2334 J. El ectrochem. Soc., Vol . 138, No. 8, August 1991 9 The Electrochemical Society, Inc.

5. Uni on Carbide Corporation, Carbon Product s Division

(now AMOCO Performance Products), Technical In-
format i on Bulletins 465-223,465-225, 465-246.
6. P. Wagner, J. Am. Cer ami c Soc., 55, 214 (1971).
7. O. M. Baycura, I EEE Trans. Indust . , 5, 208 (1968).
8. K. Ki noshi t a and S. C. Leach, Thi s Journal , 129, 1993
(1982).
9. "Chemi cal Engi neers Handbook, " 5th ed., R. H. Perry
and C. H. Chilton, McGraw-Hill, New York (1973).
10. W. L. I ngmanson et aI., TAPPI , 42, 840 (1959).
Polymer Electrolyte Fuel Cell Model
T. E. Springer,* T. A. Zawod zi nski , * and S. Got t e s f e l d *
Los Al amos Nat i onal Laborat ory, Los Al amos, Ne w Mexi co 87545
ABSTRACT
We present here an isothermal, one-dimensional, steady-state model for a compl et e pol ymer electrolyte fuel cell
(PEFC) wi t h a 117 Nation | membrane. In this model we empl oy water diffusion coefficients electro-osmotic drag coeffi-
cients, wat er sorption isotherms, and membr ane conductivities, all measured in our laboratory as functions of membr ane
water content. The model pre.dicts a net-water-per-proton flux ratio of 0.2 H20/H under typical operat i ng conditions,
whi ch is much less t han t he measured electro-osmotic drag coefficient for a fully hydrat ed membrane. It also predicts an
increase in membr ane resistance with increased current density and demonst rat es t he great advant age of a t hi nner mem-
brane in alleviating this resistance problem. Bot h of t hese predictions were verified experi ment al l y under certain condi-
tions.
Fuel cells empl oyi ng hydrat ed Nation or other hydrat ed
perfluorinated i onomeri c materials as t he electrolyte are
promi si ng candi dat es for electric vehi cl e applications (1).
The pol ymer electrolyte provi des room t emperat ure start-
up, el i mi nat i on of many corrosion problems, and the po-
tential for low resi st ance losses. Resistive losses wi t hi n t he
fuel cell result, in part, from t he decrease of membr ane
protonic conduct i vi t y following partial dehydrat i on of the
membrane. On t he other hand, cat hode flooding probl ems
are caused when too much wat er is in t he system. Clearly,
water management wi t hi n the fuel cell involves walking a
t i ght rope bet ween t he two ext remes.
Spatial variations of wat er cont ent wi t hi n t he pol ymeri c
electrolyte of a current~carrying fuel cell result from the
el ect ro-osmot i c draggi ng of wat er with prot on t ransport
from anode to cathode, t he product i on of wat er by the oxy-
gen reduct i on reaction at t he cathode, humi di fi cat i on con-
ditions of the inlet gas streams, and "back-diffusion" of
wat er from cat hode to anode, whi ch lessens t he concentra-
tion gradient.
The wat er di st ri but i on wi t hi n a pol ymer electrolyte fuel
cell (PEFC) has been model ed at various levels of sophisti-
cation by several groups. Verbrugge and Hill (2-4) have
carried out ext ensi ve model i ng of t ransport properties in
perfluorosulfonate i onomers based on dilute solution
theory. Fales et al. (5) report ed an i sot hermal wat er map
based on hydraul i c permeabi l i t y and electro-osmotic drag
data. Though t he model was relatively simple, some broad
concl usi ons concerni ng membr ane humi di fi cat i on condi-
tions were reached. Ful l er and Newman (6) applied con-
cent rat ed solution t heory and empl oyed literature data on
t ransport properties to produce a general descri pt i on of
water t ransport in fuel cell membranes. The last contribu-
tion emphasi zes wat er di st ri but i on wi t hi n the membrane.
Boundary values were set in t hese cases rather arbitrarily.
A different approach was t aken by Bernardi (7). She con-
sidered t ransport t hrough the gas diffusion electrodes, as-
sumi ng t he membr ane to be uni forml y hydrated, corre-
spondi ng to an "ul t rat hi n membr ane" case.
We present an isothermal, one-dimensional, steady-state
model for wat er t ransport t hrough a compl et e PEFC. The
model i ncl udes t ransport t hrough t he porous electrodes,
based on calculated diffusivities correct ed for porosity,
and t ransport t hrough t he membr ane electrolyte, based on
experi ment al l y det ermi ned t ransport parameters. In this
model, we empl oy water-diffusion coefficients, electro-
osmotic drag coefficients, water sorption isotherms, and
membr ane conductivities, all of whi ch are measured in our
laboratory as funct i ons of membr ane wat er content. We
deemed it highly desirable to use in our model a compl et e
* Electrochemical Society Active Member.
set of experi ment al data generat ed under condi t i ons in
whi ch t he membr ane is rout i nel y handl ed (for example,
pretreated) and t est ed for PEFC work as consistently as
possible. Furt hermore, we expl i ci t l y measured paramet ers
over t he fullest possible range of wat er cont ent s to enabl e
us to i ncl ude t he effects of t he variation of wat er cont ent as
a function of position wi t hi n the membr ane during any
current flow.
Gener al Aspects of t he Mod el
The distribution of water in a PEFC at steady state (con-
stant current and fluxes) is calculated in this model by con-
sidering wat er flow t hrough the following five regions of
uni t cross-sectional area wi t hi n t he fuel cell, as schemati-
cally illustrated in Fig. 1: t he t wo inlet channels, the t wo
gas diffusion electrodes, and the Nation membrane. Not
only does wat er enter t he fuel cell assembl y as a com-
ponent of the humi di fi ed fuel and oxi dant streams, but
water is also generat ed at t he cat hode by t he oxygen re-
duct i on reaction. We ent ered into the model the cell cur-
rent, cel] and humi di fi er t emperat ures, anode and cat hode
pressures, inlet gas flow rates, and oxygen/ ni t rogen ratio in
t he cat hode gas feed. The cell is consi dered i sot hermal be-
t ween t he inlet channels.
The wat er flow into t he inlet channel s is set by t he tem-
peratures of t he ext ernal gas humidifiers and the cell.
Water vapor is equi l i brat ed at t he saturation pressures set
by the humi di fi er t emperat ures in the inlet flow streams.
Ent rai ned droplets may be consi dered to form and be
t ransport ed wi t h t he flow stream if t he cell t emperat ure is
less than t he humi di fi er t emperat ure. These droplets will
re-evaporate in t he inlet flow channels if t he condi t i on of
the assumed t horoughl y mi xed fluid t here become less
t han saturation. Under t hese isothermal, t horoughl y
mi xed or mean conditions, t he model can use ent rai ned
droplets as a t ransport mechani sm for wat er wi t hout hav-
ing to specify t he details. We will discuss el sewhere a qual-
itative t reat ment of el ect rode "flooding" (large excess of
liquid water) when it occurs. Water vapor leaves the two
inlet flow channels at the mean role fraction of t he respec-
tive channels. React ant gases split their flow bet ween the
gas-diffusion el ect rodes and t he channel exits, as deter-
mi ned by the current and t he respect i ve stoichiometry. Bi-
nary diffusion of hydrogen and wat er vapor occurs
t hrough t he anode, and ternary diffusion of oxygen, nitro-
gen, and wat er vapor occurs t hrough the cathode.
The flow of gas streams t hrough the gas diffusion elec-
trode is model ed in a manner similar to that descri bed by
Bernardi (7). Int erdi ffusi on of gases t hrough the porous
el ect rode is calculated from t abul at ed data using t he
Stefan Maxwel l equat i ons wi t h a Br uggemann correction
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
J. El ect r ochem. Soc., Vol . 138, No. 8, A u g u s t 1991 9 The Electrochemical Society, Inc.
2335
H 2 0 , 0 2 , N2
H. O, H.
I sat 1 psat/p
= PA/ PA; = [2] XwA X wc C C
Fr om fl ow bal ance, t he anode i nl et wat er fl ow less t he exi t
wat er fl ow is t he fl ow cr ossi ng i nt er f ace 1
I
VHXwhI (VH -- 1)XwlI
NIwA - - N L A = NwA; - -- aI [3]
1 - XawA 1 - X~l
wher e VH, t he st oi chi omet r i c coeffi ci ent , is t he ratio: N~2/
NH2,~. On t he cat hode si de t her e ar e t hr ee speci es. The i nl et
dr y gas mol e f r act i on of oxygen, XON, is known. The i nl et
02 mol e f r act i on of t he sat ur at ed gas is x~ = (1 - I
X wc ) X oN.
The t hr ee speci es i nl et fl ow rat es and exi t fl ow rat es ex-
pr essed pr opor t i onal to I ar e
I
Niwc X~cVoI voI voI(1 - Xor~)
- - - _-Z-7~ -; N ~ = ~ - ; N ~ - [4]
2(1 - Xwc)XoN 2XoN
H2 0 , O2 , Nz Hz O, Hz
CATHODE ANODE
EXIT EXIT
Fig. 1. Schematic diagram of fuel cel l model.
appl i ed t o t ake account of t he el ect r ode porosi t y. The ef-
fect of t he pr es ence of wat er dr opl et s is mor e di ffi cul t to
t r eat r i gor ousl y. I n t hi s initial at t empt at model i ng wat er
t r anspor t i n t he fuel cell, we deal wi t h t he dr opl et pr obl em
onl y qual i t at i vel y (see bel ow).
