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5/26/2018 Polymer Electrolyte Hybrid Membranes Prepared by Radiation Grafting of P-styryl...
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Membrane hibride polimer electrolit pregtite de radiaie altoire de p-styryltrimethoxysilane n poli etilen- -tetrafluoroetilen filme
Jinhua Chen , , Masaharu Asano, Yasunari Maekawa, Masaru Yoshida Quantum Direcia Stiinta Beam, Japonia Agenia pentru Energie Atomic,1233 Watanuki-machi, Takasaki, Gunma 370-
1292, Japonia
Abstract
n scopul de a pregti o membran electrolit polimer hibrid cu att de nalt conductivitate de protoni i
stabilitate termic ridicat, un monomer vinil aromatic avnd un grup trimetoxisilil, i anume p-
styryltrimethoxysilane, a fost altoit n primul rnd n poli (etilen- co-tetrafluoretilen) (ETFE), film de -ray
preirradiation. P -grefat-styryltrimethoxysilane Filmul a fost apoi sulfonat pentru a ataa grupe de acid
sulfonic pe inelele aromatice ale lanurilor de gref, i n cele din urm hidrolizat i condensat de a
introduce silan-reticulare ntre lanurile de gref. Astfel, a fost obinut un polimer reticulat membran
electrolit hibrid-conductoare de protoni.Condiiile de preparare pentru altoire i sulfonare, i proprietile
membranei electrolit polimer rezultat, cum ar fi capacitatea de schimb ionic, protoni conductivitate,
absorbie de ap, i o stabilitate termic au fost investigate n ceea ce privete aplicarea acesteia n
celule de combustie. Se concluzioneaz c proprietile noului p -altoit-styryltrimethoxysilane electrolitpolimer membrana hibrid sunt comparabile cu Nafion, i sunt superioare o membran grefat-stiren.
Cuvinte cheie
Polymer membranelectrolitic; Radiaii altoire ; Hibrid ; Celule de combustibil
1. Introducere
Membrane hibride polimer electrolit au fost intens studiate pentru aplicarea n celule intermediare
combustibil temperatur[1],[2],[3],[4],[5] i [6]. Aceste membrane sunt n general preparate prin
ncorporarea particulelor anorganice n electrolii de polimer organic. Particulele anorganice mbunti
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retenia apei i stabilitatea termic a membranelor hibride electrolit polimer. Pentru a dispersa uniform
particulele anorganice nano n electrolii de polimer, n cretere situ a particulelor folosind tehnici sol-gel
este preferat[7]. Cu toate acestea, din cauza lipsei de legturi covalente ntre cele dou componente,
particulele anorganice sunt uor de separat de la electrolii de polimeri organici n timpul stare de
transport pe ap, datorit efectului electro-osmotic sau de difuzie napoi n celule de combustibil[3].Pe de alt parte, radiaii grefare este o metod promitoare pentru modificarea materialelor, i este de
un interes special, pentru realizarea proprietilor chimice dorite n mod special, precum i proprietile
mecanice excelente. Grefarea radiaii a fost folosit pentru prepararea materialelor inteligente, cum ar fi
termo-i materiale de pH sensibil[8] i [9], ion metalic selectiv materiale adsorbante[10]i de
membran conductoare de protoni[11],[12],[13] i [14].
Pentru prepararea membranelor conductoare de protoni, stiren este adesea altoite in filme fluoropolimer
prin radiaie altoire, astfel nct grupurile de acid sulfonic poate fi introdus prin sulfonare a lan urilor
polistiren[11],[12],[13] i [14]. Membranele electrolit polimer grefat-stiren dezvoltate arata mai mare
conductivitate mai mic de protoni i permeabilitate metanol dect cele ale Nafion, o membran
comercial scump produs de DuPont[15].n plus, stabilitatea chimic a membranelor altoit de radiaii
poate fi mbuntit prin introducerea unei structuri de re ea reticulat, care este realizat fie prin
utilizarea de ageni de reticulare chimic sau prin radiaie de reticulare[16] i [17]. Cu toate acestea,
agenii de reticulare chimic poate aciona ca o impuritate care reduce stabilitatea termic [18], iar
iradierea poate induce deteriorarea n membranele, de asemenea, ceea ce duce la scderea stabilitii
termice a membranelor electrolit polimer[19].
