INTERCHAPTER U

Batteries
A representative sample of commercially available batteries.
University Science Books, 2011. All rights reserved. www.uscibooks.com
U1 U. BATTERI ES
A battery is a device that uses a chemical reaction
to produce an electric current. Strictly speaking, a
battery consists of two or more electrochemical cells
that are connected together; however, the term bat-
tery is often applied to single electrochemical cells as
well. Batteries are especially useful as electric power
sources when mobility is a prime consideration. They
are adaptable to a wide range of power requirements,
from the production of very high currents over short
periods to the production of stable voltages under low
current drain for long periods.
Batteries are classed as primary if they are not
rechargeable and as secondary (can be used a second
and further times) if they are rechargeable. Examples
of primary batteries are the alkaline batteries used in
ashlights and the silver-zinc button batteries often
used in wristwatches. Some examples of secondary
batteries include the lead storage battery commonly
used in cars and trucks, the rechargeable nickel-
metal hydride batteries now used instead of alkaline
batteries in many appliances, and the lithium ion
batteries used in cellular telephones and handheld
electronics.
U-1. The Lead Storage Battery Is Used
in Vehicles
The 12-volt lead storage battery (Figure U.1) used
in vehicles consists of six cells of the following type
(each generating about two volts) arranged in series:
()Pb(s)|PbSO
4
(s)|H
2
SO
4
(aq)|PbO
2
(s),PbSO
4
(s)|Pb(s)(+)
The minus and plus signs denote the electrode polari-
ties during discharge (i.e., current drain), and the
comma between PbO
2
(s) and PbSO
4
(s) denotes a
heterogeneous mixture of the two solids. The battery
electrolyte is a 10-M H
2
SO
4
(aq) solution. The equa-
tions for the electrode reactions during discharge are
Pb(s) + SO
4
2
(aq) PbSO
4
(s) + 2 e

(oxidation)
2 e

+ PbO
2
(s) + 4 H
+
(aq) + SO
4
2
(aq)
PbSO
4
(s) + 2 H
2
O(l ) (reduction)
The equation for the overall cell reaction is obtained
by adding together the equations for the two half
reactions:
2 PbSO
4
(s) + 2 H
2
O(l )
discharge
recharge
Pb(s) + PbO
2
(s) + 2 H
2
SO
4
(aq)


A good-quality lead storage automobile battery
can provide a current of over 650 amperes for short
periods and a power output of 7.8 kW, a very impres-
sive power output for a portable battery.
According to the above overall equation, sulfuric
acid is consumed and water is produced on discharge.
Both of these effects dilute the H
2
SO
4
(aq) electrolyte.
The reaction quotient, Q, for the equation, given by
Anode
Cathode
Negative plates:
lead grills filled
with spongy
lead and PbSO
4
(s)
Positive plates:
lead grills filled
with a mixture of
PbSO
2
(s) and
PbSO
4
(s)

+
Author
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Artist
Date
Title
Check if revision Approved
General Chemistry - 4th ed
McQuarrie/Gallogy
George Kelvin

08/07/10
U.1
Figure U.1 Cutaway view of one-half of a 12-V
lead storage battery.
U2 GENERAL CHEMISTRY, FOURTH EDITION | McQuarrie, Rock, and Gallogl y
University Science Books, 2011. All rights reserved. www.uscibooks.com
Q = 1/[ H
2
SO
4
], increases upon discharge, and so the
cell voltage, which is given by the Nernst equation
RT

