Batteries come in a lot of different varieties. The most common are
carbon-zinc, alkaline, lead acid, nickle metal hydride, nickle cadmium and lithium ion. But
there are many other battery chemistries, each with their own advantages and disadvantages.
Below we discuss different of the battery designs currently used, some of the chemistry
involved, and advantages and disadvantages of each design. We have also included some useful
definitions and a list of parameters to guide you in matching your battery requirements to a
specific battery design.
Table of Contents
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- Anode: The electrode where oxidation (loss of electrons) takes place. While
discharging, it is the negative electrode; while charging it becomes the positive
- Amps: Also known as Amperes. This is the rate at which electrons flow in a
wire. The units are coulombs per second, or since an electron has a charge of 1.602 x
10-19 coulombs, an amp is 6.24 x 10+18 electrons per second. Think of
marbles rolling through a tube. If 6.24 x 10+18 pass by in 1 second you wuld have an
amp of marbles.
- Amp hours: Also known as ampere hours. This a measure of the amount of charge
stored or used. For example if you had an amp of marbles flowing out of your tube into a bucket
for an hour, you would have one amp-hour of marbles in the bucket ( 6.24 x 10+18
times 3600 seconds = 2.2 x 10+22 marbles. A 1 amp hour battery contains enough
charge to supply 1 amp for 1 hour, if you discharge at the same rate. Usually if you discharge
faster than the rate at which the the amp hours were specified you will get fewer amp-hours
out. You may notice that amp-hours and coulombs measure the same quantity-charge. One amp-hour
is 3600 coulombs, but amp hours are easier to use in battery design. So remember, amps are flow
( "this motor requires 2 amps to run at 1800 rpm.") Amp hours measure capacity, quantity, or
amount of charge ("this 100 amp-hour battery will supply 2 amps for 50 hours before recharge."
Amp-hours are amps times hours, not amps divided by hours.
So Amp-Hours, (AH), or milliamp-Hours (mAH) is a measure of the size of the battery a 10 mAH
battery has half the capacity of a 20 mAH battery, even though they may be in the same physical
- Batteries: Two or more electrochemical cells, electrically interconnected, each of
which contains two electrodes and an electrolyte. The redox (oxidation-reduction) reactions
that occur at these electrodes convert electrochemical energy into electrical energy. In
everyday usage, 'battery' is also used to refer to a single cell.
- C:C represents the capacity of a battery divided by 1 hour, its units are amps. It
represents a 1 hour discharge rate using the nominal capacity of the battery. So a discharge
rate of 10C for a 5AH battery would be 50 amps. The concept of "C" is also used for charge
currents, since both charge and discharge properties are proportional to the capacity of the
battery, so a 5C charge rate for a 5 AH battery would be 25 amps.
- Capacity: The total quantity of electricity or total ampere-hours available from a
fully charged cell or battery.
- Cathode: The electrode where reduction (gain of electrons) takes place. When
discharging, it is the positive electrode, when charging, it becomes the negative
- Charge: The conversion of electrical energy, provided in the form of current from an
external source, into chemical energy stored at the electrodes of a cell or battery.
- Discharge: The conversion of the chemical energy of a cell into electrical energy,
which can then be used to supply power to a system.
- Discharge curve: A plot of cell voltage over time into the discharge, at a constant
temperature and constant current discharge rate.
Each curve in this graph represents cell performance at a different discharge rate. The
farther right the curve ends, the lower the discharge rate (Crompton 31.4).
A Leclanché cell, so called because of its non-fluid electrolyte (to prevent
spillage). This is achieved by adding an inert metal oxide so that the electrolyte forms a gel
- Efficiency: For a secondary cell, the ratio of the output on discharge to the input
required to restore it to its initial state of charge under specified conditions. Can be
measured in ampere-hour, voltage, and watt-hour efficiency.
- Electrolyte: The chemistry of a battery requires a medium that provides the ion
transport mechanism between the positive and negative electrodes of a cell.
- Energy density (specific energy): These two terms are often used interchangeably.
Energy density refers mainly to the ratio of a battery's available energy to its volume
(watt hour/liter). Specific energy refers to the ratio of energy to mass (watt hour/kg).
The energy is determined by the charge that can be stored and the cell voltage (E=qV).
- Fuel cell: A cell in which one or both of the reactants are not permanently
contained in the cell, but are continuously supplied from a source external to the cell and the
reaction products continuously removed. Unlike the metal anodes typically used in batteries,
the fuels in a fuel cell are usually gas or liquid, with oxygen as the oxidant. The
hydrogen/oxygen fuel cell is the most common. In this fuel cell, hydrogen is oxidized at the
Hydrogen/oxygen fuel cell systems work well in space travel applications
because of their high efficiency, high power-to-weight and volume ratios, and usable reaction
product (water). They can function for many months as long as fuel is supplied and therefore
the energy density cannot be measured.
||V vs SHE
|2H2 > 4H+ + 4e-
|4H+ + O2 + 4e- > 2H2O
- Half-reaction: Refers to the chemical processes occurring at each electrode. The
potential of the two half-reactions add to give us the overall cell potential. We can see this
in the zinc mercury cell, for example:
||Zn + 2OH- > Zn(OH)2 + 2e-
||HgO +H2O + 2e- > Hg + 2OH-
||Zn + HgO + H2O > Zn(OH)2 + Hg
- Polarization: The voltage drop in a cell during discharge due to the flow of an
electrical current. The cell's internal resistance increases with the buildup of a product of
oxidation or a reduction of an electrode, preventing further reaction.
- Power: Defined by voltage (V) and current (I), P=VI.
Since V=IR, P=I2R and P=V2/R
Power also can be described by energy emitted per unit of time: P=E/t.
- Power density (specific power): Power density is the ratio of the power available
from a battery to its volume (watt/liter). Specific power generally refers to the ratio of
power to mass (watt/kg). Comparison of power to cell mass is more common.
- Primary cells: A cell that is not designed for recharging and is discarded once it
has produced all its electrical energy.
