Papers Chemical Energy Storage

MAGNESIUM AND ALUMINIUM BATTERIES

GROUP I
AULIANY JULISTA H311 15 001
DANIEL HENDRIK MOLLE H311 15 004
RISKAWATI H311 15 021
NURAINI H311 15 017
A. GITA TENRI SUMPALA H311 15 025
MILA RESKI SUCIANA L H311 15 313
ST. FADLIZAH ARIS H311 15 505

DEPARTMENT OF CHEMISTRY

FACULTY OF MATHEMATICS AND NATURAL SCIENCE

HASANUDDIN UNIVERSITY

MAKASSAR

2017
Background

In this era of globalization, the role of technology and information is very

important for human life. Because of technology and information, the distance is not
an obstacle. Humans can communicate easily at great distances. It can not be
separated from the development of technology and information. In the rapid
advances in technology and information, there are various technologies that enable
us to easily carry various devices that can be carried everywhere. One of them is
electrical appliances, these tools directly or indirectly can give a very big positive
effect in maximizing and realizing the purpose of our activities, the reason of time
efficiency is the main headline why electrical appliances are used. Of the many
electrical appliances, the use and utilization of the battery can not be released from
human activity in this era, mobile phones, laptops, even television. It is possible
because of the existence a battery that serves to supply the power required by the
portable equipment.
Batteries are electrical-chemical devices that store energy and emit energy in
the form of electricity. Obviously as a tool that removes electrical energy, the battery
has a function that is very much and diverse. In the world of technology especially in
this automotive world, batteries play a very important role as a major energy
provider in the combustion process of diesel engines and gasoline engines. And of
course there are many more functions of the battery.
Inside the battery itself, there is a chemical reaction that produces electrons.
The speed of this process (electrons, as a result of electrochemistry) controls how
many electrons can flow between the two poles. The electrons flow from the battery
to the wire and certainly move from the negative to the positive pole where the
chemical reaction is taking place. And this is the reason why the battery can last for a
year and still have less power, as long as there is no chemical reaction or as long as
we do not connect it with other types of cables or connectors. Instantly we connect it
with the cable then the chemical reaction begins.

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1. Magnesium And Aluminium Batteries
Magnesium has been successfully used in magnesium / manganese dioxide
(Mg/MnO2) batteries. This battery has two major advantages over a zinc-carbon
battery, which is twice the life or capacity of a zinc battery of an equivalent size and
the ability to maintain this capacity, during storage, even at high temperatures. This
excellent storageability is caused by a protective layer formed on the surface of the
magnesium anode.
Aluminum has not been successfully used with an active main battery despite
its potential advantages. Like magnesium, the form of protective film on aluminum,
which destroys battery performance, produces battery voltages far below the theory
and causes significant voltage delays for partially discharged or stored batteries.
While the protective oxide layer may be removed by means of an appropriate
electrolyte or by incorporation, the gain in such manner is accompanied by
accelerated corrosion and poor shelf life. Aluminum, however, has been more
successfully used as an anode on aluminum / air batteries.

2.
Con
stru
ctio
n
Of
Mg/
Mn
O2
Bat
teri
es

Figure 3.1 (1) Cylindrical Construction of Magnesium Primary Battery (Mg/MnO2)

and (2) Inside-Out Construction of Magnesium Primary Battery

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 Construction wise a cylindrical magnesium battery cell is similar to a
cylindrical zinc carbon battery cell. Here an alloy of magnesium is used as main
container of the battery. This alloy is formed by magnesium and small quantity of
aluminum and zinc. Here, manganese dioxide is used as cathode material. As the
manganese dioxide has poor conductivity, acetylene black is mixed with this to
improve its conductivity. This also helps to retain water inside cathode. In this
cathode mixture barium chromate is added as an inhibitor, and also magnesium
hydroxide is added as a pH buffer. Magnesium per-chlorate with lithium chromate
mixed in water is used as electrolyte. A carbon is inserted in the cathode mix as
current collector. Kraft papers, absorbed with electrolyte solution are placed in
between cathode and anode materials as separators. Special attention is to be given
during designing of sealing arrangement in magnesium battery. The sealing of the
battery should not be so porous that the moisture inside the battery will be
evaporated during storing of the battery and it should not be so nonporous that the
hydrogen gas formed during discharge cannot escape from the battery. So the seal of
the battery should retain the moisture inside it and at the same time it gives sufficient
vent to the hydrogen gas formed during discharge. This can be done by providing a
small hole on the top of the plastic seal washed under the Retainer ring. When excess
gas comes out from the hole this retainer ring is deformed due to pressure and
resulting escaping of the gas.
3. Chemical Reaction In Batteries
3.1 Magnesium Battery
The magnesium battery uses magnesium alloy for the anode, manganese
dioxide as the active cathode material but mixed with actylene black to provide
conductivity, and an aqueous electrolyte consisting of magnesium perchlorate, with
barium and lithium chromate as corossion inhibitors and magnesium hydroxide as a
buffering agent to improve storability (pH about 8,5). The amount of waters is
critical as water participates in the anode reaction and is conumed during the
discharge. The discharge reaction magnesium battery :
Anode : Mg + 2OH- Mg(OH)2 + 2e
Cathode : 2MnO2 + H2O + 2e Mn2O3 + 2OH-
Overall : Mg + 2MnO2 + H2O Mn2O3 + Mg(OH)2

