Battery History

The first evidence of batteries comes from archaeological digs

in Baghdad, Iraq. This first "battery" was dated to around 250
B.C. and was used in simple operations to electroplate objects
with a thin layer of metal, much like the process used now to
plate inexpensive gold and silver jewelry. One of the first uses
for batteries.
Batteries were re-discovered much later by a man named
Alessandro Volta after which the unit of electrical potential was
named, the volt. The jar was found in Khujut Rabu just outside
Baghdad and is composed of a clay jar with a stopper made of
asphalt. Sticking through the asphalt is an iron rod surrounded
by a copper cylinder. When filled with vinegar - or any other
electrolytic solution - the jar produces about 1.1 volts.
What is a Battery?

A battery, in concept, can be any device that stores energy for later use. A rock,
pushed to the top of a hill, can be considered a kind of battery, since the energy
used to push it up the hill (chemical energy, from muscles or combustion
engines) is converted and stored as potential kinetic energy at the top of the
hill. Later, that energy is released as kinetic and thermal energy when the rock
rolls down the hill. Common use of the word, "battery," however, is limited to
an electrochemical device that converts chemical energy into electricity, by use
of a galvanic cell. A galvanic cell is a fairly simple device consisting of two
electrodes (an anode and a cathode) and an electrolyte solution. Batteries
consist of one or more galvanic cells.

A battery is an electrical storage device. Batteries do not make electricity, they

store it, just as a water tank stores water for future use. As chemicals in the
battery change, electrical energy is stored or released. In rechargeable batteries
this process can be repeated many times. Batteries are not 100% efficient - some
energy is lost as heat and chemical reactions when charging and discharging. If
you use 1000 watts from a battery, it might take 1200 watts or more to fully
recharge it. Slower charging and discharging rates are more efficient. A battery
rated at 180 amp-hours over 6 hours might be rated at 220 AH at the 20-hour
rate, and 260 AH at the 48-hour rate. Typical efficiency in a lead-acid battery is
85-95%, in alkaline and NiCad battery it is about 65%.
Practically all batteries used in PV and al but the smallest backup systems are
Lead-Acid type batteries. Even after over a century of use, they still offer the
best price to power ratio. A few systems use NiCad, but we do not recommend
them except in cases where extremely cold temperatures (-50 F or less) are
common. They are expensive to buy, and very expensive to dispose of due the
hazardous nature of Cadmium. We have had almost no direct experience with
the NiFe (alkaline) batteries, but from what we have learned from others we do
not recommend them - one major disadvantage is that there is a large voltage
difference between the fully charged and discharged state. Another problem is
that they are very inefficient - you lose from 30-40% in heat just in charging
and discharging them. Many inverters and charge controls have a hard time
with them. It appears that the only current source for new cells is from
Hungary.

It is important to note here that ALL of the batteries commonly used in deep
cycle applications are Lead-Acid. This includes the standard flooded (wet)
batteries, gelled, and AGM. They all use the same chemistry, although the
actual construction of the plates etc can vary considerably. NiCads, Nickel-Iron,
and other types are found in some systems, but are not common due to their
expense and/or poor efficiency.

