Performance enhancement of phosphoric acid fuel cell by

using phosphosilicate gel based electrolyte

Kelompok 3

Resti Sena 1167040060

Rita Iman 1167040063
Ruminah 1167040065
Shafira Hasna 1167040068
Tria Sartika 1167040082
Zulfi Mofa Agasa 1167040086
 Abstract

 Replacement of phosphoric acid electrolyte by phosphosilicate gel based electrolytes is proposed to enhance the
performance of phosphoric acid fuel cell (PAFC). Phosphosilicate gels in paste form and in powder form are
synthesized from tetraethoxysilane and orthophosphoric acid by using sol-gel method.

 Replacement of phosphoric acid electrolyte by phosphosilicate gel paste enhances the peak power generation of
the fuel cell by 133% at a cell temperature of 120°C.

 Polyvinyl alcohol (PVA) is used to bind the phosphosilicate gel powder and to form the hybrid crosslinked gel
polymer electrolyte membrane.

 Soaking the membrane with phosphoric acid solution instead of with water improves the proton conductivity of
the membrane, enhances the fuel cell voltage and power generation and extends the maximum possible
operating temperature.

 Thus the phosphosilicate gel in paste form is found to be a good alternative of phosphoric acid electrolyte at
medium operating temperatures, while the phosphosilicate gel PVA composite performs better at low operating
temperatures.

1
 Introduction
o In the wake of the emerging importance of fuel cell based energy generation using hydrogen as raw material, it becomes imperative to
improve the real life performance of fuel cell systems. There are various types of fuel cell among which phosphoric acid fuel cell (PAFC)
represents the most mature technology.

o PAFC has the most extensive track record for operational experience of any fuel cell technologies. PAFC system can operate at a
temperature up to 190°C.

o However, the major drawback of PAFC is the crossover of the gases through the electrolyte and drying and flooding of electrolyte.

o Undesirable properties of phosphoric acid are its low oxygen solubility at high acid concentrations, low ionic conductivity at low temperature
and relatively high freezing point.

o In this work we propose the replacement of phosphoric acid electrolyte by phosphosilicate gel based electrolytes, which enhances the
performance of the fuel cell by reducing the crossover, by offering high proton conductivity and by providing low corrosiveness to electrode
materials.

o Therefore, phosphoric acid derived gels should be promising candidates as the electrolyte for the fuel cells. As an alternative candidates,
sol-gel derived phosphoric acid derived phosphosilicate gel have been reported as very promising proton conductors with high proton
conductivity in the low and medium temperature range.

o In this work, attempt has been taken to synthesize phosphosilicate gel in the form of paste as well as in powder form by varying the ratio of
Si to P (phosphorous). The paste form is used directly as the electrolyte in the fuel cell. Phosphosilicate gel paste is found to be a good
electrolyte that enhances the performance of fuel cell.

2
Experimental 1. Tools

2
Materials

2
 2. Synthesis of phosphosilicate gel paste and powder

The mole ratio of TEOS : EtOH :

H2O : HCl : H3PO4 is fixed as 1 :
4 : 4 : 0.01 : 1.5.

2
The mole ratio of TEOS : EtOH :
H2O : HCl : H3PO4 is fixed as 1 :
8 : 4 : 0.01 : 5.

2
 3. Synthesis and characterization of phosphosilicate gel-polyvinyl
alcohol hybrid membrane

PVA Solids

 Dissolved in distilled water at 60–80°C

for 8 h.
 filtered by vacuum
PVA Solution

Phosphosilicate gel powder ( case

study 1)
• heated at 150°C
• smoothed back with a diameter of less than 5m using the
planetary ball mill
• after smooth, added to the polymer solution and stirred
thoroughly for few hours until thick slurry is obtained 8

Dry composite membrane
Brownish composite
slurries
• poured on a transparent sheet
• left for drying at room temperature for 24 h
• membranes formed are then peeled off
• dried under vacuum at 60°C.

• crossed linked by Glutaraldehyde (GA) in a cross

linking bath composed of acetone, GA (10%) and HCl
(0.12% in the cross linking solution) at 40°C for 3 h The morphology of the
• dipped into the solution for a certain period of time and composite sheet
taken out as per the brittleness required
• doped with 88 wt.% H3PO4, for cell performance • observed using a scanning electron microscope
evaluation
(SEM) JEOL JSM-5800 and LEICA S440.
SEM results can be seen in electrons emerging from the electron gun are
Figure 3 accelerated by a potential of 1–30 kV
• focused on specimen

5
 Water uptake of composite
membrane

• determined by measuring the change in the

weight before and after the hydration

• The membranes are thoroughly dried at 50°C

Dry Membrane

• immersed in deionized water at ambient temperature

for 24 h

• The water uptakes of membranes are calculated in

weight percent.

Water uptake of membrane is obtained up to

41.34%

5
The value of IEC at room temperature is
calculated according to the equation:

The proton conductivity is calculated by using the

following equation:

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 4. Performance study of fuel cell using
membrane electrode assemblies (MEAs)

Composite membrane as an electrolyte and commercially available Pt-loaded carbon

paper sheets as electrodes. Oxygen and hydrogen flow rates are maintained at 100
mL/min and 200 mL/min, respectively. Hydrogen is passed through a humidifier whose
temperature is maintained at 70°C.

