1

Electrochemical sources of power: General Consideration: A battery is a device for storing electrical energy. In a battery the chemical energy is converted to electrical energy spontaneously. The electrical energy is drawn only when required. On demand the chemical reactions occur and electrical power is released. The basic requirement of a battery is two electrodes and an electrolyte. On connecting the electrodes to a load oxidation occurs at one and reduction at the other. The sum of these two potentials is the emf or voltage of the battery. Battery in fact refers to an array of cells connected in series. A cell is the single unit of two electrodes and an electrolyte. But in practice a cell also is called a battery. The voltage of a battery is inherent and depends on the system. It depends on the type of electrodes and the electrolyte. From the emf series one can infer that the maximum driving force or potential can be obtained by combining an electrode of high oxidation potential and another of high reduction potential. But in aqueous system elements like Na, K, Li, Ba, Mg etc will not be suitable, since their oxidation is so fast and uncontrollable. Even when they are not connected to the other electrode, discharge occurs. This is known as self discharge. The element should oxidize only when it is connected to other electrode. This rules out the use of elements with high oxidation potentials. Hence the choice is limited to Zn, Ni, Mg (to some extent). Extensively zinc is employed. This serves as the site of oxidation (negative electrode) of the battery. The reduction potential of an element is high, indicating that it is noble and not reactive. Nobler metals like Cu, Ag, Au, Pt are very expensive. Use of these elements in the cell makes the cost of the battery prohibitive. Further the main objective of this electrode is to provide a surface on which a reduction reaction should occur. The most economical and widely employed material as cathode is graphite in primary batteries. The aqueous electrolyte used in the battery should involve a salt, acid or alkali that is highly soluble in water. It should be stable and not decompose. Ammonium salts, acids such as HCl, H2SO4 and alkali such as KOH, NaOH and LiOH are generally employed. Thus the system consisting of electrodes and electrolyte decides the voltage or emf of the battery. Unless these are changed the potential does not change. For a system it is constant. The voltage can be increased by connecting several cells in series. Any two electrodes when dipped in a salt solution will indicate potential. This is open circuit voltage. But this combination may not become a battery because when a load is attached, the voltage will immediately drop, and no current can be obtained. For a system to function as a successful battery, the basic requisite is it should be able to supply a sustained current when a load (device) is attached, for a reasonable period. A battery in calculator works for at least six months. Batteries in an electronic flash function for at least 36-50 exposures. The current that a battery can supply and the period of its function decide the power or

2 capacity of the battery. The current is a measure of the chemical reactions that occur in a cell; it quantifies the chemical reactions. The overpotentials such as activation, concentration and IR discussed under applied potential have similar significance here. They tend to reduce the output voltage. Activation overpotential depends on the nature of the electrodes, electrolyte and surface texture, either porous or smooth. The choice is made of ones that exhibit lower AOP for the reactions that occur at the electrode surface. Concentration polarization arises out of gas evolution which covers the surface of the electrodes, hindering further reaction. Suitable substances are added to remove the gas molecules. Accumulation of reaction products around the electrodes leads concentration polarization and thus decreases the output voltage. Medium is chosen such that the products diffuse away fast. (No stirring is possible here!!) Every precaution is taken to see that the internal resistance is minimized. Highly soluble electrolytes of sufficiently high concentration are employed. The electrodes are placed very close to each other almost touching, interlacing with insulating sheets.

Anode: The electrode where oxidation (loss of electrons) takes place. While discharging, it is the negative electrode; while charging it becomes the positive electrode. Amps: Also known as Amperes. This is the rate at which electrons flow in a wire. The units are coulombs per second, or since an electron has a charge of 1.602 x 10-19 coulombs, an amp is 6.24 x 10+18 electrons per second.

Amp hours: Also known as ampere hours. This is a measure of the amount of charge stored or used. So Amp-Hours, (AH), or milliamp-Hours (mAH) is a measure of the size of the battery a 10 mAH battery has half the capacity of a 20 mAH battery, even though they may be in the same physical package. Capacity: The total quantity of electricity or total ampere-hours available from a fully charged cell or battery. Cathode: The electrode where reduction (gain of electrons) takes place. When discharging, it is the positive electrode, when charging, it becomes the negative electrode. Charge: The conversion of electrical energy, provided in the form of current from an external source, into chemical energy stored at the electrodes of a cell or battery. Discharge: The conversion of the chemical energy of a cell into electrical energy, which can then be used to supply power to a system. Energy density (specific energy): These two terms are often used interchangeably. Energy density refers mainly to the ratio of a battery's available energy to its volume (watt hour/liter). Specific energy refers to the ratio of energy to mass (watt hour/kg). The energy is determined by the charge that can be stored and the cell voltage (E=qV). Specific power and specific energy can be compared in a Ragone plot.

Power density (specific power): Power density is the ratio of the power available from a battery to its volume (watt/liter). Specific power generally refers to the ratio of power to mass (watt/kg). Comparison of power to cell mass is more common. Primary cells: A cell that is not designed for recharging and is discarded once it has produced all its electrical energy. Reserve cell: A cell that may be kept inactive and which is activated by adding an electrolyte or electrode, or melting an electrolyte in a solid state. Secondary cells: A cell capable of repeated use. Its charge may be fully restored by passing an electric current through the cell in the opposite direction to that of discharge, thus reversing the redox reactions.

Parameters for Battery Performance No one battery design is perfect for every application. Choosing one requires compromise. That's why it's important to prioritize your list of requirements. Decide which ones you absolutely must have and which you can compromise on. Here are some of the parameters to consider: 1. Voltage: Normal voltage during discharge, maximum and minimum permissible voltages, discharge curve profile 2. Duty cycle: Conditions the battery experiences during use. Type of discharge and current drain, e.g., continuous, intermittent, continuous with pulses, etc. 3. Temperature: In storage and in use. Temperatures that are too high or too low can greatly reduce battery capacity. 4. Shelf life: How rapidly the cell loses potential while unused. 5. Service life: Defined either in calendar time or, for secondary cells, possible number of discharge/charge cycles, depending on the battery application. Service life depends on battery design and operational conditions, i.e., the stress put on a battery. For stationary and motive power application, the end of service life is defined as the point at which a battery's capacity drops to 80% of its original capacity. Exceptions would include car batteries where the service life ends when the capacity falls below 60%. 6. Physical restrictions: These include dimensions, weight, terminals, etc. 7. Maintenance and resupply: Ease of battery acquisition, replacement, charging facilities, disposal. 8. Safety and reliability: Failure rates, freedom from outgassing or leakage; use of toxic components; operation under hazardous conditions; environmentally safe 9. Cost: Initial cost, operating cost, use of expensive materials 10. Internal resistance: Batteries capable of a high-rate discharge must have a low internal resistance. A battery is divided into two types- Primary and secondary.

4 A primary cell or battery is one which is not rechargeable. That is the products of reaction can not be brought back to their original state, chemically and physically. A secondary battery is one which is rechargeable. The products can be brought back to their original chemical and physical state by application of electricity from an external source. The reactions are exactly reversible. The study of a battery is done in following lines. 1. Fabrication constituents used and their function. 2. Reactions that occur in the battery equations 3. Efficiency working or functioning maintenance. For a battery the voltage being constant, current and duration or its life is important. Hence it is rated in Ampere hours Ah. Specific capacity of a battery is Ah/g.

Primary Battery (Leclanche type): 1) Fabrication Constituents: i. Anode: Zinc can serves as the site of oxidation with moderate oxidation potential, self discharge is less. ii. Cathode: Graphite rod is the site of reduction. It is a good conduct of electricity and is economical. It has a porous surface, at which reduction reaction takes place with lesser overpotential. iii. Electrolyte: 26% NH4Cl solution containing 9% ZnCl2 is taken as electrolyte. It is immobilized by gelling with wheat flour. Since it is in gel form, the cell can be used in any position. iv. Depolarizer: MnO2 acts as depolarizer in the cell. The function of the depolarizer is very important. It oxidizes the hydrogen molecule insitu in the surface of graphite to water. Otherwise accumulation of gas molecules leads to gas polarization that reduces the output voltage. Further the cell which is sealed will explode, due to build up of gas pressure inside. v. Additives: These though added in small quantity have an important function. They reduce the self discharge of the anode. The enzymes, mesonin and gliadin present in wheat flour exert a negative inhibitive action on the oxidation of zinc under no load condition. When a load is connected, the enzymatic action is overcome and Zn corrodes. A small quantity of K2CrO4 or Na2CrO4 is added. This forms a very thin film of zinc chromate on the surface of zinc, which prevents the open circuit corrosion of zinc. When the cell is connected to a load, the thin film breaks and zinc corrodes freely.

