79 ALKALINE FUEL CELL

Chapter 4
 Introduction Eng. Rawan Alhaddad

 The alkaline fuel cell (AFC), also known as the Bacon fuel
cell after its British inventor, is one of the most developed
fuel cell technologies and is the cell that flew Man to the
Moon.
 NASA has used alkaline fuel cells since the mid-1960s, in
Apollo-series missions and on the Space Shuttle.
 AFCs consume hydrogen and pure oxygen producing
potable water, heat, and electricity.
 They are among the most efficient fuel cells, having the
potential to reach 70%.

80
 Eng. Rawan Alhaddad
 The AFC employs an aqueous potassium hydroxide electrolyte. In contrast
to acidic fuel cells where H+ is transmitted from the anode to the cathode,
in an alkaline fuel cell OH– is conducted from the cathode to the anode.

 Thus, water is consumed at the cathode of an AFC while it is produced

(twice as fast) at the anode. If the excess water is not removed from the
system, it can dilute the KOH electrolyte, leading to performance
degradation.

 Depending on the concentration of KOH in the electrolyte, the AFC can

operate at temperatures between 60 and 250∘C.

 Alkaline fuel cells require pure hydrogen and pure oxygen as fuel and
oxidant because they cannot tolerate even atmospheric levels of carbon
dioxide.

 The predominant drawback with terrestrial applications is that CO2 in any

hydrocarbon fuel or in the air reacts with the ion carrier in the electrolyte. 81
 AFC Basic Principles and Operations
Eng. Rawan Alhaddad

 Hydrogen fuel is channeled through field flow plates

to the anode on one side of the fuel cell, while
oxygen is channeled to the cathode on the other side
of the cell.

 At the anode, a platinum catalyst causes the hydrogen

to split into positive hydrogen ions (protons) and
negatively charged electrons.

 The positively charged hydrogen ions react with

hydroxyl (OH-) ions in the electrolyte to form water.

 The negatively charged electrons cannot flow through

the electrolyte to reach the positively charged
cathode, so they must flow through an external circuit,
forming an electrical current.

 At the cathode, the electrons combine with oxygen

and water to form the hydroxyl ions that move across
the electrolyte toward the anode to continue the
process. 82
 AFC Basic Principles and Operations
Eng. Rawan Alhaddad

 The half-cell reactions are:

H2 + 2OH¯ → 2H2O + 2e¯ (Anode)
½O2 + H2O + 2e¯ → 2OH¯ (Cathode)
 Hydroxyl ions, OH¯ , are the conducting species in the electrolyte. The
equivalent overall cell reaction is:
H2 + ½O2 → H2O + electric energy + heat
Since KOH has the highest conductance among the alkaline hydroxides, it is the
preferred electrolyte.

83
 Cell Components Eng. Rawan Alhaddad

Electrolytes

 AFC has alkali (NaOH or KOH) as electrolyte

as a mobile liquid or in immobilized form in a
porous matrix.

 The most common alkaline electrolyte is a

potassium hydroxide (KOH) water solution,
with normalities of 6 to 8.

 The KOH used must be sufficiently pure so

that no impurities can cause catalyst
poisoning.

 Sodium hydroxide (NaOH) has been

envisaged as an alternative for potassium
hydroxide as the electrolyte of choice.
However, the performance characteristics of
NaOH are not very good compared to KOH.
84
 Eng. Rawan Alhaddad
Electrode and Catalyst
 Electrodes are usually made of metallic materials such as nickel and nickel-
based alloys
 Because of small kinetic losses, a wide range of electrocatalysts can be
used; these include Ni, Ag, metal oxides, spinels, and noble metals.
 The AFC has excellent performance compared to other candidate fuel cells
and also has flexibility to use a wide range of electrocatalysts

85
 Eng. Rawan Alhaddad

 AFC Advantages
 Improved cathode performance
 Potential for nonprecious metal catalysts
 Low materials costs, extremely low cost electrolyte

 AFC Disadvantages
 Must use pure H2–O2
The liquid alkaline electrolyte on reaction of OH– ions with carbon
dioxide contamination in the oxidant stream.
 KOH electrolyte may need occasional replenishment
 Must remove water from anode
 The electrolyte and electrode degradation caused by the
formation of carbonate/bicarbonate CO /HCO 3

