Battery Technology and Markets, Spring 2010

10 February 2010
1
Lecture 5: Voltage Drops

1. Sources of voltage drops
- Ohmic drop
- Concentration overpotential
- Surface overpotential
2. Porous electrodes

1. Sources of voltage drops in an electrochemical cell
The equilibrium potential is the potential we measure when the cell has had a long time to relax;
we get a value close to the equilibrium potential if we operate a battery very slowly (e.g.,
charging or discharging over the course of ~50 hours). Most batteries and other electrochemical
cells are operated away from equilibrium. When we drive current through a cell at an
appreciable rate, there are a number of resistances which causes voltage drops. We call the
difference between the equilibrium voltage and actual voltage the overpotential. There are a
number of different processes that lead to an overpotential:

- Ohmic drop due to electronic or ionic current flow (Ohms law)
- Concentration overpotential (a voltage drop due to the buildup of concentration gradients in a
cell)
- Surface overpotential (the voltage drop needed to drive the reactions)

Before we consider each of these in turn, lets look at results from an actual battery. [go to slide]

Notice the original ohmic drop as well as the drop at higher currents due to the buildup of
concentration gradients.

Ohmic drop

We can write this in terms of Ohms law.
= i


Battery Technology and Markets, Spring 2010
10 February 2010
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Note that this applies to both ionic and electronic current. The electronic conductivity is often
higher than the ionic conductivity. Note that the electrolyte ohmic drop depends on the
conductivity, which in turn depends on the concentration of the ions in the solution. If a
concentration profile develops, the magnitude of the ohmic drop may change.

A good question from last time: why does the ohmic drop add instead of subtract on charge?
Current always flows down a potential gradient, just like heat always flows down a temperature
gradient. When we are charging the battery, we reverse the direction of current. That means that
the ohmic drop will reverse direction as well, increasing the potential difference.

Concentration overpotential

We saw in class last time that if the transference number of the reacting ion is not equal to one, a
concentration gradient may build up. The buildup of a concentration gradient will also lead to a
voltage drop in a cell. Note that concentration gradients can also build up in the solid phase of
intercalation electrodes, and this will also lead to a voltage drop.

There is a lot of complexity associated with the concentration overpotential, but weve already
covered a few of the basic ideas that we need to understand it. One is that a difference in
concentration leads to a difference in potential; we saw this from the Nernst equation. Consider
the Li/Li cell that we studied in the context of transference.


Li Li
+
+ e
-

Li
+
+ e
-
Li
10 Li
+

10 Li
+

Concentration
Gradient




10 e
-


Battery Technology and Markets, Spring 2010
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Imagine that we have build up a concentration gradient in this cell and then turn off the current.
What will be the value of the cell voltage? Here, Ive labeled the regions right outside each of
the electrodes. If I write the Nernst equation for this cell, I would end up with

|
|

\
|
=
+
+

Li
Li
c
c
F
RT
U ln
It turns out that wed need to add one more term to this equation to get a good estimation of the
concentration overpotential,
( )
|
|

\
|
=
+
+
+

Li
Li
c
c
F
RT
t U ln 1
Again, the main point to take away from this is that a concentration gradient will lead to a
voltage drop. In our potential diagram, we add it to the ohmic drop here (make line steeper).

Surface overpotential
The surface overpotential is the difference between the actual potential drop across an interface
and the equilibrium potential drop across an interface.
U V
s
=
We saw from last time that the amount of current is a function both of the surface overpotential
as well as the concentrations of the reactants and products.
( )
)
`

RT
nF
RT
nF
i i
s o
exp
1
exp

=
1 1
O R c a o
c c k nFk i
There was a little bit of confusion last time about the Butler-Volmer equation and how it is
relevant to the battery. You can think of this the same way as you think of Ohms Law- it relates
current and voltage. [draw curve on board] If you think about this area, in the region of low
overpotential, the curve is almost linear (can do a Taylor expansion if you want to prove this to
yourself). The relationship is then

s
CT
s
o
R RT
nF i
i
1
= = just like I = V/R.

This equation also highlights the effect of the exchange
current density- as the reactant and product
concentrations change during the course of a charge or
Battery Technology and Markets, Spring 2010
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discharge, the value of the surface overpotential may also need to change in order to produce the
same current.

We can now add in our surface overpotential (kinetics) to the diagram containing ohmic
resistance (conductivity) and concentration overpotential (transference and diffusion).

