Energy Storage

Batteries
Introduction
A battery consists of two or more electric cells joined together. The cells convert
chemical energy to electrical energy. The cells consist of positive and negative electrodes
joined by an electrolyte. It is the chemical reaction between the electrodes and the
electrolyte which generates DC electricity. In the case of secondary or rechargeable
batteries, the chemical reaction can be reversed by reversing the current and the battery
returned to a charged state.
The ‘lead acid’ battery is the most well-known battery.
The first electric vehicle using rechargeable batteries preceded the invention of the
rechargeable lead acid by quarter of a century, and there are a very large number of
materials and electrolytes that can be combined to form a battery. However, only a
relatively small number of combinations have been developed as commercial
rechargeable electric batteries suitable for use in vehicles. At present these include lead
acid, nickel iron, nickel cadmium, nickel metal hydride, lithium polymer and lithium
iron, sodium sulphur and sodium metal chloride.
In this lecture the different types of the energy storage devices are presented. The
following topics are covered in this lecture:
Overview of Batteries
Battery Parameters
Lead acid batteries
Lithium ion batteries
Metal air batteries
Battery Charging
Overview of Batteries
From the electric vehicle designer’s‘blackpoint box’ which has a range of performance criter

specific energy
energy density
specific power
typical voltages
amp hour efficiency
energy efficiency
commercial availability
cost, operating temperatures
self-discharge rates
number of life cycles
recharge rates
The designer also needs to understand how energy availability varies with regard to:
ambient temperature
charge and discharge rates
battery geometry
optimum temperature
charging methods
cooling needs.
However, at least a basic understanding of the battery chemistry is very important,
otherwise the performance and maintenance requirements of the different types, and most
of the disappointments connected with battery use, such as their limited life, self-
discharge, reduced efficiency at higher currents.
Battery Parameters
Cell and battery voltages

All electric cells have nominal voltages which gives the approximate voltage when the cell is delivering
electrical power. The cells can be connected in series to give the overall voltage required. The
‘internalbatteryresistance’shown in Figure 1. The battery is represented as having a fixed voltage E, but
the voltage at the terminals is a different voltage V , because of the voltage across the internal resistance R.
Assuming that a current I is flowing out of the battery, as in Fig. 1, then by basic circuit theory we can say
that:

V E IR (1)

I
R
V External
Load
E

Fig. 1 Simple equivalent circuit model of a battery. This battery is composed of six cells

Charge (or Ahr) capacity

The electric charge that a battery can supply is clearly a most crucial parameter. The
SI unit for this is the Coulomb, the charge when one Amp flows for one second. The
capacity of a battery might be, say, 10Amphours. This means it can provide 1Amp for 10
hours.

Energy stored

The energy stored in a battery depends on its voltage, and the charge stored. The SI
unit is the Joule, but this is an inconveniently small unit, and so we use the Whr instead.

Energy in Whr V Ahr (2)

 Specific energy

Specific energy is the amount of electrical energy stored for every kilogram of battery
mass. It has units of Wh.kg−1.
Energy density

Energy density is the amount of electrical energy stored per cubic metre of battery
volume. It normally has units of Wh.m−3.
Specific power

Specific power is the amount of power obtained per kilogram of battery. It is a highly
variable and rather anomalous quantity, since the power given out by the battery depends
far more upon the load connected to it than the battery itself.

Ahr (or charge) efficiency

In an ideal world a battery would return the entire charge put into it, in which case the
amp hour efficiency is 100%. However, no battery does; its charging efficiency is less
than 100%. The precise value will vary with different types of battery, temperature and
rate of charge. It will also vary with the state of charge.

Energy efficiency

This is another very important parameter and it is defined as the ratio of electrical
energy supplied by a battery to the amount of electrical energy required to return it to the
state before discharge.

Self-discharge rates

Most batteries discharge when left unused, and this is known as self-discharge. This is
important as it means some batteries cannot be left for long periods without recharging.
The rate varies with battery type, and with other factors such as temperature; higher
temperatures greatly increase self-discharge.
 Battery temperature, heating and cooling needs

Although most batteries run at ambient temperature, some run at higher temperatures and
need heating to start with and then cooling when in use. In others, battery performance
drops off at low temperatures, which is undesirable, but this problem could be overcome
by heating the battery. When choosing a battery the designer needs to be aware of battery
temperature, heating and cooling needs, and has to take these into consideration during
the vehicle design process.

