4.

Electrochemical Energy Conversion

(Cf. Bockris and Reddy: Modern Electrochemistry, Vol. 2; Bockris and Srinivasan: Fuel
Cells; Bockris et al: Comprehensive Treatise of Electrochemistry, Vol. 3; Bagotsky:
Chemical Power Sources; Liebhafsky and Cairns: Fuel Cells and Fuel Cell Batteries;
Eyring: Physical Chemistry, An Advanced Treatise, Vol. IXB; K. Kordesh, G. Simade,
Fuel cells and their Applications )

4.1 Relations between cell current and cell voltage

Consider an energy producing cell with two interfaces 1 and 2, and let the equilibrium
electrode potentials (on the hydrogen scale) be Eeq,1 and Eeq,2. Suppose Eeq,1 is more
positive than Eeq,2. Then, if an external load is provided, oxidation takes place at electrode
2 and reduction at electrode 1.

Ex. (-)Zn|Zn2+||Cu2+|Cu(+) .

At 2: Zn = Zn + 2e; Eo = -0.77 V

at 1: Cu2+ + 2e = Cu Eo = +0.34 V

If reduction at 1 is far from equilibrium, then

RT i
i = io ,1e −α 1 Fη1 / RT , i.e. η1 = − ln 1 (1)
αF io ,1

Similarly, if oxidation at 2 is far from equilibrium, then

RT |i |
i2 = io , 2e(1−α 2 ) Fη 2 / RT . i.e. η2 = ln 2 (2)
(1 − α ) F io , 2

Since η1 = E1 – Eeq,1 and η2 = E2 – Eeq,2 (3)

η1 - η2 = (E1 – Eeq,1) – (E2 – Eeq,2) =(E1 - E2) – (Eeq,1 - Eeq,2) (4)

= V - Veq

or, V = Veq + η1 - η2 (5)

Since there is normally a potential drop in solution due to passage of current,

V = Veq + η1 - η2 -IR (6)

70
The overpotentials η1 and η2 are the total overpotentials at the two interfaces. They
include both activation overpotential ηa and concentration overpotential ηc. Thus,
V = Veq + (ηa,1 + ηc,1) - (ηa,2 + ηc,2) - IR (7)

The concentration overpotentials are defined as:

RT cx = 0
ηc = ln b (8)
nF c

C b − Cx =0
From i = − nFD (9)
δ

δ Cx = 0 δ i
C b − C x =0 = − i, or b
= 1+ b
i = 1− (10)
nFD C nFDC iL

nFDC b
where iL = − (11)
δ

RT ⎛ i⎞
Thus, ηc = ln⎜⎜1 − ⎟⎟ (12)
nF ⎝ iL ⎠

Substituting in the expression for the cell voltage V:

RT ⎛ i ⎞ RT ⎛⎜ i ⎞
V = Veq + η a ,1 + ln⎜⎜1 − 1 ⎟⎟ − η a , 2 − ln 1 − 2 ⎟ − IR (13)
nF ⎝ iL1 ⎠ nF ⎜⎝ iL , 2 ⎟⎠

RT i
Note that, because η a ,1 = − ln 1 , ηa,1 is negative. Also, ηc,1 is negative because
αF io ,1
⎛ i ⎞
⎜⎜1 − 1 ⎟⎟ < 1. (Cathodic current is positive)
⎝ iL1 ⎠
Similarly, ηa,2 is positive; ηc,2 is positive since i2 < 0 (anodic current negative).

In other words, all terms on the right-hand side of the equation above make the cell
potential V at a current I less than the equilibrium potential Veq.

If both oxidation and reduction are running under Tafel conditions, then the expression
for the voltage V is:

RT ⎛⎜ i1 ⎞⎟ RT ⎛ i ⎞ RT ⎛ i ⎞ RT ⎛ i ⎞
V = Veq − ln + ln⎜⎜1 − 1 ⎟⎟ − ln⎜ 2 ⎟ − ln⎜1 − 2 ⎟ − IR
α1nF ⎜⎝ io ,1 ⎟⎠ nF ⎝ iL1 ⎠ (1 − α 2 )nF ⎜⎝ io , 2 ⎟⎠ nF ⎜⎝ iL , 2 ⎟⎠
(14)

71
Cell potential
Theoretical Ideal P − I
1.23 rev cell pot ' l 1 .0 relation

Efficiency

due to η a
Power
due to ohmic
loss in sol ' n

mass transport
loss

Current density Current density

4.2 Efficiency and Power

The overall efficiency γ of electrochemical reactors is determined by three components:

thermodynamic efficiency, potential (voltage) efficiency, and faradaic efficiency. These
are defined as follows:

ΔG o nFVeq V I
γ therm = = − γ pot = γ farad = (15)
ΔH o ΔH o Veq Im

where I is the observed current and Im is the theoretically expected current on basis of
amount of reactant consumed.

