Module-2

Sustainable Chemistry for Energy Devices

Concentration cells
What are concentration cells? Derive an EMF equation for a electrolyte concentration cell.

“A concentration cell is an electrochemical cell in which electrode materials and electrolytes of two half
cells are composed of same material but the concentration of two solutions are different”

Ex- Cu/Cu2+(M1)|| Cu2+(M2)/Cu

A concentration cell consists of two same metal electrode dipped into their own ionic solutions of two
different concentration. Thus in a concentration cell, the electrode with lower electrolyte concentration acts as
anode and the one with higher electrolyte concentration acts as cathode. The concentration of ions at anode
increases and at cathode decreases, when the cell is in operation.

Consider two copper rods are dipped in to their own ionic solutions of C1 and C2 and it is represent

By electrochemical conventions, if C2>C1 then ,we have the following reactions.

At anode: Cu Cu2+ (C1) + 2e-

At cathode Cu2+ (C2) + 2e- Cu

The net cell reaction is Zero

The emf of the concentration will be
The emf of the cell is +ve only if C2>C1
The following characteristics of concentration cell can be noted:
1. When C2=C1, the concentration cell does not generate electrical energy.

2. When C2>C1,the Ecellis+ ve.

3. When C2<C1,Ecell is–ve.

4. Higher the ratio of C2/C1, greater is the cell potential.

Energy Storage Devices: Energy storage devices are systems or technologies that capture energy at
one time and release it for use at another.

BATTERY: A battery is a device that consist of two or more galvanic cell connected in series or parallel or
both, which converts chemical energy into electrical energy through redox reaction.

Example: Lead acid battery, Nickel-Cadmium battery, Li ion battery, Li-MnO2 battery, etc.

Uses: Batteries are used in calculators, watches and pacemakers for heart hearing aids, computers, car
engines, emergency lightning in hospitals, military and space applications.

Basic Components of Battery:

The battery consists of four major components.

1. Anode (Negative electrode): It releases electrons into the external circuit by undergoing
Oxidation.
M M+n + e-
2. Cathode (Positive electrode): It accepts electrons coming from anode through external circuit and
reduction of active species takes place.

M+n + e- M

3. Electrolyte: It provides the medium for transfer of ions inside the cell between the anode and cathode. A
solution of an acid, alkali or salt having high ionic conductivity is commonly used as an electrolyte.

4. Separator: It is used to separate anode and cathode compartments in a battery to prevent internal short
circuiting. It allows the ions from anode and cathode. Ex: Cellulose, naflon membranes.

CLASSIFICATION OF BATTERIES:

The batteries are classified as

1. Primary battery or primary cells: A battery which cannot be recharged, cell reactions are irreversible and
discarded when the battery has delivered all its electrical energy. Egs; dry cell or Zn-MnO2 Cell, Li-Mno2 cell

2. Secondary battery: A battery which can be recharged, cell reactions are reversible and A battery which
after discharging, can be recharged. Egs. Lead storage cell and nickel cadmium cell.

3. Reserve Batteries: In reserve batteries, one of the components is stored separately and is incorporated into
the battery when required. Egs: Mg-AgCl and Mg-CuCl battery.

Li-ion battery: (Secondary battery)

Construction of Li-ion battery

1. The Anode: Lithium atoms intercalated in layered graphite / Carbon metal

2. The Cathode: Lithium atoms intercalated in layered structure of MO2 (Metal Oxide)

3. The Electrolyte: The electrolyte is lithium salt such as LiPF6 dissolved in organic solvents (Ethylene
carbonate – dimethyl carbonate)

4. The separator: Made of Poly propylene membrane.

Cell representation: Li│Li+, C/ LiPF6 in organic solvents│ Li-MO2

Electrode reactions are:

During discharging of battery, lithium atoms present in graphite layer are oxidized, liberating electrons and
lithium ions. Electrons flows through external circuit to cathode and lithium ions flow through the organic
electrolyte towards cathode.

At anode: Li-C6 → Li+ + e- + 6C

At cathode, lithium ions are reduced to lithium atoms and are inserted in to the layered structure of metal
oxide.

At cathode: MO2 + Li+ + e- → Li-MO2

During charging of battery, lithium atoms present in layered structure of metal oxide are oxidized, liberating
electrons and lithium ions. Electrons flows through external circuit and lithium ions flow through the organic
electrolyte towards graphite carbon electrode.

At anode: Li-MO2 → MO2 + Li+ + e-

At graphite electrode, lithium ions are reduced to lithium atoms and are inserted in to the layered structure of
graphite.