nF

ln Q E
cell
= E
cell
=
decreases. On rapid recharge of a lead storage bat-
tery, appreciable amounts of H
2
(g) and O
2
(g) may
be formed from the electrolysis of water at the
Pb(s)|PbSO
4
(s) and PbO
2
(s), PbSO
4
(s)|Pb(s) elec-
trodes, respectively. Thus, there is signicant danger
of an explosion on rapid recharge. For this reason,
sparks and ames should not be brought near a lead
storage battery, especially during recharging, and
jumper cables should always be grounded to the chas-
sis rather than connected to the negative terminal
when jump-starting.
The most common cause of failure of lead stor-
age batteries is the development of dendrites. These
leaike structures of lead metal (Figure U.2) form on
rapid recharge and connect the anode and cathode
within the cell, thus constituting an internal short cir-
cuit that kills the battery.
U-2. NiCad and NiMH Batteries Are
Rechargeable
Another type of rechargeable battery is the nickel-
cadmium (NiCad) battery. The two half reactions
occurring in a NiCad cell are
Cd(s) + 2 OH

(aq) Cd(OH)
2
(s) + 2 e

(oxidation)
2 NiOOH(s) + 2 H
2
O(l ) + 2 e

2 Ni(OH)
2
(s) + 2 OH

(aq) (reduction)
and the overall cell equation is
Cd(OH)
2
(s) + 2 Ni(OH)
2
(s)
discharge
recharge
Cd(s) + 2 NiOOH(s) + 2 H
2
O(l )

A sealed NiCad battery is more chemically stable
than a lead storage battery and can be left inactive for
long periods. Each NiCad cell develops 1.2 V, so, for
example, a 9.6-V NiCad battery contains eight NiCad
cells in series. NiCad batteries suffer from memory
effects, which means that if they are not fully dis-
charged and recharged for the rst few cycles, their
battery life can shorten. The NiCad battery concept
was discovered by Thomas A. Edison, but Edison
chose an Fe(s)|Fe(OH)
2
(s) electrode rather than the
Cd(s)|Cd(OH)
2
(s) electrode because iron is much
less expensive than cadmium. Edison cells have been
used extensively in automobile batteries in Europe.
Today the NiCad battery is being replaced by
the nickel-metal hydride (NiMH) battery due to
concerns about the toxicity of cadmium. Moreover,
NiMH batteries have a higher energy density and do
not suffer from signicant memory effects. In place
of cadmium, the nickel-metal hydride battery uses a
metal alloy hydride (abbreviated MH) anode, where
M can stand for any of a number of metal alloys.
A single NiMH cell produces about 1.2 V. The cell
half reactions are
MH(s) + OH

(aq) M(s) + H
2
O(l ) + e

(oxidation)
NiOOH(s) + H
2
O(l ) + e

Ni(OH)
2
(s) + OH

(aq) (reduction)
and the overall cell reaction is
M(s) + 2 Ni(OH)
2
(s)
discharge
recharge
MH(s) + NiOOH(s)

