Energy Systems

Electrode System:

Introduction:
Electrochemistry deals with interaction of matter and electrical energy i.e., producing electrical energy from
chemical reaction (spontaneous process) and/or bringing out chemical reactions by the applying electrical
energy (non-spontaneous process). These reactions are referred as electrochemical reaction and are invariably
involves transfer of electrons.

Oxidation-Reduction Reactions:
Oxidation reduction reactions are very apt examples to observe transfer of electrons. Thus, oxidation is the
process of losing the electrons and reduction is the process of gaining the electrons. It is quite obvious that, if a
substance loses electrons, then there will be another substance to accept the electrons and vice- versa.
Therefore, the oxidation reduction reactions occur simultaneously.

For example, if a Zn-rod is immersed in a solution of CuSO4, precipitation of copper occurs which in turn
deposition Zn rod. This is an exothermic reaction i.e. heat energy is produced from the interaction Zn with
CuSO4 solution. Let us represent the process by electrochemical reaction.

In this interaction Zn atoms undergo oxidation to form Zn2+ ions by losing theelectrons;
+
i. e. Zn(s) → Zn2 (aq) + 2e − − − −(1)

and simultaneously Cu2+ ion of CuSO4 accepts the electrons and undergo reduction;
+
i. e. Cu2 (aq) + 2e → Cu(s) − − − −(2)
The overall reaction is represented as,
+ +
Zn(s) + Cu2 (aq) → Zn2 (aq) + Cu(s)

Origin of Electrode Potential:

In general, when currents flow between two points, a difference of potential is said to exist between
them. If so, during production of electrical energy in an electrochemical cell, how a difference of potential is
existed in an interaction of electrode and electrolyte? Let us discuss about this;
When metal electrodes are placed in their salt solution, some of them have tendency to undergo
oxidation;
i. e. 𝑀𝑠 → 𝑀𝑛+ + 𝑛𝑒
Due to this reaction metal acquires negative charge and is as shown in figure below

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On the other hand, in some other cases metal ions from salt solutions have tendency to undergo reduction;
𝑀𝑛+ + 𝑛𝑒 → 𝑀𝑠
During this process, metal acquires positive charge and is as shown in figure below.

Due to these reactions the metal acquires negative or positive charge and attracts oppositely charged ions
from the solution and form a dynamic equilibrium. Once the dynamic equilibrium is established, positive or
negative ions remain quite close to the metal and form Helmholtz electrical double layer (HED). This process
creates potential difference between metal and solution and is known as electrode potential. At equilibrium,
the potential difference between metal and solution remains constant until the charge is not allowed to
flow. Thus, “the measure of tendency of metallic electrode to lose or gain the electrons when it is dipped in
its own salt solution is called single electrode potential”.
Thus, the measure of tendency of metallic electrode to loose or gain electrons when it is
dipped its own salt solution of unit molar concentration at 25° C is called standard electrode
potential.

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Electrodes:

An electrode is a solid electric conductor that carries electric current into non metallic solids or
liquids, gases, plasma or vacuums.

Types of Electrodes:

In general, electrodes will develop potential when dipped in their salt solutions. But for specific applications,
the electrode constructed in different way.

The various types of electrodes are;

1. Metal-Metal Ion Electrodes

These are very simple type of electrodes in which the electrode material takes part directly in reaction.
In these electrodes, a metal electrode is dipped into a solution of its own ions and potential develops at
the electrode is due to potential difference between metal and solution.

Eg. Zn dipped in ZnSO4 solution

Cu dipped in CuSO4 solution
.These are represented as; Zn2+ | Zn and Cu2+ | Cu
2. Metal-Metal Salt Ion Electrode

This type of electrodes consists of a metal in contact with its insoluble salt along with a solution of
common anion of the insoluble salt.

Eg. i) Calomel electrode : Hg(l) | Hg2Cl2(s) | KCl

ii) Ag-AgCl electrode : Ag(s) | AgCl(s) | KCl

3. Gas Electrode
This type of electrodes consists of a bubbling of a gas at constant pressure on an inert electrode like
platinum dipped in a solution of ions of the gas of known concentration. These ions are capable of
undergoing either oxidation or reduction.