The overall efficiency is: γ = γtherm γpot γfard (16)

Assuming that γpot = γfarad = 1, γ = γtherm = -nFV/ΔHo (V = Veq for γpot = 1). Thus
the overall efficiency depends on current in same manner as cell voltage.

Power of an electrochemical reactor is given by: P = IV. Note that if I is small, V is

high, and if I is high, V is small. Thus power goes through a maximum.

Case 1: If both electrode reactions are fast, η is small. Then, for low overvoltages,

RT i1 RT i2
η a ,1 = − ηa,2 = − (17)
nF io ,1 nF io , 2

72
Similarly, if i1 << iL,1 and i2 << il,2
RT ⎡ i ⎤ RT i1 RT ⎡ i ⎤ RT i2
ηc ,1 = ln ⎢1 − 1 ⎥ = − ηc , 2 = ln ⎢1 − 2 ⎥ = − (18)
nF ⎢⎣ iL ,1 ⎥⎦ nF iL ,1 nF ⎢⎣ iL , 2 ⎥⎦ nF iL , 2

RT i1 RT i1 RT i1 RT i2
Thus, V = Veq − − + + - IR (19)
nF io,1 nF iL ,1 nF io ,1 nF iL , 2

If I = I1 =|I2| = i1A1 = |i2A2| ,

V = Veq - IRt = IRext

RT ⎡1⎛ 1 1 ⎞⎟ 1 ⎛⎜ 1 i ⎞⎟⎤
where Rt = ⎢ ⎜⎜ + ⎟
+
⎜
+
⎟⎥
+R (20)
nF ⎣⎢ A1 ⎝ io ,1 iL ,1 ⎠ A2 ⎝ io , 2 iL ,1 ⎠⎦⎥

The power is then P = IV = I(Veq – IRt) (21)

The condition for maximum power is:

(dP/dI) = Veq – 2ImRt = 0 (22)

or, at the maximum, Im = Veq / 2Rt

Maximum power is then: Pm = Im2 Rt = Veq2 / 4Rt (23)

and Vm = Veq – ImRt = Veq - (Veq /2) = Veq/2 (24)

i.e. maximum power occurs when cell potential is ½ the reversible cell voltage.

Power reaches a maximum if the external load is equal to Rt. Also, the higher the
exchange current density and limiting currents of the electrode reactions and the lower
the internal cell resistance, the higher the maximum the power.

Case 2: If polarization curves of both electrodes correspond to the Tafel equation and
both the concentration overpotential and ohmic potential drop are negligible,

P = I V = I(Veq + (a1 + a2) – (b1 + b2) ln I) (25)

where a1 = (RT/α1F) ln A1io,1 ; a2 = [RT/(1 – α2)] ln A2io,2 (26)

b1 = RT/ α1F b2 = [RT/(1 – α2)F (27)

The condition for maximum power is:

73
dP
= Veq + (a1 + a2 ) − (b1 + b2 ) ln I m − (b1 + b2 ) = 0
dI
(28)
Veq + (a1 + a2 ) − (b1 + b2 ) ⎡Veq + (a1 + a2 ) − (b1 + b2 ) ⎤
ln I m = ; or I m = exp ⎢ ⎥
b1 + b2 ⎣ b1 + b2 ⎦

Therefore,

Vm = Veq − (b1 + b2 ) ln I m + (a1 + a2 ) = b1 + b2 (29)

⎡Veq + (a1 + a2 ) − (b1 + b2 ) ⎤

and Pm = I mVm = (b1 + b2 ) exp ⎢ ⎥ (30)
⎣ (b1 + b2 ) ⎦

i.e. at Pm , maximum cell potential is Vm = b1 + b2 = the sum of the Tafel slopes for
anodic and cathodic reactions. The maximum current Im increases with increasing
exchange current, since a1 and a2 depend on exchange currents.

4.3 Characteristics of energy converters (cf. Pletcher: Industrial Electrochemistry)

ƒ Capacity: charge that may be obtained from the battery (quoted in ampere-
hours). Nominal capacity of each electrode may be calculated from the weight W
of the active material via Faraday’s law:

C=WnF/M

where M is the molecular weight of the active material. Capacity is determined by

monitoring voltage vs time during fixed current discharge; C = It, where t is the
time at fixed current I for voltage to reach a value where battery is no longer
useful.

ƒ Electricity storage density: capacity per unit weight of battery as a whole (C/kg) =
nF/M. (Ex. For Li → Li+ + e, electricity storage density = nF/M = 14 x 106 C kg-1;
for Al → Al3+ + 3e, electricity storage density = 10.7 x 106 C kg-1.)

