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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
Journal of Fuel Cell Science and Technology AUGUST 2014, Vol. 11 / 041001-1
C 2014 by ASME
Copyright V
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
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
Journal of Fuel Cell Science and Technology AUGUST 2014, Vol. 11 / 041001-7