Equi l i br i um of wat er act i vi t y is as s umed at t he elec-
t r ode/ membr ane i nt er f ace and det er mi nes t he l ocal
a mount of wat er at t he me mbr a ne surface. An exper i men-
t al l y det er mi ned i s ot her m for wat er sor pt i on i nt o t he
me mbr a ne is us ed to conver t f r om wat er vapor act i vi t y to
wat er cont ent i n t he me mbr a ne at t he i nt erface. The next
fl ux of wat er acr oss t he me mbr a ne is cal cul at ed usi ng t he
el ect r o- osmot i c dr ag and di f f usi on coeffi ci ent s of wat er as
f unct i ons of me mbr a ne wat er cont ent .
When t he equat i ons t hat det er mi ne t he wat er bal ance
are sol ved, t he me mbr a ne r esi st ance and t he O2 concent r a-
t i on at t he cat al yst i nt er f ace are known. The cat hode over-
pot ent i al and a V-I cur ve for t he fuel cel l can t hen be det er-
mi ned. Anode cat al yt i c act i vi t y is consi der ed so hi gh t hat
anode over pot ent i al is negl ect ed. The onset of cat hode
f l oodi ng wi l l pr ecede any anode fl oodi ng. On t he ot her
hand, me mbr a ne dr yi ng near t he anode coul d cause an ex-
t r eme i ncr ease i n t he over al l resi st ance. The act i ve cat al yst
l ayer i n t he cat hode is as s umed to exi st onl y as a t hi n pl ane
at t he cat hode/ membr ane i nt erface. The rest of t he cat hode
ser ves onl y as a gas di f f usi on regi on.
Mathematical Model
Co n t i n u i t y e quat i ons i n i nl et f l o w c hanne L- - Fi gur e 1
shows t he fi ve r egi ons and t he f our i nt er f aces of t he model .
When t he const ant cell cur r ent is J (A/cm2), t he mol ar fl ux
of H2 t hr ough t he anode is I = J/ 2F moYcm2-s. Fl ows of H2
and wat er ar e cons i der ed to be posi t i ve whe n movi ng t o
t he l eft t owar d i ncr easi ng i nt er f ace number s . The O~ fl ow
is posi t i ve i n t he opposi t e di rect i on. Unde r st eady-st at e
condi t i ons t he N2 fl ow wi l l al ways be zero. Fl uxes and fl ow
rates, desi gnat ed N, are numer i cal l y i dent i cal bet ween in-
t er f aces 1 and 4, becaus e t he cr oss- sect i onal area is uni t y.
I f c~ is t he rat i o of t he wat er fl ux cr ossi ng i nt er f ace 1 (or 2)
t o t he mol ar fl ux I, and NwA and Nwc are t he anode and
cat hode wat er fl ow rat es (or fluxes) t hr ough i nt er f aces 1
and 4, r espect i vel y, t hen t he fl uxes are all r el at ed by
I = J/ 2F = NHa, 1 : 2No2.4 = NwA/Ot = Nwc/(1 + a) [1]
The fl ui d compos i t i on i n t he anode and cat hode flo~w chan-
nel s is as s umed to be uni f or m. The anode and cat hode f eed
st r eams are each as s umed t o be sat ur at ed wi t h wat er vapor
at t he humi di f i er t emper at ur es, as
- i)!; N ~ L _ I _ _
N w c - N w c + (1 + a ) l ; N L (vo p o l ( l - X o N ) [5]
2 2XoN
The t ot al cat hode exhaus t flow, obt ai ned by s ummi ng t he
t hr ee exi t fl ows i n Eq. [5], are
N~ot~, c - 2( 1 - X~c) XoN ~ ~ + I [ 0]
The mol e f r act i on of wat er and oxygen at i nt er f ace 4 and
t hr oughout t he cat hode fl ow channel is t he rat i o of t he
wat er or oxygen fl ow t o t he t ot al f l owt hr ough i nt er f ace 4.
Thus
I
XwcVo + 2(1 + ~)(1 - I
XwC)XON
X w 4 - -
Vo + (2a + 1)(1 - X~c)XoN '
(Vo -- 1)(1 -- XIwc)XoN
XO4 -- VO + (2a + 1)(1 -- X~c)Xo~ [7]
Si mi l arl y, t hr oughout t he anode fl ow channel f r om Eq. [3]
we get, for t he mol e f r act i on of wat er at i nt er f ace 1
i ~(1 i
PHXwA - - __ XwA )
Xw, - ~wA - ~( 1 - X~wA) + , ~ - 1 [ 8]
The cont i nui t y condi t i ons have gi ven us Xwl, xw4, and Xo4
as t he i nput par amet er s and t he (as yet unknown) rat i o ~ of
wat er fl ux passi ng t hr ough i nt er f ace 1 to fl ux I. Next we
devel op t he equat i ons for wat er t r anspor t t hr ough t he t wo
el ect r odes and t he membr ane. The r egi on bet ween i nt er-
faces 1 and 2 has bi nar y di f f usi on of H~ and wat er vapor;
t he r egi on bet ween i nt er f aces 2 and 3 has wat er drag of
pr ot oni c cur r ent and wat er di ffusi on; and t he r egi on be-
t ween i nt er f aces 3 and 4 has t er nar y gas- phase di ffusi on.
Gas di f f us i on i n t he el ect rodes. - - We as s ume t hat t he
anode and cat hode gas mi xt ur es wi t h wat er vapor act as
i deal gases. Let z i ncr ease i n t he di r ect i on of r eact ant flow,
t hat is, f r om i nt er f ace 1 t o 2 and f r om i nt er f ace 4 t o 3. The
St ef an- Maxwel l equat i on for mul t i c ompone nt di f f usi on
def i nes t he gr adi ent i n mol e f r act i on of t he component s
dxi x~N~ - xj Ni
dz - R T ~ [9]
PD~j
The bi nar y di f f usi on coeffi ci ent s wer e cal cul at ed for mass
di f f usi vi t y f r om t he Sl at t er y and Bi r d (8) est i mat i on at l ow
pressures. The pr essur e- di f f usi vi t y pr oduct (atm-cm2/s) is
est i mat ed f r om cri t i cal t emper at ur e, cri t i cal pressure, and
mass of t he r espect i ve component s A and B
p . DA B =a ( T ~b(pcAP~B)l/3
~3/2 [10]
(TcATcB)5/12 + Ms /
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
2 3 3 6 J. E l e c t r o c h e m . S o c . , Vol. 138, No. 8, August 1991 9 T h e E l e c t r o c h e m i c a l S o c i e t y , Inc.
whe r e a = 0.0002745, b = 1.832 f or H2, O2, a nd N2, and
a = 0.000364 a nd b = 2.334 f or wat er vapor . The e ~/2 t e r m is
a Br ugge ma nn cor r ect i on of t he di f f us i on coef f i ci ent s t o
a c c ount for t he por os i t y of t he el ect r ode (9).
Thi s model a s s ume s onl y c onc e nt r a t i on gr adi ent s, not
t ot al pr es s ur e gr adi ent s , acr oss t he el ect r odes. (A pr es s ur e
dr op can occur acr os s t he me mbr a ne i f t he anode a nd cat h-
ode pr es s ur es ar e di f f er ent ) . Fr om Eq. [9] we obt ai n t he fol-
l owi ng di f f er ent i al e qua t i ons for x~A acr os s t he a node a nd
for X~c a nd Xoc acr oss t he c a t hode
dXwA RTI
dz P ADwn
- - [ X ~A( 1 + a) -- a] [11]
dxo RTI [ x o ( l +c O+O. 5 x wc 1- X~c - Xo]
- - - - t- [ 1 2 ]
dz' Pc Dwo -~ON
dx~c
dz'
RTI [ (1 - Xwc - Xo)(1 + ~)
L
Pc D~N
0.5X~c + xo(1 + ~)7
+ -J [13]
DoN
Equa t i on [11] can be i nt egr at ed acr oss t he anode t hi cknes s ,
tA, f r om t he i ni t i al condi t i on of Xwh = Xw~ at z = 0 at i nt er -
f ace 1, whi c h we know f r om Eq. [8], t o obt ai n Xw2 at z = tA
at i nt er f ace 2
o
Xw2 = x~, - : ~ exp ~P---~w / + - l + a [14]
Si mi l ar l y, Eq. [12] a nd [13] can be s i mul t a ne ous l y i nt e-
gr at ed f r om t he known i ni t i al condi t i ons of Eq. [7] at i nt er -
face 4 t o obt ai n Xo3 a nd Xw3 at i nt er f ace 3. Al t hough t hes e
equat i ons can be i nt e gr a t e d anal yt i cal l y, we chos e t o i nt e-
gr at e t he m numer i cal l y. We now ha ve t he wat er mol e frac-
t i on i n t he gas mi xt ur e i n cont act wi t h e a c h si de of t he
me mbr a ne i n t e r ms of a a nd t he i nput pa r a me t e r s and gas
pha s e ( el ect r ode) t r a ns por t par amet er s .