5 A small quantity of mercury compound is added, to retard the evolution of hydrogen. Hydrogen over voltage in presence of mercuric compound is high. When the reduction reaction is suppressed oxidation of zinc also gets suppressed. When it is connected to a load, the suppressive action is overcome and zinc undergoes oxidation. Circular zinc container is taken and the graphite rod is positioned at the centre, without touching the bottom. On the other end of the rod a brass cap is fitted for better conduction. In the annular space the gelled electrolyte along with the additives is packed in a muslin cloth and is taken. The top is sealed with pitch or tar. The circular side of zinc can is coated with tin, to protect from external atmospheric corrosion. The bottom is open for electrical contact. 1. Reactions: Anode: Zinc gets oxidized Zn Zn 2e Cathode:
2MnO2 2 H 2 O 2e 2MnO(OH ) 2OH
Manganous oxyhydroxide

Reduction of water is more feasible in neutral condition. The above mentioned reactions involving electrons are called primary reactions. Secondary reactions: Zn2+ produced at the anode migrate to the bulk and hydroxyl ions generated near graphite travel to the centre, where they react to form zinc hydroxide. Zn 2OH Zn (OH ) 2 Zn(OH)2 reacts with MnO(OH) forming complex adduct. Zn (OH ) 2 2MnO(OH ) ZnO.Mn2O3 2 H 2O 2. Working and efficiency: i. These batteries range from 1 Ah to 4 Ah Open circuit voltage is 1.5 ii. Heavy current discharge is not possible. If larger currents are withdrawn, larger amounts of reaction products are produced and these cannot migrate quickly in the gelled medium. Hence the potential will drop. Low currents such as 25 to 50 mA can be withdrawn for a longer period. iii. Intermittent periods of rest increase the life of the battery. iv. Formation of zinc hydroxide tends to increase the pH. At higher pH the gel is not stable. Hence the reaction of manganousoxyhydroxide with Zn(OH)2 prevents the accumulation of the latter. v. ZnCl2 added maintains the correct pH of the electrolyte and takes care of its functioning. vi. The cell can be stored, handled and transported in any position. It finds extensive use in calculator, quartz clock, electronic flashes, cameras etc., when the concentration of the products, increases beyond a point, the internal resistance increases and the cell voltage decreases steeply and cell becomes dead.

6 Limitations: These are not suitable for high-drain applications, since they readily polarize and the available capacity falls sharply with increasing discharge rate. 2. The shelf life is short compared to that of other batteries. (about two years) 3. The optimum temperature range of operation is 10 to 40oC; outside this range the performance is very poor. Hence these cells are suited to low-drain, intermittent applications, with rest periods for recuperation (depolarization) to take place. A good example is flashlight cell,. Other applications include clocks, portable radios, door chimes and smoke detectors.. MnO2 ZnCl2 Cells: Many of the problems faced in LecLanche cell are not present in ZnCl2 Cells. Here ammonium chloride electrolyte is replaced by zinc chloride. The solid products formed diffuse faster and permit higher rate of discharge. Manganese dioxide used in this cell is of a superior quality and the quantity of graphite is taken with it which increases the conductance of the mix. The electrolyte in a typical zinc chloride cell consists of 15-40% ZnCl2 and 60-85% water, sometimes with a small amount of NH4Cl for optimal performance. The overall cell reaction of the zinc chloride as the electrolyte can be expressed: Zn + 2MnO2 + 2H2O + ZnCl2 > 2MnOOH + 2Zn(OH)Cl MnO2, is only slightly conductive, so graphite is added to improve conductivity. The cell voltage increases by using synthetically produced manganese dioxide instead of that found naturally (called pyrolusite). This does drive the cost up a bit, but it is still inexpensive and environmentally friendly, making it a popular cathode. These cells are the cheapest ones in wide use, but they also have the lowest energy density and perform poorly under high-current applications. Still, the zinc carbon design is reliable and more than adequate for many everyday applications.

Alkaline Cells Anode: Zinc powder

Cathode: Manganese dioxide (MnO2) powder Electrolyte: Potassium hydroxide (KOH)

7 Applications: Radios, toys, photo-flash applications, watches, high-drain applications This cell design gets its name from its use of alkaline aqueous solutions as electrolytes. Alkaline battery chemistry was first introduced in the early 60s. Alkaline cells have many acknowledged advantages over zinc-carbon, including a higher energy density, longer shelf life, superior leakage resistance, better performance in both continuous and intermittent duty cycles, and lower internal resistance, which allows it to operate at high discharge rates over a wider temperature range. The main differences are: 1. Zinc is taken in a powdered form, which increases the surface area of the anode, allowing more particle interaction. This lowers the internal resistance and increases the power density. 2. The positive electrode mix (cathode), MnO2, is synthetically produced because of its superiority to naturally occurring MnO2. This increases the energy density. Just as in the zinc carbon cell, graphite is added to the cathode to increase conductivity. This mixture is packed around the outside of zinc negative and separator, and is in electrical contact with a nickel plated steel can ( see figure). The brass pin placed centrally connects the zinc powder to the cell base. 3. The electrolyte, KOH, allows high ionic conductivity. Zinc oxide is often added to slow down corrosion of the zinc anode. A cellulose derivative is thrown in as well as a gelling agent. These materials make the alkaline cell more expensive than the zinc-carbon, but its improved performance makes it more cost effective, especially in high drain situations where the alkaline cell's energy density is much higher. The half-cell reactions are: Zn + 2 OH > ZnO + H2O + 2 e 2 MnO2 + H2O + 2 e >Mn2O3 + 2 OH The overall reaction is: Zn + 2MnO2 > ZnO + Mn2O3 E=1.5 V

The output capacity of the three above cells (zinc chloride not required) is compared in the following diagram.

Zinc/Air Cells
Anode: Amalgamated zinc powder and electrolyte Cathode: Oxygen (O2)

9 Electrolyte: Potassium hydroxide (KOH) Applications: Hearing aids, pagers, electric vehicles Zinc-air button cells are similar in appearance to zinc-silver oxide cells, except for a snall hole in the positive base plate to admit air to the electrode. The zinc air cell fits into the alkaline cell category because of its electrolyte. It also acts as a partial fuel cell because it uses the O2 from air as the cathode. This cell is interesting technology since it uses air for an electrode. Actually oxygen is let in to the cathode through a hole in the battery and is reduced on carbon surface. The reactions that take place in the cell are: The oxygen gets reduced and zinc gets oxidized as a result electric current is produced. The open cell voltage is1.65 volts: Location Half Cell reactions Anode Zn2+ + 2OH > Zn(OH)2 Voltage 1.25

Cathode 1/2 O2 + H2O + 2e > 2 OH 0.4 Overall 2Zn +O2 +2H2O > 2Zn(OH)2 1.65 The electrolyte is potassium hydroxide of 20-40% concentration. One disadvantage is that since these hydroxides are hygroscopic, they will pick up or lose water from the air depending on the humidity. Both too little and too much humidity reduces the life of the cell. Selective membranes can help. Electro-reduction requires a catalyst and it occurs at a three point contact between air, liquid electrolyte and solid catalyst. The electrolyte must be absorbed into the pores of the catalyst but must not flood it to exclude the gas. Accordingly the catalyst layer is carefully constructed by making it hydrophilic to the electrolyte side and hydrophobic to the gas side. Oxygen from the air dissolves in the electrolyte through a porous, hydrophobic electrode a carbon-polymer or metalpolymer composite The energy density of this battery can be quite high, between 220300 Wh/kg although the power density remains low. However, the use of potassium or sodium hydroxides as the electrolyte is a problem, since these can react with carbon dioxide in the air to form alkali carbonates. For this reason large zinc air batteries usually contain a higher volume of CO2 absorbing material (calcium oxide flake) than battery components. This can cancel out the huge increase in energy density gained by using the air electrode. This cell has the additional benefits of being environmentally friendly at a relatively low cost.

