LECT.

3: FUEL CELLS TYPES

Dr. Ali Mahmoud Ali Attia
https://www.researchgate.net/profile/Ali_Attia2
Contents
◦ Fuel cell classifications
◦ Fuel Cell types per electrolyte
◦ Polymer Electrolyte Membrane Fuel Cell (PEMFC)
◦ Solid-Oxide Fuel Cell (SOFC)
◦ Alkaline fuel cell (AFC)
◦ Direct-Methanol Fuel Cell (DMFC)
◦ Phosphoric-Acid Fuel Cell (PAFC)
◦ Molten Carbonate Fuel Cell (MCFC)
◦ Fuel Cell Performance
◦ Governing Laws
Fuel Cell Classifications
◦ Fuel cells are classified mainly according to electrolyte and operating temperature. Each type
requires particular materials and fuels and is suitable for different applications.
◦ Types according to operating temperature include:
◦ High temperature fuel cells (HTFC) for temperature > 600 °C where, hydrocarbon fuels (as
methane) spontaneously reform into hydrogen and efficiently promote the electrochemical
reactions without requiring a catalyst. Its disadvantage is that cell efficiency is inversely
proportional to the reaction temperature, so there is certain temperature threshold affect
the released energy. Examples include Molten carbonate and Solid oxide fuel cells.
◦ Low temperature fuel cells (LTFC) for operating temperature below 250 °C where
catalyst (made of expensive metals) is required without internal reforming, so external
hydrogen source is needed. This low temperature range allows short start up times with
low material degradation occurring at high temperatures; this is what LTFC is attractive for
automotive applications. Examples include Alkaline, Phosphoric acid, and Proton
Exchange Membrane (PEM).
Main Fuel Cell Types according to Electrolyte
◦ Polymer Electrolyte/Proton-Exchange Membrane Fuel Cell (PEMFC) where electrode is a thin
polymer membrane made of Nafion is used as electrolyte (membrane looks and feels a lot like plastic
wrap) and porous carbon containing a platinum catalyst as electrodes. Protons are the ionic charge
carrier in a PEMFC membrane with electrochemical half reactions of H2–O2 of: 𝐻2 → 2𝐻 + + 2𝑒 −
1
& 𝑂2 + 2𝐻 + + 2𝑒 − → 𝐻2 𝑂. PEMFCs are attractive for many applications as they (i) operate at low
2
temperature, (ii) have high power density, (iii) have low volume and low mass, and (iv) can quickly
reach operation temperature starting from ambient temperature. The main problem is the use of high
expensive platinum electrodes; even platinum can b recycles easily.
Main Fuel Cell Types according to Electrolyte
◦ Solid-Oxide Fuel Cell (SOFC) where thin non-porous ceramic membrane of oxide materials as
yttria-stabilized zirconia (YSZ) is used as electrolyte (solid electrolyte). Oxygen ions (O2–) are the ionic
charge carrier in an SOFC membrane with electrochemical half reactions: 𝐻2 + 𝑂2− → 𝐻2 𝑂 + 2𝑒 −
1
& 𝑂2 + 2𝑒 − → 𝑂2− . SOFCs are characterized (i) operate at high temperature (from 500 to 1000
2
°C), (ii) do not require expensive platinum catalyst material, (iii) sensitive to sulfur contents in fuel,
and (iv) have efficiency of 50-60%. As operate at high temperature, it is suitable for heat engine
energy recovery devices or combined heat and power, to further increases the overall fuel efficiency.
Main Fuel Cell Types according to Electrolyte
◦ Alkaline fuel cell (AFC) where solution of potassium hydroxide in water is used as electrolyte with
ability to use variety of non-precious metals as a catalyst at anode and cathode. AFCs have (i) ability
to operate at high temperature (from 100 to 250 °C) and low temperature (from 25 to 70 °C), (ii) the
cheapest fuel cell cost, (iii) sensitivity to carbon dioxide that may exit in fuel, (iv) efficiency of 60% for
pure hydrogen, and (v) drinkable water product. AFCs were one of the first developed FC
technologies, and they were the first type widely used in the U.S. space program to produce electrical