I n t hi s mode l we ha ve not c ons i de r e d t he pos s i bi l i t y of
l ar ge exces s es of l i qui d wat er i n t he fl ow c ha nne l s or
wi t hi n t he el ect r ode. I n s ol vi ng t he c ont i nui t y equat i ons
we di d i ncl ude, however , ma r gi na l s i t uat i ons i n whi c h a
sl i ght vol ume of l i qui d wat er f or ms wi t hi n t he c ha nne l s of
t he el ect r odes. For t he c ont i nui t y equat i ons , no di s t i nct i on
was ma de be t we e n wat er gas a nd wat er l i qui d mol ecul es.
I f Pw e xc e e de d Psat, t he n t he exces s wat er was c ons i de r e d
i n t he c ont i nui t y equat i ons as i f i t wer e f i nel y di s per s ed
dr opl et s ( wi t h zer o vol ume) , ha vi ng t r a ns por t pr oper t i es
i dent i cal t o t hos e of wat er vapor . Onl y whe r e t he pr es s ur e
of t he r eact i ng gas ( oxygen) ha d t o be c ons i de r e d for t he
cat hode ki net i cs was t he f r act i on of l i qui d wat er , x~,q, sub-
t r act ed a nd t he r eal mol e f r act i on f or gas pha s e al one was
empl oyed. Thus , t he par t i al pr e s s ur e of oxyge n at t he cat h-
ode is PcxoJ(1 - xnq).
Wat er t ransport i n me mb r a n e . ~Me mh r a n e wat er con-
t e nt at t he i nt er f ace is de t e r mi ne d by t he act i vi t y of wat er
va por at t he e l e c t r ode / me mbr a ne i nt er f ace, a s s umi ng
equi l i br i um. The act i vi t y i n t he va por pha s e is xwP/Psat.
The s a t ur a t i on pr e s s ur e of wat er , P~t, us e d her e a nd pr evi -
ousl y i n Eq. [2] was f i t t ed t o t he f ol l owi ng empi r i cal ex-
pr es s i on accor di ng t o t a bul a t e d val ues (10)
l ogl 0P~t = - 2. 1794 + 0.02953T
- 9.1837 9 10-ST 2 + 1.4454 9 10-TT 3 [15]
Me mbr a ne wat er c ont e nt was me a s ur e d by Z a wodz i ns ki
et at., (11) as a f unc t i on of wat er act i vi t y for t he Nat i on 117
me mbr a ne by we i ghi ng me mbr a ne s e qui l i br a t e d a bove
a que ous s ol ut i ons of var i ous l i t hi um chl or i de concent r a-
t i ons. Fi gur e 2 s hows t he r es ul t i ng "i sopi est i c cur ve"
me a s ur e d at 30~ Wat er cont ent , X, is gi ven as t he r at i o of
t he numbe r of wat er mol ecul es t o t he numbe r of char ge
14
1 2 . []
, ~ 1 0 .
~ . 8 .
~t 6 .
r162
4 .
2 .
O.
0. 0 o . 2 o . 4 o . 6 o . 8 1 . 0
W a t e r V a p o r A c t i v i t y ( P w / P,a, )
F i g. 2 . M e a s u r e d m e m b r a n e w a t e r c o n t e n t vs. w a t e r a c t i v i t y f o r
Na t i o n 1 1 7 a t 30~ a n d a c c o r d i n g t o Eq. [ 1 6 ] .
(SO~H +) si t es. A fit of t he e xpe r i me nt a l r el at i ons hi p of X vs.
wa t e r va por act i vi t y, a, us e d i n t he mode l is
X(~0c) = 0.043 + 17. 81a - 39. 85a z + 36. 0a 3 for 0 < a -<- 1 [16]
The me a s ur e d val ue of h i n e qui l i br i um wi t h s at ur at ed
wat er va por at 30~ is 14 H20 per char ged si t e (see Fig. 2).
I n t he abs ence, at t he mome nt , of i sopi est i c dat a at 80~
we ar e a s s umi ng t ha t t he 30~ dat a appl i es t o me mbr a ne
e qui l i br i um wi t h wa t e r va por at 80~ Our me a s ur e me nt s
al so s how t ha t whe n t he me mbr a ne , f ol l owi ng par t i al dry-
i ng, is i mme r s e d i n l i qui d wat er , X can go as hi gh as 22
whe n at Wat er boi l i ng t e mpe r a t ur e a nd t o 16.8 whe n at
80~ Thi s a ppa r e nt anomal y, i n whi c h wat er va por a nd liq-
ui d wat er (i n e qui l i br i um wi t h e a c h ot her ) equi l i br at e sep-
ar at el y t o di f f er ent me mbr a ne wat er cont ent s , is of
t heor et i cal a nd pr act i cal i nt er es t but wi l l not be f ur t her
di s cus s ed her e. For mode l i ng pur pos es , we al l owed X t o i n-
cr ease l i near l y f r om 14 t o 16.8 as t he mol e f r act i on of wat er
e xc e e de d s at ur at i on and i ncr eas ed f r om xw.s~t t o 3Xw,~t,
t ha t is, for
)
<-- Psat ~< 3, h = 14 + . \ - ~a t -- 1 [17]
We me a s ur e d, i n Nat i on 117, t he numbe r of wat er mol e-
cul es dr agged per H i on move d by el ect r i c fi el d t hr ough
t he me mbr a ne a nd f ound i t t o be 2.5 _+ 0.2 for a ful l y hy-
dr at ed me mbr a ne i n e qui l i br i um wi t h l i qui d wat er at 30 or
50~ (12) ( t he me mbr a ne i n t hes e l ast e xpe r i me nt s had
be e n pr e t r e a t e d i n boi l i ng wat er). Ba s e d on wor k of La-
Cont i et al. (13), we a s s ume t hat t he wat er dr ag coef f i ci ent
is l i near l y pr opor t i ona l t o wat er cont ent . We ha ve r ecent l y
me a s ur e d a val ue of onl y - 0. 9 wat er mol ecul es dr agged
per H i n par t i al l y hydr a t e d Nat i on wi t h a wat er c ont e nt X
of 11, whi c h woul d i ndi cat e t ha t t hi s pr opor t i onal i t y as-
s umpt i on wi l l not unde r e s t i ma t e wat er dr ag at l ow me m-
br a ne wat er cont ent . Thus , for t he " c ompl e x" H+(H20)~ mi -
gr at i ng t hr ough t he me mbr a ne at 80~ we wi l l des i gnat e
t he numbe r of wat er mol ecul es per pr ot on as ndrag, and
t he n
~7~drag = 2.5k/22 a nd Nw,drag = ndrag " (21) [18]
( The H f l ux (2I) is t wi ce t he H2 fl ux, I.)
Us i ng t he pul sed- f i el d gr adi ent s pi n- echo nucl ear mag-
net i c r e s ona nc e (NMR) t echni que, Z a wodz i ns ki et al. (11)
al so me a s ur e d t he i nt r adi f f us i on coef f i ci ent of wat er i n
Nat i on 117 me mbr a ne s equi l i br at ed over aqueous sol u-
t i ons of LiC1 t o set t he wat er act i vi t y i n cont act wi t h t he
me mbr a ne . We a s s ume her e t ha t t hi s i nt r adi f f us i on coef-
fi ci ent , D' , r el at es a wat er di f f us i on f l ux t o t he gr adi ent i n
c he mi c a l pot ent i al or t he gr adi ent i n t he l oga r i t hm of ac-
t i vi t y. I n t ur n, t he gr adi ent , wi t h r es pect t o t he l abor at or y
coor di nat e z' of wa t e r c ont e nt h ma y be us ed
D' c w D'cw d( l n a) dk
Nw,dif = - - - V~ - - - V( RT In a) = - D' C w - -
RT RT dk dz'
[19]
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
J . E l ec troc hem. S oc., V o l . 13 8 , No . 8 , A u g u s t 19 9 1 9 T h e E l e c t r o c h e m i c a l S o c i e t y , Inc.
2 3 3 7
I n or der t o el i mi nat e t r acki ng t he me mbr a ne swel l i ng i n
t he model , we conver t t o t he equi val ent wat er concent r a-
t i on in a dr y membr ane, kpa~y/Mm, and to a new coor di nat e,
z, fi xed t o t he dr y membr ane. To account for me mbr a ne
swel l i ng, dr y me mbr a ne t hi ckness di mens i ons ar e ex-
panded by t he fact or (1 + sk). We def i ne t he cor r ect ed dif-
f usi on coef f i ci ent Dk, whi ch rel at es fl ux t o gr adi ent wi t h
r espect t o t he dr y me mbr a ne coor di nat es i n wat er cont ent
>, and whi ch is a f unct i on of },
Nw, di f = - D' c w - -
d(ln a) dk
dk dz'
= _ D, ( kpd~y/ Mmk d a ) dk pdry dk
\ ( l + s > , ) ~a ~ d~= MmDX~zz [20]
By di f f er ent i at i ng t he fit (at 30~ of k vs. a, f r om Eq. [16], to
subst i t ut e for da/ dX i n Eq. [20], t he t r ans f or med di f f usi on
coef f i ci ent f or a coor di nat e f i xed t o t he dr y me mbr a ne is
. 1 k ) D' [21]
D~.a0c = (1 + sk) ~ a(17.81 - 79.70a + 108a ~)
Fr om t he meas ur ed t hi cknes s of dr y and ful l y hydr at ed
Nat i on 117 membr anes , we det er mi ned s t o have a val ue of
0.0126. Gi ven k, Eq. [16] is sol ved i mpl i ci t l y to det er mi ne a
and is di f f er ent i at ed t o get da/ dX for use i n Eq. [21]. Fi g-
ur e 3 is a pl ot of D' , D~, and t hei r rat i o as a f unct i on of Na-
t i on 117 wat er cont ent ~. The peak i n t he cor r ect i on fact or
a n d i n D ~ a r o u n d k = 3 ( F i g . 3 ) i s v e r y s e n s i t i v e t o t h e e x a c t
f o r m o f t h e s t r o n g v a r i a t i o n i n w a t e r a c t i v i t y i n t h i s r e g i o n
( s e e F i g . 2 ). I n t h e m o d e l , D x w a s r e p r e s e n t e d b y a c u b i c
p o l y n o m i a l f o r k > 4 a n d b y t a b u l a r i n t e r p o l a t i o n f o r k -< 4 .