ƒ Energy density: energy obtainable per unit weight of battery (kWh-kg-1).

Energy density = ItVav / W = (electricity storage density) x (cell potential)

(Vav = average potential during discharge). Thus, maximum energy density =

(nF/M)Veq = 26.8 nVeq / M (kWh-kg-1). (N.B. 1 kWh = 3.6 x 106 J)

ƒ Power density: capability to deliver power (IV) per unit weight of battery.

74
 ƒ Discharge rate: measure of rate at which charge is drawn from the cell, or current
to discharge the nominal capacity C of the battery in n hours, quoted as the C/n or
n-hour rate.

ƒ Cycle life: number of charge / discharge cycles that are possible before failure
occurs.

ƒ Energy efficiency = (energy released on discharge) / (energy required for

charge) x 100

ƒ Behavior on overcharge: if battery overcharged, new electrode reactions must

occur, e.g. electrolysis of water; it is important that these reactions do not
represent a hazard.

ƒ Shelf life: essential for most batteries to be stored without self-discharge for many
years (or without corrosion…)

ƒ Tolerance to service conditions: may require that battery provide power

continuously, intermittently, or at an irregular rate.

ƒ Reliability: ability to perform to specification reproducibly and without failure

ƒ Economic factors: cost of manufacture and cost of servicing during working life
of battery

4.4 Battery components (cf. Pletcher: Industrial Electrochemistry)

ƒ Container: battery case must be resistant to corrosion; hence it must be stable to

chemical attack by the electrolyte, active materials and environment at operating
temp; also, must have required mechanical strength, be cheap and light, and there
must be a simple method of sealing.

ƒ Separators: must be chemically stable to electrolyte and to active materials at

temperature of operation; must also have correct qualities of wettability,
selectivity, resistivity and flexibility for particular battery system. Common
materials are microporous (0.01 – 10 μm pores) or macroporous (30-70 μm pores)
polymer sheets, a fraction of a mm thick; these generally have porosity of 50-80%
and resistance of 0.05 – 0.5 Ω cm2.

ƒ Current collectors: active material is almost always thick layer of porous

particulate paste and electronic conductivity of this material is seldom v. high; it
is therefore necessary to have current collector, which is usually a metal grid or
sheet to provide conductive path through paste and thereby minimize resistance of
battery. It also acts as physical support for active mass.

75
 ƒ Electrolyte: selection determined by electrode reactions; concentration also
important

ƒ Active materials: electroactive material must be readily available at sites of

electron transfer and be present in large quantities. Since intimate contact and
high surface area are required, porous electrodes often used.

4.5 Battery Systems (cf. Brooke Schumm, Non-rechargeable Batteries,

http://electrochem.cwru.edu/ed/encycl/); Storage Cell Technologies,
http://www.vectorsite.net//ttfuelc.html; YCES,
http://www.chem.orst.edu/ch411/scbatt.htm ; K-JIST, Materials Electrochemistry Lab
Shuckla et al: Resonance 2001)

4.5.1 Primary Cells

4.5.1.1 Leclanche (also called carbon/zinc or dry cells):

First developed around 1870 - 90, the Lechlanche cell uses a Zn anode, MnO2 cathode,
and an aqueous ammonium or zinc chloride electrolyte. The "dry" cell is similar, but with
the electrolyte gelled by the addition of an inert metal oxide.

The half-reactions are actually quite complicated, but the overall cell discharge can be
approximated as:

Zn + 2MnO2 + 2 H2O + ZnCl2 = 2 MnOOH + 2 Zn(OH)Cl

MnO2 is a complex and polymorphic compound.

76
Mn(IV) has a high redox potential, low cost, and is environmentally benign.

Dry cells are cheap and reliable, but suffer principally from a low energy density
(theoretically about 150 Wh/kg, practically about 1/2 this).

4.5.1.2 Alkaline cells

First commercializerd in 1950, these are similar to the Leclanche-type cells but make use
of an improved (more conductive) electrolyte - aqueous KOH. This is lowers the internal
cell resistance, and therefore allows higher discharge rates and power densities to be
achieved. Alkaline batteries also use a high-surface-area Zn powder anode and a high
grade MnO2 cathode, which also improve performance at high rate discharge. The
electrolyte is usually gelled by addition of a cellulose derivative.

The half-cell reactions in the basic environment are:

Zn + 2 OH- = Zn(OH)2 + 2 e-

2 MnO2 + H2O + 2 e- = Mn2O3 + 2 OH-

Alkaline batteries have similar theoretical energy densities and cell voltages to Leclanche
cells, but give higher experimental values, especially under high rate use. They are,
however, more expensive. Other, related, alkaline batteries use HgO or Ag2O as the
active cathode material. These are far more expensive but can provide even higher energy
densities. There are serious environmental concerns about use of many heavy metals (and
Hg and Ag are highly toxic), especially in disposable primary batteries.

