E10

Materials Science and Engineering Module: Batteries and Fuel Cells

Fall Semester 2010

Thomas M. Devine
Department of Materials Science and Engineering
University of California, Berkeley

INTRODUCTION
The performance of a battery is largely described by two types of graphs. The first
graph is a plot of charging and discharging curves. The second graph is called a
Ragone plot, and is a plot of the batteryʼs energy density vs power density.

The discharge curves were introduced in the first lecture. “Discharge” means that the
battery is providing energy. “Charge” means that energy is being stored in the battery.
Both charging and discharging curves are graphs of voltage (vertical axis) vs charge
(horizontal axis; units of amp hr or coulombs).

As shown in Figure 1, a discharge curve is a plot of the instantaneous cell voltage (e.g.,
Vcell = V1) at a given value of the amount of charge (e.g., Q1) that has been discharged
by the operation of the battery at a constant value of cell current(I1). There is a different
discharge curve for each value of cell current.

Note that the total amount of charge that a battery can provide decreases as the
discharge current increases. In other words, the faster you discharge a battery, the less
is the total amount of charge the battery provides.

A charging curve graphs the instantaneous cell voltage at a given value of the amount
of charge that has been stored in the battery as a consequence of a constant value of
charging current. As shown in Figure 2, there is one charging curve for each value of
charging current. (Note: the curves should be smooth - Iʼm not a good artist.)

The higher the current used to charge the battery the larger is the total amount of
charge supplied to the battery.

Note that the maximum value of cell voltage, Vcellmax, is identified in both figures. The
numerical value of Vcellmax is the same in both figures. Further on in these notes weʼll
discuss how Vcellmax is calculated.

One of the objectives of the Materials Science and Engineering module is to explain the
shapes of the charge/discharge curves and the effects of cell current on the charge/
discharge curves.

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A second type of graph that is used to describe the performance of a battery is known
as a Ragone curve. The Ragone curve was introduced in Lecture #2. The Ragone
curve plots the energy (per mass of the battery) that is available as a function of the
power (per mass of the battery) that the battery provides. In other words, the Ragone
curve is a graph of the energy that is available as a function of the rate at which the
energy is supplied. A point (E1, P1) on the Ragone curve indicates the total energy
density, E1, that a battery will provide at a particular power density, P1. Ragone curves
are named after David Ragone, who first presented them in 1968. An example of a
Ragone curve is presented in Figure 3. The Ragone curve indicates that there is a
value of power density, PM, at which the battery will supply a maximum amount of
energy, EM.

Another objective of the Materials Science and Engineering module is to explain the
relationship between the energy and power provided by a battery.

The selection of the most appropriate battery for a particular application is made by the
use of the charge/discharge curves and Ragone curves.

Our discussion begins with analysis of the charge/discharge curves.

DISCHARGE CURVES
Discussing the shape of a discharge curve is best done by comparing a “real” discharge
curve, such as that presented in Figure 1, to the “ideal” discharge curve. The
comparison between real and ideal is presented in Figure 4. First, note that the “ideal”
batteryʼs cell voltage is the maximum possible value, Vcellmax, independent of the
batteryʼs state of charge (i.e., independent of how much charge the battery has already
provided). Second, in the “ideal” discharge curve, the total energy that the battery can
provide (i.e., the total amount of work that the battery can do) is independent of the rate
at which the battery provides the energy. That is, for the “ideal” battery there is only one
discharge curve; it is that same curve independent of the value of the discharge current.

The total amount of work that the battery can do is equal to the area underneath the
discharge curve. If the Tesla automobile was powered by batteries that exhibited “ideal”
discharge curves, then the total distance that the Tesla could be driven in between
charges would be independent of how fast the driver accelerated and drove. For
batteries with “real” discharge behavior, the total distance the Tesla can travel depends
on how the car is driven, i.e., hard accelerations and fast speeds will limit the vehicleʼs
range (i.e., hard accelerations and fast speeds require high values of discharge
current).

You are familiar with the similar relationship that exists between the total miles driven
per tank of gasoline and the rate of the carʼs acceleration and speed.