E q u a t i o n [ 2 2 ] i s t h e f i t f o r k > 4 o f D ~ v s . ~ a t 3 0 ~ c o r r e c t e d ,
b y a n a c t i v a t i o n e n e r g y t e r m , t o t h e o t h e r t e m p e r a t u r e s w e
u s e d
_ 1
D~>4 = 10-6 exp I 2416( Z 273 + Tcell) ]
(2.563-0.33>, + 0.0264k ~ - 0.000671X a) [22]
The act i vat i on ener gy of Eq. [22] was based on meas-
ur ement s of Yeo and Ei s enber g (14) on wat er di f f usi on i n
aci d f r om Nat i on of 1155 equi val ent wei ght .
The net wat er fl ux t hr ough t he me mbr a ne is
X Pdry dk
Nw = ~I -- ndrag" (2I)" 22 -- M~ D~ d-z [23]
dk - . ~ _ ~] I M~
~Z Z - [ 2ndr a g ~ pdr ~( ~)
and hence
[24]
Equat i on [24] can be i nt egr at ed numer i cal l y f r om i nt er f ace
2, wher e ~2 is det er mi ned by x~2 and Eq. [14]. Thi s al l ows us
t o cal cul at e k3 and x' 3.
I t e r a t i v e s o l u t i o n . - - Th e key to sol vi ng t he wat er t rans-
por t t hr ough t he PEFC occur s at t hi s poi nt , wher e we
mus t appl y i n i t er at i on to det er mi ne t he pr oper val ue of u.
We di st i ngui sh x~3, whi ch is obt ai ned f ol l owi ng t he i nt e-
gr at i on of Eq. [24], f r om x~3, whi ch is obt ai ned f ol l owi ng
i nt egr at i on f r om t he cat hode end usi ng Eq. [7] and [13].
These t wo val ues wi l l be equal whe n t he pr oper val ue of
is used. Thi s i t er at i on i ncl udes Eq. [1]-[24], whi ch wer e dis-
cussed i n t he t hr ee pr evi ous sect i ons and whi ch are all
f unct i ons of ~.
Me mb r a n e r e s i s t anc e a n d v ol t age d r o p . - - Wh e n t he
wat er profi l e i n t he me mbr a ne has been det er mi ned, we
can det er mi ne t he me mbr a ne r esi st ance and t he pot ent i al
dr op acr oss it. The conduct i vi t y of Nat i on 117 was meas-
ur ed above wat er for a r ange of wat er act i vi t i es at 30~ The
conduct i vi t y was also meas ur ed at 30 and 80~ for a ful l y
hydr at ed me mbr a ne f r om whi ch an act i vat i on ener gy was
6 . . . . i . . . . , . . . .
D, , s ~
s ~
/
~
/
Z
e
r ~
o , , i i i i i i i r . . . .
0 5 1 0 5
~ , ( H ~ O / $ O ; )
Fig. 3. Measured intradiffusion coefficient, D' , at 30~ the cor-
rected diffusion coefficient, Dx, and the correction factor, DJ D', calcu-
lated f r om measured activity and swelling, plotted against water con-
t ent per charge site for Nation 117 .
f ound and as s umed to appl y at all val ues of ~. The fol l ow-
i ng fit of conduct i vi t y i n ( ~- cm) - ' as a f unct i on of k was ob-
t ai ned
~30 = 0.005139k - 0.00326 for h > 1
or(Tee,) = exp 1268 3 3 273 + Tcel] %0 [25]
Bel ow one wat er per char ge site, t he me mbr a ne conduct i v-
i t y was as s umed const ant . The me mbr a ne r esi st ance in
~- cm 2 is obt ai ned usi ng Eq. [24] and [25] by i nt egr at i on
over t he me mbr a ne t hi ckness, tin, as
f ~
m dz [26]
Rm = ~(k)
Cat hode o v e r p o t e n t i a l . - - To gener at e t he compl et e cel l
pol ar i zat i on curve, we as s ume a cat hodi c over pot ent i al
l oss i n addi t i on t o t he ohmi c l oss i n t he membr ane. To cal-
cul at e t hi s cat hode l oss we used t he si mpl e Tafel expr es-
si on for J vs. ~ gi ven i n Eq. [27]. Thus
Fo.sF ]
J =J o P c Xo3 exp L- ~- ~J [27]
1 - - X l i q
wher e ~ = Voc - Vceii - J " Rm .... The exchange cur r ent den-
si t y Jo is r ef er enced t o pur e oxygen at 1 ar m at t he open cel l
pot ent i al Voc. As ment i oned earlier, t he mol e fract i on of 02
is cor r ect ed t o a gas- phase fract i on. For t he sake of si m-
plicity, we do not consi der i n Eq. [27] t he r at her i mpor t ant
effect s of excess l i qui d wat er on oxygen mass t r anspor t
rat es wi t hi n t he cat hode.
Becaus e we i ni t i al l y speci f y t he cur r ent densi t y t o get
t he wat er and oxygen concent r at i ons and me mbr a ne
r esi st ance R . . . . Eq. [27] is sol ved i mpl i ci t l y t o det er mi ne
t he val ue of Vceu (onl y posi t i ve vol t age al l owed) corre-
s pondi ng t o t he speci f i ed cur r ent densi t y.
R e s u l t s a n d Di s c u s s i o n
The mode l has 16 i nput par amet er s pl us speci fi c i sopi es-
tic, di ffusi on, and el ect r o- osmot i c dr ag dat a t hat can var y
for di f f er ent me mbr a ne mat er i al s and many out put vari-
abl es t hat coul d be exami ned. We onl y f ocused on a f ew of
t hese par amet er s and var i abl es t o i l l ust rat e t he effect s of
wat er t r anspor t on t he fuel cel l syst em, as pr edi ct ed by t he
as s umpt i ons of t he model , and to obser ve whi ch aspect s of
t he model s uppor t and whi ch fail to s uppor t cer t ai n exper -
i ment al resul t s. Whi l e devel opi ng t he equat i ons for t he
model , i t was conveni ent to i nt r oduce c~, t he rat i o of net
wat er fl ux t o wat er fl ux pr oduced at t he cat hode. To eval u-
at e t he model resul t s, we wi l l now use ~, t he net wat er fl ux
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
2338 J . E l ectrochem. S oc., Vol.
T a b l e I . T h e b ase- case i n p u t pa r a me t e r s a nd some computed
v a r i a b l e s f o r a c e l l w i t h Na t i o n 1 1 7 me mb r a ne .
Input parameters Computed variables
J = 0.5 A/cm 2 Vcel ] = 0.668 V
j = 0.01 A]cm 2 Rm~r, = 0.285 12-cm z
v. = 4 ct = 0.4
vo = 6 ~ = 0.2 H20 flux/H + flux
PA = 3 atm xwi = 0.1015
Pc = 3 atm x~a = 0.1013
tA = 0.0365 cm x~a = 0.2327
tc = 0.0365 cm x~ = 0.2264
t ~ = 0.0175 cm Xo~ = 0.1329
Tr = 80~ Xo4 = 0.1403
T~t~ = T~tc = 80~ Rel Hum~ = 0.6515
Vo~ = 1.1 V Rel Hum4 = 1.4535
X~N = 0.21 (air) X]iq4 = 0.077
w~ X~c= 0.1558
per pr ot on, whi c h is s i mpl y 0.5~. The set of model par ame-
t er s us e d f or our bas e case is l i st ed i n Tabl e I al ong wi t h
s ome of t he c omput e d var i abl es for t hi s case. Whe n cur-
r ent dens i t y is var i ed, vH a nd Vo ar e speci f i ed her e for t he
ma xi mum c ur r e nt dens i t y of 2 A/ cm 2 a nd i nl et fl ow r at es
ar e hel d c ons t a nt at t hi s val ue ( i . e . , v = ~m~x" J ~ J J ) . Thus ,
i n Tabl e I, a l t hough vH i s 4 f or a c ur r e nt dens i t y of
0.5 A/ cm 2, vH wi l l be 1 whe n t he c ur r e nt dens i t y is in-
cr eas ed t o 2 A/ cm 2 at t he s a me hydr oge n fl ow rat e.
