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systems
Module -IV
Module IV- An Insight
Electrochemical energy systems: Basic concepts of electrochemical
energy systems.
Energy Conversion---Storage---Delivery
Batteries
• A Battery is a device that consists of one or more
galvanic cells connected in series and/or parallel,
which converts the chemical energy (redox
reaction) to electrical energy in a stored form and
can be used whenever required.
Terminology
1. EMF of a battery -G=nEF
7. Low price
8. Cycling
Classification (or) Types of batteries
Secondary batteries
Lead acid
Nickel-Cadmium
Zn metal (anode)
-
Non conducting metal
tube
Discharging Reactions of a Dry Cell
Dry cell contains Zn, NH4Cl, ZnCl2 and MnO2
Anodic reaction : Zn(s) Zn2+(aq) + 2e-
• The voltage of this cell is initially about 1.5 volts, but decreases as
energy is taken from the cell. Due to the accumulation of the
products on electrodes. It also has a short shelf life and
deteriorates rapidly
• Alkaline cells overcome some of the problems with Zn-Carbon primary batteries
by using potassium hydroxide in place of ammonium chloride in the
electrolyte.
Steel can
Cathode (HgO/Ag2O
Separator and Carbon black)
Cellulose + 40% KOH
Negative
Vent
Discharging Chemistry of Alkaline Cell
• The zinc anode does not form the container but it is in the form of a powder,
giving a large surface area. The following half-cell reactions take place inside the
cell:
Caution
1. Once a leak has formed due to corrosion of the outer steel shell, potassium hydroxide
forms a feathery crystalline structure that grows and spreads out from the battery over
time, following up metal electrodes to circuit boards where it commences oxidation of
copper tracks and other components, leading to permanent circuitry damage.
2. The leaking crystalline growths can also emerge from seams around battery covers to
form a furry coating outside the device, that corrodes any objects in contact with the
leaking device.
Ref : http://en.wikipedia.org/wiki/Alkaline_battery
Primary Lithium batteries
Introduction
• One of the main attractions of lithium as an anode material in its position as
the most electropositive metal in the electrochemical series combined with its
low density, thus offering the largest amount of electrical energy per unit
weight among all solid elements.
• Li cannot be used with the traditional aqueous electrolytes due to the very
vigorous corrosive reaction between Li and water with inflammable hydrogen
as the product.
• In the 1980s progress was made in the use of Li as an anode material with
MnO2, liquid SO2 (or) thionyl chlorides as the cathode, and hexaflurophosphate
dissolved in propylene carbonate as a typical organic electrolyte.
• Li cells are generally properly sealed against contact with air and moisture
While the primary lithium battery has been well established for nearly two
decades,
Li Primary batteries
Li Cells with solid cathode Li Cells with Soluble cathode Li Cells with Solid electrolyte
Anode: Li Li+
Li Cells with solid cathode
3 to 3.2 V High energy density, good low-temperature
performance; cost effective. Small in size, long self life,
Electrical medical devices; memory circuits
Anode: Li,
This acts both as electrochemical cell and electrolytic cell. While discharging it
acts as electrochemical (voltaic cell) and on charging it acts as electrolytic cell.
The maximum emf = 12V
Representation of Lead Storage Cell : Pb / PbSO4(s), H2SO4 (aq) / PbO2(s), Pb
Construction of Lead acid Battery +ve
Discharge Reactions
-ve
At Anode Pb
Pb + SO42- PbSO4 + 2e-
At Cathode
PbO2
Charging
Pb + PbO2 + H2SO4 PbSO4 + 2H2O + Energy
Discharging
~30% H2SO4
Overcharging
• Because of the open cells with liquid electrolyte in
most lead-acid batteries, overcharging with high
charging voltages will generate oxygen and hydrogen
gas by electrolysis of water, forming an explosive mix.
Uses /Applications
• The first NiCd battery was created by of Sweden in 1899. But only
introduced in the early 1960's
• 1.4 V battery
• Energy density about double that of lead
acid batteries.
• Their small size and high rate discharge
capacity made portable tools and other
consumer applications practical for the
first time.
-ve +ve
KOH
Cd
NiO(OH)
Discharge and charge Chemistry
Discharging
At anode: Cd(s) + 2OH- Cd(OH)2(s) +2e-
Advantages
• Constant voltage (1.4V)
• No gaseous products
• Wide temperature range (Up to 70°C)
• The sealed nickel-cadmium cell can be stored in the charged or discharged state
without damage.
• Motorized equipments
• Power tools
• Transistors
• Electronic calculators
• Commercial and industrial portable products
• Medical instrumentation
• Emergency lighting
• Toys
• Cordless and wireless telephones
Medical equipment
Personal care
Professional lighting
Radio communication and tracking
equipment
Professional tooling
Military equipment
Professional electronic devices
Nickel Metal Hydride Batteries
• Their basic structure is identical to that of Ni-Cd
• Now NiMH batteries have begun to find use in high voltage automotive
applications. The energy density is more than double that of Lead acid
and 40% higher than that of NiCads
Anode KOH
Charging
MH + OH- 2H2O + M + e-
Discharging
Cathode
Charging
2NiO(OH) + 2OH-+ 2e- 2Ni(OH)2 +2OH-
Discharging NiO(OH)
Overall Reaction
Charging
MH2 + 2NiO(OH) Ni(OH)2 + M
Discharging
Advantages
• High energy density
• Reconditioning is possible.
300
?
(Wh/kg)
250
Energy
200
Specific Energy
150 Li-Ion
100
Lead Ni-Cd
Acid Ni-MH
50
0
1850 1900 1950 2000
Year 34
Lithium batteries
Electrolyte
• Since lithium reacts violently with water, and the cell voltage is so high that
water would decompose, a non-aqueous electrolyte must be used.
• A typical electrolyte is LiPF6 dissolved in an ethylene carbonate and dimethyl
carbonate mixture.
• Polymer electrolyte
Cathode materials
• The most common compounds used for cathode materials are LiCoO2, LiNiO2
and LiMn2O4.
• Of these, LiCoO2 has the best performance but is very high in cost, is toxic and
has a limited lithium content
• LiNiO2 is more stable, however the nickel ions can disorder.
• LiMn2O4 is generally the best value for money, and is also better for the
environment.
Lithium ion-battery
Electrolyte:
• Liquid organic
solvents
• Polymers
• Gels
Anode: Cathode:
• Carbon-based • Transition-metal oxides
• Alloys and intermetallics
• Oxides
• Lithium-metal
Working
Charging Discharging
• The following reactions take place upon working
Types :
• Alkaline Fuel Cells (AFC): US spacecraft
• Phosphoric Acid Fuel Cells (PAFC): Stationary power generation, city buses
Unreacted Oxygen
Unreacted H2 or Air free from CO2
- +
e- e-
Voltage :1.15 V
Power: 10-100 KW
Porous carbon Anode with Pt/Ni catalyst
Solid oxide fuel cells (SOFC)
electrolyte all made up of ceramic substances
• High efficiency
• Long term stability
• Fuel flexibility
• Low emissions
• High operating temp – longer start up times
• Mechanical / Chemical compatibility issues.
Applications
• Auxiliary power units in vehicles
• Stationary power generation
• By product gases – channeled to turbines to generate more electricity –
cogeneration of heat and power and improves overall efficiency
Micro Fuel Cell Powered Small Gadgets
fuel cartridge