10 These batteries can last indefinitely before they are activated by exposing them to air, after which they have a short shelf life. For this reason (as well as the high energy density) most zinc-air batteries are used in hearing aids. It is promoting them for use in electric vehicles also because they are environmentally friendly and cost relatively little. The idea is to have refueling stations where the zinc oxide waste can be replaced by fresh zinc pellets. The discharge pattern of this cell is similar to that of zinc mercuric oxide cell given earlier. The configuration zinc-air cell is compared with zinc carbon cell below

The fabrication of electrodes zinc-air cell is illustrated below:

11 The hole pattern for Dura cell (Zn air) is shown below:

Zinc silver oxide cells: Zinc-silver oxide was introduced in sixties. The electrolyte is a concentrated solution of potassium hydroxide for high-rate duty or sodium hydroxide for long life. The overall cell reaction is Zn + Ag2O ZnO + 2Ag

The open circuit voltage is 1.60 V. These cells find wide applications demanding a few microamperes for watches with LCD displays to tens of milliamperes for LEDs. These cells exhibit a very flat discharge voltage profiles between 1.50 and 1.55 V, which is ideal for watches. That is the load voltage is almost independent of the current drain. This shows a low cell resistance and little polarization. These may be used up to 0deg.C at a current drain of 1 mA and to 10 deg.C at 0.10 mA. They have a high volumetric capacity (200 300 mAh cm3) much better than that of alkaline manganese or lithium miniature cells. Storage life is around 4 years. The discharge pattern of these cells is flat as shown below. Hence these cells find application in devices that require constant potential throughout the discharge period.

12

The

performance

of

the

three

cells

under

typical

conditions

is

tabulated

below:

13 Lithium Primary Batteries: Applications: Pacemakers, defibrillators, watches, meters, cameras, calculators, portable, lowpower use Lithium battery chemistry comprises a number of cell designs that use lithium as the anode. Lithium is gaining a lot of popularity as an anode for a number of reasons. Lithium, the lightest of the metals, also has the highest standard potential of all the metals, at over 3 V. Some of the lithium cell designs have a voltage of nearly 4 V. This means that lithium has the highest energy density. Many different lithium cells exist because of its stability and low reactivity with a number of cathodes and non-aqueous electrolytes. The most common electrolytes are organic liquids with the notable exceptions of SOCl2 (thionyl chloride) and SO2Cl2 (sulfuryl chloride). Solutes are added to the electrolytes to increase conductivity. Lithium cells have only recently become commercially viable because lithium reacts violently with water, as well as nitrogen in air. This requires sealed cells. High-rate lithium cells can build up pressure if they short circuit and cause the temperature and pressure to rise. Thus, the cell design needs to include weak points, or safety vents, which rupture at a certain pressure to prevent explosion. Lithium cells can be grouped into three general categories: liquid cathode, solid cathode, and solid electrolyte. Let's look at some specific lithium cell designs within the context of these three categories. The discharge from a lithium cell is flat as shown in the figure below:

14

Liquid cathode lithium cells: These cells tend to offer higher discharge rates because the reactions occur at the cathode surface. In a solid cathode, the reactions take longer because the lithium ions must enter into the cathode for discharge to occur. The direct contact between the liquid cathode and the lithium forms a film over the lithium, called the solid electrolyte interface (SEI). This prevents further chemical reaction when not in use, thus preserving the cell's shelf life. One drawback, though, is that if the film is too thick, it causes an initial voltage delay. Usually, water contamination is the reason for the thicker film, so quality control is important. LiSOCl2 Lithium Thionyl Chloride This cell consists of a high-surface area carbon cathode, a non-woven glass separator, and thionyl chloride, which doubles as the electrolyte solvent and the active cathode material. Lithium aluminum chloride (LiAlCl4) acts as the electrolyte salt. The materials react as follows: Location Reaction Anode 4Li > 4Li+ + 4e Cathode 2SOCl2 + 4e > 4Cl + SO2 + S

15 Overall 4Li + 2SOCl2 > 4LiCl + SO2 + S

During discharge the anode gives off lithium ions. On the carbon surface, the thionyl chloride reduces to chloride ions, sulfur dioxide, and sulfur. The lithium and chloride ions then form lithium chloride. Once the lithium chloride has deposited at a site on the carbon surface, that site is rendered inactive. The sulfur and sulfur dioxide dissolve in the electrolyte, but at higher-rate discharges SO2 will increase the cell pressure. This system has a very high energy density (about 500 Wh/kg) and an operating voltage of 3.33.5 V. The cell is generally a low-pressure system In high-rate discharge, the voltage delay is more pronounced and the pressure increases as mentioned before. Low-rate cells are used commercially for small electronics and memory backup. High-rate cells are used mainly for military applications.

16 Solid cathode lithium cells: These cells cannot be used in high-drain applications and don't perform as well as the liquid cathode cells in low temperatures. However, they don't have the same voltage delay and the cells don't require pressurization. They are used generally for memory backup, watches, portable electronic devices, etc. LiMnO2 This accounts for about 80% of all primary lithium cells; one reason is their low cost. The cathode used is a heat-treated MnO2 and the electrolyte a mixture of propylene carbonate and 1,2dimethoxyethane. The half reactions are

Anode

Li > Li+ + e

Cathode MnIVO2 + Li+ + e > MnIIIO2(Li) Overall Li + MnIVO2 > MnIIIO2(Li) At lower temperatures and in high-rate discharge, the LiSO2 cell performs much better than the LiMnO2 cell. At low-rate discharge and higher temperatures, the two cells perform equally well, but LiMnO2 cell has the advantage because it doesn't require pressurization. Li(CF)n Lithium polycarbon monofluoride The cathode in this cell is carbon monofluoride, a compound formed through high-temperature intercalation. This is the process where foreign atoms (in this case fluorine gas) incorporate themselves into some crystal lattice (graphite powder), with the crystal lattice atoms retaining their positions relative to one another. A typical electrolyte is lithium tetrafluoborate (LiBF4) salt in a solution of propylene carbonate (PC) and dimethoxyethane (DME). Anode nLi > nLi+ + ne

Cathode (CF)n + ne > nC + nF Overall nLi + (CF)n > nC + nLiF These cells also have a high voltage (about 3.0 V open voltage) and a high energy density (around 250 Wh/kg). All this and a 7-year shelf life makes them very suitable for low- to moderate-drain use, e.g., watches, calculators, and memory applications.

17 Solid electrolyte lithium cells: All commercially manufactured cells that use a solid electrolyte have a lithium anode. They perform best in low-current applications and have a very long service life. For this reason, they are used in pacemakers LiI2Lithium iodine cells use solid LiI as their electrolyte and also produce LiI as the cell discharges. The cathode is poly-2-vinylpyridine (P2VP) with the following reactions: Anode 2Li > 2Li+ + 2e

Cathode 2Li+ + 2e + P2VP nI2 > P2VP (n1)I2 + 2LiI Overall 2Li + P2VP nI2 > P2VP (n1)I2 +2LiI LiI is formed in situ by direct reaction of the electrodes.

Lithium-Iron-Cells
The Lithium-Iron chemistry deserves a separate section because it is one of a handful of lithium metal systems that have a 1.5 volt output (others are lithium/lead bismuthate, lithium/bismuth trioxide, lithium/copper oxide, and lithium/copper sulfide). Recently consumer cells that use the Li/Fe have reached the market, including the Energizer. These have advantage of having the same voltage as alkaline batteries with much more energy storage capacity, so they are called "voltage compatible" lithiums. They are not rechargeable. They have about 2.5 times the capacity of an alkaline battery of the same size, but only under high current discharge conditions (digital cameras, flashlights, motor driven toys, etc.). For small currents they don't have any advantage. Another advantage is the low self-discharge rate10 years storage is quoted by the manufacturer. The discharge reactions are: Type Reaction Nominal Voltage Range 1.6-1.4 V 1.5-1.2 V 1.5 Volts

FeS2 Version 2 FeS2 + 4 Li > Fe + 2Li2S 1.6 Volts FeS Version FeS + 2Li > Fe + Li2S

Both Iron sulfide and Iron disulfide are used, the FeS2 is used in the Energizer. Electrolytes are organic materials such as propylene carbonate, dioxolane and dimethoxyethane

18

The performance of all the primary batteries is shown in the above graph.

19

20

21

The batteries are classified according to the size. A common code and practice is followed by all manufacturers which is given above.

22

II Secondary batteries: Secondary battery is one which is rechargeable. These are developed for heavy current output. 1) Lead acid battery: This is one of the oldest batteries and finds wide application even today. Fabrication: Lead antimony alloy grids are coated with a paste of lead monoxide and sulphuric acid. One set of coated grids is connected to a common terminal. Another set of grids is positioned alternatively to the earlier grids and are connected to another common terminal.