Figure U.2 Metallic dendrites formed during
electrochemical deposition. Such dendrites occur in the
rapid discharge of a lead storage battery and can lead to an
internal short circuit.
U3 U. BATTERI ES
NiMH batteries are used extensively in cordless
tools, rechargeable ashlights, and in hybrid cars that
can charge a bank of onboard NiMH batteries while
braking and then use the stored energy to supplement
a gasoline engine when accelerating (Figure U.3).
U-3. Dry Cells and Alkaline Batteries Are
Used in Flashlights and Toys
The dry cell and the alkaline manganese cell, both
of which are widely used in ashlights, battery-pow-
ered toys, and similar devices, are closely related.
Both contain a zinc metal negative electrode (anode)
and an inert positive electrode (cathode), on which
MnO
2
(s) is reduced to Mn
2
O
3
(s). The positive elec-
trode is a carbon rod in the dry cell. The name dry
cell is used because the electrolyte in the cell is a
paste composed of MnO
2
(s), NH
4
Cl(s), ZnCl
2
(s),
carbon powder, water, and starch. An improvement
on the dry cell is the alkaline manganese cell or
alkaline battery (recall that alkaline means basic),
which has twice the capacity, a steadier voltage under
heavy current drain, and a higher available current
than the dry cell. The alkaline manganese cell uses
the same electrode materials as the dry cell, but the
electrolyte is a basic paste of KOH(aq) (Figure U.4).
Its main disadvantage is that it costs roughly three
times as much as the dry cell because of the more
elaborate internal construction necessary to prevent
leakage of the KOH(aq). Both of these cells produce
about 1.5 V. The equation describing the overall cell
reaction occurring in the alkaline manganese cell is
Zn(s) + 2 MnO
2
(s) ZnO(s) + Mn
2
O
3
(s) (basic)
U-4. Button Batteries Are Used in
Wristwatches and Medical Devices Where
a Constant Voltage Is Required
Another type of primary battery is the silver-zinc but-
ton battery used in wristwatches, hearing aids, light
meters, and other devices where a constant voltage
Figure U.3 Hybrid cars contain both a gasoline and an
electric motor. NiMH batteries are charged while braking
by spinning the electric motor in reverse, making it act as
a generator. The stored energy is then used to supplement
the gasoline engine when accelerating. In this way hybrid
cars can achieve fuel efciencies signicantly greater than
those of conventional vehicles.
Positive
button
Steel case
MnO
2
in
KOH paste
Zn (anode)
Graphite rod
( cathode)
Absorbent/
separator
Negative
end cap
Author
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Artist
Date
Title
Check if revision Approved
General Chemistry - 4th ed
McQuarrie/Gallogy
George Kelvin
08/16/10
U-4
Figure U.4 A cutaway view of a typical alkaline
manganese cell.
U4 GENERAL CHEMISTRY, FOURTH EDITION | McQuarrie, Rock, and Gallogl y
University Science Books, 2011. All rights reserved. www.uscibooks.com
is of primary concern (Figure U.5). The silver-zinc
button battery replaced the mercury battery in such
applications because of environmental concerns over
the disposal of mercury. The cell diagram of a silver-
zinc button battery is
() Zn(s)|ZnO(s)|KOH(aq)|Ag
2
O(s)|Ag(s) (+)
The advantages of this cell are its constant voltage
(1.55 V) during discharge (because there is no change
in the cell electrolyte composition during discharge);
its capacity (i.e., total power output), which is about
twice as great as the alkaline manganese cell; its very
long shelf life; its small size; and its ability to supply
large instantaneous currents. The main disadvantage
is its high cost.
U-5. Lithium Ion Batteries Are Used in
Portable Electronics
The most signicant advance in battery technology is
the primary lithium battery and the secondary lithium
ion battery. Although work on a lithium battery was
rst started by G. N. Lewis (Chapter 7 Frontispiece)
in 1912, it wasnt until recent decades that this battery
has become commercially available because of safety
problems in the containment of lithium. Because lith-
ium is both the most potent reducing agent known
and the metal with the lowest density, lithium bat-
teries have the highest power-to-weight ratio of all
batteries. A single lithium cell produces about 3.6 V.
Primary lithium batteries also have the longest shelf
lives of all batteries. For these reasons most modern
medical implants and some wristwatches now employ
primary lithium batteries, while cell phones, laptop
computers, digital cameras, MP3 players, and similar
devices generally use secondary (rechargeable) lith-
ium ion batteries (Figure U.6).
Primary lithium cells use the direct oxidation of
lithium metal at the anode, Li(s)|Li
+
(solv), where solv
represents a solvent other than water (with which lith-
ium reacts violently). A variety of cathode materials
are used in the cells depending on the application,
the most common of which is MnO
2
(s)|Mn(s).
Secondary lithium ion cells employ cathodes such
as Li
x
CoO
2
(s)|LiCoO
2
(s) or Li
x
Mn
2
O
4
(s)|LiMn
2
O
4
(s),
where x symbolizes that the complex can have a vari-
ety of empirical formulas. The anode is typically com-
posed of lithium in graphite with a formula Li
x
C
6
(s).
Anode cap
Cathode can
Zn in KOH gel
(anode) () Gasket
Separator
Pellet of Ag
2
O
in graphite
(cathode) (+)
Author
Figure #
Artist
Date
Title
Check if revision Approved
General Chemistry - 4th ed
McQuarrie/Gallogy
George Kelvin
08/16/10
U-5
Figure U.5 A cutaway view of a typical
silver-zinc button battery.
Figure U.6 Secondary lithium ion batteries are used to
power cellular telephones.
U5 U. BATTERI ES
The half-cell reactions and overall cell equation for a
typical lithium ion secondary cell are
Li
x
C
6
(s) xLi
+
(solv) + xe

