You are on page 1of 7

Tanmoy Paul

Department of Physics,
Indian Association for the Cultivation of Science,
2A & 2B Raja S.C. Mullick Road,
Analysis of Drying and Dilution
Jadavpur, Kolkata 700032, India
e-mail: paultanmoy00@gmail.com
in Phosphoric Acid Fuel Cell
Mrinal Seal
Department of Physics,
(PAFC) Using Galvanometric
Bengal Engineering & Science University,
Shibpur, West Bengal 711103, India
Study and Electrochemical
e-mail: mrinal.phy@gmail.com

Dipali Banerjee
Impedance Spectroscopy
Professor
Different experimental and analytical techniques namely steady state galvanometric
Department of Physics,
study and electrochemical impedance spectroscopy (EIS) are employed to generate rule
Bengal Engineering & Science University,
sets for identification of the acid drying and dilution phenomena in a phosphoric acid
Shibpur, West Bengal 711103, India
fuel cell (PAFC). The slope of steady state current versus voltage is used as a perform-
e-mail: dipalibanerjeebesu@gmail.com
ance marker. A new parameter D, which signifies the net moisture transport in PAFC, is
introduced and evaluated from the experimental data to locate the regimes of electrolyte
Saibal Ganguly dilution and drying. Based on these two parameters, the performance of a PAFC is
Professor mapped on the plane of operating variables. Performance decay at higher cell tempera-
Chemical Engineering Department, ture and lower humidifier temperature (below 60  C) signifies acid drying; on the con-
Universiti Technologi Petronas (UTP), trary the same at lower cell temperature and higher humidifier temperature is attributed
Bandar Seri Iskandar, Perak Darul Ridzuan, to acid dilution. EIS is employed by imposing a sinusoidal potential excitation on steady
Tronoh 31750, Malayasia state DC load and the shift of maximum phase angle position in the frequency spectrum
e-mail: gangulysaibal2011@gmail.com is used as a diagnostic marker. Results show absence of peak in the domain of positive
frequency for acid drying condition, while acid dilution causes the peak to be shifted at
Kajari Kargupta1 higher frequency value. Electrochemical timescales estimated from EIS increases by
Professor many order of magnitudes compared to that in a normal PAFC, when electrolyte drying
Chemical Engineering Department, occurs. The results obtained from EIS analysis are in agreement with the performance
Jadavpur University, mapping based on galvanometric steady analysis. The results are significant in context of
Kolkata 700032, India water management and humidity control in a PAFC. The tools and parameters intro-
e-mail: karguptakajari2011@gmail.com duced in the present publication show promising potential to map the performance and
SOH of a PAFC on the plane of various operating variables. Results and logics revealed
Pavitra Sandilya are of significance in development of inferential model for the online optimization of
Assistant Professor PAFC. [DOI: 10.1115/1.4026622]
Cryogenic Engineering Department,
I.I.T. Kharagpur, Keywords: phosphoric acid fuel cell, drying, dilution, performance mapping, EIS,
West Bengal 721302, India electrochemical time scale
e-mail: profsandilya@gmail.com

1 Introduction Phosphoric acid has low vapor pressure so it is used as an electro-


lyte to suppress the evaporation and dissipation with the process
In the present day context of new energy technology, fuel cell
gases. All these factors make PAFC a versatile member of the
has attracted substantial research initiatives for being highly effi-
hydrogen-oxygen fuel cell family.
cient and environment friendly. It is an electrochemical device
A typical PAFC is composed of two porous gas diffusion elec-
that converts chemical energy to electrical energy [1–3]. Phos-
trodes, namely, the anode and cathode juxtaposed against a porous
phoric acid fuel cell (PAFC) technology has the most extensive
electrolyte matrix. The gas diffusion electrodes are porous sub-
track record for operational experience of any of the fuel cell tech-
strates that face the gaseous feed. The substrate is a porous carbon
nologies [4]. Phosphoric acid has two properties; hydrogen bond-
paper or cloth. On the other side of this substrate, which faces the
ing network chain and self-dissociation to H4PO4þ and H2PO4.
electrolyte (phosphoric acid), platinized fine carbon powder elec-
The poor oxygen reduction reaction kinetics in PAFC due to high
tro catalyst is roll coated with poly-tetra-fluro-ethylene (PTFE) as
specific adsorption of H2PO4 makes it helpful to operate the cell
a binder. PTFE also acts as a hydrophobic agent to prevent flood-
up to 200  C and better combination of heat and power efficiency
ing of pores so that reactant gas can diffuse to the reaction site
(up to 80%) can also be achieved under such a running condition
easily. At anode, hydrogen ionizes to Hþ and migrates towards
[5]. A PAFC system has less sensitivity to carbon monoxide poi-
cathode to combine with oxygen, forming water. The product
soning of the Pt catalyst compared to polymer electrolyte
water then diffuses out to the oxygen stream and comes out of the
membrane fuel cell (PEMFC). Apart from catalyst, the other com-
system as water vapor. An electro motive force is generated
ponents used in PAFC are mainly made of graphite and carbon.
between the two electrodes through conversion of reaction free
energy to electrical potential energy and on connecting an external
1
Corresponding author. load, electrical power can be extracted.
Contributed by the Advanced Energy Systems Division of ASME for publication The reaction mechanism at cathode and anode are as follows:
in the JOURNAL OF FUEL CELL SCIENCE AND TECHNOLOGY. Manuscript received January
14, 2013; final manuscript received January 29, 2014; published online February 27,
2014. Assoc. Editor: Abel Hernandez-Guerrero. Cathode : 1=2 O2 þ 2Hþ þ 2e ¼ H2 O (1)

