Half Cell and Full Cell Overview
Half Cell and Full Cell Overview
Module 4
Energy Devices
Contents…. (6 hours)
Electrochemical and electrolytic cells
Electrode materials with examples
• Semi-conductors
Chemistry of Li ion secondary batteries
Supercapacitors
Fuel cells: H2-O2 and solid oxide fuel cell (SOFC)
Solar cells: Photovoltaic cells (silicon based), Photoelectrochemical
cells, Dye- sensitized cells.
Electrochemical Cell
▪ A device that is used to generate electricity from a spontaneous redox reac6on
or, conversely, that uses electricity to drive a non-spontaneous redox reac6on.
▪ An electrochemical cell typically consists of
• Two electronic conductors (also called electrodes >> anode and cathode)
• An ionic conductor (called an electrolyte)
• the electron conductor used to link the electrodes is o@en a metal wire,
such as copper wiring
▪ The electrochemical cells are broadly classified into two types:
• Galvanic or voltaic cell: Converts the energy released by a spontaneous
chemical reac6on to electrical energy. ΔG < 0
• Electroly6c cell: Consumes electrical energy from an external source to drive
a non-spontaneous chemical reac6on. ΔG > 0
Galvanic or voltaic cell
A galvanic cell uses the energy released during a spontaneous redox reaction
(ΔG < 0) to generate electricity.
This type of electrochemical cell is also called a voltaic cell after its inventor, the
Italian physicist Alessandro Volta.
Anode is written on the left-hand side >> oxidation occurs
Cathode is written on the right-hand side >> reduction occurs
Electrode on the left Electrode on the right
Metal (or solid phase)| Electrolyte (whole Electrolyte (whole formula or ion) | Metal
formula or ion) (or solid phase)
Zn|Zn(NO3)2 (1M) Cu(NO3)2 (1M)|Cu
Oxidation: M1 → M1n+ + n e- ReducFon: M2n+ + n e- → M2
Overall representation of Galvanic cell
M1 | M1n+ (C1) ║ M2n+ (C2) | M2
Daniel Cell
Invented by British chemist John Frederic
Daniell.
Zn Electrode dipped in ZnSO4 solution:
• Oxidation: Zn → Zn2+ + 2 e-
Cu Electrode dipped in CuSO4 solution:
• Reduction: Cu2+ + 2 e- → Cu
Each electrode is referred to as half cell which
are connected through a salt bridge
Salt bridge: KCl or NH4Cl in a gelatine form
Maintains the charge balance in the two half
cells
Minimizes or eliminates the liquid junction
potential
Cell emf = 1.1 V
EMF of Electrochemical Cell
The electromotive force (EMF): Maximum potential difference between two electrodes
of a galvanic or voltaic cell.
This quantity is related to the tendency for an element, a compound or an ion to acquire
(i.e. gain) or release (lose) electrons.
Cell reaction is feasible when Ecell has positive value.
Cell EMF in terms of Nernst Equation:
Gold plating:
• Anode reaction: Au (s) → Au+ (aq.) + e
• Cathode reaction: Au+ (aq.) + e → Au (s)
• Electrolyte: Aqueous K[Au(CN)2] solution
Silver plating: Silver plating:
• Anode reaction: Ag (s) → Ag+ (aq.) + e • Anode reaction: Ag (s) → Ag+ (aq.) + e
• Cathode reaction: Ag+ (aq.) + e → Ag (s) • Cathode reaction: Ag+ (aq.) + e → Ag (s)
• Electrolyte: Aqueous AgNO3 solution • Electrolyte: Aqueous K[Ag(CN)2] solution
Semiconductors
▪A semiconductor is a substance, usually a solid chemical element or compound
that can conduct electricity under some condiFons but not others, making it a good
medium for the control of electrical current.
▪It has almost filled valence band, empty conducFon band and very narrow energy gap
i.e., of the order of 1 eV. Energy gap of Silicon (Si) and Germanium (Ge) are 1.0 and 0.7 eV
respecFvely. Consequently Si and Ge are semiconductors.
Effect of temperature on conductivity of semiconductors:
▪At 0 K electrons freeze at valence band and hence all semiconductors are insulators.
▪Electrical conducFvity of a semiconductor material increases with increasing temperature
as resisFvity decreases.
▪At higher temperature transiFon from the valence band to the conducFon band gets
facilitated ⇒ higher conducFvity or lower resisFvity.
