Things covered:

1.Different kinds of voltages

2.Calculating battery capacity
3.Behavior of batteries away from equilibrium
4.Modified Peukert Plot
5.Ragone Plot
Almost all examples in this class will be on a Li-ion battery where the negative electrode is Li-metal and the
positive electrode is LiNi1/3Co1/3Mn1/3O2. The negative electrode reaction is:
The positive electrode reaction is:
A schematic of the battery is shown below:
The positive electrode material is made into a porous electrode. The particles themselves are not very conductive,
so conductive additives, like carbon are added to increase the conductivity. The reactions occur at the electrode/
electrolyte interface and the Li enters the lattice of the oxide.
Different Kinds of Voltages and ways of measuring them:
You already know about equilibrium potential and overpotential. Few more voltages:
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1.Open circuit voltage: voltage when the battery is not connected to an external load. Practically, you have a
voltmeter with a high resistance so that the current draw is very small and you measure the voltage of the battery.
This is taken to be the same as the equilibrium potential.
You can typically calculate the equilibrium potential by looking at the thermodynamic tables. But, for batteries,
this tends to be difficult to do because of the dependence on the activity coefficients.
2.Closed circuit potential: potential of the battery under a load.
3.Mid-point potential: Potential of the battery when its discharged to 50% of its capacity.
4.Cut off voltage: Voltage when the battery discharge (or charge) is stopped. For example, cutoff voltage on
charge is ~4.3 V for a cell phone battery.
State of Discharge is defined as 1.0 when the battery is fully discharge and 0.0 when the battery is fully charged.
SOD=1-SOC (or state of charge). Below is an example for a LiNi1/3Co1/3Mn1/3O2 positive electrode material with
respect to a Li-metal anode.
The open circuit potential above was measured by first discharging the battery at C/30 to a specified State of
discharge and then performing an open circuit. The potential relaxes from the closed circuit to the open circuit
(the time constant can range from minutes to days depending on the system). The vertical dotted line close to
state of discharge of 1.0 shows the potential relaxing from the closed circuit to the open circuit.
In the measurement above the battery was charged above the cut-off potential. In other words the battery was
overcharged. When the potential of the cell is increased beyond the cutoff potential other reactions (or side
reactions) become thermodynamically more favorable. Typically, side reactions tend to be detrimental to battery
performance.
Calculating battery Specific Capacity:
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1. Theoretical capacity of the battery: say a electrode as a molecular weight M kgs/mole, then capacity in mAh/g
is calculated by Faradays law as:
mAh/g
Examples:
a.
Molecular weight of Li is 6.94!10
-3
kg/mole, n=1. q=3861 mAh/g
b.
In this case, we again as Li
+
as the ionic charge carrier, however the Li
+
sits in the lattice of a host material,
FePO4. In the previous case, there is no host material. Therefore in calculating the theoretical specific capacity,
the weight of the host material needs to be accounted for. In other words, the active material is LiFePO4. So,
Molecular weight of LiFePO4 is 157.7!10
-3
kg/mole and n=1. q=170 mAh/g
2. Practical Specific Capacity:
Capacity when operating the battery at a finite rate: Pass a constant current till the battery reaches its cutoff
potential.
Practical specific capacity= mAh/g
where i is the current density in A/m
2
A the area in m
2
, tcutoff is the time to reach the cut off potential (Vcutoff) in
seconds and W is the weight of the active material in kg. Below is an example for the LiNi1/3Co1/3Mn1/3O2
positive electrode material.
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Here the x axis is calculated by multiplying the constant current density by the area and the time and dividing by
the weight of the active material. Remember that a C/30 means that the battery was discharged in 30 hours.
In this case the reaction is:
Theoretical capacity: Molecular weight of LiNi1/3Co1/3Mn1/3O2 is 96.46!10
-3
kg, n=1. q=277.8 mAh/g.
Practical capacity is 165 mAh/g. Reason why practical capacity is lower than theoretical capacity is that not all
the Li can be removed from the lattice of the host material. The rest of the Li is removed above the cutoff
potential. Therefore it is not accessible.
Behavior of Batteries away From equilibrium:
For the of LiNi1/3Co1/3Mn1/3O2 system, as we increase the current density, we see that the voltage vs. capacity
curves do not collapse.
This indicates that deviating from equilibrium conditions (C/30 discharge) results in significant ohmic drops,
surface overpotential, and concentration overpotential. Remember that 1 C means that the battery was discharged
in 1 hour, and 5C means that the battery was discharged in 1/5
th
an hour.