Journal of Fuel Cell Science and Technology AUGUST 2014, Vol. 11 / 041001-1
C 2014 by ASME
Copyright V

Downloaded From: http://fuelcellscience.asmedigitalcollection.asme.org/ on 07/30/2015 Terms of Use: http://www.asme.org/about-asme/terms-of-use


Anode : H2 ¼ 2Hþ þ 2e (2)

In PAFC, the electrolyte matrix must be sufficiently hydrated


because its conductivity solely depends on the humidity level. A
continuous operation of PAFC requires a constant acid concentra-
tion. If the acid loses moisture and gets concentrated, the ionic
conductivity decreases and ionic resistance increases. As a result,
the operating temperature should be increased to enhance ioniza-
tion. An alternative to this is to increase the humidity level in the
inlet gas so that the acid concentration decreases. However, if
the acid gets diluted, the volume increases and acid is lost from
the system as carryover mist. Excess water increases the liquid
volume fraction in catalyst pores causing starvation of the oxygen
for the reactive catalyst site and acid flooding. Flooding blocks
the porous passages and reduces the transport rate of reactants to
the catalyst site. Electrolyte drying and cathode flooding are gen-
erally recognized as the primary reasons for poor cell perform-
ance. To achieve the optimal performance of PAFC, it is crucial
to have an adequate water balance to ensure good proton conduc-
tivity of the electrolyte. Water content of electrolyte/acid concen-
tration is determined by balance between production of moisture
and different water transport processes viz. back diffusion of
water from the cathode, evaporation/condensation of water to/
from the oxidant/fuel gas stream. The moisture transport by evap- Fig. 1 Experimental setup for characterization of PAFC unit
oration or condensation is critically dependent on the saturation cell
vapor pressure of water over the electrolyte. The dependence of
vapor pressure on electrolyte concentration often helps in reduc-
phase angle position in the frequency domain is used as a diagnos-
ing the imbalance of moisture in a PAFC.
tic marker to identify drying and dilution phenomena. Time con-
For the online monitoring and optimization of a PAFC, it is im-
perative to map the performance and to predict the state-of-health stants for electrochemical reaction are estimated from the Bode
plot obtained based on EIS. Electrochemical time scale analysis
(SOH) of a PAFC by identifying the drying and dilution phenom-
aids to recognize and isolate drying from dilution. The tools and
ena. Towards this direction most of the reports available are for
parameters introduced in the present publication show promising
PEMFC. From an automotive manufacturer point of view differ-
potential to map the performance and SOH of a PAFC and to de-
ent laboratory experiments and numerical analysis based on mod-
els have been employed for PEMFC to identify the SOH and to velop inferential model for online optimization of a PAFC.
study the effect of gas flow fields, temperature, partial pressure,
type of electrolyte membrane on the performance [6–18]. Based
on relevant physical processes, Choudhury et al. [3] developed a 2 Experimental Section
two-dimensional a steady state model to study the performance of
PAFC. Hirata et al. [19] developed an analysis on evaporative and 2.1 Polarization Data Generation. Figure 1 shows the sche-
condensational dissipation of phosphoric acid. Choudhury and matic experimental setup for characterization of PAFC unit cell
Rengaswamy [20] reported the characterization and fault diagno- and Fig. 2 shows the different constituent components of unit cell.
sis of PAFC through electrochemical impedance spectroscopy Figure 3 shows the mechanism of transport of different reaction
(EIS) technique where various operational issues like electrolyte species namely oxygen, hydrogen and water in a PAFC. PAFC
concentration change due to fluctuating load and unbalanced unit cell comprises of two electrodes of carbon with thin layers of
moisture control, electrode starvation due to blockage, electrode platinum (20% Pt/C) deposited on it (anode and cathode) and
fouling were addressed by Song et al. [21], who reported the glass mat soaked in phosphoric acid (electrolyte) sandwiched
effect of reactant gas flow rates and starvation on the performance between the two electrodes. This assembly is placed between two
of phosphoric acid fuel cell. Saito et al. [22] studied the electrolyte grooved graphite plates for feeding oxygen to the cathode and
management and the effect of acid volume changes on the per- hydrogen to the anode. Two stainless steel plates act as current
formance of PAFC. Bevers et al. [23] dealt with the difficult prob- collector at the two ends and all these are pressed by two end
lem of water transport inside the oxygen electrode by assuming pusher plates which are electrically isolated. Graphite gaskets are
that the surface diffusion mechanism was dominant. Schneider used for good fitting. A heater with a PID temperature controller
et al. [24] investigated flooding and drying in the fuel cell by is introduced to set and maintain a constant cell temperature. The
employing locally resolved impedance spectroscopy and NMR
imaging.
However, the performance mapping of a PAFC with respect to
the operating variables and identification of SOH of PAFC have
not been addressed in any of the above earlier reports. In the
present publication, attempt has been made to employ different
experimental and analytical techniques namely steady state galva-
nometric study, electrochemical impedance spectroscopy (EIS) as
diagnostic tools to identify the acid drying and dilution phenom-
ena in a PAFC. Based on the steady state analysis, the voltage and
current measurements of a PAFC are mapped on the plane of
operating variables, (for example, cell temperature versus humidi-
fier temperature) that are easy-to-monitor keeping other physical
parameters intact. A parameter D, which signifies the net moisture
transport in the cell, is introduced to locate the regimes of electro- Fig. 2 Schematic diagram of the constituent components of
lyte flooding and drying. Employing EIS, the shift of maximum the PAFC unit cell