For t he bas e case, t he a node a nd c a t hode gas s t r eams
bot h ent er at s at ur at ed condi t i ons . The r el at i ve humi di t y
dr ops i n t he a node fl ow c ha nne l ( x~ < X~A) but f or ms ad-
di t i onal l i qui d wat er i n t he c a t hode c ha nne l (x~4 > X~c).
Fi gur e 4 s hows t he c omput e d wat er profi l e as a f unct i on of
t hi c kne s s f r act i on me a s ur e d f r om t he c a t hode on t he l eft
acr oss t he Nat i on 117 me mbr a ne for f our c ur r e nt densi t i es.
The J = 0.5 A/ cm 2 cur ve, c or r e s pondi ng t o t he val ues of
Tabl e I, has a net wat er f l ux r at i o [3 of 0.2 wat er mol ecul es
per H i on t r a ns por t e d t hr ough t he me mbr a ne . The net
wat er f l ux move s f r om r i ght t o l ef t or i n t he di r ect i on of in-
cr eas i ng wat er cont ent . At t he hi ghe r c ur r e nt dens i t y t her e
is mor e ne t wat er f l ux e ve n t hough t he r at i o of ne t wat er
f l ux per pr ot on i s l ess; t hus , at t he cat hode, t he val ues of
var y f r om 14.1 t o 15 as t he c ur r e nt dens i t y i ncr eas es f r om
0.1 t o 0.8 A/ cm 2. Some exces s l i qui d is pr e s e nt at t he cat h-
ode, so Eq. [17] des cr i bes t he de t e r mi na t i on of ;~ at t he
me mbr a ne s ur f ace i n t he pr e s e nc e of exces s l i qui d wat er
at i nt er f ace 3. The ma gni t ude of t he sl ope of t he wat er pr o-
files dr ops f r om c a t hode t o anode, chi ef l y be c a us e t he
wat er dr ag f l ux is pr opor t i ona l t o wat er c ont e nt and, t hus ,
l ess di f f us i on f l ux is r e qui r e d t o of f set i t at s t eady st at e
near er t he anode.
An e xa mi na t i on of t he wat er a nd oxygen mol e f r act i ons
i n Tabl e I gi ves s ome i ns i ght i nt o gas di f f us i on a nd t he
1 6
1 4
U'J 12
N 8
o 6
2
0
' 0.2 T=t~ = 8 0~
9 0.5 Tu t c = 8 0o C
* 0.8
0.o o' .= o' . , 0' . , ; . , , . o
T H I C K N E S S F R A C T I O N
Fig. 4 . C ompu t e d w a t e r profiles i n No t i o n ] ] 7 f o r t h e base case f or
f o u r c u r r e n t densities holding gas f l o w r at es constant, VH = ] a t ]
A] cm 2. T h e c a t hod e is on t h e l e f t , and t h e n e t w a t e r f l u x moves from
r i ght t o l e f t ,
1 3 8 , N o . 8 , A u g u s t 1 9 9 1 9 T h e E l e c t r o c h e m i c a l S o c i e t y , I n c .
t r a ns por t of wat er i n t he el ect r odes. Ful l y s at ur at ed wat er
va por ent er s bot h a node a nd c a t hode fl ow c ha nne l s at
3 a t m pr es s ur e, 80~ c or r e s pondi ng t o a wat er mol e frac-
t i on of 0.1558. The me mbr a ne wat er f l ux l eavi ng t he anode
fl ow c ha nne l a nd e nt e r i ng t he me mbr a ne dr ops t he re-
ma i ni ng wa t e r va por t o a mol e f r act i on, x~ of 0.1015. Thi s
s a me me mbr a ne wat er fl ux, pl us t he wat er pr oduc e d at t he
cat hode, add t o t he mol e f r act i on of wat er i n t he cat hode
a nd t he c a t hode fl ow channel . Thr ough t he gas- di f f usi ng
anode, t he mol e f r act i on of wat er va por dr ops ver y sl i ght l y
t o Xw2 of 0.1013. Thes e s l i ght var i at i ons i n a node gas com-
pos i t i on be t we e n i nt er f aces 1 a nd 2 ( acr oss t he anode)
me a n t ha t i nt er pl ay be t we e n wat er a nd hydr oge n gas
t r a ns por t acr oss t he a node are not si gni f i cant for over al l
cel l per f or mance. I n fact , c ons i de r i ng i nt er f ace 2 equi va-
l ent t o i nt er f ace 1 woul d be of l i t t l e cons equence. Unl i ke
t he case of t he anode, acr oss t he cat hode t he wat er va por
f l ux di f f uses c ount e r t o t he oxyge n fl ux, and t he c ha nge i n
mol e f r act i on acr oss t he c a t hode is not so sl i ght . Becaus e
t he i ni t i al c a t hode i nl et s t r e a m was al r eady s at ur at ed wi t h
wat er , exces s l i qui d is pr e s e nt a nd is a s s ume d t o be t hor -
oughl y di s per s ed i n t he c a t hode a nd t he cat hode fl ow
c ha nne l whe r e t he mol e f r act i on of l i qui d wat er , x]~q,4, is
0.077. Compa r i s on of Xo3 t o Xo4 ( Tabl e I) s hows t ha t t he 02
pr e s s ur e has dr oppe d (at 0.5 A/ cm 2) onl y by a bout 5%
acr oss t he cat hode. Thi s me a ns t ha t t he l i mi t i ng c ur r e nt
set by oxyge n di f f us i on t hr ough t he cat hode is a bout
10 A/ cm 2.
Unde r di f f er ent oper at i ng condi t i ons , t he mode l pre-
di ct s good pe r f or ma nc e wi t h no si gni f i cant l i qui d wat er
pr es ent . For exampl e, r ef er r i ng t o t he pr evi ous bas e case,
i f t he a node humi di f i er t e mpe r a t ur e is r ai s ed t o 105~
whi l e t he cat hode' s is l ower ed t o 20~ (cel l t e mpe r a t ur e
80~ a nd t he c a t hode s t oi chi omet r y is r ai s ed f r om 6 t o 8.4,
t he n t he r el at i ve humi di t y is 0.914 i n t he a node fl ow chan-
nel and is 0.930 i n t he cat hode fl ow channel . A ver y s mal l
a mount of l i qui d is pr e s e nt at i nt er f ace 3 (X~q,3 = 0.0035),
but t hi s evapor at es dur i ng t he di f f us i on pa t h t o i nt er f ace 4.
Exa mpl e s ar e ci t ed i n whi c h t he c a t hode humi di f i er is at
80~ becaus e, i n t he l abor at or y, l ess humi di f i cat i on t o t he
c a t hode gave poor cel l per f or mance, cont r ar y t o s uc h
model pr edi ct i ons . We bel i eve t hi s is be c a us e of t he par t i al
dr yi ng of t he me mbr a ne t ha t a ppa r e nt l y t akes pl ace be-
caus e of t he exces s i ve evapor at i ve l oss t hr ough t he gr aph-
i t e col l ect or pl at es hel d at 80~ Whe n t hi s " addi t i onal "
c a t hode wat er r e mova l pa t h be c ome s under s t ood, i t wi l l
be i nc l ude d i n f ut ur e model s .
Fi gur es 5-9 di s pl ay t hr ee var i abl es (cell vol t age, V~en,
me mbr a ne r esi st ance, Rm~m, and s t eady- s t at e wat er - per -
1. 0
0. 8
0. 6
0.4
0.2
X
~. 0.5
~" 0.4
x 0. 3
q .
0 0. 2
: ~ 0.1
0.0
0
/ '
~ o ~' ~ ~, . ~ ~
_- 8 o o c
~ ~ x tm,m = 1 7 ~ ~ t m
. c m z ) " , , \ ' ,
" ' ' ~ ' . . . . . . . . . . . . . . . " OH = 2.
. . . . . . . . " . . . . . . . . ~" - - - . : " . . . . t ) . = 4
. . . . . . . ::::::::::::::::::::::::
I
1 2
C U R R E N T D E N S I T Y A / c m 2
Fig. 5. C e l l v o l t a g e , me mb r a ne resistance, and H2 0 / H + f l u x r a t i o v s .
c u r r e nt density f o r d i f f e r e n t a n o d e stoichiometry wi t h a nod e hu mi d i f i e r
a t 8 0~
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
J. El ectrochem. Soc., Vol. 138, No. 8, August 1991 9 The E l e c t r o c h e m i c a l S o c i e t y , Inc. 2339
1.0
~ . (V) T~tA =105~
0.8 ~ tmem = 1 7 5 ~ t m
0.6 ~ " C , ~ , ~ . . _
0. 2 ~ ~ , ...~ --'~ ,.:':_
x - - ~ u = 1
" ::::.::::
1
i : '
o 1 2
CURRENT DENSI TY A / c m ~
Fig. 6 . C e l l v ol t age, membrane resistance, and H2 0/ H + f l u x r at i o vs .
current density f or d i f f e r e n t anode stoichiometry wi t h anode humidifier
a t 105~
prot on flux ratio, [3) as a funct i on of current density from 0
to 2 A/cm 2. Except where indicated, all parameters cor-
respond to the base case of Table L
Fi gure 5 shows the effect on the base case of varyi ng the
anode stoichiometry. The only effect of variations i n VHiS
t hrough the role of H2 as a carrier for water vapor in the
inlet gas stream because the model assumes that over-
potential occurs onl y at the cat hode/ membrane interface.
