A

Project
REPORT ON
Preparation of Polystyrene Membrane for Fuel Cell

SUBMITTED TO: SUBMITTED BY:

Dr. DEEPAK SRIVASTAV Alok

Aman Kushwaha

Prateek Tripathi
PREFACE
We have made this report file on the topic

Preparation of Polystyrene Membrane For Fuel Cell

I have tried my best to elucidate all the relevant detail to the topic to
be included in the report. While in the beginning I have tried to give a
general view about this topic.
My efforts and wholehearted co-corporation of each and every
one has ended on a successful note. I express my sincere gratitude
to Dr. Deepak Srivastav for assisting me throughout the
preparation of this topic. I thank him for providing me the
reinforcement, confidence and most importantly the track for the
topic whenever I needed it.
ACKNOWLEDGEMENT

I extend my sincere thanks to Dr. Deepak Mishra, Head of the

Department for providing me with the guidance and

facilities for the Project.

I express my sincere gratitude to Project coordinator Dr. Deepak

Srivastav, Staff in charge, for their cooperation and guidance

for preparing and presenting this seminar.

I also extend my sincere thanks to all other faculty members

of Polymer Technology Department and my friends for

their support and encouragement.

Name-Alok

Aman Kushwaha

Prateek Tripathi
CONTENTS
 What is a Fuel Cell?
 IMPORTANCE OF FUEL CELLS
 Polymer Electrolyte Membrane Fuel Cells
 WORKING OF FUEL CELLS
 Preparation of Poly Styrene for Fuel Cell
 MEMBRANE PREPARATION
 PURIFICATION OF THE MEMBRANES
 PROPERTIES OF THE MEMBRANES
 MEMBRANE ELECTRODE ASSEMBLY (MEA) PREPARATION
 OTHER PARTS FOR CELL ASSEMBLY
 CELL ASSEMBLY FOR FUEL CELL
FUEL CELLS
What is a Fuel Cell?
Fuel cells convert the chemical energy of fuel into electrical energy with high
efficiency and low emission of pollutants. Consequently, fuel cells have been
considered as promising alternative devices for energy conversion. Due to their
numerous benefits such as lower emissions, high efficiencies even at part load
and possibly lower requirements of maintenance are considered for attractive
alternative to combustion engines

IMPORTANCE OF FUEL CELLS

A Fuel cell is an electrochemical energy conversion device. It produces
electricity efficiently, silently and without combustion from external supplies of
fuel and oxidant that react in the presence of an electrolyte. Hydrogen fuel
(which can be obtained from water or from hydrocarbon sources such as
natural gas, methanol or petroleum products) is combined with oxygen (from
the air) to produce electrical energy. These cells can continue operation as long
as the supplies are maintained

Attractive features of the fuel cells

Fuel cell has the potential to satisfy future energy needs and the important
features of fuel cells are summarized as follows

 They are simple with the possibility of direct energy conversion.

 They show efficiencies greater than the existing fuel burning engines and
also work with a flat efficiency curve even at part loads.
 They are silent without any rotating or moving components.
 Fuel cell power plants can be constructed in modular mode to match
load and increase reliability.
 Fuel and size flexibility is possible.
 Fuel cells can be exploited for combined heat and power generation
with more electricity.
  They do not generate SO2 and NO2 emissions.

Benefits of Fuel Cells

1. Fuel cells generate electricity and heat electrochemically, providing

overall energy efficiencies of up to 80%, or even higher. Fuel cells
provide benefits in all applications – power generation, industrial
equipment, transportation, military power and consumer electronics
2. Fuel cells are essential for achieving carbon reduction goals, with CO2
reductions ranging from 40% or better using conventional fuel to nearly
100% using renewably derived hydrogen. Because fuel cells are
electrochemical systems and do not rely on combustion, they are the
most clean fuel-consuming energy technology available, with near-zero
smog-causing emissions.
3. Fuel cells using hydrogen can help provide stability and continuity to the
electric grid since they can provide continuous “base load” power in
parallel either with or independent of the grid. In addition, they can
support intermittent renewable energy. These attributes make them
ideal resources for supporting critical loads for military and civilian
consumers.
4. Fuel cells can greatly simplify the sequestration of CO2 from
hydrocarbon fuels, enabling the environmentally responsible use of
domestic fuels like coal and biomass.

