Chemistry for Everyone

Lithium Batteries:
A Practical Application of Chemical Principles
Richard S. Treptow
Department of Chemistry and Physics, Chicago State University, Chicago, IL 60628-1598

Cameras, laptop computers, cellular telephones, and auto-

mobiles have one thing in common—they all require batteries.
The devices of modern technology make ever-increasing de-
mands for sources of portable energy. The ideal battery for
every purpose would be dependable, economical, lightweight,
stable in storage, and environmentally safe. Although the per-
fect battery does not exist, and perhaps never will, electro-
chemical engineers continue to invent new varieties with
improved performance (1–7).
In recent years new batteries have emerged in the mar-
ketplace that make use of the unique properties of lithium,
the lightest metal on the periodic table. A collection of these
commercial batteries is displayed in Figure 1. They differ in
their size, shape, and voltage, and also in the chemical reac-
tions they employ. Lithium batteries are of interest to chem-
istry students because of the increasing role they play in
modern technology and also because they illustrate the prac-
tical application of principles learned in the classroom. In
this paper we imagine ourselves in the role of engineers as
we design lithium batteries through the application of these
principles. We will discuss batteries whose anodes are lithium Figure 1. Commercial lithium-metal batteries of various sizes,
metal and also those that use lithium-ion anodes. shapes, voltages, and chemistries.

The Lithium-Metal Anode

Metals have properties that make them well suited to
serve as battery anodes. They are easily oxidized from their
metallic state to produce ions and electrons, as illustrated by
the half-reaction
M Mn + + ne−
The electrons liberated are conducted through the metal,
which thereby becomes the negative terminal of the cell. The
fact that metals are physically strong and easily fashioned into
any desired shape adds to their attractiveness as anodes.
Metals commonly employed as anodes in commercial
batteries are listed in Table 1. The tabulated properties give
clues as to the ability of each metal to play this role. The
redox couple identifies the ion formed in the oxidation half-
reaction. The standard reduction potential is a measure of the
ease with which that ion is reduced back to the metallic state.
The electrochemical capacity of a metal is a practical property
defined as the quantity of electric charge produced per gram
of metal in the anode half-reaction. For example, in the case

Table 1. Metals Commonly Used as Battery Anodes

Atomic Density/ Redox Standard Reduction Electrochemical

Metal
Weight (g cm
3) Couple Potential/V Capacity/(A h g
1)

Lithium 6.94 0.53 Li+/Li
3.04 3.86

+
Sodium 22.99 0.97 Na /Na
2.71 1.17
Magnesium 24.31 1.74 Mg2+/Mg
2.70 2.21
Aluminum 26.98 2.70 Al3+/Al
1.66 2.98
Calcium 40.08 1.54 Ca2+/Ca
2.87 1.34
Iron 55.85 7.86 Fe2+/Fe
0.45 0.96
Zinc 65.39 7.14 Zn2+/Zn
0.76 0.82
Cadmium 112.41 8.64 Cd2+/Cd
0.40 0.48
Lead 207.2 11.3 Pb2+/Pb
0.13 0.26