- Prismatic: Just a word to say that the cells are not cylindrical, as nature intended
battery cells to be, but fit nicely into a parallelepiped or any other such flattened
- Peukart Effect: When a battery is discharged extremely quickly it will have less
capacity than expected. This is the Peukart effect, which is very strong for lead acid
batteries, but much less so for nickel cadmium. Peukert's equation is In · t
= C, where I is the discharge rate, t is the discharge time and C is the capacity. The exponent
"n" depends on the battery chemistry and the temperature. A log-log plot of discharge time
versus discharge load will have a slope of "n"
- Reserve cell: A cell that may be kept inactive and which is activated by adding an
electrolyte or electrode, or melting an electrolyte in a solid state.
- Secondary cells: A cell capable of repeated use. Its charge may be fully restored by
passing an electric current through the cell in the opposite direction to that of discharge,
thus reversing the redox reactions.
No one battery design is perfect for every application. Choosing one requires compromise.
That's why it's important to prioritize your list of requirements. Decide which ones you
absolutely must have and which you can compromise on. Here are some of the parameters to
- Voltage: Normal voltage during discharge, maximum and minimum permissible voltages,
discharge curve profile
- Duty cycle: Conditions the battery experiences during use. Type of discharge and
current drain, e.g., continuous, intermittent, continuous with pulses, etc.
- Temperature: In storage and in use. Temperatures that are too high or too low can
greatly reduce battery capacity.
- Shelf life: How rapidly the cell loses potential while unused.
- Service life: Defined either in calendar time or, for secondary cells, possible
number of discharge/charge cycles, depending on the battery application. Service life depends
on battery design and operational conditions, i.e., the stress put on a battery. For stationary
and motive power application, the end of service life is defined as the point at which a
battery's capacity drops to 80% of its original capacity. Exceptions would include car
batteries where the service life ends when the capacity falls below 60%.
- Physical restrictions: These include dimensions, weight, terminals, etc.
- Maintenance and resupply: Ease of battery acquisition, replacement, charging
- Safety and reliability: Failure rates, freedom from outgassing or leakage; use of
toxic components; operation under hazardous conditions; environmentally safe
- Cost: Initial cost, operating cost, use of expensive materials
- Internal resistance: Batteries capable of a high-rate discharge must have a low
- Specific energy: As discussed in the definition section, this is a measurement of
possible stored energy per kilogram of mass. This number is purely theoretical as it does not
take into account the mass of inactive materials, nor the variation in chemical reactions.
- Specific power: Also defined in the definitions section, a P=E/t, so the specific
power is discussed at a specific discharge rate. It is possible for batteries with a high
specific energy to have a low power density if they experience large voltage drops at high
discharge rates. Specific power and specific energy can be compared in a
- Unusual requirements: Very long-term or extreme-temperature storage; very low
failure rate; no voltage delay, etc.
Of course the ideal battery would perform well in all these areas with a long shelf and
service life, high specific energy and specific power, low initial and maintenance costs, low
environmental impact, and good performance in a variety of conditions (temperatures, duty
cycles, etc.). When you find one that meets all these requirements, let us know! In the
meantime, we have to make do with batteries that work very well in specific applications.
(zinc carbon or
Cathode: Manganese Dioxide (MnO2)
Electrolyte: Ammonium chloride or zinc chloride dissolved in water
Applications: Flashlights, toys, moderate drain use
The basic design of the Leclanché cell has been around since the 1860s, and until
World War II, was the only one in wide use. It is still the most commonly used of all primary
battery designs because of its low cost, availability, and applicability in various situations.
However, because the Leclanché cell must be discharged intermittently for best capacity,
much of battery research in the last three decades has focused on zinc-chloride cell systems,
which have been found to perform better than the Leclanché under heavier drain.
This figure shows typical discharge curves for general-purpose Leclanché zinc
chloride D-size cells discharge 2 h/day at 20º C. Solid linezinc chloride; broken
lineLeclanché (Linden 8.18). The zinc-chloride cell has a higher service
life and voltage than the Leclanché (at both higher and lower discharge rates).
In an ordinary Leclanché cell the electrolyte consists (in percent of atomic weight)
of 26% NH4Cl (ammonium chloride), 8.8% ZnCl2 (zinc chloride), and 65.2%
water. The overall cell reaction can be expressed:
Zn + 2MnO2 +2NH4Cl > 2MnOOH +
The electrolyte in a typical zinc chloride cell consists of 15-40% ZnCl2 and
60-85% water, sometimes with a small amount of NH4Cl for optimal performance. The
overall cell reaction of the zinc chloride as the electrolyte can be expressed:
Zn + 2MnO2 + 2H2O + ZnCl2 > 2MnOOH + 2Zn(OH)Cl
MnO2, is only slightly conductive, so graphite is added to improve conductivity.
The cell voltage increases by using synthetically produced manganese dioxide instead of that
found naturally (called pyrolusite). This does drive the cost up a bit, but it is still
inexpensive and environmentally friendly, making it a popular cathode.
These cells are the cheapest ones in wide use, but they also have the lowest energy density
and perform poorly under high-current applications. Still, the zinc carbon design is reliable
and more than adequate for many everyday applications.
Anode: Zinc powder
Cathode: Manganese dioxide (MnO2) powder
Electrolyte: Potassium hydroxide (KOH)
Applications: Radios, toys, photo-flash applications, watches, high-drain
This cell design gets its name from its use of alkaline aqueous solutions as electrolytes.
Alkaline battery chemistry was first introduced in the early 60s. The alkaline cell has
grown in popularity, becoming the zinc-carbon cell's greatest competitor. Alkaline cells have
many acknowledged advantages over zinc-carbon, including a higher energy density, longer shelf
life, superior leakage resistance, better performance in both continuous and intermittent duty
cycles, and lower internal resistance, which allows it to operate at high discharge rates over
a wider temperature range.
