Module 1
Module 1
(c) 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.
Classification of batteries
The batteries are classified as:
Primary battery or primary cells: A battery which cannot be recharged as the cell reactions
are irreversible and discarded when the battery has delivered all its electrical energy.
E.g.: dry cell or Zn-MnO2 Cell, Li-MnO2 cell.
Secondary battery: A battery which can be recharged, cell reactions are reversible and a
battery which after discharging, can be recharged.
Reserve Batteries: In reserve batteries, one of the components is stored separately and is
incorporated into the battery when required. For instance, in batteries which can be stored in
an inactive state and made ready for use by activating them prior to the applications (usage)
are called as reserved batteries.
E.g.: Magnesium batteries activated by water
E.g.: Zinc –silver oxide reserve batteries.
The key components of the batteries such as electrolyte etc., is separated from the battery. And
the battery is stored for a longer time. The electrolyte if filled before its usage. The
advantages of the reserved batteries are,
Batteries can be stored for a longer period.
To prevent corrosion at contact points during storage.
Self-discharging reactions during storage can be eliminated or avoided.
They can be used whenever they are required.
Advantages
i) High energy density.
ii) Low cost and compact
iii) Does not produce harmful products.
LiPF6
A lithium ion battery is rechargeable battery type in which lithium ion move from negative
electrode to a positive electrode during the discharge and vice-versa when charging.
Construction: Lithium ion cell has four-layer structure, cathode (+ve) is made up of
lithiated transition metal oxide (LiCoO2) covered with thin aluminum foil. Similarly, anode
(-ve) is made up of graphite with copper foil. Lithium hexafluorophosphate (LiPF6) is a
lithium salt combined with organic solvent like dimethyl carbonate used as suitable
electrolyte and thin porous polymer used as separator. For instance, electrolyte provides
conductive medium for lithium ions to move between the electrodes.
Working: Anode and cathode electrodes allows lithium ions to move in and out of their
interiors. During charging lithium in cathode electrode material get ionized and move
towards cathode to anode. During discharge Li ions are dissociated from the anode and
migrate across the electrolyte and inserted into the crystal structure of the cathode. During
this process the electrons travel through the external circuit and accepted by the host to
balance the process. The whole process is reversible.
Electrode reactions
The sodium-ion battery (SIB) is a type of rechargeable battery that uses sodium ions (Na+) as
its charge carriers.
Construction
1) Anode is made up of carbon based electrode (porous carbon) with current collector.
2) Cathode is made up of sodium metal oxide (NaMnO2) compound with current collector.
Working
The Na ion is inserted and exerted into the lattice structure of anode and cathode during
charging and discharging. During charging, Na in cathode material is ionized and move from
cathode to anode and inserted into the anode. During discharge Na ions are dissociated from the
anode and migrate across the electrolyte and are inserted into the crystal structure of the host
compound of cathode.
1. Laptops
2. Cell phones
3. Renewable energy storage for home and businesses.
4. Backup power for data and telecom companies.
5. Electric vehicles including e-bikes and e-cars.
1.2 Quantum Dot Sensitized Solar Cells (QDSSC’s)
Construction
The typical QDSSC has four major parts such as photoanode, sensitizer (Quantum dots),
electrolyte and counter electrode.
Photoanode: It consists of semiconducting metal oxide deposited on a transparent conducting
oxide substrate (fluorine-doped tin oxide (FTO) glass). Transparent conducting oxide substrate in
QDSSC supports the semiconductor layer and works as a current collector.
Sensitizer (Quantum Dots): To maximize the harvesting efficiency of the incident light, it
should possess a high absorption coefficient and appropriate band-gap energy. Example: CdS,
CdSe etc.
Electrolyte: It is a medium which transfers charges between counter electrodes and photoanodes
for the regeneration of oxidized QDs. A polysulfide redox couple aqueous solution electrolyte
is generally used in QDSSCs
Counter Electrode: It transfers electrons from the external circuit into electrolyte and catalyzes
the reduction reaction of the oxidized electrolytes at the electrolyte/ counter electrode interface.