Temperatur
e
Types of semiconductors:
Intrinsic Semiconductor
Intrinsic semiconductor material is chemically very pure and possesses poor conductivity.
It has equal numbers of negative carriers (electrons) and positive carriers (holes)
Absence of Presence of
electrical field electrical field
Extrinsic Semiconductor.
▪Extrinsic semiconductor is an improved intrinsic semiconductor with a small amount
of impuri5es added by a process, known as doping, which alters the electrical
proper5es of the semiconductor and improves its conduc5vity.
▪Introducing impuri5es into the semiconductor materials (doping process) can
control their conduc5vity.
▪Doping process produces two groups of semiconductors:
• The nega5ve charge conductor (n-type)
• the posi5ve charge conductor (p-type)
▪Semiconductors are available as either elements or compounds.
▪Silicon and Germanium are the most common elemental semiconductors.
▪Compound Semiconductors include InSb, InAs, GaP, GaSb, GaAs, SiC, and GaN.
n-type Semiconductor
An n-type semiconductor is an intrinsic semiconductor doped with pentavalent
impurity, such as, P, As, Sb, etc.
If a small amount of phosphorus is added to a pure silicon crystal, one of the
valence electrons of phosphorus becomes free to move around (free electron)
as a surplus electron.
p-type Semiconductor
An p-type semiconductor is an intrinsic semiconductor doped with trivalent
impurity, such as, B, Al, In, etc.
If a small amount of boron is doped to a single crystal of silicon, valence
electrons will be insufficient at one position to bond silicon and boron, resulting
in holes that lack electrons.
Preparation of Semiconductors: ~ 99.9999% pure Si and Ge
▪Dis6lla6on:
• Separa5on of materials is based on the difference in boiling points.
• For Ge ⇒ GeCl4 and for Si ⇒ SiHCl3
• As is removed from GeCl4 (b.p. 83.1 0 C) with the help of HCl.
• Pure GeCl4 is obtained by frac5onal dis5lla5on in presence of chlorine.
• APer cooling, the pure GeCl4 is treated with extra pure water to get germanium
oxide.
• Subsequent reduc5on of GeCl4 with pure hydrogen affords highly pure elemental Ge.
• Similarly, dis5lled trichloro silane (SiHCl3) is employed to get silicon of high purity.
Zone refining
▪Difference between solubility of impuri5es in the molten and solid phases is used to
concentrate impuri5es at the end sec5on of the ingots.
▪The technique is based on the principle that when an impure metal in a molten state is
allowed to cool, only the metal crystallizes while the impuri5es remain present in
the molten state (mass) or melt.
▪Used for the purifica5on of germanium, silicon, gallium etc.
Czochralski crystal pulling technique
Ge or Si obtained by zone refining method is polycrystalline, i.e., there is no regularity in
their crystal structure and contain crystals of different sizes.
This method involves growing the crystal on a single crystal seed; thereby the atoms
reproduce identical atomic arrangement as that of the seed crystal.
Silicon crystal with a
diameter of 300 mm and a
weight exceeding 250 kg
Solar or Photovoltaic Cell
v A solar cell is an electrical device which converts solar energy directly to electric energy by photovoltaic effect.
v Photovoltaic effect: When sun light hits the solar cell, generation of charge carrier takes place and charge carrier are
separated across the junction gives rise electric current.
N-type P-type
- - - - - - +- + +++++
- - - - - - +- + +++++
- - - - - - +- + +++++
Dopant distribution inside a
pn junction
excess holes diffuse
to the n-type region
-+
p>>n - + n>>p
-+
excess electrons diffuse
to the p-type region
DEPLETION
REGION:
Operation of a solar cells
Nafion
Process
Hydrogen fuel is processed at the anode where electrons are separated from
protons on the surface of a platinum-based catalyst.
The protons pass through the membrane to the cathode side of the cell while
the electrons travel in an external circuit, generating the electrical output of the
cell.
On the cathode side, another Pt electrode combines the protons and electrons
with oxygen to produce water.
• At anode: H2 (g) → 2 H+ + 2 e-
• At cathode: O2 (g) + 4 H+ + 4 e- → 2 H2O
• Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (I)
ECell˚= 1.23 V
Advantages
• The energy conversion is very high (75-82%).
• Fuel cell minimizes expensive transmission lines and transmission losses.
• It has high reliability in electricity generation and the by-products are environmentally
acceptable.
• Maintenance cost is low for these fuels and they save fossil fuels.