Am observat c vinylsilanes pot reticula poliolefine atunci cnd sunt grefate de procesare de topire i
ulterior sililare-condensare n prezena umiditii ap[20] i [21]. -Si-O-Si-structura formata din
membranele acioneaz ca nodul de reticulare i este legat covalent la materialele organice.n aceast
lucrare, am ncercat s combine altoirea de radiaii i silan-reticulare pentru a pregti o membran
electrolit hibrid covalent reticulat.n acest scop, am grefat un monomer aromatic special vinylsilane, i
anume p-styryltrimethoxysilane, care are inele aromatice disponibile pentru sulfonare i are trimetoxisilil
grupuri disponibile pentru silan-reticulare, n poli (etilen- co-tetrafluoretilen) (ETFE) film de baz.
2. Experimental
2.1. Prepararea membranei electrolit polimer
P-styryltrimethoxysilane fost achiziionat de la Shin-Etsu Chem. Co Ltd., Japonia. Acesta a fost pstrat la
frigider i utilizat ca atare. Filmul ETFE gros 50 pm au fost furnizate de la Asahi Glass Co, Japonia i se
spal cu aceton pentru a ndeprta impuritile de pe suprafaa sa nainte de utilizare.
Schema de preparare a noului membranei hibrid electrolit polimer ret iculat este prezentat nFig. 1, n
care trei procese principale, altoire radiaii, sulfonare i hidroliza-condensare, sunt implicate.
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Fig. 1.
Schema pentru ilustrarea pregtirea unei noi membran hibrid electrolit polimer reticulat.
Opiuni Figura
P-styryltrimethoxysilane grefarea prin preirradiation fost similar cu altoirea stiren descris n articolele
noastre anterioare[15] i [16]. Pe scurt, un tub de sticl umplut cu argon care conine filmul ETFE n 2
cm x 3 cm form dreptunghiular a fost -ray preirradiated la temperatura camerei. Dup preirradiation,
un barbotat gaz 40 wt argon. Soluie% din p-styryltrimethoxysilane n toluen s-a ncrcat rapid n tub
printr-un aparat special[16]. Grefarea a fost iniiat prin plasarea tubului ntr-o baie termostatat
meninut la 60 C. Dup timpul dorit altoire trecut, filmul grefat se spal i se usuc n vid la 40 C timp
de 24 ore. Gradul de grefare a fost calculat ca 100 ( W g - W o) / W o, unde W oi W gsunt ponderile de
film, respectiv nainte i dup grefarea.
PFilmul ETFE-styryltrimethoxysilane grefat a fost sulfonat n 0,2 M solu ie de acid clorsulfonic n 1,2-
dichloroethene la temperaturi de 30, 50, 60 i 70 C, apoi imersat n 1 M HCI soluie apoas la 80 C
timp de 24 h pentru hidroliz i condensare. Astfel, s-a obinut o nou membran electrolit polimer
reticulat hibrid-conductoare de protoni.Membrana a fost splat de electrolii i inut n ap distilat la
temperatura camerei nainte de utilizare.
2.2. FT-IR i TG-DTA msurtori
nainte de msurtorile FT-IR i TG-DTA, probele au fost uscate ntr-un cuptor cu vid la 40 C timp de
mai mult de 24 de ore. JASCO FT/IR-5300 spectrometru (Japan Spectroscopie Co Ltd.) a fost utilizat
pentru nregistrarea spectrelor de absorbie. Spectrele au fost colectate de la probele de metoda de
transmisie utiliznd 64 scanri la o rezoluie de 4 cm -1 la temperatura camerei. Thermo Plus2/TG-DTA
(Rigaku Corp, Japonia) a fost utilizat pentru analiza termogravimetric (TGA). Specimenul (aproximativ 5
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mg) a fost nclzit la 550 C, la o vitez de nclzire de 10 C / min, cu un debit de gaz de azot de 100
ml / min.
