Fuel Cells – Types and Chemistry

Proton Exchange Membrane Fuel Cells (PEMFC)

Electrolyte :Proton Exchange Membrane

Anode (catalyst Pt/C):

Cathode (catalyst Pt/C):

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Proton Exchange Membrane Fuel Cells (PEMFC)
Some Attributes of PEMFC

o Uses a solid polymer electrolyte, usually perfluorosulfonic acid (nafion) membrane.

o Membrane electrode assembly (MEA ) consists of the anode, cathode, proton exchange
membrane (PEM) and gas diffusion layers (GDLs).
o Nafion allows transport of protons while blocks electrons.
o Membrane should remain hydrated for efficient transport of protons, and hence PEMFCs can’t
be operated at higher temperatures
o Electrode poisoning in presence of OH-

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Direct Alcohol Fuel Cell (DAFC)

Anode (catalyst Pt-Ru/C) Electrolyte :Proton Exchange Membrane

Cathode (Pt/C)

o Uses lighter alcohols such as methanol or ethanol instead of hydrogen

o Can be operated at lower temperatures; 40 – 80 deg C
o Might be useful for future portable devices such as laptops, calculators
o These are fuel cells are similar to PEMFC in structure

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Alkaline fuel cell (AFC)
Anode (catalyst Ni) Electrolyte :KOH solution or anion exchange membrane

Cathode (catalyst MnO2)

o First used in space shuttle by NASA

o 60% efficiency between 150 – 200 deg C operating temp.
o Electrode poisoning is observed in presence of OH-
o During initial development and use KOH solution was used as electrolyte; Later
anion exchange membrane is used as electrolyte in which problem of carbonate
formation may be addressed.

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Phosphoric Acid Fuel Cell (PAFC)

o Operating principle is similar to that of a PEMFC

o Phosphoric acid is the electrolyte used, which
conducts protons and has good thermal stability
o Operating temperature varies between 175 – 200
deg C
o Used for heavy vehicles such as buses and trucks

Electrolyte :phosphoric acid

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Molten Carbonate Fuel Cell (MCFC)

Anode (Ni) Electrolyte :molten carbonate

Cathode (NiO2)

o Molten carbonate salt is used as electrolyte

o Operates at higher temp., around 650 deg C
Schematic of MCFC
o Hydrocarbons can also be used as fuel,
where internal reforming produces H2

Note the flow of fuel,oxidant, products, ions and electrons through

the different components of MCFC
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Solid Oxide Fuel Cell (SOFC)

Anode (Ni/YSZ); Eectrolyte : YSZ

Cathode (Perovskite/LaSrMnO3)

o Uses hard ceramic electrolyte crystal lattice

o Operates at higher temp.; 750 – 1000 deg C
o O2- migrates through crystal at this high temp.
o High efficiency upto 60% can be reached
o Natural gas can be used as a fuel due to internal
reforming at this temp.

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Regenerative Fuel Cell (RFC)
o In space application solar energy is not always available as space craft comes under the
shadow of planet (moon)
o Hence solar needs to be stored and this power will be during solar eclipse
o One of the tackle this is to use RFC in which Electrolyzer and Fuel Cell (FC) Works in tandem
o Essentially working of Fuel Cell and Electrolyzer is just opposite to each other. Thus same
cell can be used as electrolyzer and fuel cell by just changing the anode and cathode feed.
These are called unitized regenerative fuel cell
o It may noted that RFC does not come in classification of FC.

Verma, A., and S. Basu “Feasibility study of a simple unitized

regenerative fuel cell” J. Power Sources 135 62-65 (2004)

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Regenerative Fuel Cell (RFC)

Anode :

Cathode :

PEM Electrolyser:

o Water is electrolysed using solar cell

o Solar energy can be stored as hydrogen, which can be used during night using fuel cells
o Can be useful for space applications Solid Oxide Electrolyser:

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Fuel Cell
A fuel cell is an electrochemical device which converts the free energy of a chemical reaction
into electrical energy. It is composed of a non consumable anode and a cathode, a suitable
electrolyte and balance of plant. The electrodes consist of porous gas diffusion layers, usually
made of highly electronic conductive materials such as porous graphite gas diffusion layer. One
of the most common anode catalysts is platinum for low temperature fuel cells and nickel for
high temperature fuel cells. The electrolyte should have very high ionic conductivity and
theoretically zero electronic conductivity and it may be aqueous acidic or alkaline solutions or
solid polymer membrane. The charge carriers are different depending upon the different type of
fuel cells.