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 Chemistry for Everyone
of lithium the electrochemical capacity is calculated as fol-
lows:
1 mol e− mol Li 9.65 × 104 C
× ×
mol Li 6.94 g Li mol e −
1As h Ah
× × = 3.86
C 3600 s g Li
The unit used to measure charge is the ampere-hour.
Two properties of lithium listed in Table 1 suggest this
metal is an attractive choice to serve as a battery anode. First,
the lithium ion has the most negative reduction potential.
This means that the ion has the lowest tendency to be re-
duced to the metallic state. More importantly, it means that
lithium metal has the greatest tendency to be oxidized to the
ionic state. If all other factors were equal, a lithium anode
would produce a higher voltage than any of the other met-
als. Second, lithium has the greatest electrochemical capac-
ity. As the calculation above shows, this results because
lithium has an exceptionally low atomic weight. Thus, a
lithium anode will deliver the greatest quantity of charge per
unit-weight. Since the energy produced by a battery is the
product of its voltage times the charge it delivers, the two
properties cited suggest that lithium batteries can be expected
to produce exceptionally high energy per unit-weight.
A battery that we shall design employing a lithium an-
ode is illustrated in Figure 2. When the cell discharges, the
oxidation half-reaction at the anode is
Li(s) Li+(solv) + e−
The electrons produced leave the battery, pass through the
external circuit with a load of some sort, and return to the
battery at the cathode. The solvated lithium ions migrate
through the cell to the cathode where they undergo a chemical
reaction yet to be chosen. Let us first select the electrolyte
through which this ion migration occurs.
Electrolyte Salts and Solvents
The role of a battery electrolyte is to separate the anode
and cathode so they do not react directly. It must, however,
allow ions to pass between the electrodes. This movement of
ions constitutes the flow of charge inside the battery. For our
lithium battery the electrolyte must allow lithium ions to
migrate from the anode to the cathode.
Most batteries use electrolytes that are aqueous solutions
of salts or other ionic compounds. A lithium battery, how-
ever, must avoid water and other protic solvents because these
compounds react with the metal to produce hydrogen gas.
The battery must employ a solvent that is aprotic and
nonreactive toward the metal. The solvent must be sufficiently
polar to dissolve lithium salts and produce a solution with
high ionic conductivity. Many organic solvents meet these
criteria. They include acetonitrile (AN), dioxane (DIOX), γ-
butyrolactone (BL), methyl formate (MF), 1,2-
dimethoxyethane (DME), propylene carbonate (PC),
dimethylsulfoxide (DMSO), and tetrahydrofuran (THF).
1016 Journal of Chemical Education • Vol. 80 No. 9 September 2003 • JChemEd.chem.wisc.edu
e− load
– +
anode electrolyte cathode
Li FeS2 +4Li + + 4e−
Li +
Li + + e− Fe + 2Li2S
lithium metal iron disulfide
Figure 2. Lithium-metal battery with a solid cathode of iron disulfide.
Our next task is to find lithium salts that are soluble in
these solvents. In general, salts achieve high solubility if their
lattice energies are low. The small lithium ion accomplishes
this if it is paired with a large anion. Examples of such salts
include LiClO4, LiPF6, LiBr, LiBF4, LiCF3SO3, and LiAlCl4.
These salts are soluble in the solvents above, and the solu-
tions they produce have the required high ionic conductivity.
Suppose we choose a solution of LiPF6 in dimethylsulfoxide
as the electrolyte for the battery shown in Figure 2. The fi-
nal step is to select its cathode.
Solid, Liquid, and Gas Cathodes
The cathode of a lithium battery must undergo a reduc-
tion reaction that consumes the electrons and lithium ions
produced at the anode. Iron disulfide is one of many inor-
ganic solids that can serve in this role. Its reduction half-re-
action is
FeS2(s) + 4Li+(solv) + 4e− Fe(s) + 2Li2S(s)
Let us choose this compound as the cathode of the battery
in Figure 2. The overall cell reaction is then
4Li(s) + FeS2(s) Fe(s) + 2 Li2S(s)
and the shorthand notation for the cell is
Li(s)LiPF6, DMSOFeS2(s)
Chemical thermodynamics can be applied to calculate
the voltage of the battery. The process is simplified by the
fact that all reactants and products in the overall reaction are
solids. Thus, they are present in their standard states. The
standard free-energy change for the reaction can be calcu-
lated from the standard free energies of formation by use of
the equation
∆G
o
= ∑ n ∆Gfo (products) − ∑ m ∆Gfo (reactants)
 Chemistry for Everyone

cathode its reduction half-reaction is

e− load
+
+ 2 SOCl2(l) + 4 Li (solv) + 4 e−
–
S(solv) + SO2(solv) + 4LiCl(s)
anode cathode
The sulfur and sulfur dioxide produced remain dissolved in
layer

current collector
the thionyl chloride, but the lithium chloride precipitates. A
Li 2SOCl2 + 4 Li + + 4e− battery we might build using this chemistry is illustrated in
Li + Figure 3. The lithium chloride precipitate plays an impor-
tant role. It deposits on the surface of the lithium anode and
passive