2.3. Capacitatea de schimb de ioni, conductivitate de protoni i ap de absorbie
Detaliul pentru capacitatea de schimb ionic, protoni conductivitatea i absorbia de ap a fost descris n
ref.[15].nainte de conductivitate de protoni i de absorbie a apei msurtorilor, membrana a fost
scufundat n ap la 25 C, timp de mai mult de 24 de ore. Membrana a fost scos i msoar rapid
pentru a obine conductivitatea membran ntr-o stare saturat cu ap.Absorbia de ap a fost calculat ca
100 ( W umed - Wuscat) / W uscat, unde W umedi W uscatsunt ponderile membrana din statele saturat cu ap i
uscat, respectiv. Pentru a evalua efectul de temperatur i umiditate relativ de conductivitatea protoni, a
fost utilizat o camer de temperatur i umiditate.
3. Rezultate i discuii
3.1. Radiaie altoirea p-styryltrimethoxysilane n filmele ETFE
P-styryltrimethoxysilane este un monomer funcional special, care are grupe vinii disponibile pentru grefa
polimerizare, inele aromatice disponibile pentru sulfonare, i grupuri trimetoxisilil disponibile pentru silan-
reticulare (veziFig. 1). In acest studiu, altoirea p-styryltrimethoxysilane n filmele ETFE a fost realizat
prin metoda preirradiation raze[11] i [12]. In timpul preirradiation, radicali ETFE s-au format din
cauza scindare de C-F, C-H i legturi C-C din moleculele ETFE[22]. Radicalii ETFE iniiat de
polimerizare gref npsoluia-styryltrimethoxysilane.Fig. 2prezint cineticapaltoirea-
styryltrimethoxysilane la 60 C n mediu de argon.Pentru comparaie, sunt de asemenea prezentate
cinetica stiren altoire n aceleai condiii. Doza preirradiation -ray pe filmele ETFE a fost de 30 kGy.nstiren altoire, gradul de grefare a crescut cu timpul, n etapa iniial de pn la 20 de ore, iar apoi plafonat
afar ntr-o regiune starea de echilibru se extinde la 96 de ore.n cazul p-styryltrimethoxysilane, rata de
grefare a fost lent n comparaie cu altoirea stiren. Cu toate acestea, se pare c radicalii au fost
ntotdeauna prezente, iar gradul de grefare a crescut treptat pn la 100% dup 96 h de la nceperea
altoire. Prin urmare, p-grefarea styryltrimethoxysilane poate fi uor controlat prin modificarea timpului de
grefare, n mod specific, greutatea molecula a lan urilor de gref (sau lungimea lanului grefei) pot fi bine
controlate.
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Fig. 2.
Radiaie altoirea p-styryltrimethoxysilane i stiren n filme ETFE.Doza Preirradiation, 30 kGy, temperatura altoire,
60 C, n atmosfer de argon.
Opiuni Figura
Grefarea radiaie de monomer lichid la pelicula solida poate fi descris ca o interfa de
polimerizare. Lanurile grefate sunt formate iniial pe suprafa, i apoi propaga probabil spre interiorul
filmului, sporind difuzia monomer la interfaa dintre regiunile altoite i nealtoite. Acest lucru probabil va
duce la altoirea ntregul film de baz atunci cnd cele dou interfe e de altoire ntlnesc.S-a constatat c
att grosimea i aria suprafetei filmelor ETFE grefate crescut datorit umflarea tridimensional, i
transparena sczut n timpul grefare.Astfel, credem c lan urile grefa ptruns ntregul film de baz
ETFE. Acest lucru este foarte important pentru prepararea membranelor celulare combustibil electrolit
polimer.
3.2. Sulfonare si silan-reticulare a filmelor altoite
Aa cum se arat nfig. 1, sulfonarea p-altoit-styryltrimethoxysilane Filmul a fost realizat ntr-o soluie
0,2 M de acid clorosulfonic n 1,2-dicloretan. Hidroliz-Condensarea filmului sulfonat a fost realizat ntr-o
soluie apoas 1 M de acid clorhidric la 80 C timp de 24 ore. In timpul sulfonare, grupe sulfonil (-SO 2Cl)
au fost substituite la inele aromatice ale lanurilor altoi[16]. In timpul tratamentului ulterior HCl,-CO 2CIi-Si (OCH 3) 3nplanurile altoi-styryltrimethoxysilane au fost nlocuite cu-SO 3(grupe de acid sulfonic) i
H-Si (OH) 3(grupe silanol), respectiv, iar condensarea grupe silanol format un-Si-O-Si-structur.Grupele
de acid sulfonic dat conductibilitatea membrana de protoni, iar condensarea nzestrat cu membrana
structuri reticulate cu silan. In plus, ar trebui subliniat faptul c n timpul sulfonare i hidroliza-condensare,
filmele de baz cu grefa de lanuri nu se dizolv n soluie, astfel nct membrana final electrolit polimer
poate fi obinut direct, fr nici o prelucrare suplimentar membran-form.Membran electrolit polimer a
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avut aceeai form geometric ca filmul punct de plecare, dar a existat o cretere proporional n
dimensiunea sa.
