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Experimental characterization methodology for the identification of voltage losses of PEMFC: applied to an open cathode stack

Abstract

The objective of this study is to describe the methodology used to isolate the main voltage loss indicators through a simple and effective treatment of a current interrupt and current sweep. The voltage loss indicators are activation polarization, mass transport, and ohmic losses. The indicators for these losses are the Tafel slope, mass transport resistance and ohmic resistance respectively. The use of this methodology to isolate the individual voltage losses works quite well. Even though there may be some inaccuracies, the trends can be clearly seen. This methodology can be used in any PEMFC system to monitor the state of health of the fuel cell. If this method were to be automated and implemented on a periodic basis, then an on-line measurement of the individual voltage losses could be monitored. The data analysis indicates that a major objective of the controller will be to minimize the mass transport losses by implementing proper temperature control.

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Experimental characterization methodology for the identification of voltage losses of PEMFC: applied to an open cathode stack

Author: Husar, Attila Peter,Strahl, Stephan,Riera, Jordi (Riera Colomer)
Year: 2012
DOI: 10.1016/j.ijhydene.2011.11.130
Source: https://upcommons.upc.edu/bitstream/2117/15792/1/1276-Experimental-Characterization-Methodology-for-the-Identification-of-Voltage-Losses-of-PEMFC_-Applied-to-an-Open-Cathode-Stack.pdf
Expe imen al Cha ac e iza ion Me hodology o he
Iden i ica ion o Vol age Losses o PEMFC: Applied
o an Open Ca hode S ack
A. Husa *, S. S ahl, J. Rie a
Ins i u de Robò ica i In o mà ica Indus ial (CSIC-UPC)
C/ Llo ens i A igas 4-6 08028 - Ba celona (SPAIN)
(*) co esponding au ho : ahusa @i i.upc.edu
Keywo ds: Ac i a ion losses, Mass anspo losses, Ohmic losses, PEMFC, Open ca hode
Abs ac : The objec i e o his s udy is o desc ibe he me hodology used o
isola e he main ol age loss indica o s h ough a simple and e ec i e ea men o a
cu en in e up and cu en sweep. The ol age loss indica o s a e ac i a ion
pola iza ion, mass anspo , and ohmic losses. The indica o s o hese losses a e
he Ta el slope, mass anspo esis ance and ohmic esis ance espec i ely. The
use o his me hodology o isola e he indi idual ol age losses wo ks qui e well.
E en hough he e may be some inaccu acies, he ends can be clea ly seen. This
me hodology can be used in any PEMFC sys em o moni o he s a e o heal h o he
uel cell. I his me hod we e o be au oma ed and implemen ed on a pe iodic basis,
hen an on-line measu emen o he indi idual ol age losses could be moni o ed.
The da a analysis indica es ha a majo objec i e o he con olle will be o minimize
he mass anspo losses by implemen ing p ope empe a u e con ol.
1 In oduc ion
Rema kable p og ess has been made in polyme elec oly e memb ane uel cell
(PEMFC) ma e ials, componen design, p oduc ion and sys em powe densi y.
Howe e , he e is s ill signi ican wo k o be done in o de o unde s and he di e en
physical phenomena wi hin a wo king uel cell and how hey need o be con olled in
o de o imp o e e iciency, ope a ing ange and s abili y [Li 2008]. This expe imen al
s udy is ocused on iden i ying he majo ol age losses in a PEMFC wi h a simple,
ye e ec i e, me hod using only cu en , ol age, and PEMFC s ack empe a u e
measu emen s. In he li e a u e simple me hodologies ha e been sugges ed as a
way o decompose he i-V pe o mance cu es and he e o e isola e indi idual losses
[Baghalha 2010], [Wu 2008]. The majo losses o be iden i ied a e ac i a ion, mass
anspo and ohmic esis ance. Fo each o hese losses, indica o s ha e been
de e mined. The expe imen al me hodology used o ex ac he indi idual indica o s
is based on wo dynamic es s: cu en in e up and cu en sweep. The ex ac ion
me hods a e explained and he esul s using hese me hods a e p esen ed.