• Noise and thermal pollution are very low.
Disadvantages:
• The major disadvantage of the fuel cell is the high cost and the problems of durability and
storage of large amount of hydrogen.
• The accurate life time is also not known and It cannot store electricity.
• Electrodes are expensive ad short lived.
• Storage and handling of H2 gas is dangerous because it is inflammable.
▪ ApplicaFons:
• The most important applicaVon of a fuel cell is its use in space vehicles, submarine or military
vehicles.
• The product H2O is valuable source of fresh water for the astronauts.
• Fuel cell baXeries for automoVve will be a great boon for the future.
Solid Oxide Fuel Cell (SOFC)
▪ SOFC is a high-temperature FC that u6lizes solid ceramic inorganic oxide as an
electrolyte; e.g., zirconium oxide stabilized with yfrium oxide, instead of a
liquid or membrane, also known as Yfria-stabilized Zirconia (YSZ).
▪ SOFC is also referred to as ceramic FC.
▪ Both hydrogen and carbon monoxide are used as fuels.
▪ Solid oxide fuel cells work at very high temperatures, the highest of all the fuel
cell types at around 800 °C to 1,000 °C.
▪ Efficiency: over 60% when conver6ng fuel to electricity
▪ This cell rela6vely resistant to small quan66es of sulphur in the fuel, compared
to other types of fuel cell, and hence can be used with coal gas.
Structure of SOFC
Anode or fuel electrode:
• Nickel mixed with YSZ (Yttria stabilized Zirconia) or called Nickel-YSZ cermet (a
cermet is a mixture of ceramic and metal).
• It is a porous ceramic layer to allow the fuel to flow towards electrolyte.
Cathode or air electrode:
• The cathode is usually a mixed ion-conducting and electronically conducting ceramic
material.
• It is a thin porous ceramic layer coated over the solid electrolyte where oxygen
reduction takes place. One example being, strontium doped lanthanum manganite
(LSM).
Electrolyte:
• Oxide ion (O2-) conducting ceramic.
• The most popular electrolyte material is a bilayer composite electrolyte (YSZ layer +
gadolinium doped CeO2) (GDC) layer) or a mixture of ZrO and CaO.
At anode (oxidation):
H2 (g) + CO (g) + 2 O2- → H2O (g) + CO2 (g) + 4e-
At cathode (reduction):
O2 (g) + 4e- → 2 O2-
Net reaction:
H2 (g) + CO (g) + O2 (g) → H2O (g) + CO2 (g)
Advantages of SOFC:
• SOFCs have a number of advantages due to their solid materials and high
operating temperature.
• Since all the components are solid, as a result, there is no need for electrolyte
loss maintenance and electrode corrosion is eliminated.
• Also because of high-temperature operation, the SOFC has a better ability to
tolerate the presence of impurities as a result of life increasing.
• High efficiencies: Due to high-quality waste heat for cogeneration
applications and low activation losses, the efficiency for electricity
production is great.
• Low emissions. Releasing negligible pollution.
Disadvantages:
• High operating temperature (500 to 1,000 °C) which results in longer start up
times and mechanical/chemical compatibility issues.
• The cost and complex fabrication are also significant problems that need to be
solved.
• Applications:
• SOFCs are being considered for a wide range of applications, such as working
as power systems for trains, ships and vehicles; supplying electrical power for
residential or industrial utility.
• Stationary power generation
• By product gases are channeled to turbines to generate more electricity:
cogeneration of heat and power and improves overall efficiency.
• Auxiliary power units in vehicles
Differences between Primary, Secondary and Fuel cells
Supercapacitor or Ultracapacitors
▪A supercapacitor is a type of capacitor that can store a large amount of energy, typically
10 to 100 Fmes more energy per unit mass or volume compared to electrolyFc capacitors.
▪These can deliver and accept charge more quickly than baperies.
BaQeries and capacitor
Batteries and capacitors do a similar job—storing electricity—but in completely different
ways.
Batteries have two electrical terminals (electrodes) separated by a chemical substance
called an electrolyte.
When power is on, chemical reactions happen involving both the electrodes and the
electrolyte. These reactions convert the chemicals inside the battery into other
substances, releasing electrical energy as they go.
Once the chemicals have all been depleted, the reactions stop and the battery is flat
In a rechargeable battery, such as a lithium-ion power pack used in a laptop computer or
MP3 player, the reactions can happily run in either direction so that it is usually charge
and discharge hundreds of times before the battery needs replacing.