P-grefat styryltrimethoxysilane film cu un grad de grefare de 58% a fost utilizat pentru sulfonare, la 30,
50, 60 i 70 C.Fig. 3arat capacitatea de schimb ionic a membranelor electrolit polimer ob inut ca
funcie a timpului de sulfonare. Pentru comparaie, capacitatea de schimb ionic a membranei grefat-stiren
(altoire, 58%, sulfonai, la 50 C) este, de asemenea, prezentat nfig. 3. Rata de sulfonare de p-altoit-
styryltrimethoxysilane filme ETFE a fost mai lent dect cea a filmelor grefat -stiren. De exemplu, n
aceleai condiii de sulfonare, la 50 C, capacitatea de schimb ionic a membranelor de tip stiren crescut
pn la 2,4 mmol / g dup primele 6 h de sulfonare, i apoi abia schimbat deloc, n timp cep-
styryltrimethoxysilane membran-altoit-a luat aproximativ 170 de ore pentru a ajunge la capacitatea de
schimb ionic la starea de echilibru de aproximativ 1,5 mmol / g. Rata de sulfonare lent pentrup-altoit-
styryltrimethoxysilane Membrana poate fi atribuit prezenei grupuri mari trimetoxisilil, care au afectat
substituia. Rata de sulfonare a fost, de asemenea, depinde de temperatura sulfonare. Rata de sulfonare
de p-altoit-styryltrimethoxysilane filme ETFE mrit prin creterea temperaturii de sulfonare. A fost atins
nivelul de sulfonare starea de echilibru, dup sulfonare de aproximativ 200, 170, 70 i 20 de ore la 30, 50,
60 i 70 C, respectiv.
Fig. 3.
Capacitatea de schimb ionic a p-filme-styryltrimethoxysilane i grefate-stiren (ETFE gradul de grefare, 58%) ca ofuncie de timp sulfonare.
Opiuni Figura
Fig. 4prezint spectrele FT-IR tipic al filmului ETFE original,p-altoit-styryltrimethoxysilane filmul (gradul
de grefare, 58%) i membrana electrolit polimer corespunztor (PEM). Spectrul de absorbie de film
ETFE a fost simplu. CH 2se ntinde de vibraii n jurul 2976 cm-1a fost foarte slab, dar vibraiile ei
deformare la 1454 cm -1 a fost puternic i ascuit. Benzile puternice n intervalul 1000-1300 cm -1sunt
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atribuite CF 2grupuri[22].Dup altoire, spectrul FT-IR a prezentat mai multe benzi de absorbie
noi. Benzi de absorbie atribuite la inele aromatice au fost gsite la 3018 i 1601 cm -1, respectiv. -Si
(OCH 3) 3grupe silan au fost identificate de ctre banda de ascu it la 2876 cm -1i banda slab la 1400
cm -1 . Grupurile de silan au fost de asemenea identificate de Si-O ntindere vibraia puternic i larg
pentru grupele cu aproape 820 cm -1[5] i [6]. Dup sulfonare i hidroliz, spectrul de absorbie almembranei obinut electrolit polimer-conductoare de protoni a fost foarte complex. Vrfurile puternice i
largi n intervalul 900-1300 cm -1sunt datorate absorbii suprapuse ale C-F, O, S O i Si-O-Si
ntindere vibraii. Grupurile de acid sulfonic au fost identificate din-OH vibraii de ntindere la care 3000-
3600 cm -1band larg a fost atribuit.Prin urmare, se poate concluziona cp-styryltrimethoxysilane fost
grefat n film ETFE, i c lanurile grefai au fost ulterior sulfonat i reticulat prin sulfonare i ulterior
hidroliza-condensare, respectiv.
Fig. 4.
Spectrele FT-IR al filmului ETFE, filmul grefat (GETFE, altoire, 58%) i membrana corespunztoare electrolit
polimer reticulat (PEM).