Fi s , he uel cell ol age loss model will be explained in sec ion 2 ollowed by he
expe imen al me hodology o dissec ing he i-V cu e in sec ion 3. Sec ion 4
desc ibes he expe imen al se up and es condi ions ollowed by a discussion o
esul s and he conclusions.
The objec i e is o isola e and iden i y he main ol age loss indica o s wi h a
simple and e ec i e ea men o a cu en in e up and cu en sweep.
2 Fuel Cell Vol age Losses Model
In he widely published [O’Hay e 2009] basic uel cell model used in his wo k, he
uel cell ol age ( ) is equal o he he modynamic e e sible po en ial ( ( )) o a
PEM uel cell minus he h ee majo losses: ac i a ion ( ), mass anspo ( )
and ohmic ( ).
( ) [ ] (1)
The he modynamic e e sible po en ial is ep esen ed by he ollowing equa ion
[O’Hay e 2009]:
( ) (
)
(∏
∏
) (2)
whe e is he change in en halpy and is he change in en opy o he eac ion a
s anda d empe a u e and p essu e, which in his s udy is conside ed o be 25ºC and
1 a m and has a alue o -285826 J/mol and -163 J/mol/K espec i ely. I mo e
accu acy is needed hen equa ions can be in oduced o make he en halpy and
en opy a unc ion o empe a u e. ep esen s he numbe o elec ons ans e ed
pe mole, which in his case is 2 o H2, F is Fa aday’s cons an and R is he uni e sal
gas cons an . is he uel cell ope a ing empe a u e. and a e he
ac i i ies a he inle condi ions, which a e: pa ial p essu e o H2O apou ( he
p oduc ) and H2 and O2 ( he eac an ) di ided by he o al gas p essu e ha en e s
he uel cell. is he co esponding s oichiome ic coe icien o each species
pa icipa ing in he eac ion, which is 1 o all o hem excep o O2, which is
⁄.
2.1 Ac i a ion pola iza ion losses:
A ce ain p opo ion o ene gy is needed o s a he chemical eac ion. This
phenomenon p oduces a non-linea ol age d op called ac i a ion pola iza ion. These
losses occu on bo h anode and ca hode ca alys s. Howe e , he oxygen educ ion
eac ion kine ics is much slowe han hyd ogen oxida ion eac ion, and he educ ion
eac ion p oduces a much la ge magni ude o ac i a ion pola iza ion loss. The
oxida ion eac ion on he anode is much as e and p ac ically cons an h ough ou
he cu en ange. I only a single eac ion is conside ed hen he ol age loss due o
ac i a ion pola iza ion can be desc ibed by he Ta el equa ion [Ba bi 2005]:
(
)
(
) [ ] (3)
The pa ame e is he cha ge ans e coe icien and exp esses how he change
in he elec ical po en ial ac oss he eac ion in e ace changes he eac ion a e. I
depends on he ype o eac ion and he elec ode ma e ial. I s alue is heo e ically
be ween 0 and 1 depending on he ca alys ma e ial [La minie 2003]. I physically
ep esen s he ac ion o addi ional ene gy ha goes owa d he ca hodic educ ion
eac ion a an elec ode. The cha ge ans e coe icien can also be hough o as a
symme y coe icien o he elec ode eac ion and i is ypically conside ed o be
a ound 0.5 wi h hyd ogen and oxygen eac ing on a pla inum ca alys [Mench 2008].
The exchange cu en densi y [ ] is he a e a which he eac ion p oceeds
(simul aneously in bo h di ec ions) a equilib ium po en ial ( ( )) when he ne
cu en equals ze o [Ba bi 2005]. The exchange cu en densi y is a measu e o he
e ec i eness o he elec ode in p omo ing he elec ochemical eac ion whe e he
highe he exchange cu en densi y, he lowe he o e all ac i a ion losses. The uel
cell cu en densi y is deno ed by [ ]. The ac i a ion losses a e gene ally he
dominan e ec on he uel cell ol age, as is shown in igu e 1.