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 The theoretical potential of the battery is greater than 2.8 V, but this voltage
is not realized in practice. The observed values are decreased by about 1.1 V, giving
an open-circuit voltage of 1.9–2.0 V, still higher than for the zinc-carbon battery.
The corrosion of magnesium under storage conditions is slight. A film of
Mg(OH)2 that forms on the magnesium provides good protection, and treatment with
chromate inhibitors increases this protection. As a result of the formation of this
tightly adherent and passivating oxide or hydroxide film on the electrode surface,
magnesium is one of the most electropositive metals to find use in aqueous primary
batteries. However, when the protective film is broken or removed during discharge,
corrosion occurs with the generation of hydrogen :
Mg + 2H2O Mg(OH)2 + H2
The efficiency of the magnesium anode is about 60 to 70% during a typical
continuous discharge and is influenced by such factors as the composition of the
magnesium alloy, battery components, discharge rate, and temperature. On low
drains and intermittent service, the anode efficiency can drop to 40 to 50% or less.
The anode efficiency also is reduced with decreasing temperature.
2.2 Aluminium Battery
In the aluminium battery, aluminium use for the anode. The standard
potential for aluminum in the anode reaction,
Al Al3+ + 3e
is reported as 1.7 V. A battery with an aluminum anode should have a potential about
0.9 V higher than the corresponding zinc battery. However, this potential is not
attained, and the potential of an Al/MnO2 battery is only about 0.1 to 0.2 V higher
than that of a zinc battery. The Al/MnO2 battery never progressed beyond the
experimental stage because of the problems with the oxide film, excessive corrosion
when the film was broken, voltage delay, and the tendency for aluminum to corrode
unevenly. The experimental batteries that were fabricated used a two-layer aluminum
anode (to minimize premature failure due to can perforation), an electrolyte of
aluminum or chromium chloride, and a manganese dioxideacetylene black cathode
similar to the conventional zinc /manganese dioxide battery. The reaction mechanism
is:
Al + 3MnO2 + 3H2O 3MnO.OH + Al(OH)3

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4. Primary and Secondary Battery
Primary magnesium cells have been developed since the beginning of the
20th century. A number of chemicals for this type of spare battery have been studied,
with cathode materials including silver chloride, copper (I) chloride, palladium(II)
chloride, copper(I) iodide, copper(I) thiocyanate, manganese dioxide and air
(oxygen).
Magnesium air batteries are primary cells, but have the potential to be
replenished by anode and electrolyte replacements. Magnesium air batteries have
been commercialized and used as land-based backup systems as well as underwater
resources, using seawater as electrolytes. Compared with lithium as an anode
material, magnesium has an energy density (theoretical) per unit mass below half of
lithium (18.8 MJ/kg vs. 42.3 MJ/kg), but the volumetric energy density is about 50%
higher (32.731 GJ/m3 vs. 22,569 GJ / m3). Compared with the metal lithium anode,
the magnesium anode has not shown the formation of dendrites during filling,
allowing magnesium metal to be used without intercalation at the anode, the ability
to use magnesium anodes without intercalation layer increases maximum theoretical
maximum volumetric energy density to about 5 times than in ion cells lithium.
Potential use of Mg-based batteries has been recognized since the 1990s, and
rechargeable cells were first reported in 2000.
As the metal is exposed to water, a blocking layer such as Mg(OH)2 formed
the equation with the formation of hydrogen gas. To recharge the battery, applying a
large overpotential was necessary due to the very resistive blocking of the layer, and
finally the interface between the anode and the electrolyte, which determines the
battery performance, can not fully recover because of the main hurdle with the
anode, the Magnesium battery cathode challenge may have been covered. In fact, a
correct understanding of cathode reactions and furthermore, improving cathode
performance is essential for realizing the current reload system (the study of refills).
The Mg battery cathode has gained more momentum for it to improve the main
battery characteristics such as voltage, capacity, life cycle and so on. Currently
traditional cathode materials briefly summarized have been intensively reconsidered,
while other candidates, for example, MgO.5Ti2(PO4)3, MgxMnSiO4, W, sulfur and
oxygen. To find the next generation of Mg battery cathodes, the most important