Counter electrode used in QDSSCs is Pt (because of its good electrocatalytic ability)
1. Upon light irradiation, the sensitizer is photo excited. The excited electrons of quantum dots
are injected into the conduction band of the TiO2.
2. The electrons penetrate through the nanocrystalline TiO2 film to the back contact of the
conducting substrate, and flow through an external circuit to the counter electrode s.
3. At the counter electrodes, the oxidized component of redox couple in the electrolyte is
reduced.
4. The oxidized form of the sensitizer (quantum dots) is finally regenerated by the reduced
component of redox couple in the electrolyte.
5. Oxidized quantum dots get recharged by the redox electrolyte and the positive charge also
brought by diffusion to the platinum electrode.
QD + h ν → QD*
QD+ + Re → QD + Ox
Ox + e- → Re
Properties of QDs
1. Quantum dots has narrow band gap.
Application of QDs
1) Biological labeling,
2) Imaging, and detection and as efficient fluorescence resonance energy transfer donors.
3) It is used as light-emitting diodes
4) It is used as photo conductors and photo detectors.
5) It is used as photovoltaic.
6) It is used in bio-medicine and environment.
7) It is used in catalysis and others.
Advantages
1) They have a favorable power to weight ratio with high efficiency.
2) Their power consumption is low.
3) There is an increase of electrical performance at low production costs.
4) Their use is versatile and can be used in windows, not just rooftops.
Disadvantages
1. Cadmium selenide-based quantum dot solar cells are highly toxic in nature and require a very
stable polymer shell.
2. Cadmium and selenium ions which are used in the core of quantum dots are known to be
cytotoxic.
1.3 SENSORS
Definitions
Sensors: These are devices that we use to convert any physical characteristics or events into
electric signals.
Transducers: A transducer is an electronic device that converts energy from one form to another.
Principle: An electrochemical sensor is one in which a specific sensing element reacts with a
target analyte to produce a sensing signal. It converts this signal into a recognizable
electrical signal that is proportional to the concentration of the target analyte, by means of
a specific transducer, thus achieving a qualitative or quantitative analysis.
The electrochemical sensor is mainly composed of the following two parts: a solidified sensing
element (recognition system) and a transducer (conversion system).
Working
1. Diffusion of the analyte to the electrode/electrolyte interface.
2. Adsorption onto the electrode surface.
3. Electrochemical reaction with electron transfer.
4. Desorption of the products.
5. Diffusion of the products away from the reaction zone to the bulk of electrolyte.
Characteristics
a) Electrochemical sensing always requires a closed circuit.
b) Current must flow to make a measurement in most electrochemical sensors; an electrode surface
is used as the site of the reaction.
c) The electrode will either oxidize or reduce the analyte of interest.
d) The current that is produced from the reaction is monitored and used to calculate important data
such as concentrations from the sample.
Applications
1) Electrochemical sensors used for the detection of blood glucose.
2) Electrochemical sensors are used for pH measurements.
3) Used to detect pesticides.
4) Used in the detection of hydrocarbon and other pollutants.
5) These are used to measure the concentration of biological important molecules.
1.3.2 In electrochemical sensors the electrode is used as transducer element. They are divided into
several types:
a) Potentiometric sensors (measure voltage)
b) Amperometric sensors (measure current)
c) Conductometric sensors (measure conductivity), etc..(explained in 1.4)
1.3.3 Thermometric sensors
These are the based on the measurement of thermal changes during the interaction
between analyte and receptor. Thermal changes are converted to measurable change in the
temperature or potential.
Contact type temperature sensors: There are a few temperature meters that measure the degree
of hotness or coolness in an object by being in direct contact with it. They can be used to detect
solids, liquids or gases over a wide range of temperatures. E.g: liquid-in-glass thermometers,
thermocouples, RTDs, and thermistors.
Non-contact type temperature sensors: These types of temperature meters are not in direct
contact of the object rather, they measure the degree of hotness or coolness through the radiation
emitted by the heat source. E.g.: infrared thermometer or area inspection (infrared camera).
Applications
1. Computers – within computers there are temperature sensors to ensure the system does not
overheat
2. Home appliances – kettles, toasters, washing machines, dishwashers and coffee machines will
all contain temperature sensors.