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Alkaline fuel cell (AFC)
The working principle of an alkaline fuel cell is shown
schematically in fig. 1. The alkaline fuel cell generally
operates on hydrogen and oxygen gases. The solution of
potassium hydroxide in water is used as the electrolyte. At
the anode, hydrogen gas reacts with the OH- ions to
produce water and electrons. Electrons generated at the
anode conduct through a load connected to an external
circuit and migrate towards cathode.
Fig.1. Alkaline fuel cell

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Proton Exchange Membrane Fuel Cells (PEMFC)
The proton exchange membrane (PEM) fuel cell as shown in fig. 2, uses a solid polymer electrolyte (perfluorosulphonic acid
membrane) in the form of a thin, permeable sheet for the transport of proton (7). Generally, platinum, Pt-black or Pt/Ru
catalyst is used as anode and cathode catalysts respectively.

The proton exchange membrane is sandwiched between anode and cathode catalyst, which is
pasted on gas diffusion layer made of carbon cloth or paper. The composite structure of gas
diffusion layer, anode, proton exchange membrane, cathode and gas diffusion layer is known as
membrane electrode assembly (MEA) and is the heart of polymer electrolyte membrane fuel
cell. Gas diffusion layer works as substrate for catalyst and ensure the proper distribution of
reactants over the catalyst. Hydrogen molecules are stripped at the anode electrode-catalyst into
electrons and protons (H-). Electrons are collected at low resistance material, which helps to
conduct the electrons from the fuel cell to the outer circuit. This low resistance material is
known as the bipolar plate made of graphite and it has channels to supply the reactants over the
diffusion layer both on the anode and cathode sides (Fig 2). The protons permeate through
membrane and reaches cathode side, where it reacts with oxygen and conducted electrons from
the outer circuit to produce water. The proton exchange membrane made of perfluorosulphonic Fig. 2. Proton exchange membrane fuel cell
acid allows proton to pass through it and restricts the passage of electrons. The migration of
proton in membrane is promoted by sulphonate group present in polytetrafluoroethylene
membrane structure through the formation of hydronium ion. Thus, the membrane needs to be
hydrated for efficient transport of proton in the form hydronium ion. Moreover, the PEM fuel
cell cannot be operated above 80oC because of the water loss from the membrane and
subsequent poor conduction of proton. The reaction scheme for proton exchange membrane is
shown as :

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Direct Alcohol Fuel Cells (DAFC)
Direct Alcohol Fuel Cells (DAFC) The direct alcohol fuel cell (DAFC) is a variant of PEM cell. The
direct alcohol fuel cell uses lighter alcohols like methanol or ethanol instead of hydrogen gas. The
alcohols dissociate to electrons, hydrogen ions and carbon dioxide at the anode. The positively
charged hydrogen ions diffuse from anode to cathode through the polymer electrolyte membrane
and electrons migrate toward the cathode through an external circuit. At the cathode, the electrons,
hydrogen ions and oxygen from the air react to form water. The reactions involved in direct
methanol fuel cell are shown below (9):

The direct alcohol fuel cells are operated at lower temperature (40 oC - 80oC) and
thought to be power source in future for portable equipments like laptop, calculator etc.
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Phosphoric Acid Fuel Cells (PAFC)
The reactions occurring on the anode and cathode are similar to PEMFC as given in equations 4
to 6. A PAFC as shown in fig. 3 consists of an anode and a cathode made of finely dispersed
platinum catalyst on carbon and the electrolyte is housed in silicon carbide structure.