23

The two sets of grids are separated by insulating microporous PVC sheets. The entire assembly is housed in an ebonite or PVC container. Several grids or plates are attached for increasing the area of the plates so that the current output is increased. One such assembly is attached to another assembly in series to increase the potential. After housing the assembly in the container, sulphuric acid of specific gravity 1.3 is poured to completely immerse the plates. The container is closed with an ebonite lid or PVC and sealed. Suitable vents are provided which are closed with plastic knobs. Two terminals project outside, for electrical connections. First charge: All the plates carry a coating of PbO and H2SO4. One terminal of a set of plates is connected to the positive terminal of a DC power supply and the other to the negative terminal. The required current is passed for the required time. During this charging, lead monoxide on the plates, connected to positive terminal, is oxidized to porous, spongy and electroactive lead dioxide PbO 2. This PbO2 is different from the ordinary PbO2. It is electroactive and energized. Lead monoxide present on the other set of plates, connected to negative terminal, gets reduced to porous, spongy and electroactive lead. This is different from ordinary lead in the sense, it is electroactive. During this first charge the plates transform to electrodes and the battery in ready for use. Discharge cycle: Cathode (+ve electrode-convention) PbO, which has been oxidized to PbO2 undergoes reduction during discharge. Hence it is cathode. Reactions are:

24
PbO2 4 H 2e Pb2 2 H 2O Pb2 SO4
2

PbSO4

Total cathodic: PbO2 4H SO42 2e PbSO4 2H 2O Anode: (-ve electrode-convention) PbO, which has been reduced to Pb during first charge, is in a reduced state. It can undergo oxidation and hence anode.
Pb Pb2 2e Pb2 SO4
2

PbSO4

Total anodic

Pb SO4

PbSO4 2e

Total cell reaction is (anodic and cathodic)

PbO2 Pb 4 H 2SO 4
2

2 PbSO4 2 H 2O
2F

i.e., PbO2 Pb 2 H 2 SO4 2 PbSO4 2 H 2O

Charge cycle: All reactions that occur during discharge cycle are exactly reversed during charging. The electrodes on which PbO2 is converted to PbSO4, should be oxidized back to PbO2, ie from Pb+2 to Pb4+. Hence these are connected to positive terminal of a DC supply. The electrodes on which Pb is transformed to PbSO4 have undergone oxidation, i.e., Pb0 to Pb2+. Hence reduction should occur to bring PbSO4 back to Pb. These are attached to the negative terminal of the DC power supply. Required quantity of current is passed while the discharge reactions are reversed. Oxidation:

PbSO4 2H 2O PbO2 4H SO4 Reduction:

PbSO4 2e Pb SO4
2

2e

Total 2F 2 PbSO4 2 H 2O PbO2 Pb 2 H 2 SO4 Sign convention PbO2 Plates terminal is marked (+ve) Pb Plates terminal is marked (-ve) Flow of electrons occurs from Pb to PbO2. Hence positive current flows from PbO2 to Pb: hence this sign convention. An interesting feature of this charge discharge cycle is that starting material is same on both electrodes and material at the end is same. It is shown schematically as.

25

1 charge PbO 1 charge

st

st

PbO2 Discharge charge Discharge Charge Pb PbSO4

Functioning of the battery: Rating of the battery: The battery is rated in Ah. From the total cell reaction, it is clear that theoretically 1 mol of Pb. 1 mol of PbO2 and 2 mol of sulphuric acid are required to produce 2F of current i.e 2 26.8 Ah. But in practice deriving this quantity of electricity depends on many factors. 1. Material Quantity: Only theoretical quantity will not deliver this current. As the reaction proceeds water formed, dilutes the sulphuric acid and specific gravity decreases. The rate of reaction will decrease. Formation of PbSO4 increases the internal resistance as PbSO4 is a poor conductor. As the internal resistance increases the output voltage decreases. Hence an excess quantity to the tune of 25 to 30% over the theoretical quantity is normally taken. Theoretical quantity is calculated based on the balanced cell equation and it forms the basis. 25 to 30% over this quantity is normally taken. 2. Discharge Cycle: i. The open circuit voltage is 2.0. When a load is connected it decreases immediately to 1.98 and there after gradually to 1.75 -1.1. Below that the decrease is steep. Hence the duration of one discharge is upto the point of steep decrease. This is called useful period. It is advisable not to draw any current beyond 1.1 V. It is to be recharged. i. Period of use depends on discharge rate: A 20 Ah rated battery theoretically means 20 ampere current can be drawn for one hour or 1 Ampere for 20 hrs and several combinations in between. But the optimum rate of discharge depends on the area of the plate and thickness of the coating. For heavy current output and for shorter period of discharge a thin coating on a large area is preferred. The electrolyte can easily percolate through the coating and react with the inner layers quickly. More quantity of electroactive material will react in unit time and produce heavy current. If the coating is too thin, the material would have reacted fast and calls for frequent recharging. Hence an optimum thick coating is given. The electrode area is decided by the end use. Motor cycles and scooters have 6 to 12 volt battery, consisting of 7-11 plates (anode-cathode assembly). Batteries used for cars vary from 11-19 plates depending on the size of self motor and engine capacity. Batteries used in lorry contain 21-27 plates. The coating thickness is such that

26 it gives the necessary high current during starting of the engine. These batteries are designed to give heavy output of current if required. They can be in continuous use. Batteries used in UPS, have moderate thick coating. They can supply current for 6-8 hours, for an UPS, of 1KW capacity. They are designed to give the required current for specific period and thereafter need to be recharged. Where low current upto 0.5 to 1 A is to be drawn continuously for a long period, for example, batteries used in laboratories, thick coating is given on the designed plate area. An oversimplified rule is if 5A current is to be drawn continuously the battery capacity should be 4 to 5 times i.e., 20 25 Ah. It can supply higher current upto 15 A for a short period. Charging cycle: Similarly the rate of charging a battery plays an important role in deciding the life of a battery. Generally it is better to charge at a lower rate for a longer period than at a higher rate for a shorter period. For example a 20 Ah battery with an optimum discharge rate of 5A may be charged at 1-2 A current; at 1 A for 20 hrs or 2 A for 10 hrs. Here again a simplified, unwritten rule is that the charging rate should not exceed 30 -35% of optimum discharge rate. Charging at a lower rate for long period allows the electrolyte to penetrate the coating slowly reach the inner layers and convert them back to the charged condition. If charging is done rapidly, the inner layers are not reached by the electrolyte and will not be converted. Charging voltage is slightly higher than the cell voltage. At 2.1 to 2.15 the required current should be reached. Otherwise some cells in the battery are defective. Charging at still a higher potential involves gas evolution and the coating porosity increases and eventually becomes weak. These batteries are to be used in upright position, since the electrolyte is a solution and holes are made in the vent-knobs for release of gas, occasionally produced. But small sized batteries are now manufactured which are sealed and can be used in any position. The cell is closed and pressure valve is provided. The oxygen produced inside is converted to water by combining with hydrogen discharge. The oxygen reaches the cathode area and reacts with the discharged hydrogen. This type of cell is called VRLA (valve regulated lead acid battery). In case of excess pressure the valve opens up to release the pressure.

Maintenance: Theoretically a battery can undergo any number of charge-discharge cycles. But in practice, a well maintained battery withstands about 300-350 charge-discharge cycles. The electroactive coating of PbO2 and Pb lose their activity slowly, porosity decreases by slow accumulation of PbSO4 and finally crumples into loose particles. Points to observe for well maintenance 1. Overcharging or undercharging should be avoided. Overcharging is charging for a longer period than required or at a higher voltage than prescribed. This leads to gas evolution (H2 and O2) which erode or scour the coating and weaken it. Undercharging is charging for a lesser period or at