Opiuni Figura
3.3. Absorbie de ap i de protoni conductivitate
Att peliculei de baz ETFE i p -altoit-styryltrimethoxysilane filmul ETFE sunt materiale hidrofobe, dar
membrana electrolit polimer rezultat purtnd grupri de acid sulfonic este un material extrem de
hidrofil.Absorbia de ap a membranei electrolit polimer este strns legat de capacitatea de schimb ionic
i activitatea apei n jurul ei.Conductivitatea protoni depinde foarte mult de capacitatea de schimb ionic,
absorbia de ap i capacitatea de disociere de protoni n ap.Pentru a evalua o membran nou de
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celule de combustibil electrolit polimer, relaia reciproc ntre protoni conductivitatea, capacitatea de
schimb de ioni i absorbia de ap ar trebui s fie stabilite n prealabil.n aceast seciune, absorbie de
ap i protoni conductivitatea pmembrane electrolitice-styryltrimethoxysilane-grefat au fost determinate la
temperatura camerei, iar rezultatele sunt prezentate nFig. 5 i Fig. 6, respectiv.
Fig. 5.
Absorbia apei de pmembranei electrolit polimer-styryltrimethoxysilane-grefat ca o funcie a capacitii de schimb
ionic.
Opiuni Figura
Fig. 6.
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Proton conductivitate de pmembranei electrolit polimer-styryltrimethoxysilane-grefat ca o funcie a capacitii de
schimb ionic.
Opiuni Figura
Fig. 5prezint absorbia de ap a membranelor electrolit polimer n funcie de capacitatea de schimb
ionic.Evident, absorbia de ap a crescut cu creterea capacitii de schimb ionic, i a fost independentde temperatura sulfonare.n mod similar, conductivitatea protoni a membranei electrolit polimer aa cum
se arat nFig. 6, de asemenea, mrit prin creterea capacitii de schimb ionic, i a fost independent
de temperatura sulfonare. Conductivitate mai mare a fost ntotdeauna gsit unde nu a fost mai mare
capacitate de schimb ionic, i, astfel, nu a fost mai mare asimilare a apei, care indic prezena a mai
multor site-uri hidrofile interiorul peliculei de baz hidrofob pentru transportul de protoni. Mai mare
conductivitate protoni se arat nFig. 6a fost de 0,15 S / cm, care corespunde capacitii de schimb ionic
de 1,56 mmol / g, i absorbia de ap de 56,7%. O astfel de absorbie de ap de mare poate fi un
dezavantaj pentru aplicaii n pilele de combustie.Cu toate acestea, chiar i n cazul membranei electrolit
polimer grefat pe styryltrimethoxysilane cu absorbie redus de ap aproape 30%, la fel ca i Nafion,
membrana prezentat capacitatea de schimb ionic i protoni conductivitate de 0,99 mmol / g i 0,058 S /
cm, respectiv, care au fost comparabile cu Nafion.
Fig. 7arat conductivitatea protoni din nou membranei (capacitatea de schimb ionic: 1,56 mmoli / g) n
funcie de temperatur n intervalul de 20-100 C. Mediul de msurare a fost controlat pentru a avea o
umiditate relativ de 95%, similar cu condiiile celulelor de combustie operate n condiii de umidificare
saturate. Pentru comparaie, a fost de asemenea prezentat conductivitatea protoni din Nafion n aceleai
condiii de msurare.Pentru fiecare msurtoare, membrana a fost echilibrat pn conductivitatea
protonului a fost aproape de nivel de 1 or.Conductivitatea protoni din nou membranei grefat pe
styryltrimethoxysilane crescut liniar cu creterea temperaturii. Dimpotriv, conductivitatea protoni de
Nafion crescut treptat temperatura pn la 70 C, iar apoi a crescut rapid n creterea temperaturii la 80
la 100 C. O astfel de tendin poate fi atribuit comportamentului Arrhenius i schimbarea absorbie de
ap.Este bine cunoscut faptul c Nafion are fazele hidrofile i hidrofobe bine separate, faza hidrofil este
format de clustere ionice ale grupurilor de acid sulfonic i ap[23]. La temperaturi mai ridicate, echilibrul
ntre faze hidrofile i hidrofobe pot fi distruse, ceea ce conduce la o cretere drastic absorbie de ap,
precum i creterea dramatic a protonului conductivitate. Distrugerea faze hidrofile / hidrofobe cauzat,
de asemenea, o scdere drastic a rezistenei sale mecanice. Prin urmare, Nafion nu este adecvat
pentru aplicarea ntr-o celul de combustibil care funcioneaz la temperaturi de peste 80 C. Dimpotriv,n noua membrana grefat-styryltrimethoxysilane, nici o cretere drastic a protonului conductivitate a fost
gsit n intervalul de temperatur testat, indicnd microstructura stabil a acestei membrane i caracterul
lor adecvat pentru utilizare n celule de combustibil mai mari de temperatur.