The current vs. voltage characteristic (DC polarization) of the phosphosilicate gel
polymer membrane fuel cell (PGMFC) is measured at different operating temperatures.

The phosphosilicate gel powder -PVA composite membrane is assembled with the
electrodes for performance study. Phosphosilicate gel in paste/slurry form, directly used
as the electrolyte pasted between two electrodes. The effective surface area of the
electrodes is 50 cm2.

7
Results and  Characterization of materials
Discussion

This figure shows the optical microscopic image of phosphosilicate gel-PVA

composite membranes with a thickness of less than 150 μm

This figure shows the XRD patterns of phoshphosilicate gel when the sol-gel
synthesis route leads to the formation of an amorphous structure with
amorphous halo at around 26°

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This igure 3 shows the SEM image of the phosphosilicate gel-PVA composite
membrane. The gel powder is homogeneously dispersed and the membrane
is non-porous and uniform.

Figure 4 depicts the variation of proton conductivity of the phosphoric acid-

soaked phosphosilicate gel-PVA composite membrane with the variation of
phosphoric acid concentration in the solution and with the temperature. The
conductivity of phosphosilicate gel paste is measured by using a four-probe
conductivity meter; at 25°C, the measured value of conductivity is 14.30 mS.

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 Performance study of phosphosilicate gel-PVA
composite membrane fuel cell (PGMFC)

• It shows that the increase in temperature from 50°C to

90°C enhances the performance of a PGMFC; the
voltage increases the same load current

• The proton conductivity of the membrane increases with

the temperature, which allows it to operate at higher
voltage for the same load current.

• As the temperature exceeds 90°C, the property of

polymer PVA matrix and thus of the membrane gets
affected. It is noteworthy that the doping of composite
membrane with 88% phosphoric acid allows the
PGMFC to be operated up to 130°C, which is far above
the glass transition temperature of PVA (85°C).

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 • It shows good repeatability of results obtained by using
PGMFC with phosphoric acid soaked composite
membrane.
• It can be inferred that the soaking of the composite
membrane with phosphoric acid instead of water
enhances the performance to a great extent; more than
100% increase in peak power generation is achieved
• Moreover, it causes almost 40% increase in peak power
generation compared to that produced by PAFC
• It is also observed that the proposed electrolyte
membrane offers the maximum enhancement in the
ohmic regime where the change of voltage with current
density becomes steady.

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 The comparison of the polarization curve and power
vs. current curves of PGMFC doped with 88 wt.%
phosphoric acid and PAFC operating at 90°C.

The PGMFC offers the best performance at 90°C ;

compared with PAFC, it offers almost 10%
enhancement of peak power generation.

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 Figure 8 depicts the temperatur dependence of
volatge vs. Current profiles of a single fuel cell. An
increase of cell temperature enhances the voltage
and power generation. In this case, the absence of
any polimer can extends the maximum operating
temperature.

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 Performance study of fuel cell with phosphosilicate
gel paste electrolyte

Compared with phosphoric acid fuel cell (PAFC),

phosphosilicate gel paste electrolyte fuel cell can
increase electricity generation by almost 133% at
120˚C ( figure 9). Gel pasta electrolyte can
increase voltage generation in the ohmic regime
and also extend the maximum load current.

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To check stability of paste gel electrolyte, the fuel cell is operated at constant load
current of 2 A for 3 hours. The coresponding voltage variation with time is noted and
plotted in figure 10.
In summary, phosphosilicat gel in paste is found to be a good alternative of
phosphoric acid electrolyte at medium operating temperature. Phosphosilicate gel
powder-PVA composite electrolyte may be considered to be an alternative of
phosphosilicate acid electrolyte at low operating temperatures.

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 The membranes are characterized by SEM and ion exhange
capacity, water uptake capability and proton conductivity are
measured. The composite membranes are assembled with
unit fuel cell and the performance of the phosphosilicate gel
membrane fuel cell (PGMFC) has been studied at different
operating temperatures. Soaking the membrane with
phosphoric acid solution can increase the conductivity of
proton membranes, increase voltage, and generate electricity
by fuel cells and extends the maximum possible operating
temperature. The PGMFC using 88% phosphoric acid
soaked composite membrane performs the best at 90˚C, the
performance decays with the increase of temperature due to
the swelling/dissolution and crossover of polymer
membranes. At lower operating temperature of 70˚C, peak
power produced by PGMFC is increased by 40% compared
with that by PAFC, at 90˚C, PGMFC offers almost 10%
enhancement of peak power generation than PAFC.

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 Conclusions

PVA is used to bind the phosphosilicate gel Phosphosilicate gel proton based on
powder and to form the hybrid cross-link gel- conductive electrolyte is synthesized and
polymer electrolyte membrane. characterized and its performance in fuel
cells tested.

Replacement of phosphoric acid electrolyte by Gel phosphosilicate in the form of paste and
phosphosilicate gel paste can anhances the powder form is synthesized by using sol-gel
voltage in the ohmic regime and extends the
method for P/Si ratios of 5 and 1.5
maximum possible load current. Using
phosphosilicate gelpaste electrolyte, 133% respectively.
enhancement of peak power generation is
achieved at temperature of 120˚C
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