Letʼs consider the factors that contribute to the nonideality of a real batteryʼs discharge
curves. The two main factors are the electrolyteʼs resistance and something called the
“polarization resistance.” Weʼll begin with the polarization resistance.

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Polarization Resistance
Of all the topics that we will discuss, the polarization resistance is the concept you are
probably the least familiar with. However, understanding polarization resistance is well
within your ability and once you understand this topic the rest of the module is
“downhill.”

The theoretical value of cell voltage, Vcell = Vtheor, is determined by the chemistry of the
cell and is independent of how the cell is operated. Vtheor is the maximum possible
value of Vcell. That is, Vcellmax = Vtheor. Recall that Vcellmax is identified in Figures 1, 2
and 4. Vtheor is supplied by the battery only when the current supplied by a real battery
is zero (see Figure 1 and Figure 4). That is, the battery provides zero power at the
maximum value of cell voltage: P = Vcell•Icell and P(at Vtheor) = Vtheor•0 = 0. The fact that
the battery cannot supply any current at Vtheor will be considered further on in these
notes. Suffice it to say at this point that the battery has an internal resistance, Ri. Any
current that flows through the external circuit connecting the anode to the cathode
necessarily returns to the anode by flowing from the cathode, through the electrolyte
and into the anode (this “internal” current completes the circuit between anode and
cathode). Consequently, some amount of voltage = Icell•Ri, must be dropped within the
cell. The voltage dropped inside the battery decreases the voltage that can be
established between the anode and cathode below Vtheor.

“Polarization” of the anode and cathode is one cause of the internal resistance, Ri. The
other contributors to Ri are the electrical resistances associated with the movement of
electrical charge in the two electrodes, the wires connecting the electrodes to the device
powered by the battery, and the batteryʼs electrolyte.

As already mentioned, “polarization” contributes to the voltage drops that occur within a
real battery. Weʼll use Kirchhoffʼs Voltage Law to bound the magnitude of the voltage
drop due to polarization.

A fundamental law of electrical circuits (Kirchhoffʼs Voltage Law, KVL) states that the
sum of all of the voltage drops around a complete circuit is zero. (For those interested,
KVL is described in more detail on a separate document loaded onto the MSE moduleʼs
bSpace.) This law is applied to a battery with the aid of the sketch presented in Figure
5. When the battery is not connected to an electrical circuit the voltage that is
measured between the anode and cathode (using a high input impedance voltmeter so
that approximately zero current is drawn) is Vtheor. Since the sum of all voltage drops
around a complete circuit is zero, the sum of the voltage drops within the battery must
be -Vtheor. Where in the battery do the voltage drops that sum to -Vtheor occur? As will
be made clear below, when there is no current flowing the only voltgae drops occur at
the interfaces between the electrolyte and the two electrodes (anode and cathode).

When the battery is used to power a device, which is represented by the resistance RL,
the voltage drop between the two electrodes of the battery is now equal to Icell• RL. The

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sum of all of the voltage drops within the battery and external wires is -Icell• RL. Where in
the battery and external circuit are the voltage drops that sum to -Icell• RL?

Two contributions to Icell• RL are easy to identify. These are the voltage drops due to the
electrical resistances of the electrolyte and the wires that make up the external circuit
and the electrodes. In addition, there are voltage drops associated with the energy that
is required to push electrical charge across the electrode/electrolyte interfaces. This
energy is associated with the work required to convert electrons to ions and vice versa.
As already mentioned, the conversion of electrons to ions at the electrode/electrolyte
interfaces creates the “polarization resistance,” which contributes to Ri.

Converting Electrons to Ions (or ions to electrons) at the Electrode/Electrolyte Interface

When pushing electrical charge in the form of electrons through a conductor, the
relationship between current, I, and voltage, V, is linear:

I = V/R (Ohmʼs Law),

where R is the electrical resistance of the conductor and depends on the materialʼs
electrical resistivity and the geometry of the conductor.