041001-2 / Vol. 11, AUGUST 2014 Transactions of the ASME

Downloaded From: http://fuelcellscience.asmedigitalcollection.asme.org/ on 07/30/2015 Terms of Use: http://www.asme.org/about-asme/terms-of-use


Fig. 3 Schematic diagram of reactant and product transport mechanism in a fuel
cell unit

cell temperature was controlled at a given set point within gðtÞ ¼ gdc þ e0 sinð2pftÞ (3)
60.2  C. Teflon insulator plates are used to reduce the heat loss.
Pure hydrogen from a cylinder is passed through a humidifier to The experimentation was performed over a frequency range of
moisturize the gas that is passed to the anode through graphite 0.001 Hz to 10 kHz with amplitude of 10 mV. The shift of the
grooved plate. Hydrogen from the outlet of the grooved plate is maximum phase angle position in the frequency spectrum in Bode
passed through an adsorber to adsorb the moisture in the gas. Pure diagram is used as a diagnostic marker [20]. Over 150 impedance
oxygen from a cylinder is directly passed into the inlet of the spectra were recorded throughout the study and some experiments
graphite plate which is in contact with the cathode. The out flow being repeated as many times as ten.
of oxygen from the grooved plate is passed through an adsorber to
adsorb the outlet moisture. Throughout all experiments the inflow
and outflow hydrogen and oxygen is measured using rotameter. 3 Results and Discussions
All physical conditions were kept constant except cell and
In a phosphoric acid fuel cell, the supply of moisture is essential
humidifier temperature to find the effect regarding flooding and
to maintain the electrolyte concentration for cell performance.
drying out of the cell. The active surface area (approximately
The difference between the partial pressure of water vapor in gas
50 cm2) was kept constant throughout all experiments. To gener-
phase (either in cathode or in anode) and the saturation vapor of
ate a polarization curve the cell was tested under constant voltage
water over the electrolyte (function of cell temperature and acid
mode for 5 mins time interval and the cell currents were averaged
concentration) leads to evaporation/condensation of water vapor
over these 5 min intervals.
from/to the electrolyte. Thus, over time the electrolyte concentra-
tion varies. With respect to electrolyte concentration, the system
2.2 Steady State Experimentation. Before starting the may attain a steady state when the water transport from humidi-
experiment, the adsorbents were heated to 60  C to desorb any fied hydrogen (in anode) to electrolyte balances the water evapo-
earlier adsorbed moisture. During the experimental studies the gas ration from electrolyte to oxygen (in cathode). In extreme
flow rates were kept constant. The cell was connected with an conditions these water transport processes may lead to drying/
electrochemical work bench (AUTOLAB PGSTAT 302 N manu- flooding of the electrolyte. The variation of electrolyte concentra-
factured by Ecochemie BV). Standard hydrogen electrode was tion affects the proton conductivity.
used as the reference point for the measurement (Fig. 1). V0 was In PAFC, the water management issue and humidity control are
measured without connecting the load across cathode and anode. generally addressed by humidifying the hydrogen gas, impercepti-
A variable load was connected afterward between two current col- bly higher than the equilibrium vapor pressure of the target acid
lectors. For different load currents, the resultant voltages were concentration at operating cell temperatures. Oxygen was kept
measured (polarization data). After a period of 15 mins from start- dry. Depending on cell temperature, humidifier temperature and
ing the experiment, DC polarization data was noted. Subse- gas flow rates the electrolyte concentration varies and it becomes
quently, fixed current load was chosen (in the ohmic region of dried or diluted. For the unit cell experimentation, the flow rates
polarization data) and applied for a time period of next 4 h. of oxygen and hydrogen are kept fixed and the effect of humidifier
Adsorber weights were taken after regular interval of time and temperature and cell temperature on the performance of the unit
corresponding changes in the water levels at the humidifier was PAFC is investigated and analyzed. The phenomena like acid dry-
noted. A dry bulb thermometer was placed at the outgoing path of ing and flooding are identified quantitatively.
hydrogen and oxygen as shown in Fig. 3 and the temperatures
were noted. To measure the wet bulb temperature the thermome-
ters were kept at the same positions with wet cotton wrapping. 3.1 Effect of Acid Drying and Dilution on I-V Characteris-
tics. Figure 4 shows the polarization graph of the PAFC unit cell
2.3 Electro Chemical Impedance Spectroscopy (EIS). The at a cell temperature (Tcell ¼ 150  C) for different steady humidi-
AC impedance measurements were conducted in potentiostatic fier temperatures. From Fig. 4, it can be shown that the cell per-
mode. The sinusoidal potential excitations are expressed as formance is satisfactory above 60  C (THumid). Below this

