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Molecules 2020, 25, 1712 14 of 44 Table 2. Summary of DMFC best performance using composite membranes. Membrane Nafion/silica [79] Nafion/TiO2 [83] Nafion/SiO2 [83] Nafion/sulfonated montmorillonite [87] Nafion/GO [98] Nafion/SGO [99] Sandwich Nafion/GO [100] Nafion/mordenite [95] Nafion/analcime [95] Nafion/mordenite/GO [96] Nafion/polypirrole [64] Nafion/polyaniline [65] Nafion/PVA [53] Nafion/PBI [58] Nafion/PTFE [47] Nafion/PTFE/zirconium phosphate [50] Nafion/SPAEK [72] Nafion/SPEEK [73] SPEEK [112] SPEEK/MMT [112] SPEEK/GO [116] SPEEK/PBI [113] PVA/montmorillonite [129] PVDF/zirconium phosphate [131] Type of DMFC Active Active Active Active Active Active Passive Active Active Active Active Active Active Active Active Active Active Active Active Active Active Active Active Active Voltage Current (V) Density (A.cm−2) 0.3 0.2 0.3 0.214 0.3 0.204 0.2 0.336 0.31 0.46 0.40 0.1 0.17 0.15 0.18 0.06 0.18 0.04 0.23 0.12 0.30 0.15 0.23 0.3 0.26 0.5 0.36 0.06 0.25 0.35 0.20 0.3 0.38 0.3 0.18 0.15 0.20 0.076 0.20 0.1 0.35 0.21 0.28 0.16 0.29 0.023 0.54 0.060 Power Density (mW cm−2) 60.0 64.2 62.9 67.2 141.0 43.0 25.0 10.8 7.2 27.5 45.0 70.0 130.0 21.7 87.5 60.0 114.0 27.0 15.2 20.0 72.2 45.0 6.8 32.3 Temperature (◦ C) Methanol Concentration (M) 75 5 80 1 80 1 40 2 70 1 - 1 - 5 70 4 70 4 70 1 60 60 6 70 1 60 2 70 2 80 2 80 2 80 2 60 1 60 1 65 1 60 1 25 2 60 1 According to the data collected into the two tables above, membranes with fillers guarantee the highest performance. This is due to the fact that the reduced alcohol permeability counterbalances the reduced proton conductivity in the composite membranes. Materials, such as; PTFE, PVA and metal oxided are not proton-conducting materials so result in a reduction in the electrolyte proton conductivity, however they increase the tortuosity of the membrane thereby leading a reduced amount of crossover. Two approaches to increase the proton conductivity were adopted to further enhance the performance, namely; by optimising the filler content or by functionalising the filler (most commonly by incorporating sulphonic groups) to increase the overall electrolyte proton conductivity. Polarization curves, proton conductivity, water uptake and methanol crossover are tests commonly carried out for all the membranes described in this section. However, durability tests are still lacking in the literature. Therefore, only commercial Nafion provides guarantees in terms of lifetime and degradation, therefore it cannot be completely substituted up to this time. Research activities on the lifetime time and the degradation of Nafion based composite membranes should be carried out. 3. Composite Membranes for H2 PEMFCs 3.1. Inorganic Fillers Inorganic fillers have a long history of use as fillers in membranes for fuel cells. The general explanation of their suitability is due to their high thermal stability, mechanical strength, and water-absorbing nature. Therefore, the main aim of introducing fillers into the polymer membrane is to enhance its properties and enable its operation at elevated temperatures and/or low relative humidities. Figure 3 illustrates the change in proton conductivity and hydrogen crossover with the change in operating conditions to higher temperatures and lower relative humidities (Figure 3b) and the incorporation of fillers (Figure 3c).PDF Image | Composite Polymers for Electrolyte Membrane Technologies
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