Battery life and number of deep cycles

Most rechargeable batteries will only undergo a few hundred deep cycles to 20% of the
battery charge. However, the exact number depends on the battery type, and also on the
details of the battery design, and on how the battery is used. This is a very important
figure in a battery specification, as it reflects in the lifetime of the battery, which in turn
reflects in electric vehicle running costs.
Lead Acid Batteries
Introduction
The best known and most widely used battery for electric vehicles is the lead acid battery.
Lead acid batteries are widely used in IC engine vehicles and as such are well known.
However for electric vehicles, more robust lead acid batteries that withstand deep cycling
and use a gel rather than a liquid electrolyte are used. These batteries are more expensive
to produce.
In the lead acid cells the negative plates have a spongy lead as their active material,
whilst the positive plates have an active material of lead dioxide. The plates are immersed
in an electrolyte of dilute sulphuric acid. The sulphuric acid combines with the lead and
the lead oxide to produce lead sulphate and water, electrical energy being released during
the process. The overall reaction is:

Pb PbO2 2H 2 SO4 2PbSO4 2 H 2O (3)

The reactions on each electrode of the battery are shown in Fig. 2. In the upper part of the
diagram the battery is discharging. Both electrode reactions result in the formation of lead
sulphate. The electrolyte gradually loses the sulphuric acid, and becomes more dilute.
When being charged, as in the lower half of Figure 2, the electrodes revert to lead and
lead dioxide. The electrolyte also recovers its sulphuric acid, and the concentration rises.
The lead acid battery is the most commonly used rechargeable battery in anything but the
smallest of systems. The main reasons for this are that the main constituents (lead,
sulphuric acid, a plastic container) are not expensive, that it performs reliably, and that it
has a comparatively high voltage of about 2V per cell. The overall characteristics of the
battery are given in Table I.
The figure given in Table I of 0.per022cell is Ωarule of thumb figure taken from a range
of good quality traction batteries. A good estimate of the internal resistance of a lead acid
battery is thus:
0.022
R No. of Cells Ohms (4)
C
10
 Table I Nominal battery parameters for lead acid batteries

Specific energy 20–35 Wh.kg−1 depe

Energy density 54–95Wh.L−1
Specific power ∼250 W.kg−1 befo
very greatly
Nominal cell 2V
voltage
Amphour ∼80%, varies with rate of discharge &

efficiency temp.
Internal resistance Extremely low, ∼0.022_ per cell for 1

Amphour cell
Commercially Readily availablefrom several
available manufacturers
Operating Ambient, poor performance in extreme
temperature cold
Self-discharge ∼2% per day, but see text below

Number of life Up to 800 to 80% capacity

cycles
Recharge time 8 h (but 90% recharge in 1 h possible)
 Positive electrode changes from lead to lead sulphate

Pb SO 2 PbSO 2e
4 4

2 H SO 4H 2SO2
2 4 4
Load
2 eg Electric Motor
PbO 4H SO 2 e PbSO 2H O
2 4 4 2

Electrons flow round

Negative electrode changes from lead peroxide to lead sulphate
the external circuit

Reactions during the discharge of the lead acid battery.

Note that the electrolyte loses suphuric acid and gains water.

Positive electrode changes back from lead sulphate to lead.

PbSO 2e Pb SO2
4 4

2 2
2H 2O 4H 2O ;4H 2SO 4 2H 2 SO4
External DC Power
2 2 Supply
PbSO 2O PbO SO 2 e
4 2 4

Negative electrode changes back from lead sulphate to lead peroxide

Reaction during the charging of the lead acid battery.

Note that the electrolyte suphuric acid concentration
increases.

Fig. 2 The reactions during the charge and discharge of the lead acid battery
 Battery charging

Charging a lead acid battery is a complex procedure and, as with any battery, if carried
out incorrectly it will quickly ruin the battery and decrease its life. As we have seen, the
charging must not be carried out at too high a voltage, or water loss results.
There are differing views on the best way of charging lead acid batteries and it is essential that, once a
battery is chosen, th
The most commonly used technique for lead acid batteries is called multiple steps
charging. In this method the battery is charged until the cell voltage is raised to a
predetermined level. The current is then switched off and the cell voltage is allowed to
decay to another predetermined level and the current is then switched on again.

Lithium Batteries

Since the late 1980s rechargeable lithium cells have come onto the market. They offer
greatly increased energy density in comparison with other rechargeable batteries, though
at greatly increased cost. It is a well-established feature of the most expensive laptop
computers and mobile phones that lithium rechargeable batteries are specified, rather than
the lower cost NiCad or NiHM cells that we have been considering earlier.
The lithium batteries are of following types:
Lithium polymer batteries
Lithium ion batteries
In the following subsections each of the above two battery types are described.