Note that the steady-state water flux per H ratio decreases
with i ncreasi ng current densi t y for a fixed H2 flow, and it
increases with increased He stoichiometry when more
water vapor is suppl i ed at the anode. A higher water flux
results i n lower membr ane resistance and higher cell volt-
age at a given current density.
Fi gure 6 shows the effect of raising the anode humidifier
t emperat ure above t he cell t emperat ure. The membr ane at
low current s mai nt ai ns a water cont ent near 14 water mol-
ecules per membr ane charge site t hroughout its thickness,
1.0
. , , . - - ' l / /
T . , = 8 0 ~ /
,, / i
0.6 , , \
Ir - ~ 9
0.4
0.2 . . . . . . \
. - - : 2 . . . . . . . . . . . . . , \ ",
7 ) - ' , _ ~
.... t 501xm
r -
. . . . ............ t . . . . 1001xm
~ _ o.2 . -. -~. "-..~ ......... t . . . . 140gi n
o 0.1
ff . . . . . . t . . . . 175gin
0.0
0 1 2
CURRENT DENSITY A/ c m ~
Fig. 8 . V~u, R~u, and H~ O/ H + f l u x r at i o [3 vs . J f or f ou r Nation 117
membrane thicknesses a t T , , ~ = 8 0~
and the resistance approaches 0.13 ~-cm 2. The addition of
more water vapor by raising the humidifier t emperat ure
has i mproved cell performance by lowering the membr ane
resistance considerably. This is clearly seen by compari ng
the cell resistance and cell polarization curves shown i n
Fig. 5 and 6. The initial hi gh H20/H + flux ratio [3 of about
2.3 at 0.1 A/cm ~ occurs because t he 105-80~ difference i n
anode-to-cathode humidifier t emperat ures provides a gra-
di ent i n membr ane water content. (Remember that we al-
lowed (in Eq. [17]) >, to increase with excess liquid water at
the interface.) At higher current and lower vH, the flux ratio
drops. At VH = 1, we cannot t ransport much water vapor
to the anode, whi ch causes h to drop i n the membrane.
This drops the electro-osmotic drag but also raises the re-
sistance.
Fi gure 7 shows the effect of hol di ng VHat i (defined for
2 A/cm ~) and varyi ng the t emperat ure of the anode humi di -
fier, T~tA. Here the resistance increase with current is
much hi gher t han i n Fig. 5, because less water is available
from the anode feed stream for the membrane. The flux
ratio [3 increases as T~atA increases, principally because the
1.0
0. 8
0. 6
0.4
0. 2
- , t
\ / /
i / /
~ tme m = 1 7 5 g m/ i /
.... x~:,~,, / .,.,.- ,,,, ,
,.,%+, ,o .o S o o O,S ~ . o
,...... , ,
R~. . -~O' cmZ> , ~' , J j ", . . N\ .
t )
T~tA
\ - - 80oc
x ............ 88oc
9 , .......... 96 C
9 ... ' . . " , , , . . . . . . 105oc
- - " ~ ' ~ ' ~ ' - - ' " ' ~" " ~ "--= ? ~ , =~ , ' ~ . ' ~ .=--".=--= -=--=-=-'- e--" r
u I
o 1
CURRENT DENSI TY A / e m 2
Fig. 7 . C e l l v ol t age, memb r an e resistance, and H2 0/ H + f l u x r at i o vs .
current density f or d i f f e r e n t anode humidifier temperatures wi t h anode
stoichiometry o f 1 a t f u l l current density.
1.0
~ u (V) D. = 1 t
0.8
0. 6
0.4
............ \ -.,.
..~ ~ t me m 50p , m
k ............ t = . 100gm
"~ x " ~ .......... t . . 140p. m
0 1~" ~ 175~tm
-I-
r
0
0 1 2
CURRENT DENSI TY A / c m 2
Fig. 9 . V c e l l , Re,,, and H2 0/ H + f l u x r at i o [3 vs . J f or f ou r Notion 117
membrane thicknesses a t T~tA = 105~
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
2340 J. El ect rochem. Soc., Vol. 138, No. 8, August 1991 9 The Electrochemi cal Soci ety, Inc.
drag coefficient is proport i onal to k. The inflections ob-
served near ~ = 1.59 occur because t he slope of t he k v s .
water activity curve changes when t he wat er vapor at the
interface reaches saturation. (The val ue of nd~ is 1.59 at
k = 14.) In general, t he val ue of ~ is less than ndr~g because
backdiffusion amel i orat es t he effect of t he electro-osmotic
drag.
Fi gure 8 shows t he significant advant age of t hi nner
membranes. At T~tA = 80~ four membr ane t hi cknesses
are compared. With t he t hi n 50 ~m membrane, not only is
the resistance less t han 0.05 t2-cm 2, but the flux ratio ~ is
very low compared wi t h t he drag coefficient. Thus, t he
need to cont i nuousl ~ repl eni sh t he anode wi t h water from
the cat hode in real stack operat i on becomes much smaller.
The backdi ffusi on of wat er is now able to suppl y the anode
need. Fi gure 9 shows t he effect of t he same membr ane
t hi ckness vari at i on but at an anode humi di fi er tempera-
ture of 105~ Now t he steady-state gradient of membr ane
water cont ent keeps t he resistance l ower for t he t hi cker
membranes, but it also causes more wat er to move to the
cathode.
We performed several measurement s to verify the pre-
dictions of t he wat er t ransport aspects of this model. In the
first measur ement we collected wat er from t he outlet gas
streams of a 50 cm 2 cell with a 117 Nation membrane, usi ng
Prot ot ech electrodes, and compared it wi t h t he inlet
streams. We found at 500 mA/ cm 2 that 0.2 H20 was trans-
port ed per H + at 80~
The second t ype of measur ement was that of high-fre-
quency resistance ("ohmic resistance") of a 1 cm 2 Nation
117 cell operat i ng on air and hydrogen at 80~ cell and hu-
midifier t emperat ures, and at 3 at m anode pressure and
5 at m cat hode pressure. The anode-cat hode high-fre-
quency resistance is measured at 5 kHz, where concentra-
tion polarization and faradaic effects are eliminated, leav-
ing, presumabl y, only t he membr ane resistance and any
contact resistance. Fi gure 10 shows that bot h t he experi-
ment and t he model indicate an increase in hi gh-frequency
resistance (RHF) wi t h cell current. When the anode and
cathode humi di fi er t emperat ures were raised to 105~ t he
hi gh-frequency resi st ance actually decreased slightly wi t h
current density. We do not yet underst and t he observed
de pe nde nc e of RHF on cell current when t he cell is well hu-
midified (Tsat = 105~
Some general comment s about t he approach descri bed
in this manuscri pt are in order. We woul d like to stress
again t he strong reliance, in this model i ng effort, on mem-
brane paramet ers that have been measured in our labora-
tory. We bel i eve that in t he effort to model a compl ex sys-
t em such as this, where t he results depend on so many
model parameters, the results of t he code are of little val ue
unless t hey rely to the maxi mum ext ent possible on exper-
i ment al l y deri ved parameters. In this context, let us briefly
r
0.5 t 80~
ANODE STOI CH = 3
MEASURED Hi GH @2 AJcm
0.4 FREQUENCY
PLUS 0.065 CONTACT
RESISTANCE
C~ o , 3
Z
~p, 0.2.
oo
LU
r r 0.1.
0.0
o . o 0: 2 0'.4 o : s o . s
C U R R E N T D E N S I T Y A / c m 2
Fig. 10. M e a s u r e d hi gh- f r e q u e nc y resistance o f a f u e l c e l l w i t h
Na t i o n i 1 7 compar ed w i t h mod el me mb r a ne resistance plus
0 . 0 6 5 ~ - c m 2 resistance. T h e c a t h o d e pressure was raised t o 5 a t m
( 3 a t m on a n o d e ) t o s q u e e z e t h e me mb r a n e a n d e l e c t r od e s .
revi ew the experi ment s performed, to hi ghl i ght several
aspects. The isopiestic t echni que has been shown here and
el sewhere (11) to provi de a good basis for establishing a
range of well-defined wat er cont ent s in the i onomeri c
membrane, allowing us to derive t he dependence of mem-
brane protonic conduct i vi t y and water diffusion coeffi-
cient on water content. Water (intra)diffusion coefficients
have been deri ved over a range of membr ane water con-
tents usi ng t he 1H-pulsed gradi ent spin-echo (PGSE) NMR
t echni que (11). The ~H intradiffusion coefficient was found
to vary across a full order of magni t ude as the mem-
brane water cont ent varies bet ween 2 and 14 water mole-
cules per sulfonate group. Fr om argument s of H~O/H + pop-
ulation ratio in the membr ane at hi gh water contents and
from similar apparent values of D deri ved from NMR and
from protonic conduct i vi t y at small membr ane water con-
tents, we concl ude t hat t he NMR measured D of 1H is very
close to D~20 in t he range of wat er contents probe (11). We
do intend, however, to further test t he full accuracy of this
concl usi on in some future 170 NMR experi ment s.
