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Polymers 2021, 13, x FOR PEER REVIEW 11 of 15 Polymers 2021, 13, 1386 10 of 14 membranes, known as the tortuosity factor, but also to the occurrence of tightly bonded mweamtebrrmanoeles,cuklneoswon tahsethyedtorortpuhoislictyacfiadcitcosr,ilbicuat(aSlPsoSft-oSitOh2e_osucclfu)rcrleunscteros.fTtihgehstelyrebsounltdseadre 6 4 2 0 0 2 but not enough to achieve the conductivity of pristine sPSf membrane (Figure 6a). 2.5 winatleirnme wolietchunleosnonpetrhfeluhoyrdinroaptehdilibcaasceidimc seimlicbara(SnPeSsfr-SepiOor_tesdulfi)nctlhuestleirtse.raTthuerseearnesdulatsrgaerely 2 inlolwineer twhiatnh cnuornrepnetrsfltautoer-oinf-attheed-abratsNedafmionembermanbersanrepoofrstiemdilianrttheiclkitneersastu(Nreaafinodn l1a1r5g,e1l2y5 −2 loμwme)r,wthainchcsuhrorewnstastcartoes-soofv-tehrec-uartreNntafidoensimtyemofb1r9a5nmeAof·csmimialatr60th°iCck,nfeesdsin(NgathfieonDM11F5C, 1w25itμhma)2, wMhmicehthshanowolssaolcurtoiossno[v2e8r,4c9u]r.rent density of 195 mA·cm−2 at 60 ◦C, feeding the DMFCHwowithevaer2,Mthemaecthiaenvoeml seonluttoiofnhi[g2h8,D49M].FC performance depends on many properties of thHeomweemvebr,atnhe; ancohtieovnelymwenatteorf ahnigdhMDeMOFHCtpraenrfsopromrta,nmcetdheapneonldcsonocnemntarnatyiopnroapnedrtpiesr- omftehaebmilietymobfrathne;mnoetmobnrlaynweatreeriamndpoMrteaOnHtptarraanmspeotertr,smdethearmnoilncinognctehnetrfauteiolncealnldbephearvmioer-. aHbilgithyporfothtoenmceomndburacntieviatryeismapnoertsasnetnptiarlaimndeitcearstodreftoermasisneinssginthgethfueeslucietlalbielihtayvoiofra. Hmiegmh- brane for fuel cell applications. proton conductivity is an essential indicator for assessing the suitability of a membrane for As further study to highlight the different features of the membranes, in-situ electro- fuel cell applications. chemical impedance spectroscopy (EIS) measurements were carried for all MEAs. Figure 6a As further study to highlight the different features of the membranes, in-situ electro- chemical impedance spectroscopy (EIS) measurements were carried for all MEAs. Figure 6a shows Nyquist plots for the single cells tested under potentiostatic condition at 0.3 V and 30 °C. The total impedance spectra profiles result from the overlapping of two distorted semi- shows Nyquist plots for the single cells tested under potentiostatic condition at 0.3 V and ◦ circles. The high frequency semicircle occurs in the frequency range from 5 kHz to 4–5 Hz, 30 C. The total impedance spectra profiles result from the overlapping of two distorted whereas the low frequency semicircle occurs from 4–5 Hz to 100 mHz. The series resistance semicircles. The high frequency semicircle occurs in the frequency range from 5 kHz to (Rs) values obtained from the high frequency intercept on the x-axis were 0.25, 0.54 and 0.90 4–5 Hz, whereas the low frequency semicircle occurs from 4–5 Hz to 100 mHz. The series resis2tance(R)valuesobtainedfromthehighfrequencyinterceptonthex-axiswere0.25, s cm for the MEAs based on filler-free SPSf, sPSf-SiO2_sulf and SPSf-SiO2, respectively. This 0.54 and 0.90 cm2 for the MEAs based on filler-free SPSf, sPSf-SiO _sulf and SPSf-SiO , 22 indicates that, although the best performance, in terms of power output, in a DMFC is ob- respectively. This indicates that, although the best performance, in terms of power output, tained with the composite membrane based on acidic silica followed by that one with bare in a DMFC is obtained with the composite membrane based on acidic silica followed by silica, the presence of an inorganic filler, such as silica, not presenting additional ionic con- that one with bare silica, the presence of an inorganic filler, such as silica, not presenting duction characteristics, decreases the proton conductivity of the SPSf-SiO2 membrane. This additional ionic conduction characteristics, decreases the proton conductivity of the SPSf- latter is increased by functionalizing silica with sulfonic acid groups, but not enough to SiO membrane.Thislatterisincreasedbyfunctionalizingsilicawithsulfonicacidgroups, 2 achieve the conductivity of pristine sPSf membrane (Figure 6a). 30°C SPSf SPSf-SiO2 SPSf-SiO2_sulf 100 mHz f 3.9 Hz 5 kHz 60 °C SPSf SPSf-SiO2 SPSf-SiO2_sulf f 5 kHz 5 Hz 62.4 mHz 100m Hz Z' (Ω cm2) 4 6 2 1.5 1 0.5 00 0.5 1 1.5 2 2.5 Z' (Ω cm2) (a) FFigiguurere6.6E.Elelcetcrtorcohcehmemiciaclailmimpepdeadnacnecsepespctercatr(Nay(Nquyiqsutpisltoptsl)oftos)rtfhoerMthEeAMsEeAqusiepqpueidpwpeitdhwthiethdtifhferdeniftfemrenmtbmraenmesbreacnoersdreedc- orded at 0.3 V and 5 M MeOH solution a◦t (a) 30 °C and◦ (b) 60 °C. at0.3Vand5MMeOHsolutionat(a)30 Cand(b)60 C. IIttiisimportant topoiinttoouutththatathtehpeoplaorlaizraiztiaotniornesriesstaisntacenc(Rep()Rwa)swloaws leorwfoerrthfoerstPhSef- p sSPiSOf-2S_isOulf_msuelfmmbreamnber;atnheis; tihsias ifsuarthfuerthcoernfciornmfiartmioantiofntohfetmhetmheatnhoalncorlocsrso-ossv-eorvreerdruedctuioc-n 2 tiuosninugsitnhgistmhiesmbermanber,aensep, ecsipaellcyiaaltly30at°3C0(FCig(uFriegu6are),6bau),t baulstoaalsto60at°6C0(FCig(uFriegu6bre).6Ibn).faIcnt, fathcet,cthonetcroibnutrtibountoiofnthoef tahneoadneoadnedacnadthcoadtheotdoetthoetihmepimedpaendcaenwceaswcalseacrlelyarvlyisivbilseibflreofmrotmhe thtweotwseomsiecmircicleirsclsehsoswhnowinnFinguFriegu6are, b6eai,nbgetihneg ftihrsetfiornset oatnheiagthhfirgehqufreenqcuyeantctryibauttreidbumteodre more to the anode and second one at low frequency (i.e., 5 Hz to 100 mHz) to the cathode ◦◦ (b) - Z'' (Ω cm2) - Z'' (Ω cm2)PDF Image | Properties of Methanol Transport for Direct Methanol Fuel Cells
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