energy and water on-board spacecraft operate at high temperature
Main Fuel Cell Types according to Electrolyte
◦ Direct-Methanol Fuel Cell (DMFC) where fuel of pure methanol mixed with steam can be fed
directly here anode is fed with liquid methanol or methanol vapor and cathode receives air. DMFCs
can be considered as the evolution of PEMFC, as they use a polymer membrane as an electrolyte with
platinum-ruthenium catalyst at anode that is able to draw hydrogen from liquid methanol without
need of fuel reformer. DMFCs are (i) low temperature FC (from 60 to 130 °C), and (ii) used in
applications with modest power requirements, such as mobile electronic devices or chargers and
portable power packs.
Main Fuel Cell Types according to Electrolyte
◦ Phosphoric-Acid Fuel Cell (PAFC) where liquid phosphoric acid contained in a teflon-bonded
silicon carbide matrix is used as electrolyte and porous carbon contain a platinum catalyst as
electrodes. PAFCs are (i) suitable for stationary applications due to enhanced features of instability,
performance and cost, (ii) operate at temperature of 150 to 200 °C), (iii) produce water used for air
and water heating in Combined Heat and Power applications, (iii) efficient FC with 70% efficiency
that deteriorates at low temperature where phosphoric acid is a poor ionic conductor, and CO
poisoning of the platinum catalyst in the anode becomes significant, and (iv) much less sensitive to
CO than PEMFCs and AFCs.
Main Fuel Cell Types according to Electrolyte
◦ Molten Carbonate Fuel Cell (MCFC) where natural gas (or biogas, syngas, methane and propane)
is fed to FC operating at high temperature (>650°C) for power generation electrical utility, industrial,
and military applications. MCFCs use electrolyte composed of a molten carbonate salt mixture
suspended in a porous, chemically inert ceramic lithium aluminum oxide (LiAlO2) matrix allowing to
the transport of carbonate-ions from cathode to anode with unprecise metals as catalyst. MCFCs
have efficiency of 60% when applied for power generation and 85% for cogeneration.
◦ Even use of high temperature FCs allows the use of unexpensive catalyzers, this high temperature
shorten the useful life of the FC and promote corrosion. Moreover, the MCFCs have low power
density. Notice that, the solid electrolyte of lithium potassium carbonate salt becomes liquid at high
temperatures, enabling the movement of carbonate ions.
 FC type Applications Temp. & Eff. Advantages Limitations
Proton Exchange Portable, 50–100°C; Compact design, long Expensive catalyst; needs
Membrane - stationary and 80°C typical; operating life, quick start- chemical grade fuel; complex
PEMFC automotive 35–60% eff. up, well developed heat and water control
Space, military, Low parts and, operation Large size; sensitive to
90–100°C;
Alkaline - AFC submarine, costs; no compressor; fast hydrogen and oxygen
60% efficient
transport cathode kinetics impurities
Molten Carbonate Large power 600–700°C; High efficiency, flexible to High heat causes corrosion,
- MCFC generation 45–50% eff. fuel, co-generation long startup, short life
Phosphoric Acid - Medium to large 150–200°C; Good tolerance to fuel Low efficiency; limited life;
PAFC power generation 40% eff. impurities; co-generation expensive catalyst
Solid Oxide - Medium to large 700–1000°C; Lenient to fuels; can use High heat causes corrosion,
SOFC power generation 60% eff. natural gas, high efficient long startup, short life
Direct Methanol Portable, mobile 40–60°C; Compact; feeds on Complex stack; slow
DMFC and stationary use 20% eff. methanol; no compressor response; low efficiency
Summary of reactions and
ion changes in various FCs
FC Anode Cathode Overall
AFC 𝐻2 + 2𝑂𝐻− → 2𝐻2 𝑂 + 2𝑒 − 1/2𝑂2 + 𝐻2 𝑂 + 2𝑒 − → 2𝑂𝐻− 𝐻2 + 1/2𝑂2 → 𝐻2 𝑂