Anot her subtle aspect needs to be ment i oned in the con-
t ext of appl yi ng an intradiffusion coefficient, (as deri ved
from NMR or from a radioisotope labeling experiment), as
an interdiffusion coefficient, that is, usi ng the intradiffu-
sion coefficient in a Fi ck' s first l aw formal i sm (see Eq. [t9]).
In a strict analysis the intradiffusion coefficient (NMR) and
t he interdiffusion coefficient (Eq. [19]) are not necessarily
identical (15). However, to compl et e this stage of work on
the PEFC model, we felt t hat t he prot on diffusion coeffi-
cient deri ved by NMR as a funct i on of membr ane water
cont ent can yield, upon correct i on for activity coefficient,
a satisfactory approxi mat i on for t he interdiffusion coeffi-
ci ent of wat er in t he membrane. The val ues we obt ai ned
for t he intradiffusion coefficient of wat er are reasonable;
t hey fall bet ween one order of magni t ude smaller (for a
fully hydrat ed membrane) and two orders of magni t ude
smaller (for a membr ane wi t h k = 2) t han the intradiffusion
coefficient of wat er in l i qui d water, and t hey are in general
agreement wi t h other report ed val ues of D(intra) at high
(2-4) and very l ow (16) wat er contents. In fact, when the
water activity gradi ent is used in a Fi cks first law expres-
sion (Eq. [19]), t he effect D becomes al most i ndependent of
wat er cont ent (Fig. 3), at a level of 1.2 - 10 -6 cm2/s. This,
again, is a very reasonabl e result for t he diffusion coeffi-
cient of wat er in a water-absorbing i onomeri c membr ane
like Nation. It is similar in magni t ude to that reported by
Yeo and Ei senberg (14) for measurement s under interdif-
fusion conditions. The reasonabl e order of magni t ude of
Dwat~r eval uat ed here is stressed because, in other previous
contributions, much hi gher values of Dwater we r e men-
tioned, In fact, Dwate r hi gher t han t he diffusion coefficient
of wat er in liquids at t he same t emperat ure was i nvoked
(6). Such large values of Dwater we r e requi red to explain ex-
peri ment al observations, because it was assumed (4, 6)
that t he el ect ro-osmot i c drag is not l owered as the mem-
brane wat er cont ent becomes smaller. Our results show
clearly t hat experi ment al observat i ons can be fully ac-
count ed for wi t h t he apparent l y very conservat i ve IeveIs of
Dw,ter in t he membrane. These observations are based on
t he NMR measur ement s and their interpretation. The ca-
pability to account for observed cell performance with
such conservat i ve wat er diffusion coefficients is, in turn,
based on t he l oweri ng of t he electro-osmotic water drag in
the membr ane wi t h t he l oweri ng in membr ane water con-
t ent (Eq. [18]). It is t he i nt erpl ay bet ween t he diffusion
coefficient of wat er and t he degree of wat er drag, i ncl udi ng
the variations of these two paramet ers wi t h membr ane
wat er content, which, together, det ermi ne the wat er pro-
file in t he membr ane under gi ven humi di fi cat i on condi-
tions and cell current density.
In t he cont ext of t he latter point, we woul d like to stress
t he difference bet ween the electro-osmotic drag, desig-
nated by nd~,g in this paper, and t he steady-state flux ratio
H20/H + desi gnat ed by ~ because t hese t wo paramet ers
have somet i mes been i nt ermi xed in previ ous discussions
of this system. It should be clear t hat nd~g is what one
measures for a membr ane fully i mmer sed in liquid water,
when t he electro-osmotic drag is recorded at uni t activity
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
J. El ect rochem. Soc., Vol . 138, No. 8, August 1991 9 The Electrochemi cal Soci ety, Inc. 2341
of water t hroughout the system. On the other hand, i n a
fuel cell operating at steady state at a certain current den-
sity, there woul d be usual l y a significant gradient of water
cont ent (see Fig. 4), and, hence, the measured flux of water
from anode compart ment to cathode compart ment per
prot on passed t hrough the membr ane ~ would be signifi-
cantly smaller t han ndrag (see Eq. [23]). This di st i nct i on be-
t ween 13and ndrag has significant practical implications i n
the cont ext of t he ext ent of "back- pumpi ng" of water from
cathode to anode, whi ch woul d be requi red duri ng steady-
state cell operation. It shoul d be clear that the level of
water recirculation required is given by ~, not by nd~g, and
t hus is significantly lower t han woul d be suggested by
naive i nspect i on of only nd~ag.
Finally, we shoul d bri ng up two discrepancies bet ween
the real PEFC system wi t h which we have experi ment ed
and the validity domai n of this model. One noticeable dis-
crepancy is that the model does not predict the need to hu-
midify the cathode feed stream cont i nuousl y at any appre-
ciable current density. I n practice,however, we found that
i n cells based on the Nation 117 membrane, the highest
performance is obt ai ned only with well-humidified cath-
ode feed streams. We believe that this is because evapora-
tive water losses from the cell are substantial, i n practice,
at least i n our test cell configurations. Unless supplied
with an aerosol of water (T,,t = 105~ the membr ane loses
water at an excessive rate, which cannot be compensat ed
by water product i on at the cathode. This evaporative loss
is not consi dered i n our model at present, and, therefore,
the model does not predict the need for extensive cathode
humidification. On the other hand, as stressed before, the
model does not consider the effect of subst ant i al excess of
l i qui d water i n the cathode. One i mport ant effect expected
is an additional t hi n film diffusion barrier for reactant gas
t ransport (17). Such an excess of l i qui d water may be es-
sential, however, to achieve the highest degree of mem-
brane hydration, and, thus, the highest possible protonic
conductivity. How to compromi se bet ween these two con-
flicting effects of excess liquid water at the cathode is a
key to the successful operation of a PEFC.
Conclusions
We developed a simple, one-dimensional, isothermal
model of a complete pol ymer electrolyte fuel cell that has
provided useful i nsi ght into the cell' s water t ransport
mechani sms and their effect on the cell' s performance. We
applied equi l i bri um condi t i ons bet ween membr ane water
and electrode water vapor at the membrane/ el ect rode in-
terfaces and considered the electro-osmotic and diffusion
dri vi ng forces for water i n t he membr ane and diffusion for
water vapor and reactant gases i n the electrodes to obt ai n
material balances t hroughout the cell. The model used
data that we measured for 117 Nation membranes, includ-
i ng water cont ent vs. water activity and water diffusion co-
efficient, protonic conductivity, and electro-osmotic water
drag as a funct i on of membr ane water content.
The model was desi gned for water i n the vapor state i n
the electrodes, but it could accommodat e some excess liq-
uid water assumed to be very finely dispersed. Experi men-
tal verification of some of the model predictions was suc-
cessful when the measured cell was operated under
condi t i ons in which excess liquid was not present in the
cathode. Measured net steady-state water flux per H i n a
50 cm 2 cell of 0.2 H20/H + agrees with model predictions at
80~ cell and humi di fi er temperatures. Likewise, the meas-
ured hi gh-frequency resistance of a 1 cm 2 cell at an 80~
humidifier t emperat ure increased with current density, as
the model predicted. This effect was not observed when a
105~ humi di fi er t emperat ure was used.
An i mport ant concl usi on is that the net water per H flux
ratio i n a PEFC can be as little as one-t ent h of the electro-
osmotic drag coefficient measured for a fully hydrated
membrane, t hus reduci ng the probl em of water manage-
ment for PEFC stacks.
Acknowledgments
We wish to acknowl edge our many fruitful discussions
with Mr. Thomas Fuller, who cont ri but ed to the develop-
ment of the work described herein. This work was sup-
ported by the U.S. Depart ment of Energy, Office of Con-
servation and Renewabl e Energy.
Manuscri pt submi t t ed Dec. 10, 1990; revised manuscri pt
received Feb. 11, 1991.
Los Alamos National Laboratory assisted in meeting the
publication costs of this article.
LIST OF SYMBOLS
Subscri pt s
1 anode pl enum to anode interface
2 anode electrode to membr ane interface
3 membr ane to cathode interface
4 cathode to cathode pl enum interface
A anode region, or component A
B component B
C cathode region
H hydrogen, H2
N nitrogen, N2
O oxygen, O2
mem membr ane
sat saturation
w water
Superscripts
I initial val ue ent eri ng inlet flow channel s
L final value leaving i nl et flow channel s
Paramet ers and variables
D diffusion coefficient, cm2/s
F Faraday constant, 96,484 C/mol
I water mol ar flux produced at cathode J/2F, mol/
c m 2 s
J current density, A/cm 2
Mm equi val ent weight of membr ane
Mw molecular weight of water
ndrag electro-osmotic drag coefficient
N mol ar flux, mol/cm 2 S
p~ critical pressure, at m
P pressure, at m
R molar gas const ant
Rcell membr ane resistance, tl c n~ 2
t thickness, cm
T temperature, ~
Tc critical temperature, K
V cell potential, V
x mole fraction
z distance variable, cm
ratio of net H~O flux i n membr ane to H20 flux prod-
uct at cathode
ratio of net H20 flux i n membr ane to H flux i n mem-
brane
water cont ent or local ratio H~O/SO~ i n the mem-
brane
p density, g/cm 3
stoichiometric coefficient
REFERENCES
1. R. A. Lemons, J. Power Sources, 29, 251 (1990).
2. M. Verbrugge and R. Hill, J. Phys. Chem., 92, 6778
(1988).