Eg. i) Hydrogen electrode : Pt │ H2 (g) (1atm) │H+ (0.1M)

ii) Chlorine electrode : Pt │ Cl2 (g)│Cl ˉ (0.1M)

4. Amalgum Electrode
In these electrodes a metal is dissolved in mercury or in the form of an amulgum which is in contact
with ions of the metal. The elctrical contact is established by dipping a platinum wire in amalgum. This
type electrode assembly facilitates the use of more active metals like Na, K etc., as reversible
electrodes by dissolving them in mercury.

Eg. i) Cadmium amulgum electrode: Cd – Hg(l)│Cd2+(aq)

ii) Sodium amalgum electrode: Na - Hg(l) | Na2+(aq)

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5. Redox (Oxidation - Reduction) Electrodes:

In this type of electrodes, an inert platinum electrode is dipped in a solution containing a substance of
two different oxidation states. The electrons transfer in such electrode occurs between ions and
molecules or between two ions in the solution through platinum electrode.

Eg. i) Pt | Fe2+(C1) | Fe3+(C2)

ii) Pt | Quinone | Hydroquinone

6. Ion Selective Electrodes :

The electrodes which selectively responds for specific ions in solution and the potential developed at
these electrode is a linear function of concentration of they/those ions for which are sensitive. Such
electrodes are called ion sensitive electrodes. In this electrode specific membranes are used to sense
the ions. Hence these are also referred as embrane electrodes.

E.g : Glass electrode : In this electrode a thin glass membrane is used to sense H+ ions in the solution.
Therefore it is used to determine pH of the solution.

Reference Electrodes:
The potential of a single electrode cannot be measured, because, when it is coupled with another
electrode it becomes cell and the potential observed is cell potential. Therefore, to determine the electrode
potential of any other electrodes, an electrode of known potential required such electrodes are called
reference electrodes. Thus;
“The reversible electrodes of known electrode potential, which are used to determine the electrode
potential of other electrodes, are called reference electrodes”.

Types of Reference Electrodes:

There are two types of reference electrodes:
i) Primary reference electrode
ii) Secondary reference electrode.

i ) Primary Reference Electrode:

The first reference electrode ever constructed was standard hydrogen electrode (SHE). Its electrode
potential is orbiterely fixed as zero for all emf measurements. However, due to the following limitations,
the use of SHE as reference electrode is stopped.

Limitations:
i) It is difficult to maintain 1 molar concentration of H + ions always and to pass H2 gas at 1 atm
pressure.
ii) The impurities like arsenic etc., are adsorbed on platinum foil and poison the surface, which reduce
the efficiency of electrode and affect the equilibrium.
iii) SHE cannot be used in presence of oxidizing and reducing agents

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Secondary Reference Electrodes:
To overcome the limitations of primary reference electrode, other electrodes of good reliability have
been constructed and are referred as secondary reference electrodes. One such reference electrode is;
Calomel Electrode : Construction:

Calomel electrode consists of a glass tube in which mercury is placed at the bottom. A paste of calomel
and mercury is placed on the layer of mercury. The remaining space is filled with saturated KCl. A platinum
wire fused in a glass tube is dipped into mercury to provide external electrical contact. The side tube filled
with KCl functions as salt bridge.

Working:
Since the calomel electrode is reversible electrode, it functions as anode as well as cathode depending
on the nature of coupled electrode of the cell.
The electrode reactions are;
𝐴𝑠 𝐴𝑛𝑜𝑑𝑒 ∶ 2𝐻𝑔(𝑙) + 2𝐶𝑙 − → 𝐻𝑔2 𝐶𝑙2(𝑠) + 2𝑒

𝐴𝑠 𝐶𝑎𝑡ℎ𝑜𝑑 ∶ 𝐻𝑔2 𝐶𝑙2(𝑠) + 2𝑒 → 2𝐻𝑔(𝑙) + 2𝐶𝑙 −

From the electrode reactions it is evident that Cl--ions are consumed at anode, but are released at
cathode. Hence calomel electrode is reversible with respect to Cl--ions. Therefore, potential of calomel
electrode depends on concentration of KCl and are as given below:

KClconcentration Electrode potential

Saturated KCl 0.2422V
1.0 N KCl 0.282V
0.1 N KCl 0.3338V

Applications :
i) Used determine potential of metallic electrodes.
ii) Most commonly used in all potentiometric measurements.
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Ion Selective Electrodes:
Electrochemical systems are used to interface between chemical processes and electronic devices.
These devices are very selective and sensitive as well. These are constructed with membranes which sense
chemical species selectively and send data to electronic devices for measurement. Such electrodes are
called ion selective electrodes.
Thus, “ion selective electrodes are those, which selectivity responds for specific ions in the mixture
and potential developed at the electrode is a function of concentration of those ions in the solution”.
Ion selective electrodes are classified in to two classes;