thereby forms a passive layer between the anode and cath-

Li+ + e− S + SO2 + 4LiCl
ode. This layer prevents the anode and cathode from react-
ing directly and yet it allows the lithium ions produced at
lithium metal thionyl chloride the anode to pass through. The lithium chloride plays the
role given to the electrolyte phase in most other batteries.
Figure 3. Lithium-metal battery with liquid cathode of thionyl chloride.
Next, we dissolve LiAlCl4 into the thionyl chloride to increase
its ionic conductivity. Finally, a current collector of carbon
or some other electronically conducting material is placed in
contact with the cathode. The cell is now complete; its over-
Substituting the appropriate ∆G f values from the literature all reaction is
gives ∆G =
718.1 kJ. We then calculate the cell potential
from 4Li(s) + 2SOCl2(l) S(s) + SO2(solv) + 4LiCl(s)

o ∆G o
Ecell = −
nF
where F is the Faraday constant and n = 4 mol for this reac-
tion. The result is E cell = 1.86 V. Electrochemical engineers
refer to this as the open-circuit voltage. It is the potential be-
tween the terminals of a battery when it is not delivering a
current. When a battery is delivering a current its voltage
decreases as a result of cell-polarization effects (1, 4, 8). Com-
mercial batteries that employ the FeS2 cathode are rated at
an operating voltage of 1.5 V.
A few inorganic liquids are able to serve as both the cath-
ode and the electrolyte solvent of a lithium battery. Thionyl
chloride is the most common example. In the role of the
and its notation is
Li(s)LiAlCl4, SOCl2(l)C(s)
Applying the calculation method described above we find that
E cell = 3.71 V for this battery. The calculation must be re-
garded as approximate, however, when applied to any cell
with a liquid cathode because the reactants and products in
the liquid phase are not in their standard states. Commercial
batteries based on this chemistry are called inorganic lithium
batteries because no organic solvent is present. They have an
operating voltage of 3.6 V.
Various solid and liquid compounds employed as cath-
odes in lithium batteries are listed in Table 2. The table gives

Table 2. Solid and Liquid Cathodes for Lithium Batteries

Cathode Compound Cell Reaction E cell / V

Solids
Oxides
CuO 2Li(s) + CuO(s) → Cu(s) + Li2O(s) 2.25
Bi2O3 6Li(s) + Bi2O3(s) → 2Bi(s) + 3Li2O(s) 2.06
Sulfides
FeS 2Li(s) + FeS(s) → Fe(s) + Li2S(s) 1.75
FeS2 4Li(s) + FeS2(s) → Fe(s) + 2Li2S(s) 1.86
Ni3S2 4Li(s) + Ni3S2(s) → 3Ni(s) + 2Li2S(s) 1.73
CuS 2Li(s) + CuS(s) → Cu(s) + Li2S(s) 2.00
Halides
CuF2 2Li(s) + CuF2(s) → Cu(s) + 2LiF(s) 3.55
CuCl2 2Li(s) + CuCl2(s) → Cu(s) + 2LiCl(s) 3.08
AgCl Li(s) + AgCl(s) → Ag(s) + LiCl(s) 2.84

Liquids
SOCl2 4Li(s) + 2SOCl2(l) → S(solv) + SO2(solv) + 4LiCl(s) 3.71
SO2Cl2 2Li(s) + SO2Cl2(l) → SO2(solv) + 2LiCl(s) 3.90

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 Chemistry for Everyone

the overall reaction for the cell in which each compound Table 3. ∆Gf° for Selected Compounds
serves as the cathode, and it lists E cell calculated from theory in Lithium Batteries
as discussed above. The ∆G f values at 25 C needed to cal- ∆Gf°/ ∆Gf°/
Compound Compound
culate these cell potentials are given in Table 3 (9). (kJ mol
1) (kJ mol
1)
Another class of lithium-metal batteries uses dissolved AgCl(s)
109.77 LiF(s)
588.66
sulfur dioxide gas as the cathodic reactant. The cell reaction
Bi2O3(s)
493.47 LiCl(s)
384.02
is
CuF2(s)
491.64 Li2O(s)
562.11
2 Li(s) + 2 SO2(solv) Li2S2O4(s)
CuCl2(s)
173.81 Li2S(s)
439.08
The sulfur dioxide is dissolved in an electrolyte solution such CuO(s)
128.29 Ni3S2(s)
210.39
as a solution of LiBr in acetonitrile. The lithium dithionite
CuS(s)
53.47 SO2(g)
300.10
precipitate forms a passive layer on the anode preventing it
from reacting directly with the sulfur dioxide. As with the FeS(s)
101.96 SOCl2(l)
202.61
battery shown in Figure 3, a current collector is placed in FeS2(s)
160.07 SO2Cl2(l)
315.30
contact with the liquid cathode. The resulting battery would
be symbolized