3. Temperature sensors are used to measure water temperatures in reservoirs and boreholes. They
can also be used to interpret temperature-related stress and changes in volume in dams.
4. Temperature sensors are vastly used in Medical equipment such as MRI imaging equipment
and portable ultrasound scanners.
Working
The conductivity is result of dissociation an electrolyte, into ions. The migration of the
ions is induced by an electrical field. When a potential difference is applied to the electrode,
there is an electrical field within the electrolyte, so the positively charged ions move towards
cathode and negatively charged ions are move towards anode (as shown in figure).
Thus, the current in the electrolyte is caused by the ion movement towards the electrodes
where the ions are neutralized and isolated as neutral atoms (or molecules). This chemical
change is recognized by working electrode and transducers converts this chemical change into
electrical signal.
Applications
1) The conductometric measuring method can be used to determine analyte concentration and
enzyme activity and selectivity.
2) To detect polycyclic aromatic hydrocarbons (PAHs) in water.
3) Used to determine urea.
4) Determination of organophosphorus pesticides.
Principle: “When a monochromatic light of intensity (Io) is incident through the colored
solution, a part of light is absorbed (Ia), a part of it reflected (Ir) and remaining part is
transmitted (It)”.
3. A sample cell
4. A photocell detector
Working principle
Applications
1) It is most widely used in clinical laboratories for the analysis of bio-molecules such as
glucose, creatinine, urea, etc.
2) It is used in soil testing laboratories for the analysis of pesticides, soil nutrients and plant
nutrients.
3) It is also used in water and food testing laboratories to check the concentration of critical
chemical parameters periodically.
4) Colorimetry is used in the estimation of copper in sample solutions.
1. Filter: The filter is used to prevent unwanted contaminants, mainly particulate matter from
entering in to sensor.
2. Membrane: A gas-permeable membrane is used to regulate the gas flow into the sensor. Its
selectivity allows only the analyte gas to pass and also acts as a barrier to prevent leakage of the
electrolyte from the interior of the sensor. Hydrophobic porous membranes are used with
aqueous electrolytes.
3. Electrodes: Two or three electrode system is used based on the requirement. Working or
sensing electrode, counter electrode, and reference electrodes are used.
4. Electrolyte: Electrolyte used should be a good ionic conductor, and chemically and physically
Working principle
The following steps are involved in the working of a typical electrochemical gas sensor:
1. The diffusion of gas analyte through filter, membrane and then finally through electrolyte on
to the surface of sensing Electrode.
5. Diffusion of the products away from the reaction zone to the bulk of electrolyte or gas phase.
Recently, SOx sensors utilizing a solid electrolyte such as K2SO4 , Na2SO4 , LiSO4 have
been widely studied, because this type of sensor has its own advantages; continuous quantitative
measurement, high selectivity and sensitivity, easy operation and fast response; simple
construction and low price.
Sensing mechanism
The sensor was composed of the following electrochemical cell:
Applications
1. It is sued in thermal power plant.
The first cell electrochemically pumps oxygen out of the sample so it does not interfere
with the NOx adsorber and selective catalytic reduction (SCR) after treatment.
The oxygen in the first cell is reduced and the resulting Oxide ions are pumped through
the zirconia electrolyte by applying a bias of approximately -200mV to -400mV. The pumping
current is proportional to the oxygen concentration.
The remaining gases diffuse into the second cell where a reducing catalyst causes NOx to
decompose into Nitrogen and oxygen gas. As with the first cell, a bias of -400mV applied to the
electrode dissociated the resulting oxygen which is them pumped out of the cell; the pumping
current of the second cell is proportional to the amount of oxygen from the NOx decomposition.
The direct electro oxidation of NO in solutions follows a 3-step reaction
All hydrocarbons and CO in the exhaust gas should be oxidised before the NOx sensing
cell to avoid interference. Also, any nitrogen dioxide in the sample should be converted to NO
prior to NOx sensing to ensure the sensor output is proportional to the amount of NOx.