COMPONENTS OF CELLS AND BATTERIES

A battery is a device that converts the chemical energy contained
in its active materials directly into electric energy by means of an
electrochemical oxidation-reduction (redox) reaction. In the case
of a rechargeable system, the battery is recharged by a reversal
of the process. This type of reaction involves the transfer of
electrons from one material to another through an electric circuit.
In a nonelectrochemical redox reaction, such as rusting or
burning, the transfer of electrons occurs directly and only heat is
involved. As the battery electrochemically converts chemical
energy into electric energy, it is not subject, as are combustion or
heat engines, to the limitations of the Carnot cycle dictated by the
second law of thermodynamics. Batteries, therefore, are capable
of having higher energy conversion efciencies. While the term
battery is often used, the basic electrochemical unit being
referred to is the cell.A battery consists of one or more of these
cells, connected in series or parallel, or both, depending on the
desired output voltage and capacity.* The cell consists of three
:major components
The anode or negative electrodethe reducing or fuel .1
electrodewhich gives up electrons to the external circuit and is
.oxidized during the electrochemical reaction
The cathode or positive electrodethe oxidizing electrode .2
which accepts electrons from the external circuit and is reduced
.during the electrochemical reaction
Cell vs. Battery: A cell is the basic electrochemical unit providing *
a source of electrical energy by direct conversion of chemical
energy. The cell consists of an assembly of electrodes, separators,
electrolyte, container and terminals. A battery consists of one or
more electrochemical cells, electrically connected in an
appropriate series/parallel arrangement to provide the required
operating voltage and current levels, including, if any, monitors,
controls and other ancillary components (e.g. fuses, diodes), case,
terminals and markings. (Although much less popular, in some
publications, the term battery is considered to contain two or
more cells.) Popular usage considers the battery and not the
cell to be the product that is sold or provided to the user. In
this 3rd Edition, the term cell will be used when describing the
cell component of the battery and its chemistry. The term
battery will be used when presenting performance
characteristics, etc. of the product. Most often, the electrical data
is presented on the basis of a single-cell battery. The performance
of a multicell battery will usually be different than the
.performance of the individual cells or a single-cell batter
The electrolytethe ionic conductorwhich provides the .3
medium for transfer of charge, as ions, inside the cell between
the anode and cathode. The electrolyte is typically a liquid, such
as water or other solvents, with dissolved salts, acids, or alkalis to
impart ionic conductivity. Some batteries use solid electrolytes,
which are ionic conductors at the operating temperature of the
.cell
The most advantageous combinations of anode and cathode
materials are those that will be lightest and give a high cell
voltage and capacity (see Sec. 1.4). Such combinations may not
always be practical, however, due to reactivity with other cell
components, polarization, difculty in handling, high cost, and
other deciencies. In a practical system, the anode is selected
with the following properties in mind: efciency as a reducing
agent, high coulombic output (Ah/g), good conductivity, stability,
ease of fabrication, and low cost. Hydrogen is attractive as an
anode material, but obviously, must be contained by some
means, which effectively reduces its electrochemical equivalence.
Practically, metals are mainly used as the anode material. Zinc
has been a predominant anode because it has these favorable
properties. Lithium, the lightest metal, with a high value of
electrochemical equivalence, has become a very attractive anode
as suitable and compatible electrolytes and cell designs have
been developed to control its activity. The cathode must be an
efcient oxidizing agent, be stable when in contact with the
electrolyte, and have a useful working voltage. Oxygen can be
used directly from ambient air being drawn into the cell, as in the
zinc/air battery. However, most of the common cathode materials
are metallic oxides. Other cathode materials, such as the
halogens and the oxyhalides, sulfur and its oxides, are used for
special battery systems. The electrolyte must have good ionic
conductivity but not be electronically conductive, as this would
cause internal short-circuiting. Other important characteristics are
nonreactivity with the electrode materials, little change in
properties with change in temperature, safety in handling, and
low cost. Most electrolytes are aqueous solutions, but there are
important exceptions as, for example, in thermal and lithium
anode batteries, where molten salt and other nonaqueous
electrolytes are used to avoid the reaction of the anode with the
electrolyte. Physically the anode and cathode electrodes are
electronically isolated in the cell to prevent internal short-
circuiting, but are surrounded by the electrolyte. In practical cell
designs a separator material is used to separate the anode and
cathode electrodes mechanically. The separator, however, is
permeable to the electrolyte in order to maintain the desired ionic
conductivity. In some cases the electrolyte is immobilized for a
nonspill design. Electrically conducting grid structures or
materials may also be added to the electrodes to reduce internal
resistance. The cell itself can be built in many shapes and
congurationscylindrical, button, at, and prismaticand the
cell components are designed to accommodate the particular cell
shape. The cells are sealed in a variety of ways to prevent
leakage and dry-out. Some cells are provided with venting devices
or other means to allow accumulated gases to escape. Suitable
cases or containers, means for terminal connection and labeling
are added to complete the fabrication of the cell and battery

Starting, Marine, and Deep-Cycle .

Batteries

Starting (sometimes called SLI, for starting, lighting, ignition)