4.5.1.3 Silver oxide button cells

The silver oxide cell is similar in construction to the zinc-air type (see below), with an
anode of powdered zinc in gel with a potassium hydroxide electrolyte, except that instead
of having a cathode made of carbon and exposed to the air, it is a silver screen pasted
with silver oxide (Ag2O).

77
They have a cell voltage of 1.55 volts, a flat discharge curve, and long shelf life. They
can be recharged a limited number of times, but this is not generally done in practice.

4.5.1.4 Lithium Batteries

Lithium has the lowest redox potential of all metals, is very light-weight, and non-toxic in
oxidized form.

For these reasons, Li has been widely studied and utilized as an anodic material. Primary
cells can have voltages of nearly 4 V and practical energy densities exceeding 200 W hr /
kg. Li cells also have very long shelf-lives, and are extensively used as small cylindrical
or button cells in low-rate devices such as watches and calculators, where they can
operate for several years. The long shelf-lives also make them the best choice for
pacemaker batteries.

Some disadvantages of these cells are the decomposition of Li when contacted with
ambient water or air, requiring sealed cells. The reaction of Li with water can produce
hydrogen gas, and cells can be hazardous if punctured or improperly disposed.
Nonaqueous electrolytes are employed, these are comprised of polar organic liquids (such
as dimethyl ether or propylene carbonate) containing a dissolved lithium salt.

The use of polymer-based electrolytes such as poly(ethylene oxide)/salt complexes has

also been investigated in detail.

One of the big problems with lithium is that reacts violently with moisture, and
manufacturing lithium cells requires a moisture-free environment. Lithium cells also
require venting and other safety systems to keep them from exploding if moisture does
infiltrate the case, or if such cells are heated. This delayed their use for a very long time.

There are a bewildering range of lithium cell technologies. They can be basically divided
into non-rechargeable lithium cells, and rechargeable "lithium-ion" cells.

The conceptually simplest and most common nonrechargeable lithium cell is the
"lithium-manganese" cell. This has a lithium anode, a manganese dioxide cathode, and a
carbonate electrolyte. The anode reaction is:

Li → Li + e-

The cathode reaction is:

MnO2 + Li+ + e- → MnO2(Li)

The cell voltage is about 3 volts. Such cells are are constructed in a "wound" or "jelly
roll" configuration, with a sheet of lithium foil, a separator sheet containing electrolytic
salts, and a sheet of manganese dioxide rolled up together. They have an indefinite shelf
life.

78
There are many other nonrechargeable lithium cell configurations, such as "lithium sulfur
dioxide", "lithium thionyl chloride", and "lithium polycarbonate monofluoride", with
complicated constructions and chemistries that are substantially more capable than
lithium-manganese but not as cheap, and so not in as widespread use.

The latest generation of nonrechargeable lithium cells uses a polymeric electrolyte. Such
"lithium polymer" cells of course have electrical characteristics similar to those of the
predecessors, but they can be more easily built in flat or rectangular configurations that
are very useful for lightweight portable equipment.

The high cell voltage of the lithium ion cell means that such cells are not interchangeable
with standard zinc-carbon or alkaline cells. A nonrechargeable "lithium disulfide" cell or
"voltage compatible lithium cell" has been introduced that does provide a cell voltage of
1.5 volts.

Lithium disulfide cells are also built in a jelly roll configuration, with a lithium anode, an
electrolytic separator sheet, an iron disulfide (FeS2) cathode, and an aluminum cathode
collector. They are lighter than alkaline cells, have high capacities, and have a very long
shelf life.

Lithium is easier to handle in its ionized form, and so rechargeable lithium cells, which
have to deal with the hazards of being recharged, have been traditionally based on lithium
compounds. Again, there are many variations, but a typical "lithium ion" cell has a
carbon anode, a lithium cobalt dioxide or manganese dioxide cathode, and an electrolyte
consisting of a lithium salt in solution.

Lithium-ion cells have a cell voltage of about 3.6 volts. They have high internal
resistance and are not suited to high current applications. They have very long cycle lives,
up to a thousand cycles for single cells, and their storage capacity does not degrade
significantly with cycling. They are increasingly becoming the rechargeable battery of
choice for portable consumer electronics equipment, though they are expensive.

4.5.2 Secondary Cells : Rechargeable Batteries

4.5.2.1 Lithium secondary battery

Cathode: Oxide (LiCoO2, LiMn2O4, V2O5, LiNiO2); Chalcogenides (MoS2, TiS2 layered
structure)

Anode: Li alloy; carbon compounds

Cathode reaction: Li1-xCoO2 + xLi+ + xe → LiCoO2 (Eo = 0.6 V vs SHE)

or, TiS2 + xLi+ + xe → LixTiS2

79
Anode reaction: Li(alloy) → Li+ + alloy + e

or, LiC → Li1-xC + xLi+ + xe (Eo = -3.0 V vs SHE)

The net cell reaction is written as

LiC + Li1–xCoO2 → Li1–x C + LiCoO2 (Eo cell = 3.6 V ).