Li(s)LiBr, SO2, ANC(s)

e− load
Commercial batteries employing the SO2 cathode have an
operating voltage of 2.8 V. +
–
Intercalation Cathodes anode electrolyte cathode
Some inorganic solids have the ability to serve as cath-

current collector
odes for lithium batteries through a unique type of reaction Li
known as intercalation. These solids have layered or tunneled
Li + Li+ Li+
crystal structures. In the cathode half-reaction, the crystal acts
as a host for lithium ions that diffuse into it, as illustrated in
the battery shown in Figure 4. The host is reduced by the Li + + e−
gain of electrons required for electro-neutrality as the inser- manganese dioxide
tion occurs. The host undergoes only minor structural change lithium metal and carbon
in the process. The half-reaction can be written as
Figure 4. Lithium-metal battery with intercalation cathode of man-
HOST(s) + n Li+(solv) + n e− LinHOST(s) ganese dioxide.

The intercalation compound formed in the process is nonsto-

ichiometric.
The most popular intercalation cathode for commercial
lithium-metal batteries is manganese dioxide. Its reduction Table 4. Intercalation Hosts Used as Cathodes
half-reaction is for Lithium Batteries
Host
Cell Reaction Ecell/V
MnO2(s) + nLi+(solv) + ne− LinMnO2(s) Compound
CoO2 nLi(s) + CoO2(s) → LinCoO2(s) 3.8–4.5
and its overall cell reaction is
V2O5 nLi(s) + V2O5 (s) → LinV2O5(s) 2.9–3.6
nLi(s) + MnO2(s) LinMnO2(s) MnO2 nLi(s) + MnO2(s) → LinMnO2(s) 2.5–3.2

The cathode consists of manganese dioxide with carbon par- TiS2 nLi(s) + TiS2 (s) → LinTiS2(s) 1.6–2.5
ticles added for improved conductivity. A suitable electrolyte MoO2 nLi(s) + MoO2(s) → LinMoO2(s) 0.8–1.9
is a solution of LiClO4 in propylene carbonate (PC). With
these components the cell shown in Figure 4 is symbolized as

Li(s)LiClO4, PCMnO2(s)C(s)
Commercial versions of this battery are rated at 3.0 V or at
multiples of this voltage if they are composed of two or more
individual cells connected in series.
Several intercalation hosts used as cathodes for lithium
batteries are listed in Table 4. The cell reaction is shown for
each cathode. The Ecell listed is the measured open-circuit
voltage of the cell (1). It has a range of values because the
voltage changes with n, the extent of intercalation of the host.
The Lithium-Ion Anode
The reactions discussed above in which lithium ions dif-
fuse into a host structure have the advantage of being revers-
ible. Hence, they can be used to produce rechargeable

1018 Journal of Chemical Education • Vol. 80 No. 9 September 2003 • JChemEd.chem.wisc.edu

 Chemistry for Everyone

called a lithium-ion battery to emphasize that it contains no

e− load or e− lithium metal.
dc power source
discharge charge The electrode that serves as the cathode during discharge
– +
of the battery in Figure 5 is cobalt dioxide. Its reduction half-
reaction is

CoO2(s) + n Li+(solv) + n e− LinCoO2(s)

Li +
current collector

current collector
+ +
Li Li
discharge Thus, the overall discharge reaction is
+
Li + Li+
Li LinC6(s) + CoO2(s) 6 C(s) + LinCoO2(s)
charge
This reaction occurs in the opposite direction when the bat-
lithiated cobalt
graphite
electrolyte
dioxide tery is charged. The battery requires an electrolyte, conduc-
tive carbon particles in the CoO2(s), and current collectors
as described above. Commercial versions have an operating
Figure 5. Lithium-ion rechargeable battery with intercalation posi- voltage of 3.7 V.
tive and negative electrodes during discharge and charge.
The rechargeable battery in both the discharging and
charging modes is illustrated in Figure 5. When discharging
the battery delivers energy to the external load and when
charging it receives energy from a dc power source. The elec-
trons and lithium ions reverse directions whenever the mode
changes. Batteries of this type are called “swing” or “rocking
chair” batteries to emphasize this back and forth motion. As
with any rechargeable battery, use of the terms anode and cath-
ode to describe electrodes can cause confusion. The electrode
that acts as an anode during discharging becomes a cathode
during charging. Electrochemical engineers avoid confusion
by referring to the electrodes as positive and negative. These
properties remain unchanged when the battery changes mode.