Zinc in a powdered form increases the surface area of the anode, allowing more particle
interaction. This lowers the internal resistance and increases the power density. The cathode,
MnO2, is synthetically produced because of its superiority to naturally occurring
MnO2. This increases the energy density. Just as in the zinc carbon cell, graphite
is added to the cathode to increase conductivity. The electrolyte, KOH, allows high ionic
conductivity. Zinc oxide is often added to slow down corrosion of the zinc anode. A cellulose
derivative is thrown in as well as a gelling agent. These materials make the alkaline cell more
expensive than the zinc-carbon, but its improved performance makes it more cost effective,
especially in high drain situations where the alkaline cell's energy density is much
The half-reactions are:
Zn + 2 OH- > ZnO + H2O + 2 e-
2 MnO2 + H2O + 2 e- >Mn2O3 +
The overall reaction is:
Zn + 2MnO2 > ZnO + Mn2O3 E=1.5 V
There are other cell designs that fit into the alkaline cell category, including the mercury
oxide, silver oxide, and zinc air cells. Mercury and silver give even higher energy densities,
but cost a lot more and are being phased out through government regulations because of their
high toxicity as heavy metals. The mercury oxide, silver oxide, and zinc air (which is being
developed for electronic vehicles) are all discussed below.
Anode: Zinc (or cadmium)
Cathode: Mercuric Oxide (HgO)
Electrolyte: Potassium hydroxide
Applications: Small electronic equipment, hearing aids, photography, alarm systems,
emergency beacons, detonators, radio microphones
This is an obsolete technology. Most if not all of the manufacture of these cells has been
stopped by government regulators. Mercury batteries come in two main varieties: zinc/mercuric
oxide and cadmium/mercuric oxide. The zinc/mercuric oxide system has high volumetric specific
energy (400 Wh/L), long storage life, and stable voltage. The cadmium/mercuric oxide system has
good high temperature and good low temperature (-55 C to +80 C, some designs to +180 C) and has
very low gas evolution.
|Basic Cell Reaction
|Zn + HgO = ZnO + Hg
||820 mAH/g(Zn), 250 mAH/g(Hg)
|Cd + HgO + H2O = Cd(OH2) + Hg
The electrolytes used in mercury cells are sodium and/or potassium
hydroxide solutions, making these alkaline cells. These cells are not rechargeable.
Anode: Amalgamated zinc powder and electrolyte
Cathode: Oxygen (O2)
Electrolyte: Potassium hydroxide (KOH)
Applications: Hearing aids, pagers, electric vehicles
The zinc air cell fits into the alkaline cell category because of its electrolyte. It also
acts as a partial fuel cell because it uses the O2 from air as the cathode. This
cell is interesting technology, even aside from the question "how do you use air for an
electrode?" Actually, oxygen is let in to the cathode through a hole in the battery and is
reduced on a carbon surface.
A number of battery chemistries involve a metal oxide and zinc. The metal oxide reduces, the
zinc becomes oxidized, and electric current results. A familiar example is the old mercury
oxide/zinc batteries used for hearing aids. If you leave out the metal oxide you could double
the capacity per unit volume (roughly), but where would you get the oxygen? Right!
First let's look at the electrochemical reactions and find that the open cell voltage should
be 1.65 volts:
||Half Cell reactions
||Zn2+ + 2OH- > Zn(OH)2
||1/2 O2 + H2O + 2e > 2 OH-
||2Zn +O2 +2H2O > 2Zn(OH)2
The electrolyte is an alkali hydroxide in 20-40% weight solution with water. One
disadvantage is that since these hydroxides are hygroscopic, they will pick up or lose water
from the air depending on the humidity. Both too little and too much humidity reduces the life
of the cell. Selective membranes can help. Oxygen from the air dissolves in the electrolyte
through a porous, hydrophobic electrodea carbon-polymer or metal-polymer composite.
Since there is no need to carry around the cathode, the energy density of these batteries
can be quite high, between 220300 Wh/kg (compared to 99123 Wh/kg with a HgO
cathode), although the power density remains low. However, the use of potassium or sodium
hydroxides as the electrolyte is a problem, since these can react with carbon dioxide in the
air to form alkali carbonates. For this reason large zinc air batteries usually contain a
higher volume of CO2 absorbing material (calcium oxide flake) than battery
components. This can cancel out the huge increase in energy density gained by using the air
This cell has the additional benefits of being environmentally friendly at a relatively low
These batteries can last indefinitely before they are activated by exposing them to air,
after which they have a short shelf life. For this reason (as well as the high energy density)
most zinc-air batteries are used in hearing aids. There is a company promoting them for use in
electric vehicles also because they are environmentally friendly and cost relatively little.
The idea is to have refueling stations where the zinc oxide waste can be replaced by fresh zinc
Aluminum / Air Cells
Although, to our way of thinking, the metal/air batteries are strictly primary, cells have
been designed to have the metal replaceable. These are called mechanically rechargeable
batteries. Aluminum/air is an example of such a cell. Aluminum is attractive for such cells
because it is highly reactive, the aluminum oxide protective layer is dissolved by hydroxide
electrolytes, and it has a nice, high voltage. The overall chemical reaction is:
||Half Cell reactions
||Al + 4 OH-> Al(OH)4- + 3e
||3/4 O2 + 3/2 H2O + 3e> 3OH-
||Al + 3/2 HO + 3/4 O2 > Al(OH)3
As I mentioned above, alkali (chiefly potassium hydroxide) electrolytes are used, but so
also are neutral salt solutions. The alkali cell has some problem with the air electrode,
because the hydroxide ion makes a gel in the porous electrode, polarizing it. The typical
aluminum hydroxide gel is a problem on either electrode because it sucks up a lot of water.
Using a concentrated caustic solution prevents this, but is very reactive with the aluminum
electrode, producing hydrogen gas. Another way to prevent the gel formation is to seed the
electrolyte with aluminum trihydroxide crystals. These act to convert the aluminum hydroxide to
aluminum trihydroxide as the crystals grow. To prevent hydrogen gas evolution tin and zinc have
been used as corrosion inhibitors. A number of additives are used to control the reactions. A
disadvantage of the alkaline electrolyte is that it reacts with atmospheric carbon dioxide.