When “pushing” electrical charge across an electrode/electrolyte interface the relation

between current and voltage is not linear. The relationship is exponential:

I/A = i = ioexp(bV),

where A = electrode/electrolyte interfacial area

i = current density
io = constant = exchange current density
b = constant = Tafel slope
V= voltage drop across the electrode/electrolyte interface.

The reasons for the exponential relationship (as opposed to linear) are beyond the
scope of this course and are treated in upper division Materials Science courses (e.g.,
MSE 112). For now, I need you to accept the fact that converting electrons to ions
depends exponentially on voltage.

It is worth describing the reactions that occur at the electrode/electrolyte interfaces and
that convert electrons to ions.

Consider, for example, a battery composed of a zinc anode and a platinum cathode
immersed in an aqueous solution of 0.01M KOH. This is referred to as the zinc-air
battery. Graphite rather than platinum is used as the cathode of commercial zinc-air
batteries. In both cases, the graphite and platinum behave similarly: they provide a
surface off of which the reaction that converts electrons to ions (during battery
discharge) occurs. Otherwise, the graphite and platinum are inert. The inertness of the

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platinum/graphite cathodes is in contrast to the zinc anode which is consumed in the
process by which the battery provides electrical energy.

At this point it is worth noting that the battery provides electrical energy by converting
chemical energy to electrical energy. The chemical energy is provided in two steps: by
the conversion of (1) Zn to Znaq+2 and (2) 1/2O2 to OH-. The details of the process of
energy conversion are provided below. Right now, before we get into the details, I just
want you to be mindful of the “big picture.”

When the battery is operating, atoms of zinc at the zinc/electrolyte interface are
oxidized, as described by the following oxidation reaction

ZnZn -> Znaq+2 + 2eZn-

where ZnZn represents a zinc atom at the surface of a zinc crystal.

Znaq+2 is a zinc ion dissolved in the aqueous solution.
eZn- is an electron in the zinc crystal.

You should be wondering, “what causes the zinc to do this?” Weʼll answer that
question shortly.

Current across the Zn/electrolyte interface consists of Zn+2 leaving the surface of zinc
and entering the aqueous electrolyte. The rate at which Zn+2 cross the zinc/electrolyte
interface depends exponentially on the voltage drop across the interface.

When the zinc ions enter the aqueous electrolyte, there is an excess charge of -2
electrons left in the zinc, 2eZn-. The two excess electrons leave the zinc crystal through
the external wire connected to the device that is powered by the battery. The electrons
flow through the device and then flow through the wire connecting the device to the
cathode of the battery. Once in the cathode the electrons leave the cathode and enter
into oxygen atoms adsorbed on the surface of platinum, Oads. The latter reaction is
described by

1/2 O2(ads) + H2O + 2ePt- -> 2 OHaq-.

As was the case for the oxidation of Zn to Zn++, you should be wondering, “What causes
the oxygen to do this?” Again, weʼll answer this question after we finish the discussion
of polarization and other causes of the batteryʼs internal resistance.

The rate at which electrons cross the cathode/electrolyte interface depends

exponentially on the voltage drop across the interface, just as was the case for the rate
at which zinc ions cross the zinc/electrolyte interface. The distinction between the
voltage dependency of the rate of electrons transferring from the platinum cathode to
oxygen adsorbed on the platinumʼs surface, and the voltage dependency of the rate of

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zinc ions leaving the zinc crystal and entering the electrolyte is a consequence of the
different directions of charge flow across the two interfaces. That is, the zinc ions are
positively charged and the electrons are negatively charged so a positive voltage drop
across the electrode/electrolyte interface will increase the rate of zinc ions leaving the
surface of the zinc crystal and entering the electrolyte. A negative voltage drop across
the the electrode/electrolyte interface will increase the rate of electrons leaving the
surface of the platinum cathode and entering adsorbed oxygen.