3. M. Verbrugge, This Journal, 136, 417 (1989).
4. R. Hill and M. Verbrugge, ibid., 137, 886 (1990).
5. J. L. Fales, N. E. Vanderborgh, and P. Stroeve, in "Dia-
phragms, Separators, and Ion-Exchange Mem-
branes," J. W. van Zee, R. E. White, K. Kinoshita,
and H. S. Burney, Editors, PV86-13, p. 179, The
Electrochemical Society Soft bound Proceedings
Series, Penni ngt on, NJ (1986).
6. T. Ful l er and J. Newman, i n "Fuel Cells," R. E. White
and A. J. Appleby, Editors, PV 89-14, p. 25, The Elec-
trochemical Society Soft bound Proceedings Series,
Penni ngt on, NJ (1984).
7. D. Bernardi, ibid., p. 51.
8. J. C. Slattery and R. B. Bird, At ChE J., 4, 137 (1958).
9. R. E. De La Rue and C. W. Tobias, This Journal, 106,
827 (1959).
10. "Handbook of Chemi st ry and Physics, " 62nd ed., C R C
Press, Boca Raton, FL (1981).
11. T. Zawodzinski, M. Neeman, L. Sillerud, and S.
Gottesfeld, J. Phys. Chem., Submi t t ed.
12. C. Derouin, J. Pafford, S. Radzinski, T. Springer, and
S. Gottesfeld, Abst ract 627, p. 903, The Electrochem-
ical Society Ext ended Abstracts, Vol. 89-1, Los
Angeles, CA, May 7-12, 1989.
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP
2342 J . E l ec troc hem. S oc., V ol . 138, No. 8 , Au gu st 19 9 1 9 The Electrochemical Society, Inc.
13. A. B. LaConti, A. R. Fragala, and J . R. Boyack, in
"El ect rode Materials and Processes for Energy Con-
versi on and Storage, " J. D. E. McIntyre, S. Srini-
vasan, and F. G. Will, Editors, PV 77-6, p. 354, The
El ect rochemi cal Soci et y Soft bound Proceedi ngs
Series, Penni ngt on, NJ (1977).
14. S. C. Yeo and A. Ei senberg, J. Appl . Pol ym. Sci., 21, 875
(1977).
15. J. Crank, "The Mat hemat i cs of Diffusion," 2nd ed.,
Clarendon, Oxford (1975).
16. T. Nguyen, J. C. Hedst rom, and N. Vanderborgh, in
"Fuel Cells," R. White and A. Appleby, Editors,
PV 89-14, p. 39, The El ect rochemi cal Society, Soft-
bound Proceedi ngs Series, Penni ngt on, NJ (1989).
17. T. E. Spri nger and I. D. Raistrick, Thi s Journal , 136,
1594 (1989).
Measurements of Double-Layer Capacitance at the Preoxidized
Ni/Fused Na2S04 Interface
Y i i n g - M e i Wu * "
De par t me nt of Mat er i al s Sci ence and Engi neeri ng, The Ohio St at e Uni versi t y, Col umbus, Ohio 43210
ABSTRACT
The doubl e-l ayer capaci t ance in a fused Na2SO4 film on a preoxi di zed Ni el ect rode at 1200 K was measured by elec-
t rochemi cal i mpedance spectroscopy. The capacitance-potential curve has a maxi mum at a potential of -0. 6 V vs.
Ag/Ag2SO4, silica reference electrode, resul t i ng from the additional cont ri but i on of a faradaic reaction.
Most of t he studies of doubl e-l ayer properties have been
conduct ed on met al el ect rodes in aqueous solutions (1-5).
Only a few researchers i nvest i gat ed t he capacitance (C)-
pot ent i al (E) relation in mol t en salt electrolytes. Graves
and I nman (6) have revi ewed t he case for a liquid lead elec-
t rode in KC1-LiC1 melts. The capaci t ance is t hought to
compri se bot h t he doubl e layer and faradalc contributions.
The shape of t he C-E curve is parabolic wi t h a mi ni mum at
the Epzc (potential of zero charge). More recently, Pai nt er
et al. (7) used a model of charged hard sphere fluid in con-
t act wi t h a charged hard el ect rode wall to expl ai n t he fea-
t ures of t he capaci t ance for t he metaYmolten salt (alkali
halides) interface. Al t hough t he magni t ude of the calcu-
lated capaci t ance is comparabl e wi t h experi ment al values,
t he t emperat ure dependence of capaci t ance at Epzc cannot
be reproduced by the hard sphere model. This probabl y
arises from "rel axat i on" of t he structure, especially near
t he met al / mol t en salt interface, where t he interactions be-
t ween metal-ion and ion-ion are strongest.
In t he current study, t he capaci t ance in a fused Na2SO 4
film on a preoxi di zed Ni el ect rode was measured by elec-
t rochemi cal i mpedance spectroscopy. With an appropri at e
equi val ent circuit, obt ai ni ng capaci t ance val ues from im-
pedance measur ement s is straightforward and accurate, as
compared to ot her pulse met hods (8). This syst em was
chosen because of its rel evance to t he hot corrosion degra-
dation of metals or alloys in gas t urbi nes and ot her fuel
combust i on systems. Furt hermore, as t he devel opment of
t he mol t en salt fuel cells and batteries advances, t he need
for i nformat i on on t he st ruct ure of t he el ect rode/ mol t en
salt interface has become rat her urgent. Double-layer ca-
pacitance, among ot her surface properties, is an i mport ant
and experi ment al l y accessible paramet er in that respect.
Experimental Procedure
Thin film i mpedance measur ement at 1200 K were car-
ried out usi ng t he apparat us and procedures report ed ear-
lier (9). The worki ng el ect rode (WE) was a 99.9975% pure
preoxi di zed Ni wire wound around t he out er surface of an
yttria-stabilized zirconia reference el ect rode (RE). A plati-
num foil count erel ect rode (CE) enci rcl ed t he zirconia RE
wi t hout t ouchi ng t he preoxi di zed ni ckel WE. The space
bet ween t he CE and WE was made small (about 2 mm) so
t hat a t hi n layer of used salt coul d be hel d t here during an
experi ment . A fused silica reference el ect rode also con-
* Electrochemical Society Student Member.
Present address: Mobil Research and Development Company,
Paulsboro, New Jersey 08066-0486.
t act ed t he nickel WE to act as t he second RE. The combi-
nation of t he zirconia and silica reference el ect rodes pro-
vi ded measures for bot h t he basicity and oxygen pressure
at t he WE. The Ni WE was preoxi di zed in pure oxygen at
1200 K for 2 h, resul t i ng in an oxi de t hi ckness of 4.3 ~m.
Aft er this preoxi dat i on, Ni WE arrangement was im-
mersed briefly into fused Na2SO4 cont ai ned in a silica cru-
cible, and t he gas at mosphere was changed to a catalyzed
0.1% SO2-O2 gas mi xt ure. Upon wi t hdrawal of t he sampl e
from t he melt, a t hi n fused salt film covered t he electrodes.
The t hi ckness of t he fused salt film bet ween t he WE and
CE was about 2 mm. The previ ous st udy (9) had shown
that t he WE was passive under t hese conditions, i.e., t he
salt film did not directly cont act t he Ni met al substrate.
El ect rochemi cal i mpedance measur ement s were per-
formed wi t h a Pri ncet on Appl i ed Research (PAR) 5208
t wo-phase lock-in analyzer and a PAR 273 pot ent i ost at in-
terfaced t hrough an I EEE 488 bus to an IBM PS-2 com-
puter. This syst em generat ed a sinusoidal voltage whi ch
was appl i ed to t he WE wi t h a maxi mum ampl i t ude less
t han 10 mV for frequenci es ranging from 10 -3 to 105 Hz. A
fast Fouri er t ransform (FFT) t echni que was empl oyed for
frequenci es from 10 -3 to 10 Hz to increase measur ement
speed and l ower t he degree of pert urbat i on to t he cell.
Through use of t he potentiostat, polarization of t he WE
wi t h respect to t he silica RE was performed and imped-
ance measur ement s were made after t he polarization cur-
rent was stabilized (change of less t han 10% per 10 min).
I mpedance data were st or ed and pl ot t ed by t he comput er.
Pot ent i odynami c polarization was conduct ed with t he
same pot ent i ost at in a separate experi ment . The scan rate
was 1 mV/s.
Results and Discussion
Fi gure 1 shows t he typical i mpedance spect rum at t he
open-circuit pot ent i al and t he correspondi ng equi val ent
circuit, whi ch were report ed earlier (9). In Fig. 1, the low-
frequency Warburg i mpedance corresponds to t he diffu-
sion of oxidant, $2072-, in t he t hi n salt film
Wo = ~or - j), j = ~ [1]
where % is t he Warburg coefficient, as shown in the equiv-
alent circuit in Fig. 1, co = 2~rf and f is the frequency. The
t wo semicircles at medi um and hi gh frequenci es were at-
t ri but ed to t he i mpedance for t he charge transfer at t he ox-
ide-salt interface, Ro/s, and t he resistance to t he movement
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 181.95.205.114 Downloaded on 2014-08-26 to IP