Journal of Fuel Cell Science and Technology AUGUST 2014, Vol. 11 / 041001-3

Downloaded From: http://fuelcellscience.asmedigitalcollection.asme.org/ on 07/30/2015 Terms of Use: http://www.asme.org/about-asme/terms-of-use


Theoretically, a steady acid concentration would reach when the
overall moisture balance over the electrolyte is satisfied. Accord-
ingly, a parameter D is defined as follows:
Id
D ¼Nwa þNwc þ (4)
2F
In a PAFC cell, for a value of D very close to zero, a steady
state electrolyte concentration is reached. The performance study
clearly indicates that both the extreme dilution and drying condi-
tion have detrimental effect on current versus voltage characteris-
tics of the cell. In reality, the steady state over the electrolyte may
not reach or may reach at longer time. In the case of drying, the
sign must be negative and in the case of dilution it must be posi-
tive. Evaluation of this changing sign of D can be used as a simple
useful tool to identify the acid dilution and drying phenomena. In
this section, a mapping of cell flooding and drying out with the
value of D is presented. To evaluate D from experimental data the
average water flux to anode, Nwa and to cathode, Nwc over the ex-
perimental run time are estimated.
The average flux of water in to the cathode side over experi-
mental run time, texp is obtained from the following expression:
Fig. 4 Voltage responses for different currents at fixed cell ð texp
temperature of 150  C ½DWac þ YO2 WO2 
0
Nwc ¼  (5)
ðtexp  A  18  60Þ
temperature, there is voltage degradation (higher value of dV/dI
in the ohmic regime). where WO2 is the mass flow rate of exit oxygen stream can be
Figure 5 shows the performance of the PAFC unit cell at differ- written as
ent steady state temperatures TCell for a constant humidifier tem-   
perature (THumid ¼ 70  C). For low cell temperature (below Id
130  C), Fig. 5 shows decay in performance and increase in slope WO2 ¼ 32 mO2i  (6)
4F
of the polarization curve (higher –dV/dI in the ohmic regime).
Dilution of acid enhances the proton conductivity. However, too
The average flux of water in to the anode side over experimental
less acid concentration causes acid loss and flooding of catalyst
run time texp is
pores by liquid and thus, starvation of reactant. The sharp decay
ð texp
shown by the experimental results is attributed to the acid dilution
and flooding phenomena. To summarize, the performance decay ½DWH  DWaa  YH2 WH2 dt
0
in a PAFC due to electrolyte drying and flooding can be identified Nwa ¼ (7)
ðtexp  A  18  60Þ
from the change in slope of current versus curve. A more detailed
analysis of flooding and drying will be given in Sec. 3.2. WH2 is the mass flow rate of exit hydrogen stream can be written
as
3.2. Evaluation of Parameter D and Performance   
Id
Mapping on the Plane of Operating Variables. The acid con- WH2 ¼ 2 mH2i  (8)
centration in a PAFC changes continuously from its initial con- 2F
centration of 88% depending on the net moisture transport.
From the calculated values of Nwa and Nwc the net moisture flux
to the electrolyte has been computed using Eq. (4).
Depending on the sign of D it can be inferred that whether the
cell is operating in the electrolyte drying or dilution regime.