27 a lesser rate than prescribed. This leaves PbSO4 unconverted to PbO2 and Pb. This increases the internal resistance of the battery. The useful period till next charge is considerably reduced. Repeated undercharging, leads to accumulation of PbSO4 and beyond a point, the cell cannot be charged. 2. Wrong polarity connection should be avoided totally. During discharge cycle, the entire coating of PbO2 would not have been reduced to PbSO4 and similarly the entire coating of Pb would not have been oxidised to PbSO4. 30-40 % of the respective coating will be present. During charging PbSO4/PbO2 plates should be connected to the positive and PbSO4/Pb plates to the negative terminal of DC supply so that PbSO4 on PbO2 will be oxidized to PbO2 and PbSO4 on Pb will be reduced to Pb. If a wrong polarity connection is given, a mix up of PbO2 and Pb will occur on both sets of plate i.e it is mix up of oxidized and reduced species which are electroactive. This mixing up of the electroactive material amounts to the formation of hundreds of short circuited local cells. Sparks will be produced and the battery will get totally discharged and within minute it becomes dead. 3. Withdrawal of current more than the prescribed level is to be avoided. This weakens the coating. 4. The electroactive coating is very sensitive and its texture should not be tampered with. The plates need no cleaning. 5. The terminals often get a coating of CuSO4 due to reaction of spilled acid with copper or brass connections. Periodically, they should be cleaned. 6. The specific gravity of the acid is to be checked periodically and if it falls below 1.1, acid is to be added or if it is high, distilled water should be added, to the mark. Disadvantages: 1. It is very difficult to maintain. Even though maintenance free batteries are advertised today larger sized batteries need to be maintained. 2. The weight of lead acid battery speaks much against its use. Rules out its application in space related appliances. For example a battery to deliver 2F electricity, will weigh One mol. Lead 208 One mol PbO2 - 240 Two mole H2SO4 196 644 650 plus the container weight For higher rated batteries the weight will be high. Lead is toxic and pollutes the area. But in spite of the disadvantage mentioned above, its application is very wide and is still on the increase. In Summary, 1. The battery is rugged and dependable, 2. It can supply high current. 3. Continuous withdrawal of current is possible. 4. It is economical.

28

VALVE-REGULATED BATTERIES: Lead acid batteries available in the market until recently are vented type and hence had to be used in the upright position. This is a very serious limitation in small size portable units. In military aircraft where large size batteries are used, aerobatic maneuvers will cause acid spillage. Many attempts were made to develop hermetically sealed batteries but the problem of buildup of an explosive mixture of oxygen and hydrogen at the approach of top-of-charge or during overcharge. For conventional flooded cells hydrogen and oxygen produced during overcharge are allowed to escape. A unique aspect of the VRLA design is that the majority of oxygen discharged within the cell at normal overcharge rate is recombined in the cell. To solve this problem, platinum metal catalysts were used to facilitate the recombination of hydrogen and oxygen. The platinum metal was supported generally on a pellet of finely divided silica, alumina or carbon and it was located above the acid at the top of the cell. Initially, catalytic recombination works well, but after a while the pores of the pellet get clogged with water, which restricts further access of the gas. No fully satisfactory catalytic device has been developed so far. The alternative approach is to recombine the oxygen at the negative electrode through internal oxygen cycle as follows: At the positive electrode: H2O 2H+ + O2 + 2e (c)

At the negative electrode: Pb + O2 + H2SO4 PbSO4 + 2H+ + 2e PbSO4 + H2O Pb + H2SO4 (a) (b)

In this cycle the oxygen discharges chemically at the negative electrode (Pb). This shifts the potential to a more positive value (favouring oxidation) and decreases the rate of hydrogen evolution. At the negative electrode which is on charge, reduction of Lead sulphate to lead takes place as per the equation (b). Now a path should be provided for the oxygen liberated at the positive electrode (c) to reach the negative electrode so that it can react as per the equation (a). For this the design of VRLA is such that the plates are positioned closely and are separated by a glass mat which is composed of fine glass strands in a porous structure. The cell is filled with only enough electrolyte to coat the surfaces of the plates and the individual glass

29 strands in the separator, thus creating the starved electrolyte condition. Oxygen diffuses through the separator easily, reaches the negative electrode and undergoes recombination. The pressure release valve maintains an internal pressure and this condition aids recombination by retaining the gases long enough within the cell for diffusion to take place. The net result is that water is cycled electrochemically to take up the excess overcharge current beyond that used for conversion of active material. Thus the cell can be overcharged sufficiently to convert all the active material without loss of water particularly at the recommended recharge rates. If overcharged excessively gases accumulate and finally escape through the emergency vents. To help the diffusion of oxygen the electrolyte is immobilized between the plates in VRLA. This is done by mixing sulphuric acid with very finely-divided silica (fumed silica). This forms a viscous solution which converts to a gel on standing. Oxygen transfer occurs through fissures in the gel that arise during the early stages of battery life. Another design bears the name AGM battery. AGM stands for Absorptive Glass Micro-fiber, from which the separator is made. It is saturated with acid to about 90% of its absorptive capacity. The remaining pore volume is available for the passage of oxygen to the negative plate. The advantages and disadvantages of VRLA in comparison with flooded design are listed below: Advantages: No addition of water or acid is necessary No acid spillage, no acid fumes and hence there is no corrosion of contact points. Operable in any orientation and easy transportation. Less overcharge at room temperature. Disadvantages: Careful charging is required. Thermal management is more critical. Significant variation of top-of-charge voltage. Increase in overcharge is required at higher temperatures. Cannot measure relative density. Not available in dry charged state. Shelf life is 2 years maximum.

RECHARGEABLE ALKALINE-MANGANESE CELLS Though Zn-MnO2 cells are normally regarded as primary type, recent research has led into the design of rechargeable Zn-MnO2 cells. It is possible to recharge this type of cell provided the correct design is used and charge-discharge conditions are tightly controlled. This new type of cell

30 is called Rechargeable Alkaline-Manganese cell (RAM) which combines the performance of alkaline-manganese technology with the benefit of reusability for a limited number of cycles. Such a system might be termed quasi-secondary battery Highly alkali-resistant separators were developed and used. The capacity of the zinc electrode is limited such that the discharge does not take place beyond the first electron transfer. MnO2 + H2O + e MnOOH + OH This corresponds to a cut-off voltage of 0.9 V. On recharging the above reaction is reversed. Charging is controlled not to exceed a voltage of 1.65 to 1.68Charging to higher voltage produces a hexavalent manganate and oxygen gas. The soluble manganate disproportionates into tetra-valent MnO2 and a non-rechargeable divalent manganese species, which results in a loss in cycle capacity. The use of special catalysts is now being investigated to suppress the manganate formation and overcome the poor reversibility of the discharge of MnO2. The electrolytic manganese dioxide is replaced with a specially prepared bismuth-doped form of manganese dioxide (BMD). This modified cathode permits a two electron MnO2 Mn(OH)2 reversible discharge.` The RAM technology has now been commercialized and cells (bobbin design) are available up to the D size with custom-designed chargers. The performance of RAM cells indicates that their capacity is higher than conventional rechargeable cells of similar size. Cost-wise it is highly economical. These do not suffer from memory effect and disposal problem with toxic material. The output voltage being 1.5 these cells can replace primary cells without any difficulty. However these cells are suitable for low-rate applications such as portable compact discs and tape players, laptop computers, hand held video games and toys. The maximum power output is much lower than that of either Ni-Cd or lead acid battery.
[ An interesting demonstration was mounted in Austria, in May 1990 when RAM was in developmental stage. A pack of 400 AA size cells were connected in a 20 X 20 array to give a 30 volt battery with a specific energy of more than 60 Wh per kg. This was used to drive an electric bicycle in a race across a 2400 meter mountain pass in the Austrian Alps. The bicycle won the race in conditions of freezing rain and thunder storms. The battery provided 600W continuously (1A per cell) on the uphill stretches and received regenerative recharging on the downward slopes. Regeneration was done with the help of a motor as a generator during hill descent and this converts the vehicles potential energy into electrical energy which recharges the battery. This may not be economical but the demonstration points out the capacity of the battery.]

Nickel-Cadmium battery: Nickel cadmium cell popularly known as Ni-Cd battery is a reversible one and has come into commercial use. It is available in various shapes and sizes. Fabrication: Nickel sulphate solution (10 %) is mixed with sodium hydroxide solution to precipitate nickelous hydroxide.