PAFC 𝐻2 → 2𝐻 + 2𝑒 − 1/2𝑂2 + 2𝐻 + 2𝑒 − → 𝐻2 𝑂 𝐻2 + 1/2𝑂2 → 𝐻2 𝑂

PEMFC 𝐻2 → 2𝐻 + 2𝑒 − 1/2𝑂2 + 2𝐻 + 2𝑒 − → 𝐻2 𝑂 𝐻2 + 1/2𝑂2 → 𝐻2 𝑂

DMFC 𝑀𝑒𝑂𝐻 + 𝐻2 𝑂 3/2𝑂2 + 6𝐻 + 6𝑒 − → 3𝐻2 𝑂 𝑀𝑒𝑂𝐻 + 3/2O2

→ 𝐶𝑂2 + 6𝐻+ + 6𝑒 − → 𝐶𝑂2 + 2𝐻2 𝑂
MCFC 𝐻2 + 𝐶𝑂3 2− 1/2𝑂2 + 𝐶𝑂2 + 2𝑒 − → 𝐶𝑂3 2− 𝐻2 + 1/2𝑂2 → 𝐻2 𝑂
→ 𝐶𝑂2 + 𝐻2 𝑂 + 2𝑒 −
SOFC 𝐻2 + 𝑂2− → 𝐻2 𝑂 + 2𝑒 − 𝑂2 + 4𝑒 − → 2𝑂2− 𝐻2 + 𝐶𝑂 + 𝑂2 → 𝐻2 𝑂 + 𝐶𝑂2
𝐶𝑂 + 𝑂2− → 𝐶𝑂2 + 2𝑒 −
Fuel Cell Performance
◦ FC performance is described by characterizing its current-
voltage relation; i-v curve that provides the FC output
voltage for given output current output.
◦ Ideal FC would supply any amount of current (as fuel is
supplied), with constant V determined thermodynamically.
◦ The output voltage of real FC is less than the ideal
thermodynamically predicted voltage that limits the
delivered power given by 𝑃 = 𝑖𝑉 providing P-i curve.

Power density curve is obtained from i–V

curve by multiplying V at each point on i–
V curve by the corresponding current density.
The FC power density increases with
increasing current density until maximum
value; where FC is designated to operate.
In contrast to the ideal, thermodynamically
predicted voltage of a fuel cell (dashed line), the
real voltage of a fuel cell is lower (solid line) due
to unavoidable losses. There are major three losses
influencing the shape of this i–V curve
Fuel Cell Performance
◦ FC supplied current is proportional to consumed fuel as each fuel mole provides n moles of electrons
thus decrease of FC voltage reduces the produced power per unit of fuel. Thus, the FC voltage can
measure the FC efficiency, so FC voltage can be changed to be “efficiency axis”.
◦ The output voltage of real FC is less than the thermodynamically predicted output voltage due to
irreversible losses. There are three major types of FC losses affecting FC i–V curve including:
◦ Activation losses (losses due to electrochemical reaction)
◦ Ohmic losses (losses due to ionic and electronic conduction)
◦ Concentration losses (losses due to mass transport)
◦ Real output voltage of FC using the predicted output thermodynamically voltage subtracted from
voltage drops due to the various losses: 𝑉 = 𝐸𝑇ℎ𝑒𝑟𝑚𝑜 − 𝜂𝑎𝑐𝑡 − 𝜂𝑜ℎ𝑚𝑖𝑐 − 𝜂𝑐𝑜𝑛𝑐 where V is the real
output voltage, 𝐸𝑇ℎ𝑒𝑟𝑚𝑜 is the thermodynamically predicted output voltage, 𝜂𝑎𝑐𝑡 is the activation
losses due to reaction kinetics, 𝜂𝑜ℎ𝑚𝑖𝑐 is the ohmic losses from the ionic and electronic conduction,
and 𝜂𝑐𝑜𝑛𝑐 is the concentration losses due to mass transport.
◦ There are four major steps in electricity from FC including (1) reactant transport, (2) electrochemical
reaction, (3) ionic (and electronic) conduction, and (4) product removal.
Main units and corresponding dimensions
applied in electrochemical investigations
as per SI system.
Electrochemical Reactions
and Standard Potentials