Fig. 6 Performance mapping of a single cell for different cell


Fig. 5 Voltage responses for different operating currents at temperatures and humidifier temperatures with the variation
fixed humidifier temperature of 70  C of D

041001-4 / Vol. 11, AUGUST 2014 Transactions of the ASME

Downloaded From: http://fuelcellscience.asmedigitalcollection.asme.org/ on 07/30/2015 Terms of Use: http://www.asme.org/about-asme/terms-of-use


Figure 6 depicts the performance mapping of PAFC on the operat- drops. As a matter of fact, the overall resistance including ionic
ing variables cell temperature versus humidifier temperature resistance increases. So the higher arc represents the drying condi-
plane. Performance of PAFC is categorized based on the slope of tion of the cell (TCell ¼ 160  C THumid ¼ 50  C). Under dilution/
current versus voltage characteristics discussed in Sec. 3.1. It also flooding condition of the cell the ionic movement increases and as
depicts the sign of D on this plane. Performance mapping clearly a result both the ionic and electronic conductivity increases and
shows four different regimes: overall resistance decreases. So the inset arc representing dilution
condition of the cell (TCell ¼ 100  C THumid ¼ 90  C). As frequency
(1) Poor performance regime at low humidifier temperature
is not explicitly shown in Nyquist diagram, the direct log fre-
due to acid drying denoted as 䉱 symbol
quency variation with phase angle in a Bode diagram is more con-
  venient to represent the data. Figures 8(a) and 8(b) depict the
dV
  0:1 ; D < 0 electrochemical response at different combination of cell tempera-
dI johmic ture and humidifier temperature. Here, for medium cell tempera-
ture of 150  C and 70  C humidifying temperature, for which the
cell performance is satisfactory, the curve shows a peak of phase
(2) Good, satisfactory performance denoted by 䉲 symbol: cur- angle in the domain of positive logarithm of frequency (Fig. 8(a)).
rent versus voltage curve is steady and almost flat in ohmic It is noteworthy that for high cell temperature and low humidifier
regime temperature for which acid drying occurs (Fig. 6), there exists no
  such peak of phase angle in the domain of positive logarithmic
dV frequency (Fig. 8(a)). The peak of phase angle exists in the do-
  0:025
dI johmic main of negative logarithmic frequency (Fig. 8(b)). On the con-
trary, for low cell temperature and high humidifier temperature
D is very close to zero. the peak of phase angle shifts towards higher value of log fre-
(3) Medium performance at low cell temperature regime quency. As described in earlier reports [25–28], the time constant
denoted by 3 symbol: current versus voltage curve is s of a particular physical or chemical process corresponds to a fre-
steady but showing decay in ohmic regime quency peak in the Bode diagram. The electrochemical reaction
time constants are calculated according to sEC ¼ 1/fpeak [28]. By
  calculating the electrochemical reaction time constants for drying
dV
0:025 <   0:075 and dilution conditions of a fuel cell a conclusive result can be
dI johmic
obtained. A comparison of electrochemical time constants for dry-
ing and dilution are given in Table 1. The electrochemical reac-
tion rate exponentially varies with the cell overpotential which is
(4) Poor performance due to acid flooding, at low cell tempera- function of proton conductivity [3]. In case of drying, poor proton
ture and high humidifier temperature. This regime is conductivity of the electrolyte decreases the electrochemical reac-
denoted by " symbol tion rate drastically and thus increases the electrochemical time
  constant (Table 1). In case of dilution the electrochemical reaction
dV rate slightly increases due to increase in proton conductivity.
  0:1 :D > 0
dI johmic