4.5.2.2 Pb/acid battery (cf. http://www.vectorsite.net/ttfuelc.html)

The cells are constructed from a PbO2 cathode, Pb anode, and sulfuric acid electrolyte.
The half-cell reactions and the overall reaction are:

(-) Pb + SO42- = PbSO4 (sl) + 2 e-

(+) PbO2 + 4 H+ + 2 e- + SO42- = PbSO4 (s) + 2H2O
Pb + PbO2 + 2SO42- + 4H+ = 2PbSO4(s) + 2H2O

Both electrodes dissolve into the electrolyte during the discharge reaction.

Current collectors: both Pb.

The cells have a nominal discharge potential of 2 V, are inexpensive, and are capable of
high power densities (necessary for starting a car, these can be as high as 600 W / kg).
However, the cells undergo relatively rapid self-discharge, are environmentally
unfriendly, have low energy densities ~24-32 Wh-kg-1. Pb/acid cells can only be cycled a
few hundred times, and far fewer cycles are possible if the battery is fully discharged.

Concentration of H2SO4 in charged storage cell is ~30-40%. Open circuit voltage of

charged cell ~ 2.06-2.15 V.

Sulphatation: gradual transformation of fine-grain lead sulfate into hard dense layer of
large-grain sulfate; sulphatation occurs if cell is stored in discharged state or is regularly
undercharged; difficult to charge.

4.5.2.3 Nickel – Cadmium (NICAD) batteries: These batteries contain a Ni(OH)2

cathode, Cd anode and aqueous KOH electrolyte. The electrode and overall cell reactions
are:

(+) 2 x [NiOOH + H2O + e = Ni(OH)2 + OH- (-) ]

(-) Cd + 2OH- = Cd(OH)2 + 2e
2 NiOOH + 2H2O + Cd = 2 Ni(OH)2 + Cd(OH)2

80
Ni(OH)2 has a layered CdI2 structure, and NiOOH is apparently a complex, multiphase
material. Advantages are the high cycles (often 1000's) and long shelf life (possibly
months without significant self-discharge), but disadvantages relative to Pb acid include
lower power densities and greater cost.

Current collectors: Ni and Cd; reversible cell potential: 1.48 V; electrolyte: aq. KOH
Applications: standby supplies; industrial; plane engine starting; railway lighting, …

4.5.2.4 Nickel Metal Hydride (NIMH )Cells

The "nickel-metal hydride (NiMH)" cell is similar to nicad, but replace the cadmium
anode with a "metal hydride", based on complex metallic alloys that can store large
quantities of hydrogen, The cathode is nickel oxide, the electrolyte is a solution of
potassium hydroxide, stored in a polymer separator sheet. The electrode and net cell
reactions are given by:

(+) NiOOH + H2O + e → Ni(OH)2 + OH– (E0 = 0.49 V vs. SHE ).

(-) MH + OH → M + H2O + e→ (E0 = –0.83 vs. SHE ).

NiOOH + MH → Ni(OH)2 + M (Ecell = 1.32 V) .

NiMH cells have a typical cell voltage of 1.2 volts, which tends to remain flat through the
cell discharge cycle. They tend to have a high self-discharge rate, but are relatively
environmentally benign.

4.5.2.5 Zinc – Air Battery

This is actually a hybrid battery / fuel cell, where the fuel (O2 in air) is free, unlimited,
and adds no weight to the cell. This is convenient, and this dramatically increases the
specific energy density to about 300 W hr / kg and 900 (!) W hr / L. The Zn/air battery
has long been thought of for use in electric vehicles, and some prototypes have been
developed. While the cell is not directly reversible, ZnO can be removed from the spent
cell and electrolyzed to reform Zn metal. This technology would presumably replace gas
stations with Zn electrolysis stations.

The electrodes and cell reactions are given by:

(+) O2 + 2 H2O + 4 e → 4 OH– (E0 = 0.4 V vs. SHE ).

(-) 2 Zn + 4 OH-→ 2 Zn O + 2 H2O + 4 e (E0 = –1.24 V vs. SHE ).

Net: 2 Zn + O2 → 2 ZnO (Ecell = 1.64 V )

81
Zinc-air batteries have a cell voltage of about 1.65 volts. They have a very high energy
density, but have a high internal resistance and are not well suited to high-current
applications. They have to be sealed in storage to keep the air out, but as long as they are
kept sealed they have a long storage life.