Aluminum / air cells have also been made for marine applications. These are "rechargeable"
by replacing the seawater electrolyte until the aluminum is exhausted, then replacing the
aluminum. Some cells that are open to seawater have also been researched. Since salt water
solutions tend to passivate the aluminum, pumping the electrolyte back and forth along the cell
surface has been successful. For those cells that don't need to use ocean water, an electrolyte
of KCL and KF solutions is used.
Air electrodes of Teflon-bonded carbon are used without a catalyst.
Applications: Pacemakers, defibrillators, watches, meters, cameras, calculators,
portable, low-power use
Lithium battery chemistry comprise a number of cell designs that use lithium as the anode.
Lithium is gaining a lot of popularity as an anode for a number of reasons. In this comparison
of anode materials, we can see some reasons why:
Note that lithium, the lightest of the metals, also has the highest standard potential of
all the metals, at over 3 V. Some of the lithium cell designs have a voltage of nearly 4 V.
This means that lithium has the highest energy density. Many different lithium cells exist
because of its stability and low reactivity with a number of cathodes and non-aqueous
electrolytes. The most common electrolytes are organic liquids with the notable exceptions of
SOCl2 (thionyl chloride) and SO2Cl2 (sulfuryl chloride).
Solutes are added to the electrolytes to increase conductivity.
Lithium cells have only recently become commercially viable because lithium reacts violently
with water, as well as nitrogen in air. This requires sealed cells. High-rate lithium cells can
build up pressure if they short circuit and cause the temperature and pressure to rise. Thus,
the cell design needs to include weak points, or safety vents, which rupture at a certain
pressure to prevent explosion.
Lithium cells can be grouped into three general categories: liquid cathode, solid cathode,
and solid electrolyte. Let's look at some specific lithium cell designs within the context of
these three categories.
Liquid cathode lithium cells:
These cells tend to offer higher discharge rates because the reactions occur at the cathode
surface. In a solid cathode, the reactions take longer because the lithium ions must enter into
the cathode for discharge to occur. The direct contact between the liquid cathode and the
lithium forms a film over the lithium, called the solid electrolyte interface (SEI). This
prevents further chemical reaction when not in use, thus preserving the cell's shelf life. One
drawback, though, is that if the film is too thick, it causes an initial voltage delay.
Usually, water contamination is the reason for the thicker film, so quality control is
LiSO2 LithiumSulfur Dioxide
This cell performs very well in high current applications as well as in low temperatures. It
has an open voltage of almost 3 V and a typical energy density of 240280 Wh/kg. It uses a
cathode of porous carbon with sulfur dioxide taking part in the reaction at the cathode. The
electrolyte consists of an acetonitrile solvent and a lithium bromide solute. Polypropylene
acts as a separator. Lithium and sulfur dioxide combine to form lithium dithionite:
2Li + 2SO2 > Li2S2O4
These cells are mainly used in military applications for communication because of high cost
and safety concerns in high-discharge situations, i.e., pressure buildup and overheating.
LiSOCl2 Lithium Thionyl Chloride
This cell consists of a high-surface area carbon cathode, a non-woven glass separator, and
thionyl chloride, which doubles as the electrolyte solvent and the active cathode material.
Lithium aluminum chloride (LiAlCl4) acts as the electrolyte salt.
The materials react as follows:
||Li > Li+ + e-
||4Li+ + 4e- + 2SOCl2 > 4LiCl + SO2 +
||4Li + 2SOCl2 > 4LiCl + SO2 + S
During discharge the anode gives off lithium ions. On the carbon surface, the thionyl
chloride reduces to chloride ions, sulfur dioxide, and sulfur. The lithium and chloride ions
then form lithium chloride. Once the lithium chloride has deposited at a site on the carbon
surface, that site is rendered inactive. The sulfur and sulfur dioxide dissolve in the
electrolyte, but at higher-rate discharges SO2 will increase the cell pressure.
This system has a very high energy density (about 500 Wh/kg) and an operating voltage of
3.33.5 V. The cell is generally a low-pressure system
In high-rate discharge, the voltage delay is more pronounced and the pressure increases as
mentioned before. Low-rate cells are used commercially for small electronics and memory backup.
High-rate cells are used mainly for military applications.
Solid cathode lithium cells:
These cells cannot be used in high-drain applications and don't perform as well as the
liquid cathode cells in low temperatures. However, they don't have the same voltage delay and
the cells don't require pressurization. They are used generally for memory backup, watches,
portable electronic devices, etc.
These account for about 80% of all primary lithium cells, one reason being their low cost.
The cathode used is a heat-treated MnO2 and the electrolyte a mixture of propylene
carbonate and 1,2-dimethoyethane. The half reactions are
||Li > Li+ + e
||MnIVO2 + Li+ + e >
||Li + MnIVO2 >
At lower temperatures and in high-rate discharge, the LiSO2 cell performs much
better than the LiMnO2 cell. At low-rate discharge and higher temperatures, the two
cells perform equally well, but LiMnO2 cell has the advantage because it doesn't
Li(CF)n Lithium polycarbon monofluoride
The cathode in this cell is carbon monofluoride, a compound formed through high-temperature
intercalation. This is the process where foreign atoms (in this case fluorine gas) incorporate
themselves into some crystal lattice (graphite powder), with the crystal lattice atoms
retaining their positions relative to one another.
A typical electrolyte is lithium tetrafluorobate (LiBF4) salt in a solution of
propylene carbonate (PC) and dimethoxyethane (DME).
||Li > Li+ + e
||MnIVO2 + Li+ + e >
||Li + MnIVO2 >
These cells also have a high voltage (about 3.0 V open voltage) and a high energy density
(around 250 Wh/kg). All this and a 7-year shelf life makes them very suitable for low- to
moderate-drain use, e.g., watches, calculators, and memory applications.
Solid electrolyte lithium cells:
All commercially manufactured cells that use a solid electrolyte have a lithium anode. They
perform best in low-current applications and have a very long service life. For this reason,
they are used in pacemakers
LiI2Lithium iodine cells use solid LiI as their
electrolyte and also produce LiI as the cell discharges. The cathode is poly-2-vinylpyridine
(P2VP) with the following reactions:
||2Li > 2Li+ + 2e
||2Li+ + 2e + P2VP· nI2 >
P2VP· (n1)I2 + 2LiI
||2Li + P2VP· nI2 > P2VP· (n1)I2 +2LiI
LiI is formed in situ by direct reaction of the electrodes.