I) Crystalline membranes II) Non-Crystalline membranes

Membrane Material Sensing Ions Membrane Material Sensing Ions
LaF2 F- Silica glass Na+ & H+
Ag2S+ PbS S2- & Ag+ Liquid-liquid ion exchangers Ca2+ & K+
in Silicon rubber Pb2+ PVC matrix NO3

Applications of Ion Selective Electrode:

i) Glass electrode is sensitive to H+ ions and is used to determine the pH of water samples and other
liquids.
ii) Used to estimate calcium and CO2 in blood sample.
iii) Used to estimate CO2 in boiler feed water.
iv) Used to determine nitrates in water samples, soil and plant materials.
v) Used to determine fluoride in water samples.

Glass Electrode:

Glass electrode is an ion selective electrode and it is sensitive to H+ ions. Therefore, it is used to
determine pH of solutions and water samples.

Principle
When two solutions of different pH are separated by a thin-walled glass membrane, there develops a
difference of potential between two surfaces of the membrane. The magnitude of potential depends on
difference between pH of two solutions. If pH of one of these is held constant, the glass electrode potential
is a linear function of pH of second solution.

Construction
It consists of glass tube with thin-walled bulb at the bottom. The bulb is made up of special quality
glass of high electrical conductance. The bulb is filled with a solution of constant pH (0.1M HCl). A silver
chloride coated silver electrode is dipped in HCl inside bulb provide external electrical contact. The upper
portion is sealed to maintain constant pH of solution inside the bulb. During pH measurements, it is
dipped in analyte solution. The glass electrode set up is as shown in figure below;

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Working of Glass Electrode (Potential at glass electrode):
The glass electrode assembly is represented as,
Ag - AgCl(s) | HCl (0.1M) | Glass
When dipped in solution, it is represented as

𝑨𝒏𝒂𝒍𝒚𝒕𝒆 𝒔𝒐𝒍𝒏. ⧸ ⧸ 𝑯𝑪𝒍

𝑮𝒍𝒂𝒔𝒔 𝒎𝒆𝒎𝒃𝒓𝒂𝒏𝒆 ⧸𝑨𝒈 − 𝑨𝒈𝑪𝒍
[𝑯+ ] = 𝑪𝑨 𝐄 𝑪𝑹 = 𝟎. 𝟏𝑴
𝐀 𝐄 𝐁

Now, Eb = EA - ER
Where, Eb = Boundary potential,
EA = Potential due to analyte solution
ER = Potential due to reference solution

Now, the electrode reaction is given by

+
𝐻(𝑎𝑞) + 𝑀𝐺𝑙 → 𝑀+ + 𝐻𝐺𝑙

This electrode reaction involves the reduction of H+ ions. Therefore, by convention glass electrode is
always cathode.
When a glass electrode dipped in analyte solution, a potential develops across the membrane. The
potential so developed is called boundary potential and is given by the equation,

𝐸𝑏 = 𝐸𝐴 − 𝐸𝑅 [ Here, EA - is cathode type and ER is anode type]

0.0591 0.0591
𝐸𝑏 = { log[𝐶𝐴 ]} − { log[𝐶𝑅 ]}
𝑛 𝑛

0.0591 [𝐶𝐴 ]
𝐸𝑏 = log
𝑛 [𝐶𝑅 ]
Where CA is concentration of H+ ions of analyte solution and
CR is concentration of H+ ions of reference solution
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 𝒐𝒓, 𝑬𝒃 = 𝟎. 𝟎𝟓𝟗𝟏𝒍𝒐𝒈𝑪𝑨 − 𝟎. 𝟎𝟓𝟗𝟏𝒍𝒐𝒈𝑪𝑹 [∵ 𝒏 = 𝟏]

But, CR = constant [Because, concentration of reference solution is constant]

∴ 𝐸𝑏 = 𝑋 + 0.0591𝑙𝑜𝑔𝐶𝐴 [∵ 𝑋 = −0.0591𝑙𝑜𝑔𝐶𝑅 ]

𝑁𝑜𝑤, 𝐶𝐴 = [𝐻 + ] (𝑪𝑨 𝒊𝒔 𝒄𝒐𝒏𝒄. 𝑶𝒇 𝒂𝒏𝒂𝒍𝒚𝒕𝒆 𝒔𝒐𝒍𝒏. 𝒊. 𝒆. , [𝑯+ ] 𝒐𝒏𝒍𝒚)