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challenge is to overcome the negative impacts arising from Mg2+ divalent ions and
also maintain the mobility of higher Mg2+ ions in the diffusion path. So far, despite
research efforts to overcome this challenge, the very slow Mg2+ ion diffusion and
structural instability remains a major hurdle in the development of high voltage
cathode work. Here, we are very strongly focused on the recent advances of
representative cathode materials for Mg rechargeable batteries.
The basic structure of a Mg–air battery is shown schematically in Fig. 3.2,
composed of an Mg (or Mg alloy) anode, an air cathode and a saline electrolyte. The
reactions involved in Mg–air batteries are as follows:

Figure 3.2 Basic Structure of a Mg Air Battery

During the discharge process, the anode Mg is oxidized to Mg2+, producing
two electrons, while at the opposite electrode, O2 passes through the air cathode and
is then reduced to OH- by reaction with H2O and electrons.8 The theoretical voltage
of the Mg–air battery is 3.1 V and the specifc energy density is 6.8 kW h kg-1. The
Mg–air battery is a promising electrochemical energy storage and conversion device
since Mg is abundant on the earth, has a high reaction activity, is light weight, has
low toxicity and has relatively high.
Secondary magnesium cell batteries are an active research topic, particularly
as a replacement or repair on lithium battery-based battery chemistry because Li-ion

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replacement magnesium cells are possible with solid magnesium anodes, which
allow higher energy density than that.
Aluminum can be used as a primary battery. One type of primary battery that
uses aluminum is the aluminum-air primary battery. Aluminum-air batteries or Al-air
batteries generate electricity from the reaction of oxygen in the air with aluminum.
They have one of the highest energy densities of all batteries, but they are not widely
used due to problems with high anode costs and removal of byproducts when using
traditional electrolytes and have limited their use for military-primarily applications.
However, electric vehicles with aluminum batteries have the potential of up to eight
times the range of lithium-ion batteries with a significantly lower total weight.
Battery Aluminum-air primary cell; ie, non-refills. After the aluminum anode is
consumed by the reaction with atmospheric oxygen at the cathode soaked in a water-
based electrolyte to form hydrated aluminum oxide, the battery will no longer
produce electricity. However, it is possible to mechanically recharge the batteries
with a new aluminum anode made from recycled hydrated aluminum oxide. Such
recycling will be important if the aluminum-air battery has to be widely adopted.
Aluminum can also be used in secondary batteries, such as an aluminum-ion
secondary battery. The Aluminum-ion battery is a rechargeable battery class in
which the aluminum-ions provide energy by flowing from the negative electrode
from the battery, the anode, to the positive electrode, the cathode. When charging,
the aluminum-ion back to the anode.
Aluminum-ion batteries have a relatively short shelf life. The combination of
heat, filling levels, and renewal can dramatically reduce the energy capacity. When
the metal ion batteries are completely discharged, they can no longer be refilled. The
ionic electrolyte is expensive. Like most batteries, they have a much lower energy
density than gasoline.

4. The Advantages and Disadvantages of Magnesium And Aluminium Batteries

Advantages of Magnesium Battery
1. It has very good self life; it can be stored for long even under high-temperature.
These battery can be stored up to 5 years at the temperature 20 oC.
2. It has twice capacity compared to equivalent size Leclanche battery.
3. Higher battery voltage than zinc-carbon battery.

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4. Cost is also moderate.
Disadvantages of Magnesium Battery
1. Delayed action.(voltage delay)
2. Evolution of hydrogen during discharge.
3. Heat generated during use.
4. Poor storage after partial discharge.
5. The battery are no longer manufactured commercially.

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 BIBLIOGRAPHY

Linden, D. and Reddy T, B., 2002, Handbook Of Batteries, McGraw-Hill Companies

Inc., New York.

Mohtadi, R., and Mizuno, F., 2014, Magnesium batteries: Current state of the art,
issues and future perspectives, Beilstein Journal of Nanotechnology, 5(1):
1291-1311.

Tian, H., Gao, T., Li, X., Wang, X., Lou, C., Fan, X., Yang, C., Suo, L., Ma, Z., Han,
W., and Wang, C., 2017, High power rechargeable magnesium/iodine battery
chemistry, Nature Communications, 8(1): 1-8.