We can use the math that we learnt about in the electrochemistry section that describes the ohmic, kinetic, and
transport losses in the battery and try to estimate how much each of these contribute to the losses in the battery.
The plot below shows this graphically for the 2 C discharge.
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The plot shows the ohmic resistance in the electrode is important and mass transport in the solid oxide material
results in a decrease in the capacity. Nanostructured particles can help with minimizing this effect.
Modified Peukert Plot:
Often, the above data is represented by plotting the capacity when the voltage reaches Vcutoff as a function of
either the current or the C-rate in a log-log plot. This is called a Modified Peukert Plot. Note that the Peukert
plot is a plot of log (i) vs. log (tcutoff). The modified Peukert plot for the LiNi1/3Co1/3Mn1/3O2 system is shown
below:
The dotted line represents the maximum attainable capacity when charging the battery to the cut-off potential. As
we increase the rate of discharge, the battery is discharged to a lesser extent than the maximum capacity.
One can define utilization as
Utilization=
In the above case the utilization at C/30 is 100% and at 5C is ~50%. In other words, when you discharge the
battery at a fast rate (12 mins), 50% of the total amount of active material is not used. This low utilization would
also occur on charge. In other words, charging this battery in 12 mins would result in only 50% of the battery
being charged. This is the reason why cell phone and laptop batteries typically charge in 2 to 3 hours.
Theoretical specific energy of the battery material:
Specific energy= Wh/kg.
Where i is in A/m
2
, A is in m
2
, V in volts, t in seconds, and W in kg.
Graphically, it is the area under the voltage vs. specific capacity curve. From the slow discharge (C/30) of the
LiNi1/3Co1/3Mn1/3O2 system, we get a value of 641.3 Wh/kg. Often, the maximum capacity of the battery is
%
multiplied by the mid-point potential to report the energy. For this system, this comes out to be 3.8 V!166 Ah/
kg=630.8 Wh/kg; a close approximation.
Note that in reality, one should include the weight of both electrodes, and the weights of the various components
in the cell in reporting the energy density. For the purposes of clarity, we shall continue to use the weight of the
active material alone.
To increase the energy of the battery, there are two options, (i) increase the specific capacity or (ii) increase the
voltage.
Average specific power of a battery:
Average specific power= W/kg
Where i is in A/m
2
, A is in m
2
, V(t) in V, t in s, and W in kg.
Practically when discharging the battery under a constant current, one can evaluate the specific energy of the
battery and divide it by the time of discharge to get the specific power.
While energy is a measure of the amount of work, power denotes the rate at which the work is done. In other
words, power tells us how quickly one can access the energy.
Ragone Plot:
Using the discharge curves for the LiNi1/3Co1/3Mn1/3O2 system, one can find the area under the curve for each of
the discharges and evaluate the specific energy. We can then divide the energy by the cutoff time to get the
average specific power. A log-log plot of the specific energy and the average specific power is called a Ragone
Plot. This is plotted below for our system.
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A Ragone plot is similar to the Modified Peukert plot in that it captures the losses in the system as we operate the
battery at higher power densities. However, the Peukert plot only captures the loss in the utilization of the battery,
while a ragone plot is more complete in that it captures both the loss in utilization and the voltage losses in the
system. The ratio of energy to power is time and these are typically plotted on the graph as cross lines. This time
is referred to as the time of discharge (or charge). For example, a battery used in a Photovoltaic application
would require discharging for ~10 hours during nighttime. On the other hand, a cell phone battery would be
discharged in 2 hours. The plot above tells us how much energy and power one can get for each of these
applications.
Ragone plots provide a very useful means of comparing various energy storage systems and allow identification
of an optimum system. Below is a ragone plot of three rechargeable batteries and an electrochemical capacitor.
The plot shows that for applications in which the time of discharge is greater than ~ 5 s, Li-ion batteries have the
best performance. For shorter times of discharge (e.g., start-stop hybrid cars), electrochemical capacitors are
more appropriate.
Increasing the energy of the battery is accomplished by increasing the voltage or the specific capacity. Increasing
the power of the battery requires us to minimize the voltage drops in the cell with increasing current. This can be
accomplished by decreasing the ohmic, kinetic, and mass transfer limitations in the system. Porous electrodes can
be designed to optimize batteries to increase the energy and/or the power of the battery. We will discuss battery
design later in the course.
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