The Lithium-Iron chemistry deserves a separate section because it is one of a
handful of lithium metal systems that have a 1.5 volt output (others are lithium/lead
bismuthate, lithium/bismuth trioxide, lithium/copper oxide, and lithium/copper sulfide).
Recently consumer cells that use the Li/Fe have reached the market, including the Energizer.
These have advantage of having the same voltage as alkaline batteries with much more energy
storage capacity, so they are called "voltage compatible" lithiums. They are not rechargeable.
They have about 2.5 times the capacity of an alkaline battery of the same size, but only under
high current discharge conditions (digital cameras, flashlights, motor driven toys, etc.). For
small currents they don't have any advantage. Another advantage is the low self-discharge
rate10 years storage is quoted by the manufacturer. The discharge reactions are:
Both Iron sulfide and Iron disulfide are used, the FeS2 is used in the Energizer.
Electrolytes are organic materials such as propylene carbonate, dioxolane and dimethoxyelthane
||2 FeS2 + 4 Li > Fe + 2Li2S
||FeS + 2Li > Fe + Li2S
Magnesium-Copper Chloride Reserve Cells
The magnesium-cuprous chloride system is a member of the reserve cell family. It can't
be used as a primary battery because of its high self-discharge rate, but it has a high
discharge rate and power density, so it can be made "dry charged" and sit forever ready, just
add water. The added advantage of being light-weight has made these practical for portable
It works by depositing copper metal out onto the magnesium anode,
just like the old copper-coated nail experiment.
Variations of this battery use silver
chloride, lead chloride, copper iodide, or copper thiocyanate to react with the
The water does not have to be pure, sea water, tap water, or even bio-derived
waste fluids have been used. The torpedo batteries force seawater through the battery to get up
to 460 kW of power to drive the propeller.
||Mg + 2 CuCl > MgCl2+ 2 Cu
Anode: Sponge metallic lead
Cathode: Lead dioxide (PbO2)
Electrolyte: Dilute mixture of aqueous sulfuric acid
Applications: Motive power in cars, trucks, forklifts, construction equipment,
recreational water craft, standby/backup systems
Used mainly for engine batteries, these cells represent over half of all battery sales. Some
advantages are their low cost, long life cycle, and ability to withstand mistreatment. They
also perform well in high and low temperatures and in high-drain applications. The chemistry
lead acid battery half-cell reactions are:
||V vs SHE
|Pb + SO42- > PbSO4 + 2e-
|PbO2 + SO42- + 4H+ + 2e- >
PbSO4 + 2H2O
There are a few problems with this design. If the cell voltages exceed 2.39 V, the water
breaks down into hydrogen and oxygen (this so-called gassing voltage is temperature dependent,
for a chart of the temperature dependence click here
). This requires replacing the cell's water. Also, as the hydrogen and oxygen vent from the
cell, too high a concentration of this mixture will cause an explosion. Another problem arising
from this system is that fumes from the acid or hydroxide solution may have a corrosive effect
on the area surrounding the battery.
These problems are mostly solved by sealed cells, made commercially available in the 1970s.
In the case of lead acid cells, the term "valve-regulated cells" is more accurate, because they
cannot be sealed completely. If they were, the hydrogen gas would cause the pressure to build
up beyond safe limits. Catalytic gas recombiners do a great deal to alleviate this problem.
They convert the hydrogen and oxygen back into water, achieving about 85% efficiency at best.
Although this doesn't entirely eliminate the hydrogen and oxygen gas, the water lost becomes so
insignificant that no refill is needed for the life of the battery. For this reason , these
cells are often referred to as maintenance-free batteries. Also, this cell design prevents
corrosive fumes from escaping.
These cells have a low cycle life, a quick self discharge, and low energy densities
(normally between 30 and 40 Wh/kg). However, with a nominal voltage of 2 V and power densities
of up to 600 W/kg, the lead-acid cell is an adequate, if not perfect, design for car
Cathode: Nickel oxyhydroxide Ni(OH)2
Electrolyte: Aqueous potassium hydroxide (KOH)
Applications: Calculators, digital cameras, pagers, lap tops, tape recorders,
flashlights, medical devices (e.g., defibrillators), electric vehicles, space applications
The cathode is nickel-plated, woven mesh, and the anode is a cadmium-plated net. Since the
cadmium is just a coating, this cell's negative environmental impact is often exaggerated.
(Incidentally, cadmium is also used in TV tubes, some semiconductors, and as an orange-yellow
dye for plastics.) The electrolyte, KOH, acts only as an ion conductor and does not contribute
significantly to the cell's reaction. That's why not much electrolyte is needed, so this keeps
the weight down. (NaOH is sometimes used as an electrolyte, which doesn't conduct as well, but
also doesn't tend to leak out of the seal as much). Here are the cell reactions:
||V vs SHE
|Cd + 2OH- > Cd(OH)2 + 2e-
|NiO2 + 2H2O + 2e- > Ni(OH)2 +
|Cd +NiO2 + 2H2O > Cd(OH)2 +
Advantages include good performance in high-discharge and low-temperature applications. They
also have long shelf and use life. Disadvantages are that they cost more than the lead-acid
battery and have lower power densities. Possibly its most well-known limitation is a memory
effect, where the cell retains the characteristics of the previous cycle.
This term refers to a temporary loss of cell capacity, which occurs when a cell is recharged
without being fully discharged. This can cause cadmium hydroxide to passivate the electrode, or
the battery to wear out. In the former case, a few cycles of discharging and charging the cell
will help correct the problem, but may shorten the lifetime of the battery. The true memory
effect comes from experience with a certain style of NiCad in space use, which were cycled
within a few percent of discharge each time.
An important thing to know about "conditioning " a NiCd battery is that the deep discharge
spoken of is not a discharge to zero volts, but to about 1 volt per cell.
Cathode: Nickel oxyhydroxide
Electrolyte: Potassium hydroxide
Applications:Space satellites that require long cycle life, over 40,000 cycles.
