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temperature and lower humidity) and therefore their durability must be investigated and demonstrated in-situ. It is also important to study the change in the membrane degradation mechanisms due to the presence of fillers, for instance; how does the filler affect the membrane mechanical properties due to the humidity cycling and what is the impact of the filler on the catalyst stability or dissolution into the membrane. Molecules 2020, 25, 1712 32 of 44 4. Composite Membranes for Electrolysers although those membranes showed high conductivity, mechanical stability and dimensional properties, Composite membranes with metal oxides as fillers (SiO2, TiO2, or WO2) showed promising they are not appropriate for water electrolysis application. To reinforce those membranes, organic properties for high temperature operation of PEM water electrolysers allowing achieving high fillers can be included in the Aquivion matrix. Boaretti et al. [216] included SPEEK reinforcement performance with respect to a commercial membrane. Baglio et al. [212] and Antonucci et al. [213] which led to an improvement in the mechanical strength but resulting in low proton conductivity. focused their work on Nafion-TiO2 and Nafion-SiO2 respectively, to allow efficient operation at high Another approach to reinforce proton exchange membrane is to physically separate the properties temperature, above 100 °C. Both works claimed that the high temperature operating conditions were of mechanical strength and proton transport embedding a porous nanofibre web into the matrix. allowed by the better water retention and more uniform distribution of water across the composite Aquivion membranes reinforced with electrospun polysulfone (PSU) fibre webs were prepared by membrane due to the presence of inorganic hygroscopic fillers inside the polymeric matrix. This Giancola et al. [217]. The fibrous reinforcement strongly enhanced the mechanical strength and also resulted in reduced ohmic resistance and therefore better electrolyser performance [214]. The reduced hydrogen crossover. However, the addition of the reinforcing fibre in membranes had little performance of composite membranes was better than that of Nafion membrane under high effect on the cell electrochemical performance: the cell voltage at 2 A cm−2 was 1.760 V which is slightly temperature and high pressure so the application of this technology is very promising especially higher than the performance obtained with a non-reinforced membrane (1.758 V). Therefore, increased when high electrical efficiency is required. As evidence of this result, Figure 10 illustrates mechanical and dimensional stability and reduced hydrogen crossover of the composite membrane are characteristics curve of cell equipped with commercial Nafion and composite Nafion-SiO2 promising properties for electrolysis application but with little effect on performance. membranes at high temperature and pressure. Figure 10.. Comparison of voltage and current density of Nafifion 115 aand ccoompoossiittee Naafifoion--SSiiO2 2 ◦ Ion-Ebrasu et al. [218] produced a composite membrane by spray coating graphene on commercial These alternative composite membranes also showed a decrease of the cross-over of the gases PEM material. They exploited the properties of this material to enhance the efficiency of PEM through the membrane. However, a slight decay of performance was observed during the membrane at100and112200°CCanadndata1tb1abrarbsab(as)(an)dan3dba3rbaabrs(ab)s; r(ebp);rordepurcoeduwceitdhwpeitrhmpisesrimonisfsriomn f[r2o1m3].[213]. electrolysers and reducing costs by achieving high surface area to volume ratio, good mechanical and experiment; thus, a further amelioration of membrane is necessary to improve the stability and thermal properties. The composite membrane showed an improved behaviour in term of thermal and lifetime. electrochemical characterization when compared to pristine commercial membrane: the interaction of Another way to produce electrolyte membranes with high conductivity and durability for graphene with fluorinated membrane led to an increased conductivity and a better water adsorption. water electrolysers is using perfluorosulfonic acid with shorter and non-branched pendant In spite of all this benefits, further experimental work has to be carried out to investigate the behaviour side-chain with higher crystallinity than longer side-chain perfluorosulfonic acid. Aricò et al. [215] of these graphene-modified membranes under current voltage measurements. used the Aquivion short side chain perfluorosolfonic membrane using Nafion 111 for comparison. Linkous et al. [219] evaluated different types of engineering polymers and identified a few options Authors claimed that although those membranes showed high conductivity, mechanical stability that could withstand the conditions found in PEMWEs. Among them, polybenzimidazoles (PBI), and dimensional properties, they are not appropriate for water electrolysis application. To reinforce poly(ether ether ketones) (PEEK), poly(ether sulfones) (PES) and sulfonated polyphenyl quinoxaline those membranes, organic fillers can be included in the Aquivion matrix. Boaretti et al. [216] (SPPQ), were selected to be used for PEM electrolysis. In particular, SPEEK polymer is considered to included SPEEK reinforcement which led to an improvement in the mechanical strength but have high strength and it is an easy membrane forming material. High degree of sulfonation enables resulting in low proton conductivity. Another approach to reinforce proton exchange membrane is high proton conductivity. In fact, Linkous et al. observed that high degree of sulfonation (65%) led to to physically separate the properties of mechanical strength and proton transport embedding a a higher proton conductivity that exceeded Nafion by 29%. However, these alternative membranes porous nanofibre web into the matrix. Aquivion membranes reinforced with electrospun showed low durability and low current densities compared to standard Nafion membranes and tent polysulfone (PSU) fibre webs were prepared by Giancola et al. [217]. The fibrous reinforcement to swell excessively or even dissolve at elevated temperature. An alternative would be to reinforce the SPEEK membrane with other polymer structures and/or fillers [220]. Song. et al. [221] prepared a composite membrane including tungstophosphoric acid(TPA) to increase proton conductivity and CeO2 (Cs) to improve the durability of the membrane into the SPEEK matrix. The composite membrane showed better mechanical and electrochemical properties than Nafion 117 membrane: proton conductivity, tensile strength, and elongation were enhanced. However, the cell voltages of the MEA using Nafion 117 and SPEEK-Cs/TPA membrane were 1.91V and 1.82 V at 1 A cm−2PDF Image | Composite Polymers for Electrolyte Membrane Technologies
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