Thomas F. Fuller, John N. Harb, Electrochemical Engineering, John

Wiley & Sons, Inc., 2018. (Appendix A&B)
Governing Laws:
◦ Faraday’s law: that relates the amount of current flowing through external circuit to the amount of
2+
material that is consumed/produced in a half-cell reaction. In zinc reaction: 𝑍𝑛(𝑠) → 𝑍𝑛(𝑎𝑞) + 𝑒 2− ,
two moles of electrons are produced for every oxidized mole of zinc atoms. To relate external current
to moles of electrons, a charge unit called “Equivalent” is used; Equivalent is a mole of charge (no
matter positive or negative charge). Thus number of equivalents of a compound is the amount of the
substance (in moles) multiplied by the absolute value of its charge, zi. Faraday’s constant (F) relates
𝐶
coulombs [C] and equivalents 𝐹 = 96485. . Equivalent form is attained using charge unit q
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
and Avogadro’s number, NAV; F = 𝑞. 𝑁𝐴𝑉 . Note that the total charge is 𝑄 = ‫ 𝑡𝐼 = 𝑡𝑑𝐼 ׬‬for constant
current delivered.
◦ Example: For Zinc oxidation, current of 12 A passes for 2 hours. How much zinc reacts?
2+ 𝐶 𝑆
◦ Answer: For reaction: 𝑍𝑛(𝑠) → 𝑍𝑛(𝑎𝑞) + 𝑒 2− then: 𝑄 = 𝐼𝑡 = 12 ∗ 2 ∗ 3600 = 86400 (𝐶)
𝑠 ℎ
◦ No. of Zinc moles is proportional to charge while each mole release 2 electrons, so no. of Zn moles:
𝑄 86400 (𝐶)
𝑛𝑍𝑛 = = = 0.44774 𝑀𝑜𝑙𝑒 thus mass is: 𝑚 = 𝑀 ∗ 𝑛 =
2𝐹 2 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡/𝑚𝑜𝑙𝑒 ∗96485 𝐶/𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
65.38∗0.44774=29.27 g
Governing Laws:
◦ Faraday’s law: the net Faraday’s Law to evaluate mass of consumed/produced material becomes:
𝑀𝑖 𝑔/𝑚𝑜𝑙 .𝑄 𝐶
𝑚𝑖 =
𝑛 𝐸𝑞𝑢𝑣𝑎𝑙𝑒𝑛𝑡/𝑚𝑜𝑙 .𝐹 𝐶/𝐸𝑞𝑢𝑣𝑎𝑙𝑒𝑛𝑡
◦ Example: For a lead–acid battery, calculate the rate at which Pb reacts and H+ is consumed for a cell
operating at 20 [A]. Express the rate of reaction in terms of a molar reaction rate.
◦ Answer: For overall reaction: 𝑃𝑏 + 𝑃𝑏𝑂2 + 2𝐻2 𝑆𝑂4 → 2𝑃𝑏𝑆𝑂4 + 2𝐻2 𝑂. The half reaction at
positive electrode is: 𝑃𝑏𝑂2 + 𝑆𝑂4 2− + 4𝐻 + + 2𝑒 − → 𝑃𝑏𝑆𝑂4 + 2𝐻2 𝑂 while that at negative
electrode is: 𝑃𝑏 + 𝑆𝑂4 2− → 𝑃𝑏𝑆𝑂4 + 2𝑒 −
𝑄 𝐶 20 −4 𝑚𝑜𝑙𝑒
◦ Then lead consumed rate: 𝑛𝑃𝑏 = 𝐶 = = 1.036 ∗ 10 .
𝑛 𝐸𝑞𝑢𝑖./𝑚𝑜𝑙 .𝐹 . 2∗96485 𝑠
𝐸𝑞𝑢𝑖
20 −4 𝑚𝑜𝑙𝑒
◦ For produced H+, notice that the equivalent equals 2/4, thus 𝑛 𝐻+ = = 4.146 ∗ 10
1/2∗96485 𝑠
◦ For sulfates 𝑆𝑂4 2−, there are two halves each has equivalent of 2 (or one electron for each mol), then
20∗2 𝑚𝑜𝑙𝑒
the consumed rate of sulfates is 𝑛𝑆𝑂42− = = 2.073 ∗ 10−4 .
2∗96485 𝑠
Governing Laws:
◦ Faradaic Efficiency: many of the previously stated faradaic reactions involving electron transfer that
is directly related to consumption/formation of reactants/products may occurs at a singly electrode
in practical systems. In this case only one of these reactions is the desired reaction, and the other
reactions are referred to as side reactions. Correspondingly, not all of the current goes into the desired
reaction.
◦ Faradaic efficiency is to characterize the fraction of the total current that drives the desired reaction.
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
Or 𝜂𝑓 =
𝑎𝑚𝑜𝑢𝑛𝑡 𝑡ℎ𝑎𝑡 𝑐𝑜𝑢𝑙𝑑 𝑏𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑
◦ Example: Nickel is electrodeposited from a bath of NiSO4. A current of 1.0 A is passed for 3 hours
and 3.15 g of Ni are deposited. What is the faradaic efficiency of this deposition?
◦ Answer: the reaction is: 𝑁𝑖 2+ + 2𝑒 − → 𝑁𝑖 .
𝑀𝑖 𝑔/𝑚𝑜𝑙 .𝑄 𝐶 58.7∗1∗3∗3600
◦ From Faraday’s law, then 𝑚𝑖 = = = 3.2853 𝑔
𝑛 𝐸𝑞𝑢𝑣𝑎𝑙𝑒𝑛𝑡/𝑚𝑜𝑙 .𝐹 𝐶/𝐸𝑞𝑢𝑣𝑎𝑙𝑒𝑛𝑡 2∗96485
3.15
◦ Thus Faradaic efficiency is 𝜂𝑓 = = 95.9%
3.2853
Governing Laws:
◦ Current Density: as electrochemical reactions occur on surfaces, the total current is normalized per
surface area in order for us to better understand and characterize the system. Current density is the
current divided by the area of the electrode. Similarly, the molar rate of reaction is often expressed as
a flux, [mol.m-2.s-1].
◦ Example: consider current of 20A passes for 10 min. to produce chlorine gas (2𝐶𝑙 − → 𝐶𝑙2 + 2𝑒 −)
where electrode area is 80 cm2, find the amount of produced chlorine, what is the current density?
𝑀𝑖 𝑔/𝑚𝑜𝑙 .𝑄 𝐶 70.906∗20∗10∗60
◦ From Faraday’s law, then 𝑚𝐶𝑙2 = = = 4.4093 𝑔
𝑛 𝐸𝑞𝑢𝑣𝑎𝑙𝑒𝑛𝑡/𝑚𝑜𝑙 .𝐹 𝐶/𝐸𝑞𝑢𝑣𝑎𝑙𝑒𝑛𝑡 2∗96485
𝐼 20 𝐴
◦ Current density is 𝑖 = = = 2500
𝐴 80∗10−4 𝑚2