2. Porous Electrodes

Were now going to look at one region in which these kinetic and transport losses compete for
importance. If there is only one thing you learn from this electrochemistry section, it should be
that thermodynamics limits the energy of the system. If there is a second thing you learn from
this section, it should be that there is a tradeoff between power and energy. Why is that? Lets
look at an example. Take a Li-ion cell of 1 Ah capacity. Area of the battery is 20 cm2. Exchange
current density of a typical Li-ion cathode is 110
-6
A/cm2 =0.5 and n=1
If we want to charge this battery at a current of 1 A using the Butler-Volmer equation,

( )
)
`

= =

RT
nF
RT
nF
i
cm
A
i
s o
exp
1
exp
20
1
2

we get a voltage drop of ~0.55 V. This is a significant voltage drop.
What happens is the io is larger? Does the voltage drop increase or decrease? It decreases.
How can we make this better? Maybe we can take 200 cm2 electrode and pass the same 1 A.
Your voltage drop is then ~0.43 V. 2000 cm2 gives you 0.32 V. A typical Li-ion cell can have
an area of ~5000 to 100,000 cm2, and we get this huge surface area by making what we call
porous electrodes. [go to slides]

The picture on the left is a cut out of an alkaline cell (Zn-MnO2 cell). The Zn is in the center of
the cell, the MnO2 is on the outside. Both electrodes are made porous by taking a slurry of the
active material and pasting it on a current collector. The whole cell is filled with KOH in water.
The figure on the right shows a blow up of the porous zinc electrode. The electrode has a
thickness of 0.5 cm and consists of particles of ~ 10-50 m. The next picture is of a lithium-ion
cell. The anode is made of graphite particles pasted on to copper, and the cathode is MnO2
pasted onto aluminum. If we zoom in, we can see the distinct particles more closely.

Battery Technology and Markets, Spring 2010
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So far weve been drawing a big flat sheet of zinc for the Daniel cell, which you would call a
planar electrode. In a planar electrode, where does the reaction occur? At the interface between
the electrode and the electrolyte. Where does the reaction occur in the above system? The
reaction (Zn = Zn
2+
+2e
-
) occurs all over the 0.5 cm electrode. The electrons are carried by the
Zn to the current collector. The Zn
2+
ions are carried in the KOH solution to the outside of the
electrode. Taking advantage of the thickness of the electrode, we have increased the total
surface area for reaction by many orders of magnitude, while keeping the cross sectional area the
same.

What are the advantages of porous electrodes?
1. In systems where the reaction kinetics is slow (small io) increasing the area allows for larger
currents with less voltage drops. Some Li-ion batteries fall into this category.
2. The large surface area means that a large area for double layer formation. Electrochemical
capacitors take advantage of this concept.
3. Reactants (like sulfuric acid in a lead-acid cell) can be stored very close to the reaction site
allowing for high rates by decreasing transport losses.

Disadvantages?
1. Electrons and ions have to travel long distances (0.5 cm in the above case). If the
conductivity of the electrolyte is low, this can lead to large ohmic potential drops in the solution
phase. This is the reason why Li-ion batteries have a thickness of 50-100 m as opposed to a
lead acid cell that can be ~2-3mms thick.
2. In systems where the particles are not very conductive, electronic resistance can be large in
the electrode. Reason why typical Li-ion batteries have conductive additives, like carbon.
3. In systems where transport of ions is limiting, sustained discharge can lead to large
concentration polarization due to the larger distances over which transport occurs

There are several parameters that characterize porous electrodes:
1. Thickness of the electrode, L cm
2. Porosity of the electrodes (Volume of voids/total volume of the electrode)
3. Tortuosity captures the fact that the actual distance an ion has to travel can be larger than
the point to point distance.
4. Total surface area of the electrode. Represented as total surface area per unit volume, a cm-1
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For spherical particles,
radius
a
) 1 ( 3
=

There is a lot of complexity associated with these systems, but were not going to go into the
math. The important thing to understand for this class is that there is a strong tradeoff between
power and energy. What kind of thickness and porosity would you want to maximize energy?
Thick, dense electrodes would be the most efficient use of space. What would you want for a fast
discharge or fast charge? Thin electrodes with lots of empty space for ions to move around give
the best transport. So we can see that there is a clear tradeoff between power and energy. In fact,
any electrode should be optimized for a given rate, and the best way to shoot for the optimum is
to know the time of discharge.