31
NiSO4 2 NaOH Ni (OH )2 Na2 SO4

The precipitate is filtered, washed and dried. The powder is ground well with nickel foil of 14% by wt of nickel hydroxide. The nickel foil is prepared by plating nickel over copper sheet from dull nickel plating bath. The foil is peeled off from the copper substrate. This foil is mixed with Ni(OH)2. This admixture of Ni(OH)2 and nickel is packed in steel perforated cages. Several such cages are prepared and connected to a common terminal. This set forms the cathodic material. The anode plates are made as follows. Thin cadmium sheets are made the anode in 8% Cd(NO3)2 solution and stainless steel sheets are made the cathode. A current of 5 A/dm2 is passed for about 45 minutes, when the surface of cadmium anode gets converted to cadmium oxide. This Cd/CdO plates are positioned intermittently with the cathode steel cages, containing Ni(OH)2-Ni admixture. Insulating microporous PVC sheets or cellophane sheets are interlaced. This assembly is housed in a PVC container. 20% KOH solution is added to fill the container. It is closed with a PVC lid, and sealed hermetically. First Charge: The terminal of steel grids or cages containing Ni(OH)2/Ni is connected to the positive terminal and the Cd/CdO plates terminal is connected to the negative terminal of a DC power supply. The required current is passed. Nichelous hydroxide is oxidized to electroactive, spongy and porous nickelic hydroxide, while CdO at the other electrode is reduced to spongy, porous and electroactive cadmium. The cell is ready for use. Ni (OH )2 Ni (OH )3 (active)

CdO Cd (active)
Discharge cycle: When the battery is connected to a load the following reactions occur. Cathode Ni H 2O e Ni...H OH

Ni(OH )3 Ni....H Ni(OH )2 Ni H 2O

Ni (OH )3 e Ni (OH )2 OH (2)2 Ni (OH )3 2e 2 Ni (OH )2 2OH

Total cathodic

Water is reduced and hydrogen is anchored to nickel atom and activates it. This reduces the electroactive nickelic hydroxide to nickelous hydroxide. Anode: Cd Cd 2 2e

Cd 2 2(OH ) Cd (OH ) 2
Total
Cd 2(OH ) Cd (OH ) 2 2e

32 Electroactive cadmium gets oxidized to cadmium hydroxide. Total cell reaction is 2F Cd 2 Ni (OH )3 Cd (OH ) 2 2 Ni (OH ) 2 Charging Cycle: The discharge reactions are exactly reversed during charging. 2F Cd (OH ) 2 2 Ni (OH ) 2 Cd 2 Ni (OH )3 Functioning of the cell: 1. It is to be noted from the total cell reaction that the electrolyte is not involved. Hence the quantity of the electrolyte is immaterial. It is enough to take KOH solution to just cover the entire area of the electrodes. 2. Because of this factor, the cell can be sealed air tight. No need is there to add water or alkali. No gases are evolved. The cell can be used in any position. 3. Because of this phenomenon miniaturization of the cell is possible. Two microelectrodes can be prepared and button size cells can be constructed. 4. The open circuit voltage is 1.6. When a load is connected it reduces to 1.5 and gradually decreases to 1.1 to 1.2 and there after it is to be charged. 5. The charging potential is 1.6 to 2.0. Overcharging and undercharging do not affect the cell as in lead acid. 6. Similarly wrong polarity connection during charging does not cause any damage. The reactions do not occur. 7. Since alkaline electrolyte is employed the corrosion is less. The terminals are not affected. No periodical cleaning is involved. 8. 1 mol of nickelic hydroxide and one mol of cadmium are required to generate 2 faradays or 2 26.8 Ah electricity. For generating this quantity of electricity the weight of the battery is one third the weight of lead acid battery. 9. Batteries delivering very low current to very high current are possible with Ni-Cd. (1 mAh to 500 Ah) 10. The battery is rugged, easily maintained and more efficient than lead acid on weight basis. But the cost of this is very high.

NICKEL-ZINC BATTERY

33 Zinc having a high oxidation potential is regarded as an ideal negative electrode in battery field. Hence nickel-zinc cell has a comparatively high voltage and correspondingly high specific energy. The discharge-charge cycle reactions are
Dis

Zn + 2NiOOH + 4H2O Zn(OH)2 + 2Ni(OH)2. H2O

Ch

The OCV is 1.78V and in practice the cell discharges at 1.6V and can attain 90 to 100Wh/kg, while an industrial battery pack is expected to yield 70 Wh/kg. This performance is substantially higher than that of lead-acid, nickel-iron or nickel-cadmium. Further zinc is non-toxic and cheaper while cadmium is toxic and expensive. This cell looks very attractive for electric vehicles but suffers from one serious setback. Greater solubility of zinc in potassium hydroxide compared with cadmium or iron leads to a much reduced cycle-life. Also zinc dentrites grow from the negative plate during recharging and penetrate the separator and cause an internal short circuit. Much research is in progress to get over this drawback. NICKEL-METAL HYDRIDE BATTERIES Nickel-metal hydride cells are a later development of the nickel-hydrogen battery employed in satellites. Hydrogen is stored reversibly in the form of a metal hydride which forms the negative electrode of the cell. The positive electrode is a standard nickel oxide electrode and the reactions are: At the positive electrode NiOOH + H2O + e Ni(OH)2 + OH
Ch Dis

At the negative electrode MHX + OH

Dis

Ch

MHX1 + H2O + e

The metal hydride should have the following properties to function as an effective store house for hydrogen. High storage capacity Ready formation and decomposition at an appropriate rate Repeated cycling capability without change in pressure-temperature characteristics and with low hysteresis Good corrosion resistance Proven safety in use

34 Low cost

Earlier LaNi5 alloy was used as the negative electrode and it takes up hydrogen reversibly at ambient temperature to form a hydride of the type LaNi5H6 A few commercial alloys have been developed and patented. One is called AB5 type alloy where A is a mixture of rare earths and B is partially substituted nickel. Another one is of the type AB2 where A is titanium and/or zirconium and B is partially substituted nickel. The operating voltage of a nickel-metal hydride cell is almost the same as that of Ni-Cd cell and the discharge curve is quite flat. The capacity of this cell is significantly greater than that of a Ni-Cd cell of the same size and hence the specific energy is 1.5 to 2 times greater. The cell is resilient to both overcharge and over discharge and may be operated from 30 to +45oC. Also this does not pose any toxicity problem. The disadvantages are a comparatively high cost, a higher selfdischarge rate and poor charge-acceptance at elevated temperature. Super power or Ag-Zn battery: This battery is a high power battery. It finds extensive application in space related devices. Fabrication: Formation of electrodes. Cathodic material: Thin silver sheets are made the anode in AgNO3 solution with stainless steel sheets as cathode. A current of 10 A/dm2 is passed under 6 V for 60 minutes. Silver sheets are anodized on the surface to a coating of electroactive silver peroxide. O) O) Ag ( Ag 2O ( Ag 2O2 ( Ag O O Ag ) These Ag/Ag2O2 sheets are connected to a common terminal as per current requirement. Anodic material Thin zinc sheets are used as such. These zinc sheets and Ag/Ag2O2 sheets are arranged alternate to each other with microporous PVC sheets interlaced, thus insulating the zinc sheets from Ag/Ag2O2. 40% potassium hydroxide solution serves as the electrolyte. The electrode assembly is housed in a PVC container and potassium hydroxide solution is filled up. It is closed with a PVC lid and sealed. Discharge cycle: Cathodic Ag2O2 H 2O 2e Ag2O 2OH

Ag2O H 2O 2e 2 Ag 2OH
Total Ag 2O2 2 H 2O 4e 2 Ag 4OH Hydroxyl ions are generated at these electrodes. Anodic:

35
2Zn 2Zn2 4e 2Zn2 4OH 2Zn(OH )2

Total

2Zn 4OH 2Zn (OH ) 2 4e

The hydroxyl ions which are generated at Ag/Ag2O2 plates combine with zinc ions produced at the other electrode forming Zn(OH)2.
D ) Total cell reaction Ag 2O2 2 H 2O 2Zn 4 F ( 2 Ag 2Zn (OH ) 2 Charging cycle: The discharge reactions are exactly reversed during charging. 2 Ag 2 Zn (OH ) 2 4 F ( Ag 2O2 2 H 2O 2 Zn C )

Working: This is a high power battery since 4 faradays of electricity are released for one mol of silver peroxide, one mol of zinc and two moles of water. The total weight will be much less than lead acid battery supplying the same quantity of electricity. High current output is possible here. Since the size is compact and the battery is sealed, it has wide range of applications. Since the cost of this is prohibitive it is used in specialized applications like space technology and in research field. Alkaline electrolyte does not cause any corrosion. Ag and zinc are non-toxic and hence the battery is eco-friendly. The open circuit voltage is 1.6 V. Heavy current can be withdrawn continuously for considerable period. This can also be made in any size. But its high cost prevents commercial use. Lithium Batteries: Lithium Secondary Battery The rechargeable Li cell was found to be more difficult to develop than the primary cells. It was only after 1990, practical cells of Li ion type with graphite negative electrodes have become commercially available.