◦ The molar flux and therefore current density are related with vector quantities - ones that have both a
𝐼
◦ magnitude and direction with current density, i of: 𝑖 = = 𝐹 σ 𝑧𝑖 𝑛𝑖 , where ni is the molar flux
𝐴
-2 -1
[mol.m .s ] and zi is the electrical charge of species i. This equation indicates that for current to flow,
there needs to be a net movement of charged species.
Governing Laws:
◦ Potential and Ohm’s Law: Potential is a measure of the energy of the electron in the
metal/electrolyte leading to current flow; assigned in unit of volt [V ≡ J/C]. Ohm’s law relates the
𝑑𝑉
current and potential: 𝑖𝑥 = −𝑘 , where k is the electrolyte electrical conductivity which is a material
𝑑𝑥
𝑖𝐿
property in Siemens per length (S/m). For constant current density, then: ∆𝑉 = = 𝑖𝑅.
𝑘
◦ Example: Fuel cell operates at current of 350 A having area of each electrode of 0.04 m2, what is
the current density? If the distance between the electrodes is 0.07 mm, and the conductivity of the
electrolyte is 10 S/m, what is the potential difference in volts across the electrolyte?
𝐼 350 𝐴
◦ Current density is 𝑖 = = = 8750 2
𝐴 0.04 𝑚
𝑖𝐿 8750∗7∗10−5
◦ Potential difference: ∆𝑉 = = = 61.25 𝑚𝑉
𝑘 10
THANK YOUR

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