∴ 𝐸𝑏 = 𝑋 + 0.0591𝑙𝑜𝑔[𝐻+ ]

∴ 𝐸𝑏 = 𝑋 − 0.0591𝑝𝐻 (∵ 𝑝𝐻 = −𝑙𝑜𝑔 [𝐻 + ])
Now, from equation (1), Eb = 0, when CA = CR.
But even when CA = CR, a small potential is developed. The reason for this is;
i. Ag-AgCl electrode dipped inside the bulb in 0.1M. HCl develops some potential and behaves as
internal reference electrode. It is given by EAg-AgCl
ii. Due to the unevenness of glass membrane, there develops a potential and is called as asymmetry
potential i.e., Eassy

These two potentials add to Glass electrode potential (EG) and is given by,

𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔−𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑠𝑦
= 𝑿 − 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯 + 𝑬𝑨𝒈−𝑨𝒈𝑪𝒍 + 𝑬𝒂𝒔𝒔𝒚
𝑬𝑮 = 𝑬°𝑮 − 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯
𝑊ℎ𝑒𝑟𝑒, 𝐸𝐺° = 𝑋 + 𝐸𝐴𝑔−𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑠𝑦 is a constant factor which depends on glass electrode assembly.
𝐸𝐺° value is determined using the solution of known pH.

Application of Glass Electrode:

Determination of pH of a Solution:
In order to determine pH of a solution, the glass electrode is dipped into analyte solution whose pH is
to be measured. It is then coupled to calomel electrode through electronic potentiometer. The cell so
formed is representedas,

𝑃𝑡 − 𝐻𝑔 |𝐻𝑔2 𝐶𝑙2(𝑠) |𝐾𝐶𝑙𝑠𝑎𝑡 ‖ 𝐴𝑛𝑎𝑙𝑦𝑡𝑒 𝑠𝑜𝑙𝑛. | 𝐺𝑙𝑎𝑠𝑠 𝑚𝑒𝑚 | 𝐻𝐶𝑙 (0.1𝑀)| 𝐴𝑔 − 𝐴𝑔𝐶𝑙
The emf of the cell is measured using electronic potentiometer and is calculated using the equation.

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

= 𝐸𝐺 − 𝐸𝑆𝐶𝐸

𝑁𝑜𝑤, 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐺° − 0.0591𝑝𝐻 − 𝐸𝑆𝐶𝐸

𝑜𝑟, 0.0591𝑝𝐻 = 𝐸𝐺° − 𝐸𝑐𝑒𝑙𝑙 − 𝐸𝑆𝐶𝐸

𝐸𝐺° − 𝐸𝑐𝑒𝑙𝑙 − 𝐸𝑆𝐶𝐸

𝑜𝑟, 𝑝𝐻 =
0.0591

𝐸𝐺° is given for an electrode,𝐸𝑆𝐶𝐸 is known and 𝐸𝑐𝑒𝑙𝑙 is noted from potentiometer. Using these values pH of
a solution is calculated.

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 Electrolyte Concentration Cells:
A concentration cell is an electrochemical cell, which consists of two identical electrodes immersed in
same electrolytic solution but of different concentrations. The electrical energy in this cell arises from the
transfer of substance from a solution of higher concentration to the solution at lower concentration.
A concentration cell is as shown in figure below;

Potential of Concentration Cell:

Let us consider, a metallic electrode (M) is dipped in its own salt [Mn+], then potential (E) develops
at the electrode. The potential so developed very with concentration [C] of the electrolyte.
According Nernst equation,

0.0591
𝐸 = E° + log[𝐶] 𝑎𝑡 298 𝐾
𝑛
Now, in concentration cell, the electrode dipped in dilute solution (C 1) acts as anode; while other
electrode dipped in concentrated solution acts as cathode. It is because, metal is deposited from
concentrated solution (C2) in which osmotic pressure is high. Therefore, metal dissolves at the electrode
which is in contact dilute solution (C1). Hence electrons flow from dilute solution (C1) to concentrated solution
(C1).
Thus, a concentration cell may be represented as;

𝑀(𝑠) | 𝑀𝑛+ [𝐶1 𝑀]‖𝑀𝑛+ [𝐶2 𝑀]|𝑀(𝑠)

Now, EMF of the cell is calculated using the equation;