86
 Performance Eng. Rawan Alhaddad

 Effect of Pressure compressors are needed. Compressors are

not only noisy, but incur parasitic power
 AFCs experience the typical enhanced
that lowers the system efficiency.
performance with an increase in cell
operating pressure.
 To achieve faster kinetics, operating
temperatures greater than 100 °C,
accompanied by higher pressures, are
used.
 Spacecraft fuel cells have operated for
over 5,000 hours at 200 °C at 5 atm
achieving HHV efficiencies exceeding 60
percent.
 This increase in performance can only be
realized in applications where compressed
gases are available (such as in space
vehicles or submarines). In all other cases,

87
 Eng. Rawan Alhaddad

At an operating temperature (T), the change in voltage (ΔVP) as a function of

pressure (P) can be expressed fairly accurately using the expression:

ΔVP (mV) = 0.15T (°K) log(P2/P1)

P2 is the desired performance pressure and P1 is the reference pressure at which

performance is known.

88
 Eng. Rawan Alhaddad
 Effect of Temperature
 Section 2.1 describes that the reversible cell potential for a fuel cell consuming H2 and O2 decreases
by 49 mV under standard conditions in which the reaction product is water vapor.
 However, as is the case in PAFCs, an increase in temperature improves cell performance because
activation polarization, mass transfer polarization, and ohmic losses are reduced.
 As expected, the electrode potential at a given current density decreases at lower temperatures, and
the decrease is more significant at higher current densities.
 In the temperature range of 60 to 90 °C, the cathode performance increases by about 0.5 mV/°C at
50 to 150 mA/cm2.

89
 Eng. Rawan Alhaddad

 The change in voltage (ΔVT) as a function of temperature (T) at 100

mA/cm2:
ΔVt (mV) = 4.0 (T2-T1) for T < 63 °C
or
ΔVt (mV) = 0.7 (T2-T1) for T > 63 °C
 Alkaline cells exhibit reasonable performance when operating at low
temperatures (room temperature up to about 70 °C). This is because
the conductivity of KOH solutions is relatively high at low
temperatures. For instance, an alkaline fuel cell designed to operate at
70 °C will reduce to only half power level when its operating
temperature is reduced to room temperature

90
 Eng. Rawan Alhaddad

 Effect of Impurities
 Carbon dioxide was the only impurity of concern in
the data surveyed.
 AFCs with immobilized electrolytes suffer a
considerable performance loss with reformed fuels
containing CO2 and from the presence of CO2 in air
(typically ~350 ppm CO2 in ambient air). The
negative impact of CO2 arises from its reaction with
OH¯
CO2 + 2OH¯ → CO3 + H2O
 producing the following effects:
 reduced OH¯ concentration, interfering with kinetics;
 electrolyte viscosity increase, resulting in lower diffusion rate
and lower limiting currents;
 precipitation of carbonate salts in the porous electrode,
reducing mass transport;
 reduced oxygen solubility,
 reduced electrolyte conductivity.
91
 Eng. Rawan Alhaddad

 In the case of circulating liquid electrolytes, the situation is not as

critical, but is still significant.
 With CO2-free air the performance remained much more constant
after 2,000 to 3,000 hours of operation.
 This drop in performance was caused purely by mechanical
destruction of the carbon pores by carbonate crystals.
 High concentrations of KOH are also detrimental to the life of O2
electrodes operating with CO2- containing air, but operating the
electrode at higher temperature is beneficial because it increases the
solubility of CO2 in the electrolyte. Hence, modifying the operating
conditions can prolong electrode life.
 The operational life of air electrodes with CO2-containing air in 9N
KOH at 65 °c ranges from 1,600 to 3,400 hours at a current density of
65 ma/cm2. The life of these electrodes with CO2-free air tested
under similar conditions ranged from 4,000 to 5,500 hours.
92
 Eng. Rawan Alhaddad

 Effects of Cell Life

 AFC cell stacks have demonstrated sufficiently stable
operation for at least 5,000 hours, with degradation rates
of 20 mV per 1,000 hours or less.
 For large scale utility applications, economics demand
operating times exceeding 40,000 hours, which presents
perhaps the most significant obstacle to commercialization
of AFC devices for stationary electric power generation.
 ΔVLifetime (mV) = 20 μV per 1,000 hours or less

93