Commercial Battery Construction

Figure 6. Interior of cylindrical lithium-ion rechargeable battery
showing the spiral winding of electrodes and separators. Courtesy
SANYO Energy (USA) Corporation.
batteries. The most commercially successful of these batter-
ies is illustrated in Figure 5. Both electrodes are intercalation
compounds. The electrode on the left serves as the anode
when the cell discharges. It is a special intercalation com-
pound consisting of a graphite host into which lithium ions
have been electrochemically inserted between the carbon atom
layers. The compound, known as lithiated graphite, is writ-
ten LinC6. During discharge the lithium ions are extracted
by the half-reaction
+
LinC6(s) nLi (solv) + 6C(s) + ne−
This oxidation process is nearly as favorable as that discussed
above for lithium metal. In fact, any battery that uses a lithi-
ated-graphite anode will produce a voltage only about 0.2 V
less than that of its lithium-metal anode counterpart. It is
The battery drawings featured above are schematic il-
lustrations only. They do not show the many internal fea-
tures needed to produce a practical battery. These features
may include a gas-release vent to prevent the buildup of in-
ternal pressure. Separator layers of glass or polymeric fibers
are commonly placed between the electrodes to prevent them
from making direct contact. These separators must be per-
meable to the electrolyte solution. Finally, to deliver optimum
current and power a practical battery must maximize the sur-
face area of its electrodes. This is accomplished by fabricat-
ing the electrodes into thin sheets. The internal components
of a commercial lithium-ion battery are shown in Figure 6.
It is a cylindrical cell whose electrodes are thin sheets wound
into a “jelly-roll” spiral with separator layers between them.
Further information on commercial lithium batteries can
be obtained by visiting the Web sites of companies that manu-
facture (10), market (11), or recycle (12) them. In closing,
we should note that much current research is being done
worldwide on the subject of lithium batteries. Their tech-
nology will surely change in years to come.
Literature Cited
1. Handbook of Batteries, 3rd ed.; Linden, D., Reddy, T. B., Eds.;
McGraw-Hill: New York, 2002.
2. Handbook of Battery Materials; Besenhard, J. O., Ed.; Wiley-
VCH: Weinheim, Germany, 1999.
3. Lithium Ion Batteries; Wakihara, M., Yamamoto, O., Eds.;
Wiley-VCH: Weinheim, Germany, 1998.

JChemEd.chem.wisc.edu • Vol. 80 No. 9 September 2003 • Journal of Chemical Education 1019

Chemistry for Everyone
4. Vincent, C. A.; Scrosati, B. Modern Batteries: An Introduction
to Electrochemical Power Sources, 2nd ed.; Arnold: London,
1997.
5. Julien, C. In The CRC Handbook of Solid State Electrochemis-
try; Gellings, P. J., Bouwmeester, H. J. M., Eds.; CRC Press:
Boca Raton, FL, 1997.
6. Crompton, T. R. Battery Reference Book; Butterworths: Lon-
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7. Lithium Battery Technology; Venkatasetty, H. V., Ed.; John
Wiley & Sons: New York, 1984.
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1020 Journal of Chemical Education • Vol. 80 No. 9 September 2003 • JChemEd.chem.wisc.edu
9. HSC Chemistry for Windows, version 4.1; Outokumpu Re-
search Oy: Pori, Finland, 2000.
10. Energizer. http://energizer.com. HDS Systems. http://
www.hdssystems.com. SANYO. http://sanyobatteries.com.
Sonnenschein GmbH. http://www.sonnenschein-lithium.de. Va-
lence Technology. http://www.valence-tech.com. Varta. http://
varta.com. Wilson Greatbatch Technologies. http://
www.greatbatch.com (all Web sites accessed Jun 2003).
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http://interstatebatteries.com (all Web sites accessed Jun 2003).
12. ToxCo, Inc. http://toxco.com (accessed Jun 2003).