“A positive voltage drop across the electrode/electrolyte interface” means that the
excess electrical charge on the surface of the electrode is more positive (or less
negative) than the excess charge associated with the surface of the electrolyte. [For
reasons we will not get into the excess charge on a perfect conductor (a metal is
approximately a perfect conductor) is located on its geometric surface. An aqueous
electrolyte is ionically conductive but is not a “perfect” conductor and any excess charge
is located not exactly just on its surface but rather within a very short distance of the
electrode/electrolyte interface (e.g., for sea water, the excess charge is located within
about 1 nm of the interface).]

“A negative voltage drop across the electrode/electrolyte interface” means that the
excess electrical charge on the surface of the electrode is more negative (or less
positive) than the excess charge associated with the electrolyte.

Figure 6 graphs the relationship between voltage drop across the zinc/electrolyte
interface and the rate of flow of zinc ions across the zinc/electrolyte interface. The rate
increases exponentially with increasing voltage. This makes sense. An increasing
voltage means that the zinc surface is becoming more positively charged with respect to
the solution. As the zinc surface becomes more positively charged, the voltage
“pushes” positively charged zinc ions off the surface and into the electrolyte.

If the voltage drop across the zinc/electrolyte interface is decreased, the rate of zinc
ions entering the electrolyte decreases. If the voltage drop across the interface is made
increasingly negative, then the voltage drop will now oppose the movement of zinc ions
from the zinc surface and into the electrolyte. That is, the negatively charged zinc
surface will “hold onto” the positively charged zinc ions. In fact, if the excess charge on
the zinc surface is sufficiently negative then any zinc ions in the electrolyte will be
attracted onto the zinc surface. That is, the negative voltage causes electroplating (or
electrodeposition) of zinc: Znaq+2 + 2eZn- -> ZnZn.

The influence of voltage on the rate of electrodeposition of zinc ions is presented in

Figure 7. The rates of zinc oxidation (ZnZn -> Znaq+2 + 2eZn-) and zinc ion reduction
(Znaq+2 + 2eZn- -> ZnZn) are plotted on a single graph in Figure 8.

The rates of oxidation and reduction reactions can easily change by many orders of
magnitude (i.e., by many powers of ten) so to more easily view the influence of voltage
on reaction rate, the log of the rate is plotted vs voltage. Figure 9 is a semi-log plot

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(i.e., log current (=reaction rate) vs voltage) of the rates of oxidation and reduction of
zinc. Compare Figures 8 and 9.

Self Corrosion of Zinc and Batteryʼs Shelf Life

The slope of the plot of log current vs voltage is bOX and is positive for the oxidation
reaction (e.g., ZnZn -> Znaq+2 + 2eZn-, and 2 OHaq- -> 1/2 O2(ads) + H2O + 2ePt-). The
slope of the plot of log current vs voltage is -bRED for the reduction reaction and is
negative (e.g., Znaq+2 + 2eZn- -> ZnZn and 1/2 O2(ads) + H2O + 2ePt- -> 2 OHaq-). Where
the two lines of Log IOX vs V and LogIRED vs V intersect, the rates of the oxidation and
reduction reactions are equal, and the value of potential at which the two rates are
equal is called the equilibrium potential, Ve, of that redox couple. For example, the
equilibrium potential at 25°C of the O/OH- redox couple in water of pH 7 that is
saturated with air (=> partial pressure of oxygen = 0.2 atm) is ) 0.840 mV vs the
standard hydrogen electrode (SHE).

The rate of the oxidation and reduction reactions at equilibrium is called the exchange
current density, io.

(Please donʼt get confused by the use of current, I, and current density, i. These two are
often used in discussing batteries. Current density is the parameter to use when
comparing one electrode to another. For example, if we wanted to compare the relative
effectiveness of platinum and graphite as cathodes, we would compare their current
densities for the reduction of oxygen. Batteries often make use of highly porous
cathodes so that their surface areas are very large. In fact, the surface areas are often
so large that they are not known exactly. For this reason, current, I, is also used when
discussing the performance of batteries.)

Thus, the line describing the influence of voltage drop across the electrode/electrolyte
interface on the rate of oxidation of zinc to zinc ions is

log(i/io) = box(V-Ve).

The line describing the rate of reduction of Zn+2 as a function of voltage drop across the
zinc/electrolyte interface is

log(i/io) = -bred(V-Ve).