When he uel cell is no connec ed o an ex e nal ci cui (open ci cui ol age), he
uel cell ol age would be expec ed o be close o he he modynamic po en ial,
ela i e o he ambien condi ions and eac an pa ial p essu e. Howe e , he
measu ed uel cell ol age is much lowe , usually less han 1 V/cell, which can be
a ibu ed o hyd ogen c osso e and in e nal cu en s. These losses a ise because
he memb ane in a PEMFC is sligh ly elec onically conduc i e and pe meable o
gasses. These losses can be conside ed as an in e nal cu en . The amoun o
cu en ha hese losses ep esen is a he small compa ed o no mal ope a ing
cu en s. Howe e , hese in e nal cu en losses ha e a la ge e ec on he ol age
when he ex e nal cu en is e y small. In his s udy hese losses a e conside ed
pa o he ac i a ion losses [Ba bi 2005] and should no a ec he esul s.
The Ta el slope is he main indica o o ac i a ion losses and will be explained in
mo e de ail in sec ion 3.3.
2.2 Ohmic losses:
The esis ance o he low o elec ons h ough he elec ically conduc i e uel cell
componen s and o he low o ions h ough he memb ane causes a ol age d op,
which can be exp essed by Ohm’s law:
[ ] (4)
The in e nal cell esis ance is in [ ]. The elec ic and con ac
esis ance can be conside ed cons an wi h espec o cu en and empe a u e. Thus
any change in he esis ance is only dependen on memb ane wa e concen a ion
and memb ane empe a u e. [Sp inge , 1991]
is he indica o o memb ane ionic esis ance.
2.3 Mass anspo losses:
The consump ion o eac an gases a he ca alys laye s leads o concen a ion
g adien s and hus changes he pa ial p essu e o he eac an s, which a ec s he
uel cell ol age as seen p e iously in equa ion (2). Re e ing o Fa aday's law o
elec olysis, he ans e ed cha ge and he mola lux o a eac an a e p opo ional
o he cu en densi y [Ba bi 2005]:
[ ] (5)
The highe he cu en densi y, he lowe he eac an concen a ion is a he
ca alys laye .
The cu en densi y a which he eac an concen a ion eaches ze o is called he
limi ing cu en densi y ( ). Conside ing his ela ionship be ween eac an mass
anspo and cu en densi y, he mass anspo losses can be exp essed as [Ba bi
2005]:
(
) (6)
Howe e his exp ession o mass anspo losses does no ep esen he
expe imen al alues well [O’Hay e 2009]. In a o ced low open ca hode uel cell
whe e he ai eac an s oichiome y is always o e 10 and he maximum cu en
d awn om he s ack is ela i ely low (0.27 A/cm2) i is assumed ha he mass
anspo losses a e neglec ed o cu en densi ies o less han 0.04A/cm2 and a e
conside ed linea beyond ha cu en densi y. High cu en densi ies a e no possible
wi h open ca hode s ack due o he lack o humidi ica ion and he s anda d ope a ing
condi ions, hence he mass anspo losses seem linea .
( ) (7)
3 Expe imen al Me hodology Applied o Open Ca hode PEMFC
The ollowing expe imen al app oach is used o isola e he indi idual losses in he
uel cell s ack. The da a p esen ed in he ollowing sec ion is an example o eal da a
ea ed using his me hod. The main di icul y is o isola e mass anspo om
ac i a ion losses.
As he Nyquis plo s om Elec ical Impedance Spec oscopy (EIS) only gi e
linea in o ma ion a he measu ed poin o ope a ion, ano he me hod o de e mine
he nonlinea losses caused by he ac i a ion a e desc ibed.
Al hough he da a used in his explana ion co esponds o an open ca hode uel
cell, he me hodology is alid o all PEMFC.
3.1 Cu en in e up
The pu pose o he cu en in e up (CI) is o ob ain he ohmic esis ance ( )
o he uel cell in a as and accu a e manne . The p incipal concep is o isola e he
esis ance ha is ou side o he RC ci cui , which should be seen as an
ins an aneous jump in ol age when he load is emo ed, because i has no
capaci i e componen . The de eloped algo i hm de ec s he jump in ol age when
he load is disconnec ed and sepa a es he cu e in wo s aigh lines o gene a e he
poin whe e he ins an aneous ol age inc ease s ops, as illus a ed in igu e 2. The
algo i hm de ec s he jump by looking o 3 consecu i e poin s o ising ol age and
hen uses he i s poin as he e ical line. Then looks o he poin a e he jump
whe e he di e ence be ween he poin s is less han 0.002V and hen c ea es a line
using he ollowing 10 poin s.