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

0.0591 0.0591
= {E° + log[𝐶2 ]} − {E° + log[𝐶1 ]}
𝑛 𝑛

0.0591 [𝐶2 ]
𝐸𝑐𝑒𝑙𝑙 = log 𝑎𝑡 298𝐾
𝑛 [𝐶1 ]

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Worked Examples

1) A concentration cell is constructed by immersing two iron electrodes in 0.01M and 0.1M FeSO4
solution. Represent the cell and calculate the EMF of the cell at 298K Solution

Solution:

i) The concentration cell is represented as;

Fe(s) | FeSO4(0.01M || FeSO4(0.1M) | Fe(s)

ii) EMF of the cell:

Given: C1 = 0.01M C2 = 0.1M n=2

We have,

0.0591 [𝐶2 ]
𝐸𝑐𝑒𝑙𝑙 = log 𝑎𝑡 298𝐾
𝑛 [𝐶1 ]

0.0591 [0.1]
𝐸𝑐𝑒𝑙𝑙 = log
2 [0.01]

0.0591
𝐸𝑐𝑒𝑙𝑙 = log 10
2

𝐸𝑐𝑒𝑙𝑙 = 𝟎. 𝟎𝟐𝟗𝟓𝟓𝑽

2) The EMF of the cell, Ag(s) | AgNO3(0.0093M) || AgNO3(X M) | Ag(s)is 0.086Vat 25oC. Find X.

Solution:
Given: C1= 0.0093M C2 = X Ecell= 0.086V n=1 X=?
We have,

0.0591 [𝐶2 ]
𝐸𝑐𝑒𝑙𝑙 = log 𝑎𝑡 298𝐾
𝑛 [𝐶1 ]

0.0591 [𝑋]
0.086 = log
1 [0.0093]

[𝑋]
[0.0093]
= 𝑨𝒏𝒕𝒊𝒍𝒐𝒈(𝟏. 𝟒𝟓𝟕𝟔) = 𝟐𝟖. 𝟔𝟖

⸫ X = 28.68 x 0.0093 = 0.2668M

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 3) Construct a cell using two identical copper electrodes and CuSO4 solutions of 0.02Mand 0.25M
concentrations. Calculate the EMF of the cell at 25oC.

Solution:

Given: C1 = 0.025M C2 = 0.25M n=2 Ecell = 0.086V

We have;
0.0591 [𝐶2 ]
𝐸𝑐𝑒𝑙𝑙 = log 𝑎𝑡 25°𝐶
𝑛 [𝐶1 ]

0.0591 [0.25]
𝐸𝑐𝑒𝑙𝑙 = log
2 [0.02]

0.0591
𝐸𝑐𝑒𝑙𝑙 = log 12.5
2

0.0591
𝐸𝑐𝑒𝑙𝑙 = 𝑋 1.097
2

𝐸𝑐𝑒𝑙𝑙 = 𝟎. 𝟎𝟑𝟐 𝑽

4) Construct the cell and calculate the EMF of the same when two aluminium electrodes dipped in
solutions of 0.55M and 0.03M AlCl3 at 25oC

Solution: The cell is represented by

Al/AlCl3(0.03M)//AlCl3(0.55M)/Al

Given: C1 = 0.05M C2 = 0.15M n=3 Ecell = ?

We have;
0.0591 [𝐶2 ]
𝐸𝑐𝑒𝑙𝑙 = log 𝑎𝑡 25°𝐶
𝑛 [𝐶1 ]

0.0591 [0.55]
𝐸𝑐𝑒𝑙𝑙 = log
3 [0.03]

0.0591
𝐸𝑐𝑒𝑙𝑙 = log 18.33
3

0.0591
𝐸𝑐𝑒𝑙𝑙 = 𝑋 1.26
3

𝐸𝑐𝑒𝑙𝑙 = 𝟎. 𝟎𝟐𝟒𝟖

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Battery Systems
Introduction:
Energy requirements of human being are growing exponentially. Making portable energy devices is even
more demanding. Most of medical equipment’s like, blood pressure, glucometer etc., are very well supported
with batteries. Therefore, with time, these portable devices are finding important place in daily life.
As we know, a cell has two electrodes that produce electrical energy at the expense of free energy of
redox reaction. The EMF produced by the cell depends on potential difference between two electrodes.
However, the EMF produced by simple cell may not be sufficient for some applications. Therefore, to obtain
higher potential for certain applications, more number of cells are combined in series. Such a combined
assembly is called battery.
Thus “A device that constitutes two or more number of cells connected in series or paralleled or both to
obtain higher potential is called battery”.
OR
The arrangement or assembly of two or more cells normally coupled in series to produce higher potential is
called battery.
Classification of Batteries:
Batteries are classified into three types, they are:
i) Primary batteries (non rechargeable)
ii) Secondary batteries(chargeable)
iii) Reserve batteries.