Nickel/Hydrogen batteries have a high self-discharge rate, something like 80% a month, which
isn't a problem for satellite applications.
The NiH2 cell is a welded pressure vessel. It has a high specific energy,
60WH/kg, long life, can tolerate overcharge and cell reversal, but has a low volumetric energy
density, 50 WH/liter.
Here are the cell reactions:
||½H2 + OH- > H2O + e-
||NiOOH + H2O + e- > Ni(OH)2 + OH-
||NiOOH + ½H2 > Ni(OH)2
In order to get the hydrogen gas into solution a Teflon-bonded platinum black catalyst is
used, similar to that used in fuel cells. This platinum electrode has the added advantage that
it can recombine oxygen with hydrogen extremely fast. Since the only bad chemical reaction
during over charge is the creation of oxygen at the positive electrode this means that the
Nickel/Hydrogen battery is impossible to overcharge (though there may be a thermal runaway
problem if the excess heat isn't dissipated.) A similar reaction keeps any damage from being
done if the cell is reverse-charged.
The battery weight for a 10kW satellite is about 350 kg, or 770 lbs.
Anode: Rare-earth or nickel alloys with many metals
Cathode: Nickel oxyhydroxide
Electrolyte: Potassium hydroxide
Applications: Cellular phones, camcorders, emergency backup lighting, power tools,
laptops, portable, electric vehicles
This sealed cell is a hybrid of the NiCd and NiH2 cells. Previously, this battery
was not available for commercial use because, although hydrogen has wonderful anodic qualities,
it requires cell pressurization. Fortunately, in the late 1960s scientists discovered that some
metal alloys (hydrides such as LiNi5 or ZrNi2) could store hydrogen
atoms, which then could participate in reversible chemical reactions. In modern NiMH batteries,
the anode consists of many metals alloys, including V, Ti, Zr, Ni, Cr, Co, and Fe.
Except for the anode, the NiMH cell very closely resembles the NiCd cell in construction.
Even the voltage is virtually identical, at 1.2 volts, making the cells interchangeable in many
applications. Here are the cell reactions:
||MH + OH- > M + H2O + e-
||NiOOH + H2O + e- > Ni(OH)2 + OH-
||NiOOH + MH > Ni(OH)2 + M
The anodes used in these cells are complex alloys containing many metals, such as an alloy
of V, Ti, Zr, Ni, Cr, Co, and (!) Fe. The underlying chemistry of these alloys and
reasons for superior performance are not clearly understood, and the compositions are
determined by empirical testing methods.
A very interesting fact about these alloys is that some metals absorb heat when absorbiong
hydrogen, and some give off heat when absorbing hydrogen. Both of these are bad for a battery,
since we would like the hydregen to move easily in and out without any energy transfer. The
successful alloys are all mixtures of exothermic and endothermic metals to achieve this.
Hydrogen Storage Metals Comparison:
||H2 Storage Capacity
Please notice that the density of hydrogen stored in a metal hydride is higher than that of
pure liquid hydrogen! Commercial NiMH batteries are mostly of the rare earth-nickel type, of
which LaNi5 is a representative. These alloys can store six hydrogen atoms per unit
cell such as LaNi5H6. Even misch metal nickel alloys are used to save the
cost of separation.
The electrolyte of commercial NiMH batteries is typically 6 M KOH
The NiMH cell does cost more and has half the service life of the NiCd cell, but it also has
30% more capacity, increased power density (theoretically 50% more, practically 25% more). The
memory effect, which was at one time thought to be absent from NiMH cells, is present if the
cells are treated just right. To avoid the memory effect fully discharge once every 30 or so
cycles. There is no clear winner between the two. The better battery depends on what
characteristics are more crucial for a specific application.
Anode: Molten sodium
Cathode: Molten sulfur
Electrolyte: Solid ceramic beta alumina (ß"-Al2O3)
Applications: Electric vehicles, aerospace (satellites)
This cell have been studied extensively for electric vehicles because of its inexpensive
materials, high cycle life, and high specific energy and power. Specific energies have reached
levels of 150 W-h/kg and specific powers of 200 W/kg. The half-reactions are:
||V vs SHE
|2Na > 2Na+ + 2e-
|3S + 2e- > S32-
2Na + 3S > Na2S3 2.076 V
Despite these advantages there are couple of disadvantages serious enough that other
alternatives, such as lithium-ion, nickel-metal hydride, and lithium polymer, have emerged as
the most promising solutions to electric vehicle power. One is that the power output is very
small at room temperature. The temperature must be kept at around 350 ºC to keep the
sulfur in liquid form and to be effective in motive power applications. This is achieved
through insulation or heating through the cells own power. This lowers the energy density.
The second problem has to do with electrolyte breakdown, which is one of the principal
causes of sodium sulfur cell failure. The electrolyte, ceramic beta"-alumina, has several
attractive characteristics. It has all the benefits of a solid electrolyte with the added
qualities of a high ionic conductivity with a small electronic transfer, all with the added
benefit of being a solid. However, ceramic beta"-alumina also is brittle and develops
microfissures. Thus the liquid sodium and sulfur come in contactwith explosively violent
Recently, some research efforts have focussed on replacing the molten sulfur cathode with a
poly(disulfide) such as poly(ethylenedisulfide), (SSCH2CH2)n.
These cells can be discharged just above the melting temperature of Na (90 °C). The net
cell reaction becomes:
2 Na + (SSR)n=Na2SSR
where the discharge reaction involves scission of the S-S disulfide linkage in the polymer
backbone, and charge involves repolymerization of the resulting dithiolate salt.
One of these is the sodium/metal chloride, which in addition to beta"-alumina has a
secondary electrolyte (NaAlCl4) to conduct ions from the first electrolyte to the
cathode. This is necessary because the metal chloride is a solid.