Capacitors
A capacitor is a device used to store electrical charge
and electrical energy.
Capacitors use static electricity (electrostatics)
rather than chemical substances to store energy.
Inside a capacitor, there are two conducting metal
plates with an insulating material called a dielectric in
between them - it's a dielectric sandwich.
Positive and negative electrical charges build up on
the plates and the separation between them, which
prevents them coming into contact, is what stores the
energy.
The dielectric allows a capacitor of a certain size to
store more charge at the same voltage, so it makes
the capacitor more efficient as a charge-storing
device.
Advantages of capacitors over batteries:
▪Capacitors have many advantages over baderies: they weigh less, generally don't
contain harmful chemicals or toxic metals, and they can be charged and discharged
zillions of 5mes without ever wearing out.
▪But they have a big drawback too: their basic design prevents them from storing
anything like the same amount of electrical energy as baderies.
A supercapacitor differs from an ordinary capacitor in two important ways:
• Its plates effectively have a much bigger area and the distance between them is much
smaller, because the separator between them works in a different way to a
conventional dielectric.
• Although the words "supercapacitor” and "ultra capacitor” are often used
interchangeably, there is a difference: they are usually built from different materials
and structured in slightly different ways, so they store different amounts of energy.
Like an ordinary capacitor, a supercapacitor has two plates that are separated.
The plates are made from metal coated with a porous substance such as powdery,
activated charcoal, which effectively gives them a bigger area for storing much more
charge
Unlike capacitor, in a supercapacitor, there is no dielectric as such. Instead, both plates
are soaked in an electrolyte and separated by a very thin insulator (which might be made
of carbon, paper, or plastic)
How do Supercapacitors Work?
▪When the plates are charged up, an opposite charge forms on either side of the
separator, creaFng what's called an electric double-layer.
▪This is why supercapacitors are o}en referred to as double-layer capacitors, also called
electric double-layer capacitors or EDLCs).
▪The capacitance of a capacitor increases as the area of the plates increases and as the
distance between the plates decreases.
Characteristics of Supercapacitors
Fast charging speed and it can reach more than 95% of its rated capacity within minutes
Cycle life is long and the number of charge and discharge cycles can reach 10,000 to
500,000 times, without "memory effect“.
The high current discharge capacity is super strong, the energy conversion efficiency is
high, the process loss is small, and the high current energy cycle efficiency is ≥90%;
High power density, up to 300W/KG ~ 5000W/KG, equivalent to 5~10 times of battery;
The raw material composition, production, use, storage and dismantling process of the
product are not polluted, and it is an ideal green environmental protection power source;
The charging and discharging circuit is simple, no charging circuit like rechargeable
battery is needed, and the safety factor is high, and the maintenance is long-term
maintenance-free;
Good ultra-low temperature characteristics, temperature range -40 °C - +70 °C;
Easy to detect, the remaining power can be read directly;
The capacity range is usually 0.1 F – 1000 F.
Comparison of supercapacitors with batteries and ordinary capacitors
Unlike battery, supercapacitors can store and release energy almost instantly.
That's because a supercapacitor works by building up static electric charges on solids,
while a battery relies on charges being produced slowly through chemical reactions.
Batteries have a higher energy density (they store more energy per unit mass) but
supercapacitors have a higher power density (they can release energy more quickly).
Supercapacitors are suitable for quick storing and releasing large amounts of energy.
Although supercapacitors work at relatively low voltages (maybe 2–3 volts), they can be
connected in series (like batteries) to produce bigger voltages for use in more powerful
equipment.
Since supercapacitors work electrostatically, rather than through reversible chemical
reactions, they can theoretically be charged and discharged any number of times.
They have little or no internal resistance, which means they store and release energy
without using much energy—and work at very close to 100 percent efficiency.
ApplicaTon of Supercapacitors
Supercapacitors have been widely used as the electrical equivalents of flywheels in
machines—"energy reservoirs" that smooth out power supplies to electrical and
electronic equipment.
Supercapacitors can also be connected to batteries to regulate the power they supply.
In wind turbines, where very large supercapacitors help to smooth out the intermittent
power supplied by the wind. In electric and hybrid vehicles, supercapacitors are
increasingly being used as temporary energy stores for regenerative braking (where the
energy a vehicle would normally waste when it comes to a stop is briefly stored and then
reused when it starts moving again).