The lithium polymer battery

The lithium polymer battery uses lithium metal for the negative electrode and a transition
metal intercalation oxide for the positive. In the resulting chemical reaction the lithium
combines with the metal oxide to form a lithium metal oxide and release energy. When
the battery is recharged the chemical reaction is reversed. The lithium is thus both a
reactant and the mobile ion that moves through the electrolyte. The overall chemical
reaction is:

xLi M y Oz Lix M y Oz (5)

The lithium ion battery

The lithium ion battery was introduced in the early 1990s and it uses a lithiated transition
metal intercalation oxide for the positive electrode and lithiated carbon for the negative
electrode. The electrolyte is either a liquid organic solution or a solid polymer. Electrical
energy is obtained from the combination of the lithium carbon and the lithium metal
oxide to form carbon and lithium metal oxide. The overall chemical reaction for the
battery is:

C6 Lix M y Oz 6C Lix M y Oz (6)

The essential features of the battery are shown in Table II. An important point about
lithium ion batteries is that accurate control of voltage is needed when charging lithium
cells. If it is slightly too high it can damage the battery, and if too low the battery will be
insufficiently charged. Suitable commercial chargers are being developed along with the
battery.
Table II Nominal battery parameters for lithium ion batteries.

Specific energy 90 Wh.kg−1

Energy density 153 Wh.L−1
Specific power 300 W.kg−1
Nominal cell 3.5V
voltage
Amphour Very good
efficiency
Internal resistance Very low
Commercially Only in very small cells not suitable for
available electric vehicles
Operating Ambient
temperature
Self-discharge Very low, ∼10% per month

Number of life >1000

cycles
Recharge time 2–3 h

Metal Air Batteries

The metal air batteries represent an entirely different development, in the sense that the
batteries cannot be recharged simply by reversing the current. Instead the spent metal
electrodes must be replaced by new ones. The metal electrodes can thus be considered as
a kind of fuel.
The aluminium air battery
The basic chemical reaction of the aluminium air battery is essentially simple.
Aluminium is combined with oxygen from the air and water to form aluminium
hydroxide, releasing electrical energy in the process. The reaction is irreversible. The
overall chemical reaction is:

4AI 3O2 6H 2 O 4AI (OH )3 (7)

The aluminium forms the negative electrode of the cell, and it typically starts as a plate
about 1cm thick. As the reaction proceeds the electrode becomes smaller and smaller.
The positive electrode is typically a porous structure, consisting of a metal mesh onto
which is pressed a layer of catalysed carbon. A thin layer of PTFE gives it the necessary
porosity to let the oxygen in, but prevent the liquid electrolyte getting out. The electrolyte
is an alkaline solution, usually potassium hydroxide.

The battery is recharged by replacing the used negative electrodes. The electrolyte will
normally also be replenished, as it will be contaminated with the aluminium hydroxide.
The essential characteristics of the aluminium air battery are shown in Table III. The big
drawback of the aluminium air battery is its extremely low specific power.
Table III Nominal battery parameters for aluminium air batteries

Specific energy 225 Wh.kg−1

Energy density 195 Wh.L−1
Specific power 10 W.kg−1
Nominal cell voltage 1.4V
Amphour efficiency N/A
Internal resistance Rather high, hence low power
Commercially available Stationary systems only available
Operating temperature Ambient
Self-discharge Very high (>10% per day) normally, but the
electrolyte can
be pumped out, which makes it very low
Number of life cycles 1000 or more
Recharge time 10min, while the fuel is replaced
The zinc air battery
The zinc air battery is similar in many ways to the aluminium air battery but it has a
much better overall performance, particularly with regard to specific power which is
nearly ten times that of the aluminium air battery, making it suitable for use in road
vehicles. The structure is similar, with a porous positive electrode at which oxygen reacts
with the electrolyte. The electrolyte is a liquid alkaline solution. The negative electrode is
solid zinc.
The energy from the battery is obtained by combining zinc with the oxygen in the air and
forming zinc oxide. Alternatively, depending on the state of the electrodes and
electrolyte, zinc hydroxide may be formed, as for the aluminium-air cell. The process is
normally irreversible. The general characteristics of the battery are shown in Table IV. A
few manufacturers have claimed to produce electrically rechargeable zinc-air batteries,
but the number of cycles is usually quite small. The more normal way of recharging is as
for the aluminium air cell, which is by replacing the negative electrodes.
NPTEL –Electrical Engineering – Introduction to Hybrid and Electric Vehicles

Table IV Nominal battery parameters for zinc air batteries

Specific energy 230 Wh.kg−1

Energy density 270 Wh.L−1
Specific power 105 W.kg−1
Nominal cell 1.2V
voltage
Amphour Not applicable
efficiency
Internal resistance Medium
Commercially A very few suppliers
available
Operating Ambient
temperature
Self-discharge High, as electrolyte is left
in cell
Number of life >2000
cycles
Recharge time 10min, while the fuel is
replaced
Fuel Cell
In this lecture the energy storage (fuel cell) is presented. The following topics are
covered in this lecture:
Fuel cell
Issues in fuel cell
Hydrogen fuel cell
Fuel cell thermodynamics
Main reasons for loss in voltage