Polymer Electrolyte Membrane Fuel Cells

Polymer electrolyte membrane (PEM) fuel cell, also called proton exchange
membrane fuel cells, delivers high power density and offers the advantage of
low weight and volume, compared to other fuel cells. PEM fuel cells use a solid
polymer as an electrolyte and porous carbon electrodes containing a platinum
catalyst. They need hydrogen, oxygen from the air, and water to operate and
do not require any corrosive fluids like some other fuel cells. They are typically
fueled with pure hydrogen supplied from storage tanks or onboard reformers.
PEM fuel cells are used primarily for transportation and some stationary
applications. Due to their fast startup time, low sensitivity to orientation, and
favorable power-to-weight ratio, PEM fuel cells are particularly suitable for use
in passenger vehicles, such as cars and buses. A significant barrier for using
these fuel cells in vehicles is hydrogen storage. Most fuel cell vehicles powered
by pure hydrogen must store the hydrogen onboard as a compressed gas in
pressurized tanks. Higher-density liquid fuels such as methanol, ethanol,
natural gas, liquefied petroleum gas and gasoline can also be used as fuel.
However, the vehicle requires an onboard fuel processor to reform the
methanol to hydrogen which increases costs and maintenance requirements.
The reformer also releases carbon dioxide though less than that emitted from
current gasoline-powered engines.

PEMFC uses a thin proton conductive polymer electrolyte membrane, such as

perfluoro sulphonic acid polymer as electrolyte. The polymer system seems to
be the most promising candidate for application in fuel cells. Because they
show several advantages with respect to already quite diffused devices, like
the solid oxides (Takahashi. T et al 1980), and the molten carbonates (Kreuer.
K. D 1997) devices. First of all, they work at a relatively low temperature below
200°C which allows reduction the technological problems related to the
devices case and the energy utilization.

Advantage of PEM
Fuel Cells PEM Fuel cells are clean, highly efficient, scalable power generators
that are compatible with a variety of fuel feed stocks and can therefore be
used in 17 an assortment of power generation applications. In particular, they
offer several advantages over other technologies:

Simple to design, manufacture and operate.

Longer periods of use over conventional batteries

Operate over a wide power range (10W to several 100W)

Less weight

Does not produce any hazardous emission

High fuel efficiency

No corrosion

Quick start-up

Choice of Fuels

WORKING OF FUEL CELLS

There are several kinds of fuel cells, which differs slightly by their operating
mode. But in general terms, hydrogen atoms enter a fuel cell at the anode
where a chemical reaction strips them of their electrons. The hydrogen atoms
which are ionized carry a positive electrical charge and negatively charged
electrons provide the current through wires to do work. If alternating current
(AC) is needed, the DC output of the fuel cell must be routed through a
conversion device called an inverter. Oxygen enters the fuel cell at the cathode
and, in some cell types; it there combines with electrons returning from the
electrical circuit and hydrogen ions that have traveled through the electrolyte
from the anode. In other cell types the oxygen picks up electrons and then
travels through the electrolyte to the anode, where it combines with hydrogen
ions.

The oxidation reaction takes place at the anode and involves the liberation of
electrons. These electrons travel round the external circuit producing electrical
energy by means of the external load, and arrive at the cathode to participate
in the reduction reaction. It should be noted that the fuel cell reactions that
produces electrical energy and the reaction products (for example, H2O and
CO2), also produces heat. The reaction products are formed at the anode for
SOFC, MCFC and AFC types and at the cathode for PAFC and PEMFC types. This
difference has implications for the design of the entire fuel cell system,
including pumps and heat exchangers. To maintain the composition of the
electrolyte component in the MCFC system, CO2 has to be re-circulated from
the anode exhaust to the cathode input.
Working of Proton Exchange Membrane Fuel Cells

