Engg.

Chemistry

Non-Conventional Energy Sources and Storage Devices

Unit-4 Non-Conventional Energy Sources and Storage Devices Lesson plan

Topics Lecture numbers 1 1 1 1 1 2 2

Introduction Types of Batteries , Characteristics of batteries& Primary Alkaline battery Secondary batteries- Lead Acid accumulator Nickel Cadmium battery & Lithium batteries Fuel cells- Hydrogen-oxygen fuel cells Solar cells and wind energy Nuclear energy - Fission and fusion reactions , Light water nuclear reactor , Breeder reactor

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Learning Objectives
At the end of the lecture, Student will be able to Define battery or Electro Chemical cell, Differentiate electrochemical cell from electrolytic cell and State the types of batteries. State the characteristics batteries. Explain the principle, working, applications and limitations of the following 1. The primary alkaline batteries 2. Lead Acid accumulator 3. Nickel Cadmium battery 4. Lithium batteries and lithium ion batteries 5. Fuel cells - Hydrogen-oxygen fuel cells. 6. Solar energy 7. Wind energy and 8. Nuclear energy: fusion reaction and fission reactions 9. The breeder reactor and light water nuclear reactor

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Introduction Do you know? How old are the batteries?

Prehistoric batteries: It is believed that the Parthians who ruled Baghdad (circa 250 BC) used batteries to electroplate silver. Clay jar with iron rod surrounded by copper cylinder filled with vinegar as an electrolytic solution produces 1.1 volts DC was used circa. 250 BC to 640 ADO. The Egyptians are said to have electroplated antimony onto copper over 4300 years ago.

In 1780, the Italian anatomist and physiologist Luigi Galvani created an electric circuit consisting of the frogs leg (FL) and two different metals and published a report on animal electricity in 1791. Italian physicist Alessandro Volta realized that cardboard soaked in salt water was a suitable replacement to frogs moist tissues and the frogs muscular response could be substituted by another form of electrical detection. He was able to spot electric current through this system, also called Galvanic cell. In 1800, the battery was invented by Volta by piling voltaic cells over each other, in a series. This voltaic pile gave a voltage of about 50 volts for a 32-cell pile, with an enhanced net emf.

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Volta's experimentations at the French National Institute in November of 1800 in which Napoleon Bonaparte was present.

In 1802, Dr. William Cruickshank designed the first electric battery capable of mass production. Cruickshank arranged square sheets of copper soldered at their ends, intermixed with sheets of zinc of equal size. These sheets were placed into a long rectangular wooden box that was sealed with cement. Grooves in the box held the metal plates in position. The box was filled with an electrolyte of brine, or watered down acid.

Daniel cell (by John Frederic Daniell) in 1836, batteries began to provide more reliable currents and were adopted for industrial use. Benjamin Franklin coined the term battery to refer to an arrangement of multiple Leyden jars, after a battery of cannons. These fragile wet cells were replaced by dry cell batteries, developed in the end of 19th century.

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BATTERIES NEVER DIE....THEY ARE MURDERED!.......by over charging and discharging

Batteries can also be subjected to premature death by:

Over-charging Over-discharging Short circuiting Drawing more current than it was designed to produce Subjecting to extreme temperatures Subjecting to physical shock or vibrations

1. Why do mobile phones suffer by a sudden complete discharge? NiCd batteries suffer from a so-called "memory effect" if they are recharged before they have been fully discharged. The battery "remembers" the point where its recharging began and during subsequent use suffers a sudden drop in voltage at that point and the battery will be discharged fully. 2. Which batteries are called as THE CELL OF FUTURE? Lithium-ion batteries is the fastest growing and most promising battery chemistry because of its advantages over the other batteries are called as THE CELL OF FUTURE..

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3. Why do cars have starting troubles in cold whether? At very low temperatures the electrolyte may freeze giving a lower voltage as ion movement is impeded. Battery becomes dead. In winter season, cars have starting troubles in cold whether and can be recovered by warming the electrolyte.