EIS da a has been compa ed o he ohmic esis ance measu emen ia he
cu en in e up me hod in o de o calib a e he de ec ion algo i hm o he EIS
esul s, shown in igu e 3.
3.2 Cu en sweep
The pu pose o he cu en sweep is o ob ain an i-V cu e o he uel cell wi h
minimal changes o he in e nal condi ions. This is done by quickly passing h ough
speci ically selec ed cu en se poin s.
In his s udy cu en sweeps we e pe o med when he uel cell eached s eady
s a e condi ions, howe e i is no necessa y. The ime cons an o he sys em was
de e mined om he EIS bode diag am and is de e mined o be in he o de o
. I is in e es ing o no e ha he ime cons an o he uel cell inc eases as
he cu en dec eases. The ime needed o he ol age o s able ou a a cu en se
poin o 0 A/cm2 is much longe han a he o he cu en s, which can be clea ly seen
in igu e 4.
In his s udy he uel cell is le a each cu en se poin o only 300ms, which
p o ided enough ime o he uel cell o s able ou .
As can be seen in igu e 4 he e a e 10 cu en es poin s, 4 poin s wi h a
di e ence o he ope a ing cu en o 5% o he ope a ing cu en and 6 poin s in he
nonlinea egion a lowe cu en densi ies. The 4 poin s a ound he ope a ing
condi ion gi e a good eading o he linea slope o he uel cell. The 6 poin s a he
low cu en densi ies gi e a good eading on he nonlinea egion o he uel cell. The
black line in igu e 1 shows he plo o he ex ac ed cu en sweep (i-V) om igu e 4.
The es ime a each se poin has o be kep o a minimum due o he na u e o
he open ca hode sys em whe e he wa e con en and he empe a u e in he uel
cell a e d i en by he cu en . The o al ime o he cu en sweep could be educed
o less han 1s i necessa y. Howe e i can be no ed in his es ha e en a a o al
o 3s, he ol age be o e and a e he es a e he same.
3.3 B eakdown o he cu en sweep
Using he esis ance da a om he CI and assuming ha mass anspo losses
a e negligible ( ) a cu en densi ies o less hen 0.04A/cm2 ( he nonlinea
pa o he sweep), equa ion (1) was sol ed o .
(8)
A loga i hmic unc ion is i ed o he da a om 0.00 o 0.04 A/cm2 as shown in
igu e 5. The slope o his line in he loga i hmic scale is he Ta el slope, and he
in e cep on he x axis is he exchange cu en densi y.
(9)
Using he i ed Ta el slope and exchange cu en densi y he line was
ex apola ed ou o he s eady s a e cu en se poin . Thus he di e ence be ween
he he modynamic e e sible po en ial ( ) and he ex apola ed cu e gi es
ac i a ion losses ( ) seen in igu e 1.
Now looking back a equa ion (1) all he a iables a e known excep o ( ),
which now can be sol ed. Wi h his, he b eakdown o he indi idual losses can be
plo ed, as shown in Figu e 6.
The x-axis in e cep o he mass anspo losses a e a i icially se o 0.04 A/cm2
due o he assump ion ha he e a e no mass anspo losses a he lowe cu en
densi ies. This can be seen in igu e 5 whe e he do ed end line sepa a es om he
solid line.
Take no e ha he losses calcula ed using his me hod is only alid o he cu en
and empe a u e a which he sweep and CI we e aken, which in his case is he
middle poin a 4 Amps and 32.2ºC.
I his me hod is au oma ed and implemen ed on a pe iodic basis hen an on-line
measu emen o he indi idual ol age losses could be moni o ed.
4 Expe imen al se up & ope a ing condi ions
A Ho izon® H-100 open ca hode, 20 cell, 22cm2 ac i e a ea uel cell s ack in an
en i onmen al chambe was es ed. The only ac i e con ol mechanism employed is
a single an ha bo h cools and p o ides he oxygen needed o he eac ion. All he
o he con ol mechanisms a e disconnec ed and a cons an pu e, d y hyd ogen low
is supplied o he s ack.