At cathode: Li+ + e- + 6C → Li-C6

Applications: Used in cell phone, Laptops, Electrical vehicles, Aerospace applications, Portable LCD TV etc.

Na-ion battery:
 Construction: -
 Anode: Sodium Hard Carbon Material (NaxC6)
 Cathode: Sodium Layered Transition Metal Oxides (Na1-xMO2)
 Electrolyte: Sodium Salts (NaPF6) Dissolved in Polar Organic Solvents
 Separator: Porous poly propylene Separator.

Working:

During charging the sodium ion is extracted from the cathode material and inserted in to the anode and
the electrons are travel through the external circuit.

During discharging the sodium ions are extracted from the anode and reinserted in the cathode with
the electron through the external circuit.

Applications:

 Electric vehicles
 Energy storage systems for solar, wind
 Power backup in electric utilities
 Portable LCD TV, CD player.
Flow Battery (Vanadium redox flow battery):

Construction:
 It consists of two chambers ie, a Positive (Cathode)
chamber and a Negative (Anode) Chamber, both
chambers consists of electrolyte and electrode.
 The electrolyte in the negative chamber contains V3+
and V2+ ions.
 The electrolyte in the positive chamber contains VO2+
and VO2+ ions.
 The two chambers are separated by an Ion-exchange
membrane.

Working:

 At anode V2+ loses an electron become V3+.

 Hydrogen ions are exchanged between cells to maintain charge neutrality.
 The liberated H+ ions diffuse to cathode through ion-exchange membrane.
 At cathode VO2+ gains the liberated electrons and reduced to VO2+ with release of energy.
-
Anode Reaction : V2+ V3+ +e
+
Cathode Reaction : VO2 + 2H+ + e- VO2+ +HO 2

+ D
Net Reaction : V2+ + VO2 + 2H+
R
VO2+ +V +HO 3+
2

Applications:-

 Utility scale wind and solar systems

 Uninterruptible power supply (UPS)
 Micro grids power applications
 Renewable energy generation integration

Super capacitor:
In chemistry, a super capacitor is an electrochemical energy storage device that stores energy by separating
ions at the interface between an electrode and an electrolyte.
Construction and working of ultra-small asymmetric super capacitor:

1. Electrodes: The two electrodes are the core components and are made from different materials.
Negative Electrode: material with high surface area, such as activated carbon.
Positive Electrode: a pseudocapacitive material, like a metal oxide (e.g., MnO2)or a conducting
polymer.
2. Electrolyte: solid state gel
[Link]: A porous separator
4. Current Collectors: Metal foils coated with the electrode materials are used to collectcurrent and provide
the connection to the external terminals.

Working Principle:

Charging: When voltage is applied, ions from the electrolyte migrate to the surface of the electrodes.
At the negative electrode, ions accumulate to form an electric double layer, which is an electrostatic storage
mechanism.
At the positive electrode, the ions participate in fast, reversible Faradaic (redox) reactions with the
pseudocapacitive material, further enhancing charge storage.

Discharging: When the device is connected to a load, the stored charges are released. The ions move back
from the electrodes into the electrolyte, and the process reverses.

Applications
 Wearable Electronics – smart watches, health tracker, smart glasses.
 Medical IoT devices- sensors, drug delivery system.
 Wireless sensor network- environmental, temperature, humidity.
 Smart home and consumer electronics- smart locks, security sensors, remote controls.
 RFID and NFC devices- Smart cards, contactless payments, logistic trackers.
 Energy harvesting system.

Questions
1. Define Concentration cells. Derive the EMF equation for the concentration cell.
2. Numerical problems on concentration cells.
3. Define battery. Explain the classification of battery with example.
4. Describe the construction, working and application of lithium ion battery.
5. Describe the construction, working and application of sodium ion battery.
6. Describe the construction, working and application of vanadium redox flow battery.
7. Describe the Construction and working and application of ultra-small asymmetric super
capacitor.
 FUEL CELLS
Definition: Fuel cell is a device used to convert chemical energy of fuel into electric current by
direct oxidation of fuel at anode and reduction of oxidant at cathode.
Here, the fuels are supplied from outside and do not form integral part of the cell. These do not store
energy. Electrical energy is obtained continuously as long as the fuels are supplied and the products are
removed simultaneously. In these aspects fuel cells differ from conventional electrochemical cells.
In a fuel cell, at anode, fuel is oxidized liberating electrons.
Fuel oxidized products + e-
The liberated electrons flow through the external circuit to cathode compartment.
At cathode, oxygen from air is reduced
O2 + 4H+ + 4e-  2H2O

Advantages of fuel cell:

 Power output is high.
 Electrical energy can be obtained continuously.
 Only a small number of moving parts
 Low noise level.
 Low maintenance, exchangeable parts.
 No need of charging.
 It converts fuel to electrical energy with minimum emision of pollutants
 Space required is less
Limitations of fuel cells:
 Fuel cells produce energy only as long as fuels and oxidants are supplied.
 Fuels in the form of gases and oxygen need to be stored in tanks under high pressure
 Cost is high because electro catalyst used in anode and cathode contain costly noble metal-
platinum

Differences between Batteries and fuel cells.