batteries are commonly used to start and run engines. Engine
starters need a very large starting current for a very short time.
Starting batteries have a large number of thin plates for
maximum surface area. The plates are composed of a Lead
"sponge", similar in appearance to a very ne foam sponge. This
gives a very large surface area, but if deep cycled, this sponge
will quickly be consumed and fall to the bottom of the cells.
Automotive batteries will generally fail after 30-150 deep cycles if
deep cycled, while they may last for thousands of cycles in
.normal starting use (2-5% discharge)
Deep cycle batteries are designed to be discharged down as
much as 80% time after time, and have much thicker plates. The
major difference between a true deep cycle battery and others is
that the plates are SOLID Lead plates - not sponge. Unfortunately,
it is often impossible to tell what you are really buying in some of
the discount stores or places that specialize in automotive
batteries. The popular golf cart battery is generally a "semi" deep
cycle - better than any starting battery, better than most marine,
but not as good as a true deep cycle solid Lead plate, such the L-
16 or industrial type. However, because the golf cart (T-105, US-
2200, GC-4 etc) batteries are so common, they are usually quite
.economical for small to medium systems
Many (most?) Marine batteries are usually actually a "hybrid",
and fall between the starting and deep-cycle batteries, while a
few (Rolls-Surrette and Concorde, for example) are true deep
cycle. In the hybrid, the plates may be composed of Lead sponge,
but it is coarser and heavier than that used in starting batteries. It
is often hard to tell what you are getting in a "marine" battery,
but most are a hybrid. "Hybrid" types should not be discharged
more than 50%. Starting batteries are usually rated at "CCA", or
cold cranking amps, or "MCA", Marine cranking amps - the same
as "CA". Any battery with the capacity shown in CA or MCA may
not be a true deep-cycle battery. It is sometimes hard to tell, as
the terms marine and deep cycle are sometimes overused. CA
and MCA ratings are at 32 degrees F, while CCA is at zero degree
F. Unfortunately, the only positive way to tell with some batteries
.is to buy one and cut it open - not much of an option
Using a deep cycle battery as a starting battery
There is generally no problem with this, providing that allowance
is made for the lower cranking amps compared to a similar size
starting battery. As a general rule, if you are going to use a true
deep cycle battery (such as the Concorde) also as a starting
battery, it should be oversized about 20% compared to the
existing or recommended starting battery group size to get the
same cranking amps. That is about the same as replacing a group
24 with a group 31. With modern engines with fuel injection and
electronic ignition, it generally takes much less battery power to
crank and start them, so raw cranking amps is less important
than it used to be. On the other hand, many cars, boats, and RV's
are more heavily loaded with power sucking "appliances", such as
megawatt stereo systems etc. that are more suited for deep cycle
batteries. We have been using the Concorde SunExtender AGM
batteries in most of our vehicles for some time now with no
.problems
Battery Construction Materials
Nearly all large rechargeable batteries in common use are Lead-
Acid type. (There are some NiCads in use, but for most purposes
the very high initial expense, and the high expense of disposal,
does not justify them). The acid is typically 30% Sulfuric acid and
70% water at full charge. NiFe (Nickel-Iron) batteries are also
available - these have a very long life, but rather poor efficiency
(60-70%) and the voltages are different, making it more difficult
to match up with standard 12v/24/48v systems and inverters. The
biggest problem with NiFe batteries is that you may have to put in
100 watts to get 70 watts of charge - they are much less efficient
than LeadAcid. What you save on batteries you will have to make
up for by buying a larger solar panel system. NiCads are also
inefficient - typically around 65% - and very expensive. However,
NiCads can be frozen without damage, so are sometimes used in
areas where the temperatures may fall below -50 degrees F. Most
AGM batteries will also survive freezing with no problems, even
though the output when frozen will be little or nothing

CLASSIFICATION OF CELLS AND

BATTERIES
Electrochemical cells and batteries are identied as primary
(nonrechargeable) or secondary (rechargeable), depending on
their capability of being electrically recharged. Within this
classication, other classications are used to identify particular
structures or designs. The classication used in this handbook for
the different types of electrochemical cells and batteries is
.described in this section

Primary Cells or Batteries

These batteries are not capable of being easily or effectively
recharged electrically and, hence, are discharged once and
discarded. Many primary cells in which the electrolyte is
contained by an absorbent or separator material (there is no free
or liquid electrolyte) are termed dry cells. The primary battery
is a convenient, usually inexpensive, lightweight source of
packaged power for portable electronic and electric devices,
lighting, photographic equipment, toys, memory backup, and a
host of other applications, giving freedom from utility power. The
general advantages of primary batteries are good shelf life, high
energy density at low to moderate discharge rates, little, if any,
maintenance, and ease of use. Although large highcapacity
primary batteries are used in military applications, signaling,
standby power, and so on, the vast majority of primary batteries
are the familiar single cell cylindrical and at button batteries or
.multicell batteries using these component cells