Electrochemical reactions happen at the surface of the catalyst at the

interface between the electrolyte and the membrane. Hydrogen, which is
fed on one side of the membrane (the hydrogen side is negative and it is
called the anode, whereas the oxygen side of fuel cell is positive and it is
called as cathode), splits into its primary constituents, protons and
electrons. Each hydrogen atom consists of one electron and one proton. In
the case of PEMFC protons travel through the electrolyte membrane,
whereas the electrons travel through electrically conductive electrodes
through the current collectors, and the outside circuit, where they perform
useful work and come back to the other side of the membrane to produce
electric power. At the catalyst site between the membrane and the other
electrode the electrons meet with the protons that travelled through the
membrane and oxygen that is fed at cathode. Water is created in the
electrochemical reaction, and thus pushed out of the cell with excess flow
of oxygen. More protons are pulled through the electrolyte to continue
driving the reaction and resulting in further power production. The net
result of these simultaneous reactions is flow of electrons through an
external circuit i.e, direct electrical current.
PARTS OF THE PEM FUEL CELLS
PEM fuel cells are made from several layers of different materials, as

shown in the Figure 1.4. The three key layers in a PEM fuel cell include:

Membrane Electrode Assembly

The electrodes (anode and cathode), catalyst and polymer electrolyte

membrane together form the membrane electrode assembly (MEA) of a PEM

fuel cell.

1. Anode: The anode side of the fuel cell, conducts the electrons that are

free from the hydrogen molecules so that they can be used in an

external circuit.

2.Cathode: The cathode side of the fuel cell, also containing channels

that distribute the oxygen to the surface of the catalyst, conducts the

electrons back from the external circuit to the catalyst, where they can

recombine with the hydrogen ions and oxygen to form water.

3.Polymer electrolyte membrane: The PEM is a specially treated

material that conducts only positively charged ions and blocks the

electrons. PEM is the key to fuel cell technology that must permit only

the necessary ions to pass between the anode and cathode. Other

substances passing through the electrolyte would disrupt the chemical

reaction.
Catalyst
All electrochemical reactions in a fuel cell consist of two separate reactions: an
oxidation half-reaction at the anode and a reduction half-reaction at the
cathode. Normally, the two half-reactions would occur very slowly at the low
operating temperature of the PEM fuel cell. So, each of the electrodes is
coated with a catalyst layer that speeds up the reaction of oxygen and
hydrogen. It is usually made up of platinum powder very thinly coated onto
carbon paper or cloth. The catalyst is rough and porous so that the maximum
surface area of the platinum can be exposed to the hydrogen or oxygen, where
platinum-coated side of the catalyst faces the PEM. Platinum-group metals are
critical to catalyse reactions in the fuel cell, but they are very expensive.

Hardware
The backing layers, flow fields and current collectors are designed to maximize
the current from a membrane electrode assembly. The backing layers, one
next to the anode, the other next to the cathode are usually made of a porous
carbon paper or carbon cloth, as thick as 4 to 12 sheets of paper. The backing
layers have to be made up of a material (like carbon) that can conduct the
electrons which leaves the anode and enter the cathode. The porous nature of
the backing material ensures effective diffusion (flow of gas molecules from a
region of high concentration to a region of low concentration) of each reactant
gas to the catalyst on the membrane electrode assembly. The gas spreads out
as it diffuses so that when it penetrates the backing, it will be in contact with
the entire surface area of the catalyzed membrane.
The backing layers also help in managing water in the fuel cell; too much or too
little water can cause the cell to stop operating. Water can build up 24 in the
flow channels of plates or can clog the pores in the carbon cloth, which
prevent reactive gases from reaching the electrodes. The correct backing
material allows the right amount of water vapor to reach the membrane
electrode assembly and keep the membrane humidified. Pressed against the
outer surface of each backing layer is a piece of hardware called a bipolar plate
that typically serves as both flow field and current collector. In a single fuel cell,
these two plates are the part of the components that makes up the cell. The
plates are made of a lightweight, strong, gas-impermeable, electron-
conducting material. Graphite or metals are commonly used, although
composite plates are now being developed.The first task served by each plate
is to provide a gas "flow field."
Channels are etched into the side of the plate next to the backing layer. The
channels carry the reactant gas from the place where it enters the fuel cell to
the place where it exits. The pattern of the flow field in the plate (as well as the
width and depth of the channels) has a large impact on how evenly the
reactant gases are spread across the active area of the membrane or electrode
assembly. Flow field design also affects the water supply to the membrane and
water removal from the cathode. Each plate also acts as a current collector.
Electrons produced by the oxidation of hydrogen must (1) conduct through the
anode, backing layer, along the length of the stack, and through the plate
before they can exit the cell (2) travel through an external circuit and (3) re-
enter the cell at the cathode plate. With the addition of the flow fields and
current collectors, the PEM fuel cell is complete. Only a load-containing
external circuit, such as an electric motor, is required for electric current to
flow. An exploded view of PEMFC components is shown in Figure 1.4.