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Fig. 7.
Efectul temperaturii asupra conductivitii protoni din nou pmembrana electrolit grefat-styryltrimethoxysilane
polimer i Nafion. Umiditatea relativ, 95%.
Opiuni Figura
3.4. Stabilitatea termic
Stabilitatea termic a nouluip-altoit-styryltrimethoxysilane membran electrolit polimer a fost investigat
de ctre analizei termogravimetrice (TGA) i rezultatele sunt prezentate nFig. 8. Stabilitatea termic a
Nafion i membran electrolit polimer grefat-stiren a fost de asemenea testat n aceleai
condiii. Membrana electrolit polimer grefat-stiren a fost preparat prin aceeai metod ca i membrana
nostru grefat pe styryltrimethoxysilane pentru comparaie.
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Fig. 8.
Stabilitatea termic a nouluip-membrana-styryltrimethoxysilane grefat electrolit polimer (nou membrana), Nafion
112, i altoit-stiren membrana tradiional electrolit polimer (ETFE- g-SPAS).
Opiuni Figura
Attpmembrane altoit-stiren expuse trei trepte de slabire izolate n intervalul de temperatur de 200 -550 C, din cauza distrugerilor succesive cauzate de desulfonare, dezaromatizare i scindare a coloana
vertebral ETFE-styryltrimethoxysilane i.n contrast, Nafion expuse dou etape de pierdere in greutate,
care rezult din desulfonare i degradarea fluoropolimer reziduuri. Temperatura iniial debut al etapei de
desulfonare, aa cum se arat nFig. 8, a fost definit ca temperatura de degradare n evaluarea noastr
a stabilitii termice a membranei. Nafion avut o temperatur de degradare mai mare, aproape de 320
C, iar membrana electrolit polimer grefat-stiren (ETFE- g-SPAS) a avut o temperatur de degradare mai
mic, aproape de 268 C.Membrana electrolit polimer grefat-styryltrimethoxysilane prezentat o
temperatur de degradare aproape 318 C, care a fost de aproximativ 50 C mai mare dect cea a
membranei pe baz de stiren, i a fost comparabil cu Nafion.Aceast stabilitate termic mbuntit afost datorit toleranei temperatur a reelei de siliciu reticulat n membran.n plus, siliciul asociate
cu pinelele aromatice amplasamentului sporit densitii electronice i, astfel, a crescut stabilitatea
legtur ntre cicluri aromatice i grupe de acid sulfonic.Mai mult dect att, datorit structurii reticulare
silan introdus, noul hibrid membrana artat stabilitate chimic ridicat n mod similar fa de oxidare n
H 2O 2soluie ca cea a ETFE-divinilbenzen reticulat g-PSSA membrana electrolit[16].
4. Concluzie
Noi membrane reticulate hibride electrolit polimer au fost preparate prin radiaie cu succes altoirea p-
styryltrimethoxysilane n filme ETFE i sulfonare ulterioar i silan-reticulare. Conductivitatea protoni din
nou membranei atins 0,15 S / cm, la temperatura camerei ntr-o stare de ap saturat, care corespunde
capacitii de schimb ionic de 1,56 mmol / g i absorbie de ap de 56,7%.In plus, conductivitatea protoni
expuse asemenea cretere linear cu creterea temperaturii, indicnd microstructura acesteia stabil i
adecvat pentru aplicaii npilele de combustie care funcioneaz la temperaturi de peste 80 C. Mai mult
dect att, noua membrana hibrid are o temperatur de degradare de 318 C, care este de aproximativ
50 C mai mare dect cea a unei membrane grefat-stiren, i este comparabil cu Nafion.
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