A similar set of equations can be written for any redox couple.

The redox reactions relevant to the zinc-air battery are constructed on a single graph in
Figure 10. Note that there are two sets of redox curves for the O/OH- couple. One (the
blue lines) pertains to the redox reactions taking place on the surface of zinc, and the
other (the green lines) applies to the redox reactions taking place on the surface of
platinum. The value of Ve depends only on the relative stabilities of O and OH- and is
independent of the identity of the electrode. The values of io, box, and bred are kinetic

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parameters and depend on the identity of the electrode. Generally, the value of io is
more sensitive to the identity of the electrode than is the value of box, and bred.

The fact that iO for the reduction of oxygen is greater for platinum than for zinc is a
reflection of the fact that platinum is a better catalyst than zinc for the oxygen reduction
reaction.

If the battery is not providing power (i.e., the battery is “at rest”), then the zinc electrode
“isnʼt aware of the presence of the platinum electrode (and vice-versa).” Therefore, to
describe the behavior of the zinc electrode in a zinc-air battery that is at rest we use
only the reactions that involve the zinc electrode, namely

ZnZn -> Znaq+2 + 2eZn-

Znaq+2 + 2eZn- -> ZnZn

1/2 O2(ads) + H2O + 2ePt- -> 2 OHaq-

2 OHaq- -> 1/2 O2(ads) + H2O + 2ePt-

All four reactions take place on the surface of zinc. Again, because there is no electrical
connection of the zinc and platinum electrodes we ignore the presence of platinum in
the battery when analyzing the behavior of the zinc electrode.

The behavior of the zinc electrode is known once the voltage drop across the zinc/
electrolyte interface, VZn, is known. For example, if the value of VZn is V(1), then, as
shown in Figure 11, the rate at which Zn is oxidized to Zn+2 is iox(Zn)(1); the rate at which
Zn+2 are electrochemically reduced to Zn is ired(Zn+2)(1); and the rates at which O is
oxidized to OH-, and OH- is electrochemically reduced to O are iox(O)(1) and ired(OH-)(1),
respectively. Thus, knowing the value of VZn allows us to indicate the specific reactions
that take place on the zinc surface and the rate of each reaction.

The potential drop across the zinc/electrolyte interface is that value at which the system
(zinc electrode plus electrolyte) remain electrically neutral. This value of potential drop
is referred to as “the corrosion potential” and the “rest potential.” The rest potential is
that value of potential at which the sum of the rates of all of the oxidation reactions (this
is the solid black line with positive slope in Figure 12) is exactly equal to the sum of the
rates of all of the reduction reactions (this is the solid black line with negative slope in
Figure 12). The rest potential of zinc in the battery electrolyte, Vrest, is indicated in
Figure 12 (the rest potential is defined by the intersection of the two solid black lines).

That is, as the zinc-air battery is at rest, the potential drop across the zinc/electrolyte interface is
Vrest. At this value of interfacial potential drop Figure 12 indicates that zinc is being oxidized to
Zn+2 and O is being electrochemically reduced to OH-. In other words, the zinc is corroding.
The corrosion of the zinc is one of the phenomena that limit the shelf life of the zinc-air battery.

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Clearly, if all of the zinc were to be oxidized while the battery is at rest, there would be no zinc
available to provide electrical power.

Electrodeʼs Polarization during Batteryʼs Discharge

When the battery is providing power, the zinc and platinum electrodes are connected to one
another through the device being powered, e.g., a light bulb, computer, etc. The device that the
battery powers is represented by an electrical resistance, RL, where L stands for “load.” The
situation is sketched in Figure 5. The electrical circuit that represents the battery connected to
the load is shown in Figure 13.

Applying Kirchhoffʼs voltage law (KVL) to the circuit in Figure 13 gives

Vcell = -VZn/S - IcellRS + VPt/S = IcellRL + IcellRex.

VZn/S is the potential drop across the zinc/electrolyte interface (the symbol ”S” represents
“solution.”)