Figure 1.4 An exploded view of PEMFC components

Preparation of Poly Styrene for Fuel Cell

The polystyrene is made by chain-growth polymerization. Chain-growth

polymerization involves the polymer growing by adding monomers on to the
ends of the chain of the polymer. The monomer is present throughout the
polymerization but it decreases gradually. The molecular weight increases at a
constant rate. Also a longer reaction time will produce more a longer chain
during polymerization. The four most common types of polymerization are free
radial, anionic, cationic, and coordination. Chain-growth polymerization has
three steps: initiation, propagation, and termination. The initiation step is
when the two radicals separate from the initiator. Then a monomer is added to
a radical. The propagation step is when more monomers are added to form the
chain. The termination step is when the polymer chain end of two chains join
together or the polymer chain disproportionation, or the free radical’s extra
electron is given to another free radical, ending both chains.

Styrene Monomer Production

The energy needed for the reaction is supplied by superheated steam
(at about 720 °C) that is injected into a vertically mounted fixed bed
catalytic reactor with vaporized ethylbenzene. The catalyst is iron
oxide based and contains Cr2O3 and a potassium compound (KOH or
K2CO3) which act as reaction promoters.Â
Typically, 2.5-3 kg steam are required for each kilogram of ethylbenzene
to ensure sufficiently high temperatures throughout the reactor. Â The
superheated steam supplies the necessary reaction temperature of 550-
620 °C throughout the reactor. Ethylbenzene conversion is typically
60-65%. Styrene selectivity is greater than 90%. The three
significant byproducts are toluene, benzene, and hydrogen.
After the reaction, the products are cooled rapidly (perhaps even
quenched) to prevent polymerization. The product stream (containing
styrene, toulene, benzene, and unreacted ethylbenzene) is fractionally
condensed after the hydrogen is flashed from the stream. The
hydrogen from the reaction is used as fuel to heat the steam (boiler
fuel). After adding a polymerization inhibitor (usually a phenol), the
styrene is vacuum distilled in a series of four columns (often times
packed columns) to reach the required 99.8% purity. The separation is
difficult due to the similar boiling points of styrene and ethylbenzene.
 Typical capacity per plant ranges from 70,000 to 100,000 metric
tonnes per year in each reactor and most plants contain multiple
reactors or units.

Polystyrene Production
The overall reaction describing the styrene polymerization is:

This reaction is carried out in an inert organic solvent environment which

provides the reaction medium for this cationic polymerization
reaction. The most common solvent used for this reaction is 1,2-
dichloroethane (EDC). Other suitable solvents may include carbon
tetrachloride, ethyl chloride, methylene dichloride, benzene, toluene,
ethylbenzene, or chlorobenzene. The preferred initiator is a mixture of
boron trifluoride and water. The initiator solution is prepared by
incorporating 1.5% by weight boron trifluoride gas into the organic
solvent (EDC) containing 280 ppm water. This solution is continuously
prepared in a holding vessel and will then be injected into the reactor
system.