Batteries Fuel cells

Batteries store electricity, produced elsewhere and produce electricity on the spot
supplies it whenever required
All reactants are integral part of it Reactants are not part of it
Stores chemical energy Do not stores chemical energy
Products are not removed Products are continuously removed from the fuel
cell
Solid Oxide Fuel Cell (SOFC)

Construction of a Solid Oxide Fuel Cell

An SOFC consists of three main components:

1. Electrolyte

 A solid ceramic material, commonly yttria-stabilized zirconia (YSZ).

 It conducts oxide ions (O²⁻) from cathode to anode.
 Must be dense and impermeable to gases.

2. Anode (Fuel Electrode)

 Usually made of a porous mixture of nickel (Ni) and YSZ.

 Functions:
o Oxidizes the fuel (hydrogen or hydrocarbons).
o Conducts electrons to the external circuit.
 Needs to be porous to allow fuel gas flow.

3. Cathode (Air Electrode)

 Made of materials like lanthanum strontium manganite (LSM).

 Functions:
o Reduces oxygen molecules to oxide ions.
o Supplies O²⁻ ions to the electrolyte.

4. Interconnect (in stacks)

 Connects multiple cells in series.

 Conducts electrons between cells.

Working Principle of SOFC

SOFC operates at high temperatures (typically 600–1000°C), which allows internal reforming of fuels
and fast ion conduction.

Step-by-step process:

1. At the Cathode (Reduction Reaction)

Oxygen from air gains electrons:

O2+4e− → 2O2−

2. Ion Transport

 The oxide ions (O²⁻) move through the solid electrolyte to the anode.

3. At the Anode (Oxidation Reaction)

Hydrogen reacts with oxide ions:

2H2+2O2−→2H2O+4e−

 If hydrocarbons are used, they first reform into hydrogen and carbon monoxide.

4. Electricity Generation

 Electrons released at the anode flow through an external circuit to the cathode.
 This flow of electrons produces electric current.

Overall Reaction

For hydrogen fuel:

2H2+O2→2H2O+electric energy + heat

Construction And Working Of Photovoltaic Cell:

Construction: A typical silicon photovoltaic cell is composed of a thin wafer consisting of an ultra thin
layer of Phosphorous doped (n-type) silicon on top and Boron doped (p-type) silicon at the bottom. Hence
a p-n junction is formed between the two. A metallic grid above the diode forms one of the electrical
contact and allows the light to fall on the semiconductor. The anti reflexive layer (silicon nitride or TiO2)
present in between the metallic grid increases the transformation of sunlight to a semiconductor. The
other metallic layer at the back of the semiconductor forms another electrical contact.

Working: When the electromagnetic radiations fall on the p-n junction diode, electron pair holes are
generated. Electrons move and collect at the n-type end and the holes move towards the p-type end. On
connecting these two ends through conductor current flows between them to an external circuit.
Photo Catalytic Water Splitting: -

 Splitting of water to get hydrogen by using photo catalyst and solar energy is called
photocatalytic water splitting.
 When solar energy interacts the photo catalyst, produces charge carrier’s holes and electrons due
to absorption of energy.
 Thus produced hole will react with the neighbouring water molecule liberates the hydrogen ion
and oxygen.
 Later electrons reduce the H+ ions in to hydrogen gas

Advantages

 Eco-friendly process -Produces hydrogen without CO₂ or harmful emissions.

Uses renewable solar energy
 Works on sunlight, which is abundant and free. -Abundant raw materials
Uses water as the main resource, which is easily available.
 Low-cost catalyst -Titanium dioxide (TiO₂) is inexpensive, widely available, and non-toxic.
 Simple technology -Does not require complex equipment compared to electrolysis systems.
 No external electricity required -Directly converts solar energy into chemical energy.
 Mild operating conditions -Can operate at ambient pressure and temperature.
 Sustainable and clean fuel production -Produces hydrogen, which is a clean fuel with water as the
only byproduct.