3.3 Fuel Cell’s State-of-Health Monitoring Using EIS. In


this section, experimental results of EIS at open circuit voltage are
presented. Figure 7 shows the Nyquist diagram for the two
extreme conditions of a fuel cell. The main diagram depicts one
impedance arc. The arc corroborates overall resistances (elec-
tronic at the bulk materials, electronic contact resistances and
ionic resistances of the electrolyte matrix) of the fuel cell. Under
drying conditions the ionic movements inside electrolyte matrix
gets higher resistive path for conduction. Hence, the conductivity

Fig. 8 Bode diagrams for the operation of single cell: (a) dilu-
tion has peak around positive logarithm of frequency whereas
Fig. 7 Nyquist diagrams for the operation of single cell (b) drying has peak around negative logarithm of frequency

Journal of Fuel Cell Science and Technology AUGUST 2014, Vol. 11 / 041001-5

Downloaded From: http://fuelcellscience.asmedigitalcollection.asme.org/ on 07/30/2015 Terms of Use: http://www.asme.org/about-asme/terms-of-use


Table 1 Electrochemical reaction characteristic time scale for potential to map the performance and SOH of a PAFC. The con-
single fuel cell estimated from EIS clusive results and logics are of significance for development of
an inferential model for the online optimization of a PAFC.
TCell( C) THumid( C) fpeak(Hz) sEC(s)

100 40 0.013 77 Acknowledgment


150 50 0.012 83 This work is partially supported by sponsored project from
160 50 0.01 100
100 90 517.61 0.002
NMRL, DRDO, Ministry of Defense, India.
150 70 193.20 0.005
110 90 719.45 0.001 Nomenclature
D0 ¼ diffusion co-efficient (m2 s1)
f¼ frequency (Hz)
Thus, for 110  C cell temperature and 90  C humidifier tempera- F¼ Faraday’s constant (96500 C (equivalent weight)1)
ture, the maximum peak frequency shown in the Bode plot (Fig. Id ¼current density (A cm2)
8(a)) corresponds to the lowest electrochemical time constant. mH2i ¼ the molar flow rate of hydrogen (moles s1)
Further decrease in cell temperature to 100  C causes the peak fre- mO2i ¼ the molar flow rate of oxygen (moles s1)
quency to be decreased marginally, probably due to counteracting Nwa ¼ average Moisture flux to anode (moles cm2 s1)
effects of increased proton conductivity of the electrolyte and Nwc ¼ average Moisture flux to cathode (moles cm2 s1)
onset of formation of liquid inside the catalyst pores. In the t¼ time (s)
extreme condition of flooding the pores are blocked with liquid texp ¼experimental run time (min)
water; the overall transport process becomes diffusion limited. As V0 ¼ open circuit potential (V)
tabulated in Table 1, the electrochemical reaction time constant is WH2 ¼ the mass flow rate of exit oxygen stream (gm sv)
of the order of few milliseconds for normal as well as dilution WO2 ¼ the mass flow rate of exit oxygen stream (gm s1)
operating conditions, which corroborates with the reported values YH2 ¼ exit humidity of hydrogen stream (gm H2O/gm H2)
in literature [28]. Drying of electrolyte increases the reaction time YO2 ¼ exit humidity of oxygen stream (gm H2O/gm O2)
constant by many order of magnitudes. DWaa ¼ the moisture gain by anode side adsorber over time texp
To summarize, it may be conjectured from Fig. 6 and Fig. 8 (gm)
that absence of phase angle peak in the domain of positive fre- DWac ¼ moisture gain by cathode side adsorber over the experi-
quency corresponds to acid drying condition while peak shift mental run time texp (gm)
towards higher frequency corresponds to acid dilution. Timescale DWH ¼ hydrogen line humidifier weight gain over the time texp
analysis based on the electrochemical reaction time constant, sEC (gm)
estimated from EIS, reveals that drying causes a sharp increase in
value of sEC. In other words, it makes the overall reaction rate
slower compared to normal operation. The results obtained from Greek Symbols