Figure 1: Block Diagrame for Polystyrene Process

Typical feed to the first reactor would consist of 50 weight percent

styrene monomer, 100 ppm water (based on styrene weight), 2000 ppm
boron trifluoride (based on styrene weight), with the balance being
organic solvent. Â The polymerization reaction gives off heat that is
carried away from the reactors by jacketing them with a heat transfer
fluid. The temperature of the reactants should not vary by more than
15 °C throughout the reactor series.  Temperature control is very
important in this reaction because as the reaction temperature
increases, the average molecular weight of the polystyrene decreases.
 The reaction temperature range is 40-70 °C. Temperature can also
be controlled by intermediate shell and tube heat exchangers.

Figure 2: Typical Reactor Overview

Sulphonation Of Polystyrene Polymer

Sulphonation of Polystyrene is made to occur at temperature around

40’C in presence of catalyst such as Acetyl sulphate to obtain
sulphonated Polystyerene

MEMBRANE PREPARATION
There are three types of casting of films

 Blow casting

 Doctor‟s blade method, and

 Solution casting method

Blow casting
Blow casting can be done only by melting the polymer mixture. The molten
polymer mixture is blown through a die by a blower, then cut to a required
size. This type of polymer casting will require a large amount of polymer and
the polymer should have high thermal stability.

Solution casting Method

Polymer Electrolyte Membranes (PEM) were prepared by solution casting or
solvent evaporation method. First, the weighed amount of sulphonated
polymer was dissolved in the THF solvent and filtered to remove any
undissolved portions. The clear polymer solution was poured into a clean petri
dish and allowed to evaporate the solvent slowly. After few days the solvent
free polymer electrolyte membrane was removed from the petri dish, washed
with water and the membrane was dried at 50°C for a day (D. Sangeetha
2005). During the formation of membrane, several problems like unevenness,
veins, voids, thin regions, cracks and air bubbles, were encountered, which
directly affect the quality of the membranes. To rectify these problems during
the fabrication of membranes, after casting the solution, the membranes were
62 subjected to a very slow evaporation of the solvent. For this, an atmosphere
of the solvent above the cast solution was maintained throughout its long
drying time.

PURIFICATION OF THE MEMBRANES

The purification test is generally conducted before the membranes were fed
into the fuel cell. Initially all the prepared membranes were allowed to boiling
in 3% H2O2 for half an hour, to remove any impurities present in the surface of
the membrane and then washed with water and boiled for half an hour in 10%
H2SO4 to remove any inorganic impurities and get the membrane in H+ form.
Finally washed with boiling water and dried.
PROPERTIES OF THE MEMBRANES
All the prepared polymer electrolyte membranes were subjected to various
studies to check the suitability of the membranes in electrolyte applications.
The studies followed to check the suitability of the membranes are, boiling
water test, water and methanol absorption studies, ion exchange capacity
(IEC), degree of sulphonation (DS), durability test and methanol permeability.

Hydrolytic stability test

All the membranes prepared were placed in boiling water for 30 minutes to
check the withstanding capacity of the membranes in boiling water. This is
essential to find out the stability of membranes in boiling water to operate in
the fuel cells. Membranes are expected to withstand the boiling water
condition without any disintegration. Such membranes are expected to show
better performance in the fuel cell operating conditions.

If the membrane withstands in boiling water, then it gives a promising result

that is operating at higher temperatures.

Solvent absorption and desorption study

Swelling is the process of absorption of large quantities of water molecules by
macromolecules, which results in the formation of a swelled membrane with a
considerable increase in volume. The water uptake is influenced by
sulphonation degree of the membrane. In fact the hydration of the membrane
depends on water activity and temperature thereby strongly influencing the
proton conductivity and dimensional stability. The maximum swelling depends
on the chemical nature of the polymer, molecular weight, swelling agent and
temperature.