The ambien condi ions se in he en i onmen al chambe we e 25ºC wi h 90%RH.
The s eady s a e cu en densi ies o 0.09, 0.18, and 0.27A/cm2 co espond o 2, 4
and 6A. The combined ca hode and cooling an was se o con ol a cons an uel cell
empe a u e. The uel cell empe a u e se poin s a e: om a minimum empe a u e,
30, 35, 40, 45, 50, 55ºC. Pu e d y hyd ogen was supplied o he anode a 0.36, 0.71
and 1.07 SLPM as he s eady s a e cu en was inc eased om 2, o 4 and 6A
espec i ely.
LabVIEW da a acquisi ion so wa e was used in conjunc ion wi h analog o digi al
con e e (ADC) o he NI da a acquisi ion sys em combined wi h he HCPL-788J
isola ion ampli ie om Agilen Technologies o measu e he s ack ol age. The hall-
e ec -based cu en senso ACS713 om Alleg o Mic oSys ems measu es he
cu en in he load ci cui . The swi ch used o pe o m he cu en was an in elligen
powe highside swi ch IPS6021 om In e na ional Rec i ie . Finally, he da a

acquisi ion ca d used o he high equency es was a PCI-DAS 4020/12 om
Measu emen Compu ing, whe e he sampling a e can be se om 1kHz o 20MHz.
5 Resul s and Discussion
In his sec ion se e al esul s a e discussed, wi h espec o cu en and ambien
empe a u e.
The load on he s ack ob iously has he la ges in luence on he uel cell ol age
loss as seen in igu e 7. I is in e es ing o no e ha a all h ee cu en s he ol age
losses dec ease wi h an inc ease in empe a u e bu i is only he 6A cu e ha has a
nonlinea dec ease. The sou ce o he nonlinea i y will be discussed in sec ion 5.2
and 5.3 and shows he p ac icali y o his me hodology as a diagnos ic ool.
The nex sec ions will discuss he e olu ion o he indi idual ol age losses a he
di e en cu en s and uel cell ope a ing empe a u e.
5.1 Ac i a ion losses e alua ion
The ac i a ion losses a e shown in igu e 8. They dec ease linea ly wi h uel cell
empe a u e in hese anges o cu en s and empe a u es. The eason o he linea
dec ease in ac i a ion losses is due o he dec ease in he modynamic e e sible
po en ial (Eo) which dec eases wi h uel cell empe a u e, hus causing he ac i a ion
losses o dec ease. Howe e , he o iginal cu en sweep da a does no show his
dec ease. The low cu en densi y cu en sweep da a o he same cu en a
di e en empe a u es a e iden ical o each o he a less han 0.04 A/cm2. Thus his is
only a heo e ical dec ease in ac i a ion losses due o he o de in which he da a
was decomposed.
The Ta el slope, being he indica o o ac i a ion losses, e lec s he linea i y as i
seems o emain ela i ely cons an wi h espec o empe a u e a each cu en
es ed, as shown in igu e 9.
5.2 Mass anspo losses e alua ion
The mass anspo losses inc ease g ea ly wi h he inc ease in cu en (see igu e
10), which is expec ed acco ding o equa ion 5 and 6. All he measu emen e o s a e
inco po a ed in o his indica o due o he o de in which he ol age loss
decomposi ion was done. Howe e , an in e es ing end is seen wi h ega d o
empe a u e. The e is a gene al linea dec ease in mass anspo losses wi h he
inc ease in uel cell empe a u e and seems o be linea o empe a u es lowe han
50ºC. Howe e , when empe a u es go beyond 50ºC, he e seems o be s abling ou
o he losses. This can be seen d ama ically in he mass anspo indica o shown in
igu e 11.
This elbow in he 6A da a sugges s ha he e is a change in s a e o he di usion
and/o ca alys laye s. This could possibly be due o he e apo a ion o mos o he
liquid wa e in hese laye s allowing o maximum di usion lux. The e is a possible
ade-o o maximizing di usion wi h inc eased memb ane esis ance, as will be
shown in he ohmic losses sec ion.