4. Where is the worlds largest wind farm? Denmark Building World's Largest Wind Farm Denmark is currently building the world's largest wind farm, and it's expected to be finished in August of this year (2009). Crews will install 91 wind turbines in the shallow waters of the North Sea. The electric energy produced will supply over 200,000 homes with constant power. Each windmill is nearly 375 feet high, with wings that measure 147 feet. 5. Which is the world's largest wind turbine? Enercon E-126 - E-126 by German company Enercon is record-breaking. The tower is 138 meters high (453 feet) and its walls are 45 centimeters (18 inches) thick, the diameter of the rotor is 126 meters (413 feet) and the blades feature an improved trailing edge that boosts production. Rated at 6 megawatts.

This is the Enercon E-126, the world's largest wind turbine that's currently being installed in Germany. This monster generates over 7 MW of Electricity, which is enough to power about 5,000 four-person households in Europe.

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6. What are the two nuclear power stations in Tamilnadu? K

The Madras Atomic Power Station (MAPS) KALPAKKAM

Kudankulam Nuclear Power Plant

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CONTENT

Energy Storage Devices

Battery: Battery is one or more electrochemical cells, which store chemical energy and make it available as electric current. Electrochemical cell or voltaic cell

Types of Batteries There are two types of batteries: 1. Primary batteries (disposable batteries), which are designed to be used once and discarded when they are exhausted. Primary batteries irreversibly transform chemical energy to electrical energy. Common types of disposable batteries include zinc-carbon batteries and alkaline batteries 2. Secondary batteries (rechargeable batteries), which are designed to be recharged and used multiple. Secondary batteries can be recharged; that is, they can have their chemical reactions reversed by supplying electrical energy to the cell, restoring their original composition. Ex.: Lead acid betteries, Nickel-cadmium (NiCd), Nickel-zinc (NiZn), Nickel metal hydride (NiMH) and Lithium-ion (Li-ion) cells 3. Flow cell: Reactants, products and electrolytes are continuously passing through the cell. Ex. H2-O2 fuel cell 4. Reserve batteries achieve very long storage time (on the order of 10 years or more) without loss of capacity, by physically separating the components of the battery and only assemling them at the time of use. Such constructions are expensive but are found in applications like munitions, which may be stored for years before use.

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Characteristics of Battery
Voltage Current Capacity Charge-Discharge Storage density Power density Cycle life Shelf-life Self-discharge Tolerance to service condition: Temperature and vibration Battery Cells EODV

Primary battery:
DRY CELL (or) Leclanches cell

Metal cap

Metal bottom Net reaction 2MnO2(s) + 2NH4+ (aq) + Zn2+ (aq) + 2Cl- (aq) --Mn2O3 (s) + [Zn(NH3)2] Cl2 (s) + H2O

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Electrolyte NH4Cl is acidic, Zn dissolves in NH4Cl, even not in use. This leads to self discharge and the cell run down slowly.

Alkaline Dry Cells

Alkaline cells overcome some of the problems with carbon-zinc batteries by using alkaline potassium hydroxide in place of acidic ammonium chloride in the electrolyte. Anode: Zinc (can or container or cylinder) Cathode: Carbon (graphite) rod, MnO2 is an oxidizing agent, which takes up electrons during discharging the cell Electrolytes: KOH solution The half-reactions are Net reaction: Zn (s) + 2MnO2 (s) +H2O (l) not too heavy Mn2O3 (s) + Zn(OH)2 (s)

They are used in remote controls, flash lights, clocks, transistor, radios where the power drain is

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Secondary batteries
LEAD ACID BATTERIES (or) LEAD STORAGE CELL Lead-acid batteries, invented in 1859 by French physicist Gaston are the oldest type of rechargeable battery. Cell reaction is reversible: The cell reaction can be made to precede both the directions by supplying or withdrawing the current.