These are specialty cells made by one manufacturer in England, Beta Research. They have
advantages for electric vehicles. The cell runs hot, about 300 degrees C, but this isn't a
worry, since they heat themselves up during discharge. The discharge reaction is:
||2 NaCl + Ni Z > 2Na +NiCl2
||NiCl2 + 2 Na > Ni + 2NaCl
The electrolyte on the nickel side of the alumina separator is sodium
tetracloroaluminate.NaAlCl4, which melts at 151 degrees C.. Energy density is 100 to
150 Wh/kg. These use an aluminum oxide ceramic as a separator, similar to that of the
sodium-sulfur cell. They have the same danger of rupture of the separator, but have a unique
solution to the problem. The cell is encased in a two-wall steel thermally insulated package.
If the separator breaks the energy is confined within this package. A cell that is broken in
this way has a low resistance, so it can continue to reside in the battery pack without causing
a vehicle break-down. This double-insulated case also prevents the cell from spilling in car
There are no higher-voltage reactions or other side reactions, so the
inventors claim that up to the point of full charge the cell is 100% coulomb
efficientmeaning that the amp-hours you put in is exactly the same as the amp-hours you
get out. Overcharging does not damage the cell, so the battery packs are easy to keep in
balancejust overcharge the whole pack.
It seems that the cell has no
self-discharge if the batteries are cold, (solid blocks of sodium don't migrate at room
temperature) and that a pack requires about 24 hours to get to temperature with a 230 VAC input
to the pack heater.
Anode: Carbon compound, graphite
Cathode: Lithium oxide
Applications: Laptops, cellular phones, electric vehicles
Lithium batteries that use lithium
metal have safety disadvantages when used as secondary (rechargeable) energy
sources. For this reason a series of cell chemistries have been developed using
lithium compounds instead of lithium metal. These are called generically
Lithium ion Batteries.
Cathodes consist of a a layered crystal (graphite) into which the lithium is intercalated.
Experimental cells have also used lithiated metal oxide such as LiCoO2,
NiNi0.3Co0.7O2, LiNiO2, LiV2O5,
LiV6O13, LiMn4O9, LiMn2O4,
Electrolytes are usually LiPF6, although this has a problem with aluminum
corrosion, and so alternatives are being sought. One such is LiBF4. The electrolyte
in current production batteries is liquid, and uses an organic solvent.
Membranes are necessary to separate the electrons from the ions. Currently the batteries in
wide use have microporous polyethylene membranes.
Intercalation (rhymes with relationnot inter-cal, but in-tercal-ation) is a
long-studied process which has finally found a practical use. It has long been known that small
ions (such as lithium, sodium, and the other alkali metals) can fit in the interstitial spaces
in a graphite crystal. Not only that, but these metallic atoms can go farther and force the
graphitic planes apart to fit two, three, or more layers of metallic atoms between the carbon
sheets. You can imagine what a great way this is to store lithium in a batterythe
graphite is conductive, dilutes the lithium for safety, is reasonably cheap, and does not allow
dendrites or other unwanted crystal structures to form.
Manganese-Titanium (Lithium) Cells
Anode: Lithium-Titanium Oxide
Cathode: Lithium intercalated Manganese Dioxide
Applications: Watches, other ultra-low discharge applications
This technology might be called Manganese-Titanium, but it is just another lithium coin
cell. It has "compatible" voltage 1.5 V to 1.2 Volts, like the Lithium-Iron cell, which
makes it convenient for applications that formerly used primary coin cells. It is unusual for a
lithium based cell because it can withstand a continuous overcharge at 1.6 to 2.6 volts without
damage. Although rated for 500 full discharge cycles, it only has a 10% a year self-discharge
rate, and so is used in solar charged watches with expected life of 15+ years with shallow
discharging. The amp-hour capacity and available current output of these cells is extremely
meager. The range of capacities from Panasonic is 0.9 to 14 mAH (yes, 0.9 milliamp hours). The
maximum continuous drain current is 0.1 to 0.5 mA.
Alkaline Manganese Cells
Electrolyte: Potassium Hydroxide Solution
Applications: Consumer devices
Yes, this is the familiar alkaline battery, but specially designed to be rechargeable, and
with a hot new acronymRAM (haven't I seen that acronym somewhere before?). In the
charging process, direct-current electrical power is used to reform the active chemicals of the
battery system to their high-energy charge state. In the case of the RAM battery, this involves
oxidation of manganese oxyhydroxide (MnOOH) in the discharged positive electrode to manganese
dioxide (MnO2), and of zinc oxide (ZnO) in the negative electrode to metallic zinc.
Care must be taken not to overcharge to prevent electrolysis of the KOH solution
electrolyte, or to charge at voltages higher than 1.65 V (depending on temperature) to avoid
the formation of higher oxides of manganese.
Cathode: Nickel oxide
Electrolyte: Potassium hydroxide
Applications:Electric vehicles, standby load service
The combination of nickel and zinc is very
interesting because of the low cost and low toxicity of the constituents. There have been many
technical obstacles, but a string of recent patents and a commercial start-up based on a KOH
electrolyte holds great promise for applications where light weight is an issue.
The nickel/zinc battery uses zinc as the negative electrode and nickel hydroxide as the
positive. The discharge reactions are:
||Zn + 2OH- > Zn(OH)2+ 2e
||2NiOOH + 2H2O > 2Ni(OH)2 + 2OH-
||2NiOOH + Zn + 2H2O > 2Ni(OH)2 + Zn(OH)2
These cells run between 1.55 and 1.65 V. Theoretical energy density is 334 Wh/kg, or about
1.3 kg of nickel and 0.7 kg of zinc per kilowatt-hour. The internal resistance of nickel/zinc
batteries is remarkably low, which makes this system particularly attractive for high charge
and discharge rates
Practical specific energy is around 60 Wh/kg. The technical problems that have plagued these
batteries so far are dissolution of the zinc in the electrolyte, and uneven redepositing of the
zinc during charging. Progress in these batteries has been mostly in the improvement of the
zinc electrode. The charging is tricky because the termination voltage is a strong function of
Iron Nickel Cells
Cathode: Nickel oxyhydroxide
Electrolyte: Potassium hydroxide
This battery was introduced by Thomas Edison. It is a very robust battery: it
can withstand overcharge, overdischarge, and remaining discharged for long periods of time
without damage. It is good for high depths of discharge and can have very long life even if so
treated. It has low energy density, a high self-discharge rate, and evolves hydrogen during
both charge and discharge. It is often used in backup situations where it can be continuously
charged and can last for 20 years.
