oC). Commercial perfluorosulfonic acid-based electrolyte (PFSA, e.g. NafionⓇ) shows better proton conductivity with chemical stability in wide temperatures range, though decreases under low back pressure at 100~120 oC. In order to improve the proton conductivity at the higher temperature range, composite membrane of NafionⓇ with a hydrophilic filler of Ta doped TiO2 (Ta-TiO2) was synthesized. The Ta-TiO2 nanoparticles fillers with fused-aggregate network microstructure were synthesized by the flame method, and were crushed by wet mill(Star Burst, :Sugino Machine Limited CO.). The fillers were mixed with NafionⓇsolution (20 wt.%：D2020 Chemours Co.) by use of a rotary ultrasonic dispersing processor (500 rpm, 60 min. PR-1 :Thnky Co.), a planetary ball mill (500 rpm、30 min.：PULVERISETTE 6：FRITSCH Co.), and a defoaming processor (500 rpm、5 min.：HM-400W: Kyouritu Seiki). The dispersion solution was coated in hot air by use of a die coating system (die coater: Taku-Dai Mini-50: Daimon Co., Ltd.), and were hot-pressed (140 ℃ 3 min. TCMD-2.5:TOHO KOGYO co.) to form composite membranes (9 cm×9 cm ×25 µmt).The cross-sectional backscattered electron image BSE) of the composite membrane observed by scanning electron microscope (SEM, acceleration voltage 2 kV, SU9000: Hitachi High-Tech Co.) and transmission electron microscope (TEM, H-9500: Hitachi High-Tech Co.). The proton conductivity of the composite membrane was measured by the AC four-probe method. The current-voltage (IV) polarization curves of Single cells using the prepared composite membrane (membrane thickness: 25 µm) were measured at 80 ℃ 100% RH and 120 ℃ 20% RH, back pressure 50 kPaG.The obtained composite membranes were well flexibility with softness. The BSE images indicated that the high contrast images of Ta-TiO2 parties were uniformly dispersed in composite membrane. The higher magnified of the cross-sectional TEM images also showed that the hydrophilic surface of Ta-TiO2 adhered to the Nafion® without any air pores. The proton conductivity of the composite membrane at 80% RH increased with increasing Ta-TiO2 content and showed maximum value of 0.13 S cm-1at 3 wt%, and then decreased. The maximum proton conductivity was 1.3 times higher than that of Nafion®. The IV performance of the single cell using composite membrane kept same performance to that using Nafion® membrane at 80 oC 100% RH, and then improved at 120 oC 20% RH. The water content at 120 oC 20% RH kept higher value by the effect of hydrophilicity of the Ta-TiO2, which would be one of the reasons to enhance the cell performance at 120 oC 20% RH. Figure 1