Lithium Ion Battery: The origin of this battery was from the discovery that Li ions could be absorbed or intercalated into the crystal lattice of trivalent cobalt or nickel oxides to give the compounds LiCoO2 and LiNiO2 respectively. When these oxide electrodes were used as positive against metallic lithium negatives in an organic electrolyte, a 4 v cell resulted. This led to the development of Lithium ion cell, which contains no metallic lithium and hence is safer. The principle of the cell is to use two-intercalation electrodes one positive and one negative with Li ions shuttling between the two. Graphite or amorphous carbon (coke) with a high surface area is the material for absorbing Li ions, upto a composition LiC6.

36 The cycle can be represented as follows where x > 0 but <1. LixC6 6C xLi Xe ch arge The absorbing carbon can be obtained from petroleum coke, carbon black or pyrolysed polymers. Carbon from different sources exhibits different intercalating capacity towards Li+. The concept of lithium ion cell is illustrated in the figure below.

The majority of commercial lithium cells use positive electrodes of cobalt oxide. The positive electrode reaction is Li0.55CoO2 0.45 Li 0.45 e LiCoO2 where 0.45 Li+ is the maximum amount of lithium ions that can be de-intercalated (desorbed) from LiCoO2. This electrode is very expensive. A cheaper version employing nickel oxide has also become commercial. The adsorption desorption cycle is complicated. The reaction is Li0.35 NiO2 0.5 Li 0.5e Li0.85 NiO2 When either of this is combined with a LiC6 negative electrode, a cell with a nominal voltage of 3.6 V is obtained. This is equivalent to almost 3 Ni-Cd, cells. Positive electrodes with cheaper MnO2 are being developed. The attributes of lithium ion cells are summarized: High energy density -- 125 Wh/kg; 300 Wh/litre.

37 High operating voltage -- 3.6 V More than 500 charge-discharge cycles. Low self discharge Rapid discharge, if required, is possible. Safer than cells which use lithium metal. It is very popular and over 500 million units per annum are currently produced world- wide. These are produced in coin, button and cylindrical sizes. Lithium polymer battery: Polymers containing a heteroatom, such as oxygen or sulphur have high dielectric constant and showed a tendency to dissolve lithium salts in good concentration. For example polyethylene oxide (PEO) dissolves LiClO4. This led to the development of Li-polymer battery. It is an ultra thin cell of 100200 m thick. It is a laminate of lithium metal foil (ve electrode), a thin sheet of polymer electrolyte and an intercalation compound (metal oxide) deposited as a thin layer on a metallic current collector (+ve electrode). In one production, the polymer electrolyte was a lithium salt dissolved in PEO. The electrolyte was made by dissolving PEO and Li salt in a solvent like acetonitrile (CH 3CN). A thin film is solution cast. The intercalation (+ve) electrode was vanadium oxide (V6O13). It was prepared by adding V6O13 and graphite powder to the solvent, to make slurry. This is cast as thin film on Ni foil, current collector terminal. The overall thickness was only 75 m. The voltage is 3.3 and current density is 1 mA cm-2. Low CD is compensated by large area of the electrode present. These find application in laptop and notepad computers. RESERVE BATTERIES Batteries which use highly active component materials to obtain the high energy, high power and/or low temperature performance, are designed in a reserve construction to withstand deterioration in storage and to eliminate self-discharge prior to use. These batteries are used to deliver high power for short periods of time after activation in applications like missiles, torpedoes and other weapon systems. In the reserve structure one of the key components of the cell is separated from the remainder of the cell until activation. In this condition no reaction occurs and the long term storage becomes possible. Usually the electrolyte is isolated. The reserve batteries are classified as: Water-activated batteries: Activation by fresh or sea water. Electrolyte Activated: Activation by the complete electrolyte or with the electrolyte solvent. The solute is present or formed in the cell. Heat-activated batteries: A solid sale electrolyte is heated to the molten condition and becomes ionically conductive, thus activating the cell. These are called Thermal Batteries. Water activated batteries:

38 These batteries are widely used in applications like weather balloons, sonobuoys and electric torpedoes. The anode material in these batteries is mostly magnesium alloys and cathode is a metal halide. It is activated by adding water or an aqueous electrolyte. The battery is used at moderate to heavy discharges for 24 hours after activation. They can be activated by seawater also. 1. Magnesium water activated battery: Mg/AgCl was developed by Bell Telephone Lab. as the power source for electric torpedoes. Mg/CuCl system was also widely used. The principal and overall current producing reactions are given below : 1. Mg/AgCl cell Anode: Cathode Mg Mg++ + 2e 2AgCl + 2e 2Ag + 2Cl -----------------------------------------Mg + 2AgCl MgCl2 + 2Ag

2. Mg/CuCl cell Anode Cathode Mg Mg++ + 2e 2CuCl + 2e 2Cu + 2Cl -----------------------------------------Mg + 2CuCl MgCl2 + 2Cu

3. Mg/PbCl2 cell Anode: Cathode Mg Mg++ + 2e

PbCl2 + 2e Pb + 2Cl -----------------------------------------Mg + PbCl2 MgCl2 + Pb 2. Electrolyte/spin activated batteries: The spin dependent design provides a means of activating reserve batteries using liquid electrolytes. The electrolyte is stored in a container in the center of the battery. The shock of the firing (when it is used in an artilleryprojectile) breaks or opens the container the electrolyte is distributed into the annular shaped cells by the centrifugal force of the spinning of the projectile.

39 The most commonly employed spin reserve battery is lead/fluoboric acid/lead dioxide whose chemistry is given below: At anode ( plate) Pb Pb++ + 2e Pb++ + 2BF4 Pb(BF4)2 ---------------------------------------Pb + 2BF4 Pb(BF4)2 + 2e At cathode (+ plate) PbO2 + 4H+ + 2e Pb++ + 2H2O Pb++ + 2BF4 Pb(BF4)2 ---------------------------------------PbO2 + 2BF4 + 4H+ + 2e Pb(BF4)2 + 2H2O Total cell reaction is Pb + PbO2 + 4HBF4 2Pb(BF4)2 + 2H2O Fluoboric acid performs better at very low temperatures required for military applications. 3. Thermal Batteries: Thermal batteries are primary reserve batteries that use inorganic salt electrolytes, which are non conductive at ambient temperature. Pyrotechnic materials are part of the cell which supply sufficient thermal energy to melt the electrolyte. In the molten condition the electrolyte is highly conductive and the cell supplies high currents. Initiation of a thermal battery is provided by an energy impulse from an external source to a built-in initiator, which is an electric match or an electro-explosive device and that ignites the cell stack pyrotechnics. The initiation takes place in 10 to 20 milli seconds. The shelf life of an inactivated cell is about 10 to 25 years. Once activated and discharged the battery is not reusable. Anode Materials: Earlier calcium metal attached to iron was used as anode. Now lithium is the most widely used anode in thermal batteries. Lithium alloys are also used. Li/Al,(20%Li), Li/Si(44%Li) are typical examples. These alloys are processed into powders which are cold pressed into wafers or pellets of thickness 0.75 to 2.0mm backed with a stainless steel or nickel current collector. Lithium metal is mixed with a binding material and pressed to foil or pellets. Elecrolytes: Most thermal batteries earlier used a molten eutectic mixture of lithium chloride and potassium chloride (LiCl 45:KCl55; melting point 3520C. Recently electrolytes involving bromides have been developed to achieve a lower melting point thus extending the operating life. These are

40

LiBr-KBr-LiF ---- melting point 3200C LiCl-LiBr-KBr ----- melting point 3200C LiCl-LiBr-LiF ----- melting point 4300C

At battery operating temperature the viscosity of molten salt electrolytes is very low and to immobilize the electrolytes binders are added to the salt. For LiAl/FeS2 clay, kaolin and fumed silica were used as the binders. MgO with high surface area is inert and highly suitable as a binder. Cathodic Materials: A wide variety of cathodic material has been developed. These include Chromates like calcium chromate, potassium dichromate, potassium chromate, lead chromate, Oxides such as vanadium pentoxide and tungsten trioxide and Sulphides like cupric sulphide, ferrous sulphide and cobalt sulphide. The criteria for the selection are compatibility with the electrolyte, thermal stability and high potential against the anode. Pyrotechnic Heat Sources: Two main heat sources are available: one is heat paper and the other is heat pellet. The zirconium-barium chromate heat paper is produced form pyrotechnic grade zirconium and barium chromate powders, of particle size less than 10 microns. The powder is mixed with water to a paste form and coated on a mat of glass fiber. Dried, cut into required size and are used. The heat paper burns at the rate of 10 to 300 cm/s and gives a heat of 1675J/g. Heat pellets are manufactured by cold pressing a dry blend of fine iron powder (1-10 micron) and potassium perchlorate. The heat content of these pellets ranges from 920J/g for 88% iron to 1420J/g for 80% iron. After combustion the heat pellet is an electronic conductor and is useful for inter cell connection. Thermal batteries are activated by applying an external signal to an initiation device that is incorporated in the battery. This may be Electric signal to an electric igniter Mechanical impulse to a percussion primer Mechanical shock to an inertial activator Optical energy signal (laser) to a pyrotechnic material. Thermal batteries can be equipped with more than one activation device. The multiple activators may be of the same type or of a combination of the above.