5.3 Ohmic esis ance losses e alua ion
Ohmic losses inc ease wi h an inc ease in cu en and empe a u e. The e seems
o be a dis inc upwa d end as he uel cell eaches 45ºC. This may indica e ha
beyond his empe a u e and inle ela i e humidi y he memb ane is no ully
sa u a ed, which ein o ces he hypo hesis ha he e is no mo e liquid wa e in he
laye s.
E en hough he ohmic losses a e ela i ely small compa ed o he o he losses in
he uel cell, he e may be some undesi able long- e m deg ada ion caused by a d y
memb ane.
The Ohmic esis ance anges om 0.115 o 0.140 (Ohm-cm2). This is compa able
o s udies in he li e a u e which indica e anges om 0.100 o 0.182 (Ohm-cm2) o
Na ion 212 and 117 espec i ely [Hou 2011], [Büchi 1996]. Fuel cell esis ance Rohm
is ela i ely cons an a each cu en o empe a u es below 45ºC.
6 Conclusions
The p oposed me hodology in his wo k o isola e he indi idual ol age losses
unc ions qui e well. E en hough he e may be some inaccu acies, he ends a e
clea ly seen. This me hodology can be used o moni o any PEMFC s a e o heal h
wi h espec o ac i a ion, mass anspo , and ohmic losses.
I mus be no ed ha all he powe gene a ed du ing he sweep would be los .
Thus i will a ec he in ended pe o mance o he sys em. Capaci o s could be
placed in pa allel wi h he uel cell o supply he needed powe du ing he sweep. The
e iciency loss due o he sweep will be dependen on he equency and he du a ion
o he sweeps. This analysis has no been done bu i is s ongly dependen on he
uel cells design and i s sensibili y o he ope a ing condi ions. An op imiza ion
analysis o he sweep, in o de o minimize he equency and he du a ion o he
sweeps, would also need o be done.
I his me hod is au oma ed and implemen ed on a pe iodic base, hen an on-line
measu emen o he indi idual ol age losses could be moni o ed.
Th ough analysis o he open ca hode uel cell da a i is clea ha a majo
objec i e o he con olle will be o minimize he losses h ough p ope con ol o he
empe a u e by means o he an.
Fu u e wo k will be dedica ed o de e mining how he hyd ogen pu ge a e, inle
empe a u es and ela i e humidi y a ec he indi idual losses.
7 Acknowledgemen s
All he expe imen al es s we e pe o med a he Fuel Cells Labo a o y o he
Ins i u de Robó ica i In o má ica Indus ial (CSIC-UPC, Ba celona) and a e only
possible due o i s ad anced equipmen and p o icien echnical s a . This wo k is
pa ially unded by he p ojec o CICYT DPI2010-15274 MICINN and CICYT
DPI2011-25649 MICINN
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9 Figu e Legend
Fig. 1. G aphical ep esen a ion o equa ion (1) depic ing he h ee main losses a a gi en cu en
(g aph based on eal da a 4A a 32.2ºC)
Fig. 2. CI da a o 3 es s a he same ope a ing condi ion o show epea abili y. Ohmic esis ance using
CI is 0.121-cm2
Fig. 3. Nyquis plo a he same condi ions (4A) as he CI da a. Ohmic esis ance using EIS is 0.119-
cm2
Fig. 4. A e age cell ol age and cu en densi y dynamic o a cu en sweep wi h 300ms a each poin .
No e ha he ol age be o e and a e he es is he same.
Fig. 5. The solid line ep esen s he eal da a (ETP – V c - iRohm). The linea ex apola ion o he lowe
cu en densi y poin s is ep esen ed by he do ed line. No e ha i is in a loga i hmic scale.
Fig. 6. The g aph depic s he b eakdown o he ol age losses om expe imen al da a.
Fig. 7. The g aph shows he e olu ion o o al ol age loss a h ee di e en cu en s 2, 4, 6A as a
unc ion o uel cell empe a u e wi h cons an en i onmen al condi ions
Fig. 8. Ac i a ion losses o he uel cell s ack
Fig. 9. Ta el slope as ac i a ion indica o
Fig. 10. Mass anspo losses
Fig. 11. Linea mass anspo indica o ep esen ed as a esis ance o 2, 4 and 6A.
Fig. 12. Ohmic losses wi h espec o cu en and empe a u e
Fig. 13. Ohmic esis ance as he ohmic indica o