Secondary or Rechargeable Cells or Batteries

These batteries can be recharged electrically, after discharge, to
their original condition by passing current through them in the
opposite direction to that of the discharge current. They are
storage devices for electric energy and are known also as
storage batteries or accumulators. The applications of
:secondary batteries fall into two main categories
Those applications in which the secondary battery is used as an .1
energy-storage device, generally being electrically connected to
and charged by a prime energy source and delivering its energy
to the load on demand. Examples are automotive and aircraft
systems, emergency no-fail and standby (UPS) power sources,
hybrid electric vehicles and stationary energy storage (SES)
.systems for electric utility load leveling
Those applications in which the secondary battery is used or .2
discharged essentially as a primary battery, but recharged after
use rather than being discarded. Secondary batteries are used in
this manner as, for example, in portable consumer electronics,
power tools, electric vehicles, etc., for cost savings (as they can
be recharged rather than replaced), and in applications requiring
.power drains beyond the capability of primary batteries
Secondary batteries are characterized (in addition to their ability
to be recharged) by high power density, high discharge rate, at
discharge curves, and good low-temperature performance. Their
energy densities are generally lower than those of primary
batteries. Their charge retention also is poorer than that of most
primary batteries, although the capacity of the secondary battery
that is lost on standing can be restored by recharging. Some
batteries, known as mechanically rechargeable types,are
rechargedby replacement of the discharged or depleted
electrode, usually the metal anode, with a fresh one. Some of the
metal/air batteries (Chap. 38) are representative of this type of
.battery

Reserve Batteries
In these primary types, a key component is separated from the
rest of the battery prior to activation. In this condition, chemical
deterioration or self-discharge is essentially eliminated, and the
battery is capable of long-term storage. Usually the electrolyte is
the component that is isolated. In other systems, such as the
thermal battery, the battery is inactive until it is heated, melting a
.solid electrolyte, which then becomes conductive
The reserve battery design is used to meet extremely long or
environmentally severe storage requirements that cannot be met
with an active battery designed for the same performance
characteristics. These batteries are used, for example, to deliver
high power for relatively short periods of time, in missiles,
.torpedoes, and other weapon systems

Fuel Cells
Fuel cells, like batteries, are electrochemical galvanic cells that
convert chemical energy directly into electrical energy and are
not subject to the Carnot cycle limitations of heat engines. Fuel
cells are similar to batteries except that the active materials are
not an integral part of the device (as in a battery), but are fed into
the fuel cell from an external source when power is desired. The
fuel cell differs from a battery in that it has the capability of
producing electrical energy as long as the active materials are fed
to the electrodes (assuming the electrodes do not fail). The
battery will cease to produce electrical energy when the limiting
reactant stored within the battery is consumed. The electrode
materials of the fuel cell are inert in that they are not consumed
during the cell reaction, but have catalytic properties which
enhance the electroreduction or electrooxidation of the reactants
(the active materials). The anode active materials used in fuel
cells are generally gaseous or liquid (compared with the metal
anodes generally used in most batteries) and are fed into the
anode side of the fuel cell. As these materials are more like the
conventional fuels used in heat engines, the term fuel cell has
become popular to describe these devices. Oxygen or air is the
predominant oxidant and is fed into the cathode side of the fuel
cell. Fuel cells have been of interest for over 150 years as a
potentially more efcient and less polluting means for converting
hydrogen and carbonaceous or fossil fuels to electricity compared
to conventional engines. A well known application of the fuel cell
has been the use of the hydrogen/oxygen fuel cell, using
cryogenic fuels, in space vehicles for over 40 years. Use of the
fuel cell in terrestrial applications has been developing slowly, but
recent advances has revitalized interest in air-breathing systems
for a variety of applications, including utility power, load leveling,
dispersed or on-site electric generators and electric vehicles. Fuel
cell technology can be classied into two categories
Direct systems where fuels, such as hydrogen, methanol and .1
hydrazine, can react directly in the fuel cell
Indirect systems in which the fuel, such as natural gas or other .2
fossil fuel, is rst converted by reforming to a hydrogen-rich gas
which is then fed into the fuel cell
Fuel cell systems can take a number of congurations depending
on the combinations of fuel and oxidant, the type of electrolyte,
the temperature of operation, and the application, etc. More
recently, fuel cell technology has moved towards portable
applications, historically the domain of batteries, with power
levels from less than 1 to about 100 watts, blurring the distinction
between batteries and fuel cells. Metal/air batteries (see Chap.
38), particularly those in which the metal is periodically replaced,
can be considered a fuel cell with the metal being the fuel.
Similarly, small fuel cells, now under development, which are
refueled by replacing an ampule of fuel can be considered a
battery. Fuel cells were not included in the 2nd Edition of this
Handbook as the technical scope and applications at that time
differed from that of the battery. Now that small to medium size
fuel cells may become competitive with batteries for portable
electronic and other applications, these portable devices are
covered in Chap. 42. Information on the larger fuel cells for
electric vehicles, utility power, etc can be obtained from the
."references listed in Appendix F Bibliograph