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Materials 2021, 14, 1617 15 of 20 an operating temperature of 30 ◦C and a feed of 4 M aqueous methanol solution to the anode (Figure 12). It was found that both MEAs exhibited rather similar activation losses and ohmic resistance in the overall cell reaction. However, the A100G4S-10-based MEA could deliver a slightly higher maximum power density. The improvement could be attributed to the better methanol blocking property of the A100G4S-10 membrane. The higher performance of the A100G4S-10-based MEA also prevailed at a higher operating temperature of 50 ◦C using feeds of different methanol concentrations at the anode and dry oxygen at the cathode as reported in Figure 13. The difference between the power outputs of the A100G4S-10 and Nafion 117 membranes was small except at very high methanol concentrations (16M). This trend is most apparent in Figure 13, which plots the maximum power density against the methanol concentration. Clearly, the Nafion 117 membrane was unable to sustain the same fuel cell performance at high methanol concentrations in the feed, whereas the A100G4S-10 membrane had no such failing. It should also be mentioned that the thickness of the Nafion Materials 2021, 14, x FOR PEER REVIEW 16 of 20 117 membrane was about double that of the diblock membrane. On the other hand, a separate experiment using MEA made from a thinner Nafion membrane (Nafion 112, with thickness of 50 μm, which is about one quarter of the thickness of the Nafion 117 membrane) mhaedmebxrpaenreie)nhcaedeaxnpevriencgerdeaatenrelvoessnogfrepaotwerelrodsesnosfiptyo(wmearxdimenusmityp(omwaexrimdeunmsitpyoowfeNradfieonn- 22 s1i1t2ywofaNsa1f2iomnW11/2cmwa)s.1F2omrcWom/cmpa)r.isFoonr,ctohmepmaarxisiomnu,mthepomwaexrimduemnsiptioewseorfdAensGitieSs-1o0f 100 4 Aan10d0GN4Sa-fi1o0na1n1d7Nmaefmiobnra1n1e7smwemreb4r1anaensdw1e6rmeW41/acnmd,1r6esmpWec/tcivmel,yr,ewspheilcetitvhelyo,pwenhcilierctuhiet 22 ovpoletnagceir(cOuCitVv)olftaAge(GOCS-V1)0oanfdAN100aGfi4oSn-11017anmdemNbarfaionnes1w17asmfoeumnbdratonbeseawbaosutfothuensdamtoebaet 100 4 a0b.5o4uVt.tHhensacem,ethaetp0o.5w4eVr.dHenesnictye,lothsessphoowueldrdcoernrseiltaytelowssithshtohuelmdectohrarneloaltbelwocikthintgheabmiliettyhoa-f nthoel mbleomckbirnagnea,bailnitdynoftthoethmeeomhmbriacnre,siasntadnnceotoftothtehemoemhmbricanre.siTshtaenbcettoefrtpherfmoremabnrcaenoef. TAhe GbetSte-1r0piesrrfeocrkmoannecdetofhAav10e0Gth4Se-1ro0oitscraeucskeoineditstofinheasvtehtyhderorpoohtobcaicugseraiinsit(sAfxinGeys)tahnyd- 100 4 dhrigohpehsotbhicydgroapinhsil(iAc xbGoyu)nadnadryhi(gSh) eilsltuhstyrdatreodphinilitcheboinusnedtaorfyF(iSg)uirlelu1s2t)r.aSteudchinmthoerpihnoselotgoyf Fwigourlde1m2a).kSeumchetmhaonroplhsowloegllyinwgoduilfdficmulatkjeusmtbetehcanuoselsowfethlleinhgigdhifefsitcuspltajtuiastlpbeacakuinsgeofthe hiygdhreospthspobaticiaglrpaaincks.ing of the hydrophobic grains. Figure 13. Maximum power density with different methanol feed concentrations at 50 ◦C. All Figure 13. Maximum power density with different methanol feed concentrations at 50 °C. All tests tests were carried out after conditioning the cell for 30 min at the open-circuit condition (flow rate: were carried out after conditioning the cell for 30 min at the open-circuit condition (flow rate: 5 5 cc/min for MeOH and 50 cc/min for dry oxygen). cc/min for MeOH and 50 cc/min for dry oxygen). 4. Conclusions 4. Conclusions We report an alternative design to achieve a nonfluorinated PEM by solution cast- We report an alternative design to achieve a nonfluorinated PEM by solution casting ing technique, in which the in-situ crosslinking of the hydrophobic blocks of a diblock technique, in which the in-situ crosslinking of the hydrophobic blocks of a diblock copol- copolymer, poly[(AN-co-GMA)-b-SPA], is arranged by solution casting and thermal curing. ymer, poly[(AN-co-GMA)-b-SPA], is arranged by solution casting and thermal curing. This results in the secondary “waterways channels” in the hydrophobic domains with This results in the secondary “waterways channels” in the hydrophobic domains with the the exception of the primary one formed of the hydrophilic SPA blocks. The resulting exception of the primary one formed of the hydrophilic SPA blocks. The resulting free- standing PEM delivers improved proton conductivity and alcohol resistance (with respect to Nafion 117) in addition to promising mechanical properties. The hydrophobic AN-co- GMA to the hydrophilic SPA ratio was an important structural parameter as it determines both proton conductivity and fuel permeability of the membrane. An optimal hydropho- bic/hydrophilic ratio in the ionomer leads to a balance amidst all the requisite PEM prop-PDF Image | Hydrophilic Cross-Linked Aliphatic Hydrocarbon Diblock Copolymer
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