i) Primary Batteries:
The non rechargeable batteries which produce electrical energy at the expense of free energy of
active materials and produce energy only as long as active materials are present are called primary
batteries. These are to be discarded after the use.
Eg : Zn - MnO2, battery.

ii) Secondary Batteries:

The rechargeable batteries which produce electrical energy at the expense of free energy of active
materials and active materials are capable of restoring at respective electrodes on recharge and prepare
battery for discharge once again are called secondary batteries.
Eg :Lead - Acid battery, Ni - Cd battery etc.

iii) Reserve Batteries:

The high current batteries in which active materials are isolated from electrolyte due to their high
reactivity and are brought into contact whenever high potential is required for application are called
reserve batteries.
Eg :Li - V2O5 battery, Zn - Ag2O battery.

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Lithium Ion Battery:
The batteries in which lithium ions are used instead of lithium metal and movement
lithium ion through electrolyte takes place from one electrode to another electrode. Such
batteries are called lithium-ion batteries. In general, the battery consists of soluble lithium
anode as ion into carbon. The cathode material is made up of lithium liberating compounds.

1. Lithium cobalt oxide (Li – CoO2) battery.

Construction:
Voltmeter

Lim+
recharge
Li- Ion electrolyte
+
Lim
Discharge

Anode LiC6 Cathode LiCoO2

1) Anode is made up of carbon electrode fully impregnated with lithium i.e., LiC6
2) Cathode is made up of layered lithium cobalt oxide compound.
3) A porous polymer film is used as separator.
4) A lithium salt like LiClO4in an organic solvent (ethylene carbonate) is used as electrolyte. This
electrolyte effectively transports Li+ ion to cathode during discharge of battery.

Working :
1) During discharge, the anode produces positively charged lithium ions and negatively
charged electrons along with uncharged material that remains at the anode. Li ions so
produced from anode and migrate through electrolyte to cathode.
2) During charging, lithium from cathodic material is ionized and move towards negative
electrode.
3) At the same time the electrons travel through external circuit. The reactions are;

At Anode: LiC6 C6+ Li+ + e

At Cathode: CoO2 + Li+ + e LiCoO2

Cell reaction: LiC6 + CoO2 LiCoO2 + C6

_________
The EMF of the battery is 4.0V.

Applications: Used in cardiac pacemakers, laptops, cell phones and aerospace applications.

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Sodium Ion Battery:

Introduction
So far, lithium ion batteries have occupied the majority global rechargeable battery market owning to
the high energy density, high output voltage and low self-discharging. However, as lithium demand increasing,
the sustainability of lithium resources shows up as a concern and the price of lithium is rising fast. Hence,
searching a substitute for lithium has become a crucial job of exploring sustainable secondary batteries as well
as green energy utilization. Na and Li have similar physicochemical properties as Na is right under Li in the
periodic table. Na resources are of rich reserves (the fourth richest metal element in the earth's crust) and Na
is compatible with the negative aluminum current collectors. In addition, sodium ion batteries and lithium ion
batteries work quite in the same way. The voltage is generated between the two electrodes (cathode and
anode), metal ions (Na+) move forth and back between the two electrodes during charging and discharging, so
it is also called a "rocking-chair" battery.

Sodium is a low-cost and abundant chemical element, homogeneously distributed around the world.
Given this relative wealth of necessary resources and components, as well as the limited use of critical
materials and the low starting cost of their raw materials,

Construction:

1. Anode is made up of hard carbon intercalable with sodium ions along with aluminium foil as current collector.
2. Cathode is made up of sodium cobalt oxide compound with a thin aluminium foil as current collector.
3. A porous polymer film is used as separator.
4. Ether-based electrolyte (EBE) is used as an electrolyte. This electrolyte effectively transports Na+ ions from anode
to cathode and vice-versa during discharge and charging of battery respectively.