+ C
6
(s) (oxidation)
Li
(1x)
CoO
2
(s) + xLi
+
(solv) + xe

LiCoO
2
(s) (reduction)
and the overall cell equation is
C
6
(s) + LiCoO
2
(s)
discharge
recharge
Li
x
C
6
(s) + Li
(1x)
CoO
2
(s)


where solv is an organic solvent electrolyte consist-
ing of a lithium salt such as LiPF
6
(s), LiBF
4
(s), or
LiClO
4
(s), in an organic solvent, such as ether.
One disadvantage of the secondary lithium ion
battery is that it has a limited useful lifetime regard-
less of the number of charge/discharge cycles, start-
ing from the time the battery is manufactured. Thus,
lithium ion batteries all require eventual replacement
(regardless of usage) and purchasers of new lithium
ion batteries should always check the date of manu-
facture, which is typically stamped on the battery.
TERMS YOU SHOULD KNOW
battery U1
primary battery U1
secondary battery U1
lead storage battery U1
dendrites U2
nickel-cadmium (NiCad) battery U2
Edison cell U2
nickel-metal hydride (NiMH) battery U2
dry cell U3
alkaline manganese cell U3
silver-zinc button battery U3
lithium battery U4
lithium ion battery U4
QUESTIONS
U-l. What is the difference between a battery and a
cell?
U-2. What is the difference between a primary and a
secondary battery?
U-3. Why shouldnt lead-storage batteries be rapidly
recharged?
U-4. List two advantages that nickel-metal hydride
(NiMH) rechargeable batteries have over nickel-cad-
mium (NiCad) rechargeable batteries.
U-5. Why should used lithium batteries never be dis-
posed of in a regular trash container?
U-6. The cell diagram for the Edison cell, used exten-
sively in car and truck batteries in Europe, is
Fe(s)|Fe(OH)
2
(s)|NaOH(aq)|
NiOOH(s),Ni(OH)
2
(s)|steel
where the steel electrode is nonreactive and the
comma between NiOOH(s) and Ni(OH)
2
(s) denotes
a heterogeneous mixture of the two solids. Determine
the equation for the cell reaction.
U-7. The cell diagram for the reaction occurring in
silver-zinc button batteries is
Zn(s)|ZnO(s)|KOH(aq)|Ag
2
O(s)|Ag(s)
Write the two half-reaction equations occurring in
this cell and the overall cell reaction equation. Use
the data in Appendix G to determine the value of E
cell

for the cell. Why are silver-zinc batteries used in appli-
cations where a constant voltage is required?
U-8. Standard alkaline manganese cells generate
about 1.5 volts from the reaction described by
Zn(s) + MnO
2
(s) +H
2
O(l )
ZnO(s) + Mn(OH)
2
(s) (basic)
(Recall that the word alkaline means basic.) Write
the balanced half-reaction equations occurring in
the alkaline manganese cell. Why does the voltage
of an alkaline manganese cell remain fairly constant
over the life of the cell?
U-9. Alkaline manganese cells all use the same reac-
tion described by the equation in Question U-8.
Explain why AAA- and D-sized cells both produce the
same voltage if the quantity of chemicals in the D-
sized cell is almost ve times that of the AAA-sized
cell. What advantage is there in using a D-sized cell
over a AAA-sized cell in a toy or ashlight?
U-10. A standard 9-volt alkaline battery uses the same
cell reaction as that described by the equation in
Question U-8. How is it possible to generate 9 volts of
electricity using these cells?