Anode: spongy lead (Pb) Cathode: a grid of lead-di-oxide (PbO2 packed on lead) Electrolyte: 21% dil. H2SO4 (specific gravity 1.2 at 25o c) with density of 1.3 g/cm3 Separator: glass fibre separator permit ions not electrons Cell representation: Pb|PbSO4 | H2SO4 | PbO2| PbSO4 Voltage: 2v at a conc of 21.4% H2SO4 at 25o C 6 cells are connected to produce 12v. Density of the electrolyte should be = (or) >1.2 g/cm3 Discharging Net reaction Pb + PbO2 + 2SO42- + 4H+ Charging Net reaction 2PbSO4 + 2H2O+ 2ePb + PbO2 + 2SO42- + 4H+ 2PbSO4 +2H2O

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Specific gravity (SG) of H2SO4 is going below 1.2, the battery is to be recharge Starting trouble at Cold climate: At very low temperatures the electrolyte may freeze giving a lower voltage as ion movement is impeded. Due voltage drop, batteries become dead. They can be recovered its ability by warming the electrolyte.

Ni-Cd batteries Secondary batteries- rechargeable alkaline battery Cell reaction is reversible.

Anode: Cadmium rod Cathode: NiO2 (or) NiO(OH)

Electrolyte: alkaline KOH Cell reprsentation: Cd/Cd2+ | KOH | Ni4+ / Ni2+ (or) Cd/Cd2+ | KOH | Ni3+ / Ni2+ Net reaction Cd (s) + 2NiO2 (s)+ 2H2O -(or) Cd (s) + 2NiO(OH) (s)+ 2H2O -Charging Net reaction Cd(OH)2 (s) + 2Ni(OH)2 (s) Cd (s) + 2NiO2 (s)+ 2H2O Cd(OH)2(s) + 2Ni(OH)2 (s) Cd(OH)2 (s) + 2Ni(OH)2 (s) ---------NiO(OH) ---------(NiO2)

The nominal output voltage for single cell is 1.4 v

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Troubles in Ni-Cd batteries 1. High cost 2. Toxicity due to Cd 3. Overcharging: If the anode is overcharged, hydrogen gas is produced If the cathode is overcharged, oxygen gas is produced. NiCd cells are vented, with seals that fail at high internal gas pressures. The sealing mechanism must allow gas to escape from inside the cell, and seal again properly when the gas is expelled. 4. Memory effect: It is sometimes claimed that NiCd batteries suffer from a so-called "memory effect" if they are recharged before they have been fully discharged. The battery "remembers" the point in its charge cycle where recharging began and during subsequent use suffers a sudden drop in voltage at that point, as if the battery had been discharged. 5. Dendrites Dendritic shorting NiCd batteries, when not used regularly, tend to develop dendrites which are thin, conductive crystals which may penetrate the separator membrane between electrodes. This leads to internal short circuits and premature failure, long before the 8001000 charge/discharge cycle life claimed by most vendors.

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Lithium batteries
Lithium batteries are disposable (primary) batteries that have lithium metal or lithium compounds as an anode. Depending on the design and chemical compounds used, lithium cells can produce voltages from 1.5 V to about 3.7 V, over twice the voltage of an ordinary zinccarbon battery or alkaline cell battery.

Lithium-ion batteries Li-ion batteries are a types of rechargeable battery In which lithium ions move between the anode and cathode. The lithium ion moves from the anode to the cathode during discharge and from the cathode to the anode when charging. Lithium-ion batteries are common in portable consumer electronics because of their high energy-to-weight ratios, lack of memory effect, and slow self-discharge when not in use.