Swelling enhances the proton conductivity. Greater absorption of water

molecules by the membrane will facilitate the hopping mechanism of H+ . At
the same time, too much swelling leads to a poor mechanical stability of the 66
membrane, which is a disadvantage for the application in electro membrane
processes. Hence a moderate swelling is optimum.

Ion Exchange Capacity

IEC is the measure of the ability of an insoluble material to undergo
displacement of ions previously attached and loosely incorporated into its
structure by oppositely charged ions present in the surrounding
solution.Greater the IEC better will be the proton conductivity of the
membrane.

Loss of IEC
Loss of IEC in the prepared membranes was also determined by the treatment
of the membrane in peroxide test. At particular time intervals, a piece of
membrane was taken out from the solution and dried, then IEC of the
membrane was determined by titration method. The % of IEC loss was
calculated using the following formula,

(Initial IEC – Final IE)/ Loss of IEC (%) = x 100 Initial IEC
MEMBRANE ELECTRODE ASSEMBLY (MEA) PREPARATION

Catalyst preparation and coating for PEM fuel cell

First, the electrolyte membranes were coated by catalyst using Pt/C
catalyst as per the method discussed by J. Tian et al (2004). The Pt catalyst
pastewas prepared by dissolving the 20% Pt/C mixture in alcohol and water
mixture.
0.025g/cm2 of platinum/carbon was weighed, dissolved in few drops of
propanol and water mixture, and then pasted on the carbon sheets (Figure 2.6).
Catalyst preparation and coating for water electrolyzer
The anode and cathode catalysts were prepared using Nafion solution.
Initially, the Nafion solution, water and isopropyl alcohol were taken and
allowed to stir for 30 minutes. 4 mg/cm2 of iridium was then added into the
mixture and the stirring was continued for 30 minutes. The obtained catalyst
mixture was coated on the membrane using brush.

OTHER PARTS FOR CELL ASSEMBLY

Gasket
Gaskets were used to create a tight seal between the two parts of the
cell preventing the gas leakage. A proper seal will prevent leakage during
temperature or pressure changes, so it should be more pliable than the two
adjoining surfaces. They are mold to grooves of both components for proper
functioning. Additionally the gaskets must be chemically compatible with the
two joining surfaces. This ensures a tight seal with no fluid or gas leaks.
Graphite Plates

The graphite square plate of 50mm length and 50mm breath is

machined from titanium plate. Computer numerical control was used to groove
the graphite plate and the serpentine gas delivery channel model produced. The
groove dimensions are 2mm x 2mm x 0.3mm (Figure 2.7).

Figure 2.7 Graphite plate

Fluid passage
These electrodes contain a passage for the flow of fluids such as water,
hydrogen peroxide and hydrogen. This fluid passage serves for the purpose of
uniform distribution and contact of fluid with the proton exchange membrane.
There are different types of grooves that have been used as discussed in the
literature for different flow patterns. In this study we have used serpentine
type series grooves.

Current collectors
The current collectors are the projections of the end plates. They serve for the
purpose of carrying current to the end plates, which is smaller in size when
compared to the end plates and has to withstand high current densities. So, a
proper attention has to be paid on the current carrying capacity of the metals
before choosing the material for the current collectors. Stainless steel is used
as the current collectors due to the less cost and high current carrying capacity.

End plates
Theses plates are made up of steel or aluminum, which are used for the
mechanical support purpose of the cell.
CELL ASSEMBLY FOR FUEL CELL

Membrane electrode assembly (MEA) is the assembly of various parts in

electrochemical cell. It consists of the ionically conductive membrane i.e.
Polymer Electrolyte Membrane (PEM) which is coated with catalyst on anode
and cathode sides. Along with that a pair of platinum coated titanium mesh is
placed on both sides for proper contacts of electrodes with the current carrier
plate, which is also platinum coated titanium grooved sheet of thickness 2.5mm
and possesses two threaded holes for nipple attachment on both sheets, for the
passage of reactant and product. Then finally an end plate is placed for
mechanical support, which may be stainless steel or aluminum plate.

Figure 2.9 Schematic Diagrams of Single Cell Components