The chemistry involves the movement of oxygen from one electrode to the other: 3Fe + 8NiOOH
+ 4H2O=8 Ni(OH)2 +Fe3O4.
|Fe + 2OH- > Fe(OH)2 +2e-
|3Fe(OH)2 + 2OH- > Fe3O4 +
4H2O + 2e-
The open circuit voltage of this system is 1.4 V, and the discharge voltage is
about 1.2 V. The electrolyte is 30% KOH solution, with some additives.
The ability of this system to survive frequent cycling is due to the low
solubility of the reactants in the electrolyte. The formation of metallic iron on charge is
slow because of the low solubility of the Fe3O4, which is good and bad.
It is good because the slow formation of iron crystals preserves the electrode morphology. It
is bad because it limits the high rate performance: these cells take a charge slowly, and give
it up slowly.
Iron Air Cells
The Iron/Air is another of the air-electrode batteries. The electrochemistry is
|O2 + 2Fe +2H2O=2Fe(OH)2
|O2 +2H2O +2e=H2O2 +2(OH)
These batteries require a high degree of support, since the CO2 must
be taken out of the air in order to prevent potassium carbonates forming in the KOH electrolyte.
They have been built in large backup systems. The air electrode consists of a catalyst on a
support. For example a carbon particle substrate held together with Teflon, coated with a
silver complex catalyst. Support is provided by a silver-plated nickel screen.
Iron Silver Cells
These have a very high energy density, and a good cycle life. It is an alkaline
battery with a KOH electrolyte, and the working materials are silver oxide and metallic iron.
The high cost of these batteries have long been a problem, but an ounce of silver in a cell
phone battery would probably cost less than an ounce of the rare earths now used in some NiMH
Redox (Liquid Electrode) Cells
These consist of a semipermeable membrane having different liquids on either side. The
membrane permits ion flow but prevents mixing of the liquids. Electrical contact is made through
inert conductors in the liquids. As the ions flow across the membrane an electric current is
induced in the conductors. These cells and batteries have two ways of recharging. The first is
the traditional way of running current backwards. The other is replacing the liquids, which can
be recharged in another cell. A small cell can also be used to charge a great quantity of liquid,
which is stored outside the cells. This is an interesting way to store energy for alternative
energy sources that are unreliable, such as solar, wind, and tide. These batteries have low volumetric
efficiency, but are reliable and very long lived.
Electrochemical systems that can be used are FeCl3 (cathode) and TiCl3
or CrCl2 (anode).Vanadium redox cells: A particularly interesting cell uses vanadium
oxides of different oxidation states as the anode and cathode. These solutions will not be spoiled
if the membrane leaks, since the mixture can be charged as either reducing or oxidizing components.
Unlike batteries, which store energy chemically, capacitors store energy as an electrostatic
field. Typically, a battery is known for storing a lot of energy and little power; a capacitor
can provide large amounts of power, but low amounts of energy. A capacitor is made of two conducting
plates and an insulator called the dielectric, which conducts ionically, but not electrically.
In a capacitor,
Ecap = qV = ½CV2
where the capacitance, C, is directly proportional to the surface area of the plates and
inversely proportional to the distance between them.
So in other words, as the plate surface area increases and the distance between the plates
decreases, the energy you can store in a capacitor increases. Normal every-day capacitors have
capacity on the orders of millifarads per cubic foot. Aluminum electrolytics are about a farad
per cubic foot. But for useful energy storage we need farads per cubic inch. That is where supercapacitors
First let's see how clever we can get to obtain a big surface area in a small volume.
Imagine a polymer foam cleaning sponge. It has a tremendous amount of surface area in a small area
because of all the crenulations (OK, nooks and crannies). Now, put it in a furnace, excluding the
oxygen and bake it until only the carbon is left. You now have a conductive carbon surface with
an incredible surface area in a small volume.
But to get a high capacitance there has to be two plates. You can't just go in there and
create complimentary surface as the other electrodeor can you? Yes, just fill it with a conductive
liquid (e.g., an aqueous acid or salt solution). The last thing you need is an ultra-thin insulator
on the carbon. Ultra thin to get high capacitance, and insulator so the carbon and the liquid don't
short out. This is also easy, you can electrochemically deposit an insulator on the carbon surface
(or electrochemically deposit something that could be turned into an insulator upon baking).
Now attach one electrode to the carbon, one to the liquid, and you can have a capacitor that
can have Farads of capacitance per cubic inch. Very nice.
Most practical supercapacitors have low voltage (2 to 5 Vremember that insulator is
ultra-thin and so can break down at low voltages), which is a problem for energy storage, since
the stored energy is proportional to the square of the voltage. Also, conduction through an ionic
liquid is slow, so these capacitors cannot be discharged quickly compared with standard capacitors,
but can be discharged very quickly compared to batteries!
Typical numbers for capacitors and batteries are given below:
||1 - 103
||0.05 - 5
||105 - 108
||105 - 106
Supercapacitors have several advantages over batteries: they can experience virtually
indefinite number of cycles (charging and discharging), they are maintenance free, they work well
in high-rate discharge, they recharge quickly, and they have no negative environmental impact.
- Berndt, D. Maintenance-Free Batteries. New York:: John Wiley & Sons, 1997.
- Crompton, T. R. Battery Reference Book. London: ButterworthHeinemann,
- Linden, D. (Ed), Handbook of Batteries. Maidenhead: McGrawHill, 1995.
- Linford, R. G. (Ed), Electrochemical Science and Technology of Polymers. New York:
- Ovshinsky, S. R., Fetcenko, M. A., and Ross, J. A. "A Nickel Metal Hydride Battery for
Electric Vehicles", Science 260: 1993, 17681.
- Rechargeable Batteries Applications Handbook. Stoneham: ButterworthHeinemann,
- Wells, A. F. Structural Inorganic Chemistry. Oxford: Clarendon Press, 1975.