Fuel Cell

Introduction
Fuel cells are hardly a new idea. They were invented in about 1840, but they are yet to
really make their mark as a power source for electric vehicles. However, this might be set
to change over the next 20 or 30 years. Certainly most of the major motor companies are
spending very large sums of money developing fuel cell powered vehicles. The basic
principle of the fuel cell is that it uses hydrogen fuel to produce electricity in a battery-
like device to be explained in the next section. The basic chemical reaction is:

2H 2 O2 2H 2 O (1)
The product is thus water, and energy. Because the types of fuel cell likely to be used
∼◦

in vehicles work at quite modest temperatures ( 85 C) there is no nitrous oxide produced

by reactions between the components of the air used in the cell. A fuel cell vehicle could
thus be described as zero-emission. Furthermore, because they run off a fairly normal
chemical fuel (hydrogen), very reasonable energies can be stored, and the range of fuel
cell vehicles is potentially quite satisfactory. They thus offer the only real prospect of a
silent zero-emission vehicle with a range and performance broadly comparable with IC
engine vehicles. It is not surprising then that there have, for many years, been those who
have seen fuel cells as a technology that shows great promise, and could even make
serious inroads into the domination of the internal combustion engine.
Main issues in the fuel cell
There are many problems and challenges for fuel cells to overcome before they
become a commercial reality as a vehicle power source. The main problems centre on the
following issues.

Cost: Fuel cells are currently far more expensive than IC engines, and even hybrid
IC/electric systems.

Water management: It is not at all self-evident why water management should

be such an important and difficult issue with automotive fuel cells.

Cooling: The thermal management of fuel cells is actually rather more difficult
than for IC engines.
Hydrogen supply: Hydrogen is the preferred fuel for fuel cells, but hydrogen is
very difficult to store and transport. does the hydrogen come from’ these issu

so many rival solutions.

However, there is great hope that these problems can be overcome, and fuel cells can
be the basis of less environmentally damaging transport.

Hydrogen Fuel Cells: Basic Principles

Electrode reactions
We have seen that the basic principle of the fuel cell is the release of energy following
a chemical reaction between hydrogen and oxygen. The key difference between this and
simply burning the gas is that the energy is released as an electric current, rather that heat.
How is this electric current produced?
To understand this we need to consider the separate reactions taking place at each
electrode. These important details vary for different types of fuel cell, but if we start with
a cell based on an acid electrolyte, we shall consider the simplest and the most common
type.
At the anode of an acid electrolyte fuel cell the hydrogen gas ionizes, releasing
electrons and creating H+ ions (or protons).

2H2 4 H 4e (2)
 This reaction releases energy. At the cathode, oxygen reacts with electrons taken from
the electrode, and H+ ions from the electrolyte, to form water.

O2 4e 4H 2H 2O (3)

Clearly, for both these reactions to proceed continuously, electrons produced at the
anode must pass through an electrical circuit to the cathode. Also, H + ions must pass
through the electrolyte. An acid is a fluid with free H + ions, and so serves this purpose
very well. Certain polymers can also be made to contain mobile H + ions.
Different electrolytes

The reactions given above may seem simple enough, but they do not proceed rapidly
in normal circumstances. Also, the fact that hydrogen has to be used as a fuel is a
disadvantage. To solve these and other problems many different fuel cell types have been
tried. The different types are usually distinguished by the electrolyte that is used, though
there are always other important differences as well.

2H 2 4H 4e

H Ions through electrolyte

Load
ex: electric motor
O2 4e 4H 2H2O

Oxygen, usually from Electrons flow round

the air the external circuit
Fig. 1 The reactions at the electrodes, and the electron movement, in a fuel cell with an acid Electrolyte
 Table I: Data for different types of fuel cell

Fuel cell type Mobile Operating Applications and notes

ion temp.
Alkaline (AFC) OH− 50–200°C Used in space vehicles, e.g.
Apollo, Shuttle.
Proton exchange H+ 30-100°C Vehicles and mobile applications,
membrane and for lower power CHP systems
(PEMFC)
Direct H+ 20-90°C Suitable for portable electronic
methanol(DMFC) systems of low power, running for
long times
Phosphoric acid H+ 220°C Large numbers of 200kW CHP
(PAFC) systems in use
Molten carbonate CO32- 650°C Suitable for medium to large scale
(MCFC) CHP systems, up to MW capacity
Solid oxide (SOFC) O2- 500-1000°C Suitable for all sizes of CHP
systems, 2 kW to multi MW