The electrolyte is an inorganic acid, concentrated phosphoric acid (100%),

which is like the membranes in PEMFC, conducts proton. Phosphoric acid
(H3PO4) is the only common inorganic acid that has enough thermal stability,
and very low volatility (150oC) to be considered as an electrolyte for fuel cells
(8). The pure 100% phosphoric acid has a freezing point of 42oC, which restricts
the operation below this temperature. The operating temperature of the PAFC is
in the range of 175oC to 200oC. This was the most commercially developed fuel
cell at one point of time. However, the advancement of PEMFC decreased its
value in the market. The phosphoric acid fuel cell can be used in large vehicles,
such as buses and trucks.
Fig.3. Phosphoric acid fuel cell
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Molten Carbonate Fuel Cells (MCFC)
The schematic diagram of a molten carbonate fuel cell is shown in fig.4. The molten
carbonate fuel cell uses a molten carbonate salt as the electrolyte (10).

The anode process involves a reaction between hydrogen and

carbonate ions to form water and carbon dioxide while releasing
electrons at the anode. The electrons migrate towards cathode
through the load connected to an external circuit. The cathodic
process involves oxygen and carbon dioxide from the oxidant stream
with electrons to produce carbonate ions. The need for carbon
dioxide in the oxidant stream requires a system for collecting the
carbon dioxide from the anode exhaust and mixing it with the
cathode feed stream. The reactions occur at 650oC when salts melt
and conduct carbonate ions from the cathode to the anode. The
reactions in the molten carbonate fuel cell are given below:

Fig.4. Molten carbonate fuel cell

Since MCFC operates at high temperature, it can also accept hydrocarbons (coal gas) as fuel where internal
reforming generates hydrogen required
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4th lecture for online classes 2020-21
Solid Oxide Fuel Cells (SOFC)
The schematic diagram of a solid oxide fuel cell is shown in fig. 5. Solid oxide fuel cells work at even higher
temperatures than molten carbonate fuel cells. A solid oxide fuel cell (SOFC) uses a hard ceramic electrolyte
crystal lattice instead of a liquid and operates at temperatures of 750 oC to 1000 oC (10).

Today's technology employs several ceramic materials as the active SOFC

components. The anode is typically formed from an electronically conducting
nickel/yttria-stabilised zirconia (Ni/YSZ) cermet (ie, a ceramic/metal composite).
The cathode is based on a mixed (ie, both electronic and ionic) conducting
perovskite, lanthanum manganate (LaMnO3). Yttria-stabilised zirconia (YSZ) is
used for the ion-conducting electrolyte. At this high operating temperature,
oxygen ions migrate through the crystal lattice. As hydrogen is passed over the
anode, oxide ions moves across the electrolyte to oxidize the fuel. The oxygen is
supplied, usually from air, at the cathode. Electrons generated at the anode
travel through an external load to the cathode, completing the circuit. Oxygen
combines with electrons at cathode to form oxide ions, thus completing the
reaction. These cells can reach efficiencies of around 60% and expected to be
used for combined heating and power purposes. They can be used potentially for
providing auxiliary power in vehicles. The main advantage of SOFC is possibility
of internal reforming at 750oC - 1000oC and hence natural gas can be used as
fuel in SOFC. The following reactions occur at the SOFC electrodes:

Fig.5. Solid oxide fuel cell

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Regenerative Fuel Cells (RFC)
Regenerative Fuel Cells (RFC)are actually not fuel cells by principle. The reverse technique of fuel
cell is used for RFC. In this type of fuel cells water is electrolyzed with the help of electricity from
solar photovoltaic cell to produce hydrogen and oxygen gases and utilizing these gases in the PEM
fuel cell to generate electricity (11). This technology is useful in space application. Further, using
this technology solar energy can be stored in the form of hydrogen energy and it will be of use in
the night when solar photovoltaic would not work. Fig. 6 depicts the concept of a regenerative
fuel cell.

The following reactions describe the water splitting process inside

the electrolyser:

Dr. Sanjeev Gautam, 4th lecture for online classes 2020-21 Fig. 6. Regenerative fuel cell system