Working:

The electrode reactions in Na-ion battery utilizing hard-carbon (C6) anode and a layered transition metal oxide, NaCoO2,
cathode is;
1. During discharging, Na ions leave anode site by undergoing oxidation and migrate through electrolyte towards
cathode.
2. During charging, Na ions leave cathode site and migrate through electrolyte towards anode.
3. At same time electrons travel through external circuit.
4. The charge discharge reactions are;

Na1-xCoO2 + C6Nax → NaCoO2 + C6

Green Fuels

Photovoltaic Cells

A PN junction diode made of semiconductor materials which produces electrical energy on exposure
to solar radiation is called photovoltaic cell.

Principle: The principle involved is the ejection of electrons from metal surface by striking with
photons of solar radiations, which subsequently flows in an external circuit in the opposite direction
to the conventional current to produce electrical energy.

Construction: It consists of;

1. A front contact made up of metal grids at the top for electrical contact
2. Below the metal grid, a PN junction diode made of silicon material is placed.
3. At the bottom of the PN junction material, a layer of noble metal like silver is placed.
4. A connection between metal grids at top to the bottom noble metallic layer is done through
load using an insulated wire.
5. The diagram of PV cell is as shown below;

Working:

Light travels in packets of energy called photons. The generation of electric current happens inside
the depletion zone of the PN junction. The depletion region with the diode is the area around the PN
junction where the electrons from the N-type silicon, have diffused into the holes of the P-type
material. When a photon of light is absorbed by one of these atoms in the N-Type silicon it will
dislodge an electron, creating a free electron and a hole. The free electron and hole has sufficient
energy to jump out of the depletion zone. If a wire is connected from the cathode (N-type silicon) to
the anode (P-type silicon) electrons will flow through the wire. The electron is attracted to the
positive charge of the P-type material and travels through the external load (meter) creating a flow of
electric current. The hole created by the dislodged electron is attracted to the negative charge of N-
type material and migrates to the back electrical contact. As the electron enters the P-type silicon
from the back electrical contact it combines with the hole restoring the electrical neutrality.
 Advantages of Solar Cell / PV Cells:

 The PV cells are eco friendly energy conversion devices and materials used in PV cells are
simple and long serving. Hence cause less disposal problems.
 The PV does not require recharging and produce electrical energy as long as SUN light is
available.
 The PV cells generate electrical energy at ambient temperature.
 The material used in PV cell does not undergo corrosion and serve for long duration.
 There are no moving parts in PV cell; hence there is no problem of wear and tear.
 The raw material silicon used PV cell is available abundantly.

Disadvantages of PV Cells:

 They require energy storage device i.e., battery which require maintenance and
replenishment from time to time.
 The installation cost is high.
 PV cell generate only DC current.

Applications of PV Cells:

PV cell are receiving considerable attention as one of the promising energy alternatives. The
importances of PV cells are viewed as;
 PV cells directly convert sunlight into electricity without the aid of external power.
 The process and the material of PV cell do not pollute the nature. They are not
dependent on fossil fuel and nuclear fuel.
 They can be conveniently used for wide variety of applications like remote area lighting and
other power required domestic activities, Industrial power needs and agriculture
requirements such as irrigation, harvesting, spraying etc.
 They can be conveniently used for all domestic electrical appliances. They are used
effectively for milling, sawing etc.
 PV cells are used to improve remote area communication systems. These are effectively
used in transportation systems.
Quantum dot sensitized solar cells (QDSSC)
Construction
QDSSC consists of three essential components;
 Photo-anode is made of TiO2 material
 CdSe as quantum dot material
 Electrolyte containing redox couple, and
 Counter electrode.

Working of QDSSC

When the light is incident on the solar cell through a transparent conducting oxide, photons are
absorbed to generate excitons. As the band positions between the Conduction Band (CB) of the
Photoelectrode and the CB of QD is greater than the binding energy of the exciton, then it gets
separated at the Metal Oxide (MO)/QD interface into electrons and holes. The electron moves into
the CB of MO to reach the transparent Conducting Oxide (TCO) surface before it reaches the band. In
the other way, the electrolyte reduces the reductant species (Re), i.e., hole created in the QD. The Re
turns into Oxidant species (Ox) after losing electron to the hole, which diffuses toward the Counter
Electrode (CE) to receive an electron coming from the external circuit. With the hole reduction, the
QD is ready to absorb another photon for the creation of an exciton.

Advantages of Quantum dot solar cells

 They have a favourable power to weight ratio with high efficiency.

 Their power consumption is low.