Large zinc-air cells have been used in consumer equipment, at least on a limited basis,
and very large zinc-air batteries have experimentally used in vehicular applications.

Some disadvantages of the Zn/air cell are the relatively low power densities, and the
environmental sensitivity of these cells. Since they use air as a fuel, they can be
carbonated by CO2, and require a rather narrow range of humidity for optimal cathode
peformance.

Some disadvantages of the Zn/air cell are the relatively low power densities, and the
environmental sensitivity of these cells. Since they use air as a fuel, they can be
carbonated by CO2, and require a rather narrow range of humidity for optimal cathode
peformance.

Modern zinc-air button cells are similar to alkaline cells. The anode is powdered zinc
mixed in a gel, the electrolyte is a layer of potassium hydroxide, and the cathode is a
carbon disk, designed to support cathode reactions through the oxygen in the air. A
porous Teflon membrane allows air into the cell while preventing electrolyte from
leaking out.

4.5.2.6 High temperature Zebra Batteries

The problem of dendritic-sodium growth in Na-S batteries has been cleverly

circumvented in the zebra batteries with the use of NaAlCl4 in conjunction with Na-β
alumina ceramic electrolyte. The battery operates at about 300 oC and the net cell
reaction during the cell operation is as follows:

2 Na + NiCl2 → 2NaCl + Ni (Ecell = 2.58 V)

4.6 Supercapacitors

Capacitors are devices that store energy by maintaining 2 charged interfaces of opposite
polarity, separated by an electrolyte.

The energy stored by capacitors is related to the charge at each interface, q, and potential
difference between the electrodes. Ecapacitor = q V

Since capacitors store charge at only the interface, rather than within the entire electrode,
they tend to have lower energy densities. The charge/discharge reaction is not limited by
ionic conduction into the electrode bulk, so capacitors can be run at high rates and

82
provide high specific powers. Typical numbers for capacitors and batteries are given
below:

volumetric
power number of discharge
energy
Device density charge/discharge time
density
W/L cycles s
Wh/L
Batteries 50-250 150 1 - 103 > 1000
Capacitors 0.05 - 5 105 - 108 105 - 106 <1

Since there is no bulk change in the electrodes, the charge/discharge reactions can
typically be cycled many more times than batteries (108 cycles per device have been
achieved).

4.7 Fuel Cells

(cf. Fuel cells and their Applications, K. Kordesh, G. Simader;
http://www.vectorsite.net//ttfuelc.html; Dzmitry Malevich, Electrochemical systems for
electric power generation, Departrment of Chemistry and Biochemistry, University of
Guelph; Dan Kammen, Fuel Cells, Energy Storage and Hydrogen;
http://auto.howstuffworks.com/fuel-cell.htm )

Fuel Cell: an electrochemical cell which can continuously convert the chemical energy of
a fuel and an oxidant to electrical energy.

Thermal energy Mechanical energy

conversion conversion

Chemical energy Electrical energy

of fuels conversion

Direct Energy Conversion with Fuel Cells in Comparison to Conventional Indirect

Technology (cf. Fuel cells and their Applications, K. Kordesh, G. Simader)

83
4.7.1 Classification of Fuel Cell Systems

Types of Fuel Cells

ƒ Alkali Fuel Cell (AFC) 80-100oC

ƒ Acid Fuel Cell (AFC)
The phosphoric acid fuel cell (PAFC), 2000C
Polymer Electrolyte Fuel Cell (PEFC), 80oC / The proton exchange membrane
(PEM) fuel cell /
The molten carbonate fuel cell (MCFC) 6500C.
The solid oxide fuel cell (SOFC).
Tubular solid oxide (TSOFC) 8000C
Intermediate Temperature solid oxide (ITSOFC) 10000C

See Fuel cells and their Applications by K. Kordesh and G. Simader for further
classification of fuel cells.

4.7.2 Characteristics of Fuel Cells

ƒ High efficiency and reliability: fuel cell can convert up to 90% of the enrgy
contained in its fuel into usable electric power and heat. Fuel cell power stations
located close to loads can also reduce costly transmission lines and transmission
losses. Another important attribute of the fuel cell is its ability to co-generate, i.e.
to produce hot water and low-temperature steam at the same time as it generates
electricity. As they contain fewer moving parts, fuel cell systems should have
higher reliability than internal combustion engines.

ƒ Substitution of fuel cells for conventional power plants should improve air quality
and reduce water consumption and waste water discharge. Conventional
generation of electricity produces more particulates, sulfur oxides and nitrogen
oxides than all other stationary industrial sources combined. Fuel cell power plant
emissions are ten times lower than those specified by the most stringent
environmental regulations. Fuel cells also produce lower CO2 emissions than
conventional generating plants.