That is, the sum of the voltage drops between anode and cathode through the external circuit is
equal to the negative of the sum of the voltage drops between anode and cathode through the
internal circuit (i.e., the portion of the circuit that goes through the battery).

VZn/S = VZn,e + boxZnlog(ioxZn/ioZn)

and VPt/S = VO,e - bredOlog(iredO/ioO)

Substituting into the equation for Vcell gives

Vcell = IcellRL + IcellRex = (VO,e - VZn,e) - [bredOlog(iredO/ioO) + boxZnlog(ioxZn/ioZn)] - IcellRS.

Finally, collecting all of the IR terms gives,

Vcell = Icell (RL + Rex + RS) = (VO,e - VZn,e) - [bredOlog(iredO/ioO) + boxZnlog(ioxZn/ioZn)].

The last equation provides a wealth of information about the battery. For example, the
maximum value of the cell voltage is (VO,e - VZn,e):

Vcell max = (VO,e - VZn,e).

A battery supplying power always has its cell voltage lowered by the terms inside of the square
brackets, []. The terms inside the square brackets are referred to as the “polarization voltage.”
The polarization voltage is the voltage drop across the electrode/electrolyte interface as a
consequence of current flow across the interface. When there is no current flow, the
polarization voltage is zero and the cell voltage is its maximum possible value. Once current is
flowing, the terms inside the square brackets are positive and the cell voltage is less than the
maximum possible value. The higher the current, the greater the polarization voltage and the
smaller is the cell voltage.

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Since the polarization voltage occurs within the battery, it is sometimes said to be caused by an
“internal resistance”, Ri, and the polarization voltage is then represented by IcellRi. The problem
with this terminology is that the actual polarization voltage is given by

[bredOlog(iredO/ioO) + boxZnlog(ioxZn/ioZn)].

Setting the last expression equal to IcellRi means that the “internal resistance,” is given by

Ri = [bredOlog(iredO/ioO) + boxZnlog(ioxZn/ioZn)]/Icell.

That is, the internal resistance is not a constant, but changes as the cell current changes. The
resistance of a resistor is a constant. The resistance of the the electrode/electrolyte interface is
not constant because the electrode/electrolyte interface is not a true resistor.

An equivalent circuit that models a battery connected to a load and models the polarization of
the two electrodes by the internal resistance, Ri, is sketched in Figure 14. This type of circuit is
commonly used but you need to keep in mind that the internal resistance, Ri, is a “peculiar”
resistance, with a value that changes as the cell current changes.

Returning to the equation for Vcell, note that the actual voltage that is available to power the
device is IcellRL and its value is reduced from the value Vcell by the voltage drops associated with
the finite electrical resistances of the electrodes and external wires plus the electrical resistance
of the electrolyte.

In summary, the actual value of voltage that the battery provides to power a device is lowered
from the theoretical maximum value by three factors: the polarization of the two electrodes, the
resistance of the electrolyte and the resistance of the external wires and electrodes.

Finally, we need to put all of the above information together and explain the discharge curves
and why they change with the value of the discharge current.

As shown in the sketch presented in Figure 15, the cell voltage at zero cell current is the
maximum value, Vtheor. The cell voltage then decreases as the cell current increases. For
example, at a cell current of Icell,1 the cell voltage is Vcell,1. When the cell current increases to
Icell,2 the cell voltage drops to Vcell,2.

The last factor to consider is the relatively fast drop off in cell voltage towards the end of life of
the battery. The end-of-life behavior is a consequence of a decrease in the concentration of
reactants of the oxidation and/or reduction reactions. The kinetics of the oxidation of zinc as
described by the polarization curve of the zinc electrode remain unchanged as long as the
surface of the zinc electrode remains unchanged and the Zn+2 that are injected into the battery
electrolyte diffuse away from the zinc electrode so that the concentration of zinc ions adjacent to
the zincʼs surface remains constant. As the amount of zinc tends to zero, the surface of the zinc
electrode tends to zero and the polarization curve is shifted downwards. As a result, the same
cell current is accompanied by a smaller cell voltage.

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