 There is an increase of electrical performance at low production costs.
 Their use is versatile and can be used in windows, not just rooftops.
Disadvantages of QDSC.

 Cadmium selenide-based quantum dot solar cells are highly toxic in nature and require a
very stable polymer shell.
 Cadmium and selenium ions which are used in the core of quantum dots are known to be
cytotoxic.

Quantum dots solar cell applications

 Biological labeling,
 Imaging, and detection and as efficient fluorescence resonance energy transfer donors.
 It is used as light-emitting Diodes
 It is used as Photoconductors and photodectors
 It is used as Photovoltaics
 It is used in Biomedicine and environment.
 It is used in catalysis and others
 Green hydrogen

Introduction
Hydrogen is the most abundant chemical element in the world. It is light, storable, energy-
dense, and in itself does not generate direct polluting emissions, or greenhouse gases. But not all
hydrogen is sustainable.
“If hydrogen is so marvelous, why it is already in use?”
Because more research and development still needs to be invested and governmental policies
has to be introduced to promote hydrogen, in order to overcome the barriers to its use. Also, not all
hydrogen can help us achieve carbon neutrality.

Types of Hydrogen
We currently have several different technologies that permit us to obtain hydrogen. But not all are
sustainable. A color code has been established to differentiate between the four types, based on the
impact and emissions each generates:
 Grey hydrogen: Produced with fossil fuels and emits a lot of CO2.

 Blue hydrogen: Produced with fossil fuels through carbon capture and storage technologies (less
polluting than grey). Around three quarters of the hydrogen produced today comes from natural gas.
Blue hydrogen could be an initial solution. But blue hydrogen does not eliminate carbon emissions,
only reduces them.

 Turquoise hydrogen: produced by pyrolysis from natural gas, but still a fossil fuel and, as such, is not
emission-free.

 Green hydrogen: A clean fuel that permits the storage and use of energy from renewable sources.
The best known option for producing green hydrogen is electrolysis of water from renewable
electricity. It consists of the decomposition of water (H2O) into oxygen (O2) and hydrogen (H2) gases
by virtue of a direct electric current traveling across electrodes in the water.

Advantages of green hydrogen

 Clean energy: The only waste it emits is water

 100% renewable: It is generated using natural resources that don’t run out, such as wind power and
solar energy.

 Storable: It can be compressed and stored in ad hoc tanks for long periods.

 Transportable: it is a very light element and thus tanks of compressed hydrogen can be handled
more easily than, say, lithium batteries.
 Production of green hydrogen by Alkaline water Electrolysis Cell (AEC)
The hydrogen produced through the decomposition of water and is used as renewable energy
source then it is called as green hydrogen.
Electrolysis transforms electrical energy into chemical energy by storing electrons in the form
of stable chemical bonds. The new formed chemical energy can be utilized as a fuel or converted
back to electricity when required.
Construction
The major alkaline water electrolysis cell components are;
1. Anode and Cathode are made up of Nickel (Ni) coated perforated stainless steel electrodes
2. Asbestos/ZrO2-based diaphragms are used as a separator between anode and cathode
3. Current collectors; gas diffusion layer (GDL) and porous transport layer (PTL) are placed
adjacent to the cathode and anode respectively for movement of ions. These are followed by
separator plates (bipolar plates), on both sides.
4. A concentrated alkaline solution (5M KOH/NaOH) serves as electrolyte.
5. The schematic diagram is as shown below;

Working
Alkaline water electrolysis is an electrochemical water splitting techniques in the presence of
electricity. The electrochemical water splitting consists of two individual half-cell reactions such
as hydrogen evolution reaction at the cathode and oxygen evolution reaction at the anode.
During the alkaline electrolysis process, initially at the cathode side two moles of alkaline
solution are reduced to produce one mole of hydrogen (H2) and two moles of hydroxyl ions (OH−), the
produced H2 can be eliminated from the cathodic surface and the remaining hydroxyl ions (OH −) are
transferred under the influence of electric circuit between anode and cathode through the porous
separator to the anode side. At the anode, the hydroxyl ions (OH−) are discharged to produce
the 1/2 molecule of oxygen (O2) and one molecule of water (H2O) with the release of 2 electrons.
The reactions at the electrodes are;
Advantages
• Well established Technology
• Commercialized for industrial applications
• Noble metal-free electro-catalysts
• Relatively low cost

Disadvantages
• Limited current densities
• Crossover of the gasses
• High concentrated (5M KOH) liquid electrolyte