ƒ Electrochemical reaction of the fuel cell produces water as a byproduct; little if

any external water is required for power plant operation. (NO large quantities of
water for cooling.)

ƒ The quiet, electrochemical nature of fuel cells eliminates many of the sources of
noise associated with conventional steam-powered systems.

4.7.3 The Alkaline Fuel Cell (AFC)

Although alkaline fuel cells (AFC) are the most temperamental of all fuel cells, it can
produce the maximum amount of energy (80% efficiency (4) when used as a water

84
heating device). They use KOH (potassium hydroxide) electrolytes because it is the most
conducting of all alkaline hydroxides, but this requires extremely pure hydrogen and
oxygen input to avoid poisoning. The cell cannot internally reform any fuel because of
the 80 degree Celsius cell operating temperature. Hydrogen at the anode reacts with the
electrolyte creating water and two electrons which both meet at the cathode with oxygen
to complete the circuit. The electrolyte constantly flows through the cell which provides
cooling by convection the porous (and catalyzed) graphite electrodes from which it picks
up hydroxyl ions and a small amount of water in the process. In an actual cell, one third
of the water produced drains on the cathode side while two thirds resides on the anode
side. Again, because of liquid nature of the electrolyte, semi-permeable, Teflon coated
carbon material is used as electrodes which are heavily catalyzed as compared with other
types of fuel cells because of the low operation temperature.

The earliest modern applied fuel cell technology, the alkaline fuel cell, uses a strongly
alkaline potassium hydroxide (KOH) electrolyte. As the potassium hydroxide will react
with carbon dioxide to form solid potassium carbonate, the alkaline fuel cell absolutely
must have a source of pure hydrogen to operate.

The alkaline fuel cell operates at relatively low temperatures, in the range of 80 to 95
degrees Celsius (175 to 200 degrees Fahrenheit). It uses platinum catalyst to increase the
reverse electrolysis reaction rate.

The alkaline fuel cell has a number of attractive features. It requires less platinum catalyst
than an acidic fuel cell, and has a high power to weight ratio. Improvements in the design
have resulted in reducing the electrolyte's susceptibility to carbon dioxide poisoning.

However, the alkaline fuel cell has to be supplied with pure hydrogen, since any carbon
dioxide contaminants will react with the potassium hydroxide electrolyte to form solid
potassium carbonate. It remains useful for aerospace applications, where its light weight
is valuable and the requirement for pure hydrogen not too difficult to meet, but is not
generally regarded as useful for terrestrial applications.

Characteristics

ƒ Concentrated KOH (35-85 wt%) in asbestos matrix

ƒ Anode: H2 + 2OH- → 2H2O + e-
ƒ Cathode: ½ O2 + H2O + 2e- → 2OH-
ƒ CO2 poison: CO2 + KOH produces K2CO3 altering electrolyte!
ƒ Long used by NASA on space missions
ƒ High efficiency <70%
ƒ Costly
ƒ Significant pressure differential required across membrane

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4.7.4 Acidic Fuel Cells

There are four types of acidic fuel cells:

• The phosphoric acid fuel cell (PAFC).

• The polymer electrolyte / proton exchange membrane fuel cell (PEFC / PEMFC)
• The molten carbonate fuel cell (MCFC).
• The solid oxide fuel cell (SOFC).

The PAFC and the PEM fuel cells are the best developed acidic fuel cells. The PAFC is
in modest use as a fixed AC power source for buildings and sites, while the PEM is under
intense development as a power source for automobiles. The MCFC and SOFC are also
under investigation as fixed AC power sources, but their development is not as far
advanced as that of the PAFC.

Of the four acidic fuel cells, the phosphoric acid fuel cell is the only one that is now in
commercial use, with a modest number of units installed for fixed power generation. It
has also be used experimentally with large vehicles, such as buses.

The two remaining acidic fuel cell types, the molten carbonate and solid oxide fuel cells,
remain generally experimental devices. They are being considered for fixed site power
generation systems much like the PAFC systems now in use.

4.7.5 Phosphoric Acid Fuel Cell (PAFC)

The PAFC uses a phosphoric acid (H3PO4) electrolyte. Most acids operate in solution,
which means that a fuel cell using them must operate below the boiling point of water,
reducing efficiency. Concentrated phosphoric acid does not need to be in solution and can
operate at higher temperature.

The phosphoric acid is contained in a matrix of silicon carbide and Teflon and
sandwiched by the anode and cathode, which are built as thin plates of porous graphite.
Platinum catalyst laid down on these electrodes helps accelerate the electrochemical
reactions.

The PAFC operates at 175 to 200 degrees Celsius (350 to 400 degrees Fahrenheit).
Higher temperatures of course help accelerate the reaction, but above 220 degrees Celsius
(428 degrees Fahrenheit), the phosphoric acid tends to attack the catalyst.