EIS analysis are in agreement with the performance mapping d ¼ gas diffusion thickness (m)
based on steady analysis. e0 ¼ amplitude of perturbation of sinusoidal excitation around
the DC over potential (V)
g ¼ over potential (V)
4 Conclusions gdc ¼ steady state dc over potential (V)
q ¼ conductivity of electrolyte (ohm1 cm1)
Operational issues, namely acid drying and dilution in a PAFC, qphos ¼ conductivity of phosphoric acid (ohm1 cm1)
are diagnosed based on steady state galvanometric study and elec- s ¼ characteristic time scale (s)
trochemical impedance spectroscopy. Using steady state galvano- u ¼ porosity of the glass mat
metric study performance of a PAFC is categorized as good,
medium and poor based on the slope of voltage versus current
graph (–dV/dI) in the ohmic regime. The performance of PAFC is Subscripts
mapped on a 2D phase plane of operating variables (humidifier EC ¼ electrochemical
temperature versus cell temperature). Such mapping helps to iden- eff ¼ effective
tify the acid flooding and drying regime. It also aids as a tool to peak ¼ peak frequency
quantify the extent of humidification of hydrogen stream required
for good performance and stable operation of PAFC. A parameter References
D, that signifies the net transfer of water from the electrolytes, is [1] Barthelemy, R. R., 1981, “Defense Applications of Fuel Cells,” Proceedings of
introduced and estimated from experimental data to identify the the Symposium on Fuel Cells: Technology Status and Applications, Chicago,
electrolyte drying/flooding. IL, November 16–18, Institute of Gas Technology, Chicago, Vol. A82-45318,
Nyquist plot and Bode plot based on electrochemical imped- pp. 109–115.
[2] Perry, M. L., Newman, J., and Cairns, E. J., 1988, “Mass Transport in Gas Dif-
ance spectroscopy (EIS) are used to identify and analyze acid dry- fusion Electrodes: A Diagnostic Tool for Fuel Cell Cathode,” J. Electrochem.
ing and dilution conditions of the cell. Acid drying corresponds to Soc., 145(1), pp. 5–15.
higher resistance value in the Nyquist plot compared to that for [3] Choudhury, S. Roy, Deshmukh, M. B., and Rengaswamy R., 2002, “A Two-
dilution. It is revealed that absence of phase angle peak in the do- Dimensional Steady-State Model for Phosphoric Acid Fuel Cells (PAFC),” J.
Power Sources, 112(1), pp. 137–152.
main of positive frequency corresponds to acid drying condition [4] Carlson, E., Zogg, R., Sriramulu, S., Roth, K., and Brodrick, J., 2007, “Using Phos-
while shift of peak in the Bode diagram towards higher frequency phoric Acid Fuel Cells for Distributed Generation,” ASHRAE J., 50, pp. 50–51.
corresponds to acid dilution. The electrochemical reaction time [5] Basu, S., 2007, Recent Trends in Fuel Cell Science and Technology, Springer,
constants, sEC are estimated from the peak frequency values in the New York.
[6] He, W., Lin, G., and Nguyen, T. V., 2003, “Diagnostic Tool to Detect Electrode
Bode diagram. Timescale analysis reveals that electrochemical Flooding in Proton-Exchange-Membrane Fuel Cells,” AIChE J., 49(12), pp.
reaction time constant is of the order of few milliseconds for nor- 3221–3228.
mal as well as dilution operating conditions. Drying of electrolyte [7] Dokkar, B., Settou, N. E., Imine, O., Saifi, N., Negrou, B., and Nemouchi, Z.,
increases the reaction time constant by many order of magnitudes. 2011, “Simulation of Species Transport and Water Management in PEM Fuel
Cells,” Int. J. Hydrogen Energy, 36(6), pp. 4220–4227.
The results obtained from EIS analysis are in agreement with the [8] Rubio, M. A., Urquia, A., and Dormido S., 2010, “Diagnosis of Performance
performance mapping based on steady analysis. The tools and pa- Degradation Phenomena in PEM Fuel Cells,” Int. J. Hydrogen Energy, 35(7),
rameters introduced in the present publication show promising pp. 2586–2590.