Electrochemical methods on the other hand, can be considered one of the most suitable
methods for in situ analysis of heavy metal, mainly due to the small size of equipment, easy
installation, low cost, simple sample preparation and the ability to perform multi elemental
detection. Heavy metals include lead (Pb), cadmium (Cd), zinc (Zn), mercury (Hg), arsenic (As),
silver (Ag) chromium (Cr), copper (Cu), iron (Fe), and the platinum group elements.
Electrochemical sensors (ECS) could be easily put into a compact system that is affordable,
easy to operate, and possible for the required outdoor applications. These involves three-
electrode schemes, a counter electrode (CE), the working electrode (WE), and a reference
electrode (RE), that is used to assessment of heavy metal contamination of the available water
sources. As shown in above figure.
The selection of an appropriate WE for a given analyte is therefore vital. Typically for
electrochemical sensors one would choose a WE that has: an efficient electron transporter, high
surface-to-volume-ratio, wide potential window, low background current, chemical stability and
(electrochemically) interference-free.
1. Zeolite imidazole framework and reduced graphene oxide (ZIF-67/rGO) has been
investigated as a sensory electrode material for the simple and selective electrochemical
detection of Pb2+ and Cd2+ ions simultaneously.
3. Electrochemical detection of Cr(VI) with carbon nanotubes decorated with gold nanoparticles.
1.4.6 PESTICIDE
Detection of Glyphosate
Working Electrode: A gold electrode of 4 mm diameter coated with 200nm thickness gold
nanoparticles
Counter electrode: A gold electrode of 4 mm diameter coated with 20nm thickness gold
nanoparticles
Electrolytes are added to increase the conductivity of the solution and minimizes the resistance
between the working and counter electrode.
Working
The electrochemical detection is based on the oxidation of Glyphosate on gold working
electrode. A potential of 0.78V is applied on working electrode, there is an interaction between
analyte and electrode surface. Glyphosate oxidizes on the working electrode brings a change in
current in the electrolyte medium. The change in the current is a measure of concentration of
Glyphosate.
A light source.
A transmission medium (either a fiber optic or a window through which the light travels
from the source to the fluorescent material).
The luminophore (fluorescent dye suspended in a silicone gel matrix) that comes in
contact with the aqueous solution.
A photo detector to detect the light emitted from the fluorescent dye.
2. In this state, interactions with other molecules (e.g. oxygen) can take place since the
luminophore remains in the excited state for a defined time (fluorescence lifetime).
3. When the electrons return from the excited state back to the ground state, they emit light,
thus luminescence or fluorescence.
4. Luminophore materials in the presence of oxygen gas (O2) in the excited state has two
effects on the material’s fluorescence properties.
5. When the oxygen molecule collides with the luminophore during the excited state, the
energy is transferred from the luminophore to the oxygen and:
Less fouling from contaminants in the liquid (and therefore less signal drift).
Working principle
Disposal strip is a special type paper over which receptor and electrodes are coated. They
are coated in the form of thin film strip using screen printing technology. In these systems, all the
electrodes namely reference, working and counter electrodes and receptor are printed on single
platform as shown in figure. These electrodes are called as screen printed electrodes. These strips
can be inserted into the portable systems and used for on site sample analysis.
Characteristics
1. They are portable with the capability of on-the-spot analysis.
(i) The biological recognition elements that differentiate the target molecules in the presence of
various chemicals.
(ii) A transducer that converts the bio recognition event into a measurable signal.
(iii) A signal processing system that converts the signal into a readable form
Glucose biosensors usually based on the two enzyme families, GOx and GDH. These
enzymes differ in redox potentials, cofactors, turnover rate and selectivity for glucose.
GOx is the standard enzyme for biosensors; it has a relatively higher selectivity for
glucose. GOx is easy to obtain, cheap, and can withstand greater extremes of pH, ionic strength,
and temperature than many other enzymes, thus allowing less stringent conditions during the
manufacturing process and relatively relaxed storage norms for use by lay biosensor user
The basic concept of the glucose biosensor is based on the fact that the immobilized GOx
catalyzes the oxidation of β-D-glucose by molecular oxygen producing gluconic acid and
hydrogen peroxide.