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Lithium batteries and Li-ion batteries are called as THE CELL OF FUTURE

It has the greatest oxidation potential, (Eo = very high oxidation potential), so generate very high voltage of 3 v Solid state battery: All constituents are solids , so no leakage problems Lithium is the lightest of all metals, they are currently one of the most popular types of battery for portable electronics, Lithium-ion batteries can be formed into a wide variety of shapes and sizes so as to efficiently fill available space in the devices they power. The best energy-to-weight ratios high Energy density Wh/Kg due to its light wt. Lithium-ion batteries do not suffer from the memory effect They also have a low self-discharge rate of approximately 0.1% per month, compared with over 30% per month in common nickel metal hydride batteries.

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Lithium batteries Lithium batteries have lithium metal or lithium compounds as an anode. Solid state battery Rechargeable Anode: lithium metal Cathode: Transition metal oxides or sulphides Ex.:TiS2 Electrolyte: solid polymer with Li salts -- permits only the passage of ions not the passage of electrons CELL REACTION: Net reaction: Li+ + TiS2- --Charging cell reaction By passing external current to the anode Cathode: LiTiS2 --TiS2--Li+ + TiS2TiS2 + eLiTiS2 (Li+ Ti3+S2 )

e- move from cathode to anode through external circuit Li ions move from cathode to anode through electrolyte and reduced on anode by taking the electrons Anode: Li+ + e- --Li

Overcharging and certain kinds of mistreatment may cause Li-ion batteries to explode.

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Lithium-ion batteries A lithium-ion battery (Li-ion battery or LIB) is a family of rechargeable battery types In which lithium ions move from the negative electrode to the positive electrode during discharge, and back when charging. Anode is graphite Cathode is generally one of three materials: Li intercalated transition metal oxides with variable valences, such as lithium cobalt oxide LiCoO2, lithium iron phosphate and lithium manganese oxide LiMn2O4. Electrolyte is a polymer soaked lithium salt in an organic solvent Liquid electrolytes in lithium-ion batteries consist of lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent, such as ethylene carbonate. A liquid electrolyte conducts lithium ions, acting as a carrier between the cathode and the anode when a battery passes an electric current through an external circuit. The separator is a polymer soaked in electrolyte between anode and cathode

Intercalation a reaction where (lithium) ions are reversibly removed or inserted into a host without a significant structural change to the host During the charge and discharge processes, lithium ions are inserted and extracted from interstitial space between atomic layers within the anode material of the battery.

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Lithium ion battery: Ex:

Graphite - Lithium cobalt oxide LiCoO2 battery.
Anode: Graphite electrode Cathode: - Lithium cobalt oxide LiCoO2 Charge/Discharge Chemical Reactions Charging: Net reaction LiCoO2 + C6 ------Net reaction Li1-XCoO2 + LiXC6 ------Co3+ during discharge LiCoO2 + C6 Co in LiCoO2 being oxidized from Co3+ to Co4+ during charging, and reduced from Co4+ to Li1-XCoO2 + LiXC6

Discharge Chemical Reactions

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Fuel cells
A fuel cell is an electrochemical conversion device for producing electricity by converting the chemical energy of a fuel and oxygen into electrical energy. During the combustion of fuel with O2, the oxidation of fuel liberate electrons (electrical energy). So chemical energy can be directly converted into electrical energy without production of heat Fuel Cells are classified primarily by the kind of electrolyte they employ. This determines the kind of chemical reactions that take place in the cell, the kind of catalysts required, the temperature range in which the cell operates, the fuel required, and other factors.

Types of Fuel Cells

Polymer Electrolyte Membrane (PEM) Alkaline Phosphoric Acid Direct Methanol Molten Carbonate Solid Oxide

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Alkaline Fuel Cell:

CELL REACTION Anode: 2H2(g) + 4OH-(aq) Cathode: O2 (g) + 2 H2O (l) + 4e- Net reaction: 2H2 (g) + O2 (g) 2 H2O (l) 4 OH-(aq) 4 H2O (l) + 4e-

As long as there is a flow of chemicals into the cell, the electricity flows out of the cell.

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