041001-6 / Vol. 11, AUGUST 2014 Transactions of the ASME

Downloaded From: http://fuelcellscience.asmedigitalcollection.asme.org/ on 07/30/2015 Terms of Use: http://www.asme.org/about-asme/terms-of-use


[9] Mench, M. M., Dong, Q. L., and Wang, C. Y., 2003, “In Situ Water Distribu- [19] Hirata, H., Aoki, T., and Nakajima, K., 2011, “Numerical Study on the Evapo-
tion Measurements in a Polymer Electrolyte Fuel Cell,” J. Power Sources, rative and Condensational Dissipation of Phosphoric Acid in PAFC,” J. Power
124(1), pp. 90–98. Sources, 196(19), pp. 8004–8011.
[10] Gorgun, H., Arcak, M., and Barbir, F., 2006, “An Algorithm for Estimation of [20] Choudhury, S. Roy, and Rengaswamy, R., 2006, “Characterization and Fault
Membrane Water Content in PEM Fuel Cells,” J. Power Sources, 157(1), pp. Diagnosis of PAFC Cathode by EIS Technique and a Novel Mathematical
389–394. Model Approach,” J. Power Sources, 161(2), pp. 971–986.
[11] Rourkea, J. O., Ramani, M., and Arcak, M., 2009, “In Situ Detection of [21] Song, R. H., Kim, C. S., and Shin, D. R., 2000, “Effects of Flow Rate and Star-
Anode Flooding of a PEM Fuel Cell,” Int. J. Hydrogen Energy, 34(16), pp. vation of Reactant Gases on the Performance of Phosphoric Acid Fuel Cells,” J.
6765–6770. Power Sources, 86(1–2), pp. 289–293.
[12] Fouquet, N., Doulet, C., Nouillant, C., Dauphin-Tanguy, G., and Ould- [22] Saito, T., Nishioka, M., Itoh, Y., Miyake, Y., Murakami, S., and Furukawa, N.,
Bouamama, B., 2006, “Model Based PEM Fuel Cell State-of-Health Monitor- 1992, “Study of Electrolyte Management in Phosphoric Acid Fuel Cells,” J.
ing Via ac Impedance Measurements,” J. Power Sources, 159(2), pp. 905–913. Power Sources, 37(3), pp. 347–354.
[13] Higier, A., and Liu, H., 2010, “Optimization of PEM Fuel Cell Flow Field Via Local [23] Bevers, D., Wohr, M., Yasuda, K., and Oguru, K., 1997, “Simulation of a Poly-
Current Density Measurement,” Int. J. Hydrogen Energy, 35(5), pp. 2144–2150. mer Electrolyte Fuel Cell Electrode,” J. Appl. Electrochem., 27(11), pp.
[14] Li, W., Zhou, W., Li, H., Zhou, Z., Zhou, B., Sun, G., and Xin, Q., 2004, 1254–64.
“Nano-Structured Pt–Fe/C as Cathode Catalyst in Direct Methanol Fuel Cell,” [24] Schneider, I. A., Kuhn, H., Wokaun, A., and Scherer, G. G., 2005, “Study of
Electrochim. Acta, 49(7), pp. 1045–1055. Water Balance in a Polymer Electrolyte Fuel Cell by Locally Resolved Imped-
[15] Steiner, N. Y., Hissel, D., Mocoteguy, P., and Candusso D., 2011, “Diagnosis ance Spectroscopy Batteries, Fuel Cells, and Energy Conversion,” J. Electro-
of Polymer Electrolyte Fuel Cells Failure Modes (Flooding & Drying Out) by chem. Soc., 152(12), pp. A2383–A9383.
Neural Networks Modeling,” Int. J. Hydrogen Energy, 36(4), pp. 3067–3075. [25] Iranzo, A., Mu~ noz, M., Pino, F. J., and Rosa, F., 2011, “Non-Dimensional Anal-
[16] Lee, S. Y., Ogawa, A., Kanno, M., Nakamoto, H., Yasuda, T., and Watanabe, ysis of PEM Fuel Cell Phenomena by Means of AC Impedance Measurements,”
M., 2010, “Nonhumidified Intermediate Temperature Fuel Cells Using Protic J. Power Sources, 196(9), pp. 4264–4269.
Ionic Liquids,” JACS, 132(28), pp. 9764–9773. [26] Wang, C. Y., 2004, “Fundamental Models for Fuel Cell Engineering,” Chem.
[17] Shim, J. C., and Lee, J. S., 2000, “Development of Electrode Structure and Rev., 104(10), pp. 4727–4765.
Analysis of Electrode Pore Distributions in Phosphoric Acid Fuel Cells,” Mater. [27] Bruggeman, D. A. G., 1935, “Berechnung verschiedener physikalischer Kon-
Chem. Phys., 63(2), pp. 133–138. stanten von heterogenen Substanzen. I. Dielektrizit€atskonstanten und
[18] Alderucci, V., Recupero, V., Pino, L., Leonardo, D. R., Cocke, D. L., Giordano, Leitf€ahigkeiten der Mischk€ orper aus isotropen Substanzen,” Ann. Phys.,
N., and Parmigiani, F., 1990, “Characterization of the Morphological Modifica- 416(7), pp. 636–664.
tion Induced by Long Term Operations on Phosphoric Acid Fuel Cell (PAFC) [28] Tiffee, E. I., Weber, A., and Schichlein, H., 2003, Handbook of Fuel Cells—
Electrodes,” J. Appl. Electrochem. 20(5), pp. 811–817. Fundamentals, Technology and Applications, Wiley, New York.

Journal of Fuel Cell Science and Technology AUGUST 2014, Vol. 11 / 041001-7

Downloaded From: http://fuelcellscience.asmedigitalcollection.asme.org/ on 07/30/2015 Terms of Use: http://www.asme.org/about-asme/terms-of-use