Characteristics

ƒ Up to 100% concentrated H3PO4 in SiC matrix, Pt electrocatalyst (expensive)

ƒ Anode: H2 → 2H+ + 2e-
ƒ Cathode: ½ O2+ 2H+ + 2e- → H2O

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 ƒ High temperatures required - H3PO4 poor conductor
ƒ CO < 3-5 vol% or Pt poisoned (water gas shift reaction)
ƒ In commercial use
e.g. Toshiba PC-25 Fuel Cell ; Efficiency 37-42%

4.7.6 Proton Exchange Membrane (PEMFC) / Polymer Electrolyte Fuel Cells (PEFC)

The proton exchange fuel cell, sometimes known as the polymer electrolyte fuel cell, was
originally developed by GE in the late 1950s, but still is not in commercial use.

However, there has been considerable work on its use as an automotive power source due
to its relatively light weight and low operating temperature, and even some work on using
it to replace batteries in portable electronic equipment such as laptop computers. One of
the advantages of focusing on such applications is that both electric vehicles and portable
electronics equipment run on DC electricity, reducing the requirements for power
conditioning.

The operating principles of the PEM fuel cell are very similar to those of the PAFC, the
main difference being that uses a polymer film, based on sulfonic acid, for an electrolyte
rather than phosphoric acid. The membrane-electrode assembly of a PEM fuel cell is very
thin, on the order of a few millimeters.

The PEM fuel cell operates at low temperatures, similar to those of the alkaline fuel cell,
in the range of 80 to 95 degrees Celsius (175 to 200 degrees Fahrenheit). Also like the
alkaline fuel cell, it uses platinum catalyst to increase the reverse electrolysis reaction
rate. Much work has been done on reducing the amount of platinum required, and in
current fuel cells small atomic clusters of platinum are deposited on fine carbon particles.

Characteristics

ƒ Thin plastic sheet permeable to H+’s, coated on both sides with Pt catalyst
ƒ Anode: H2 → 2H+ + 2e-
ƒ Cathode: ½ O2+ 2H+ + 2e- → H2O
ƒ High power density (power/weight)
ƒ Quick startup
ƒ Primary candidates for auto industry
ƒ Disadvantage: low CO tolerance (ppm)

4.7.7 Molten Carbonate Fuel Cell (MCFC)

The MCFC uses a mix of molten lithium, sodium, and potassium carbonate (K2CO3). It
operates at 540 to 650 degrees Celsius (1,000 to 1,200 degrees Fahrenheit), which is hot
enough to keep the electrolyte molten. The high operating temperature allow the MCFC
to convert hydrocarbon fuel into hydrogen without a separate reformer.

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The carbonate electrolyte is contained in a porous board of lithium aluminate. The anode
is made of nickel and the cathode is nickel oxide, to which silver is sometimes added.
The nickel and silver act as catalysts. The operating temperature of the MCFC is between
600 and 700 degrees Celsius, hot enough to keep the electrolyte molten. The major
problem with the MCFC is that the molten carbonate electrolyte tends to attack the
electrodes.

Characteristics

ƒ Mixture of alkali carbonates in ceramic matrix of LiAlO2 at high T (600-

8000C) where corrosive mess becomes highly conductive molten salt
ƒ Anode: H2 + CO32- → H2O + CO2 + 2e-
ƒ Anode: CO + CO32- → 2CO2 + 2e-
ƒ Cathode: ½ O2+ CO2 + 2e- → CO32-
ƒ Ni (anode) and NiO (cathode)
ƒ Promise high fuel-to-electricity efficiencies
ƒ Fuels: H2, CO, natural gas, propane, and diesel

4.7.8 Solid Oxide Fuel Cell (SOFC)

The SOFC is attractive because its electrolyte will not leak and is not corrosive. The
electrolyte consists of solid zirconium oxide, stabilized with yttrium oxide. The SOFC
operates at 980 degrees Celsius (1,800 degrees Fahrenheit) and uses titanium based
perskovite crystals for a catalyst. Like the MCFC, its high operating temperature
eliminates the need for a separate fuel reformer subsystem. However, the electrolyte
materials are expensive.

Characteristics

ƒ Hard ceramic material usually Y2O3-stabilized ZrO2

ƒ Anode: H2 + O2- → H2O + 2e-
ƒ Anode: CO + O2- → CO2 + 2e-
ƒ Anode: CH4 + 4O2- → 2H2O + CO2 + 8e-
ƒ
Cathode: ½ O2 + 2e- → O2-
ƒ Co-ZrO2 or Ni-ZrO2(anode) and Sr-doped LaMnO3 (cathode)
ƒ Two geometries:
o tubular - array of meter-long tubes; and compressed disc
ƒ Large high-power applications (electricity generating stations)

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