41 Thermal batteries are thermally insulated so that the heat generated inside does not spread outside. For this good insulation is provided along the periphery and at both ends of the cell stack. Ceramic materials and high temperature resistant plastic materials are used for insulation

Assembly of a thermal battery Cell Chemistry: Lithium/Iron Sulphide: Lithium metal, Li-Si alloy and Li-All alloy are mainly used. Electrolytes such as LiBr-KBr-LiF and LiCl-LiBr-LiF are employed. MgO is the binder used. The lithium/ferrous sulphide system is the most preferred one. The predominant discharge paths for the cathode are: i) 3Li + 2FeS2 Li3Fe2S4 (2.1 V) ii) Li3Fe2S4 + Li 2 Li2FeS2 (1.9 V)

42

iii) Li2FeS2 + 2LI Fe + 2Li2S Most batteries are designed to use only the first.

(1.6 V)

ADVANCED BATTERIES FOR ELECTRIC VEHICLES The batteries used for electric vehicles need (1) High specific energy and energy density to provide adequate vehicle driving range (2) High power density to provide acceleration (3) Long cycle life with little maintenance (4) Moderate cost. Accordingly the criteria for performance of batteries for electric vehicles are: 1. Specific energy Wh/kg 2. Energy density Wh/L 3. Specific power W/kg 4. Power density W/L 5. Life, years 6. Cycle life, cycles 7. Operating environment 8. Recharge time, h 9. Continuous discharge in 1 hour % 10. Self discharge 80 137 150 250 5 600 -30 to 650C <6 75 <15%/48 hours

The major batteries that are proposed for electric vehicle are lead-acid and nickel-cadmium rechargeable systems. These though do not match the criteria; constant research is in progress to improve the performance. 1. Redox Batteries: There are several systems of this type, one of which is the vanadium redox battery (VRB). NASA developed FeCl3/CrCl2 system. The oxidizing agent ferric chloride is the positive and the reducing agent chromous chloride is the negative electrode. Although reduction and oxidation occur in all battery systems the term redox battery refers to those systems where the oxidation and reduction involve only ionic species in solution and the reactions take place on inert electrodes. The active materials are stored externally from the cells of the battery. The electrolytes in the positive and negative electrode compartments of VRBs are different valence states of vanadium sulphate of 2 molar concentration and sulphuric acid as supporting electrolyte.

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At the positive electrode the discharge reaction is V5+ + e V4+ At the negative electrode the reaction during discharge is V2+ V3+ + e Both reactions are reversible on the carbon felt electrodes. An ion selective membrane is used to separate the electrolytes in the positive and negative compartments of the cells. Several multi-kW systems have been built and tested by Mitsubishi Chemical. 2. High temperature systems: These are also developed for electric vehicles. They operate in the range of 160 to 500oC and have high specific power and energy density. The negative material is lithium or sodium; molten salt electrolytes are used. Since high temperature is involved corrosion of cell components is high and heavy thermal insulation is required. The main battery systems are sodium/beta and lithium/iron sulphide systems. Sodium beta system includes the chemistry of sodium/sulphur or sodium/metal chloride. The terminology of sodium/beta is due to the employment of ceramic beta alumina as the electrolyte and liquid sodium is the active material. In sodium/sulphur cell during discharge sodium is oxidized at the sodium/-Al2O3 interface forming sodium ions. These ions migrate through the electrolyte and combine with sulphur that is reduced in the positive electrode compartment to form sodium pentasulphide. This pentasulphide is immiscible with the remaining sulphur and forms a two-phase liquid mixture. After all the free sulphur is consumed the pentasulphide is progressively converted into singlephase sodium polysulphides. During charging these reactions are reversed. The reactions are: Negative electrode: Positive electrode: Overall cell reaction: 2Na 2Na+ + 2e xS + 2e Sx2 2Na + xS Na2Sx (x=5-3) Eocv = 2.076

The cell voltage is almost constant at 2.076 during 60 to 75% discharge when the two phase mixture of sulphur and pentasulphide are present. When it is converted to single phase the voltage decreases to 1.9 at which the polysulphide is formed whose approximate composition is S2O4 ; when the voltage comes to 1.78 the sulphide composition is S2O3.

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Fuel cells: Fuel cell is a device in which the thermal energy due to combustion of a fuel is directly converted to electrical energy. Since the conversion is direct the efficiency is high with minimum loss. It is used in space related appliances. Several cells using fuels like carbon, hydrogen, hydrogen peroxide, methanol and hydrazine have been developed. First let us consider the working of carbon and hydrogen fuel cells which are basic. The combustion reaction of a fuel, in a fuel cell takes place as oxidation of the fuel and reduction of oxygen. For any combustion reaction different fuels may be used, but oxygen is a common constituent. Carbon Fuel cell: (Bacon cell) Carbon (graphite) powder is taken in a porous pot. A steel grid is kept inside the carbon powder and is externally connected to a terminal. Earlier the porous pot is kept immersed in a saturated solution of sodium carbonate. The porous pot is surrounded by a steel vessel, which forms the other terminal. Through the annular space between the porous pot and the steel vessel O2 gas is passed. The cell is initially heated to 600 oC. Then carbon combines with oxygen forming CO2. A potential is generated across the two terminals. As long as the fuel burns, potential is generated. Combustion reaction is C O2 CO2 This is viewed as an electrochemical system involving oxidation and reduction as shown below: C gets oxidized. Carbon ions migrate through the porous pot and react with carbonate ions present in the pores. O2 percolates through the pores and get reduced to oxygen ions, which react with Na+ forming sodium oxide, which reacts with carbon dioxide and Na2CO3 is generated.

Reactions are: Anode:

C C 4 4e 2 Na2CO3 4 Na 2CO3 C 4 2CO3

Cathode:
2 2

3CO2

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O2 4e 2O 2 4 Na 2O 2 2 Na2O 2 Na2O 2CO2 2 Na2CO3

Total

C O2 CO2

Net reaction is oxidation of carbon and reduction of oxygen leading finally to the combustion reaction. The voltage of the cell is 0.75 V. It gives a current of 250 mA/cm2 area of electrode. Hydrogen-oxygen fuel cell: (Davtyan cell) Here hydrogen is used as the fuel. 22% KOH solution is circulated from a reservoir through a loop system. Two electrodes on either side surround the tube. Oxygen gas is circulated surrounding one electrode containing graphite powder and 5% silver powder. The other electrode consists of graphite powder with 5% Nickel powder and an outer tube through which hydrogen is passed surrounds it. The electrolyte is heated to about 200oC and circulated. The following reactions occur. H 2 4OH 4 H 2O 4e Anode: Cathode: Total cell reaction:
2 H 2O O2 4e 4OH
4F 2 H 2 O2 2 H 2O

This is nothing but the combustion reaction of hydrogen. Four faradays of current are released. These reactions are not reversible and hence the fuel cells are not rechargeable. The open circuit voltage is 0.95-1.0 V and current output is 350 mA/cm2. When electricity is available it can be utilized to electrolyze water to hydrogen and oxygen, which can be used later in the fuel cell to produce electricity.

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48 Proton Exchange Membrane Fuel Cells (PEMFC) Proton Exchange Membrane Fuel Cells (PEMFC) are believed to be the best type of fuel cell as the vehicular power source to eventually replace the gasoline and diesel internal combustion engines. First used in the 1960s for the NASA Gemini program, PEMFCs are currently being developed and demonstrated for systems ranging from 1W to 2kW. PEM fuel cells use a solid polymer membrane (a thin plastic film) as the electrolyte. This polymer is permeable to protons when it is saturated with water, but it does not conduct electrons. The fuel for the PEMFC is hydrogen and the charge carrier is the hydrogen ion (proton). At the anode, the hydrogen molecule is split into hydrogen ions (protons) and electrons. The hydrogen ions permeate across the electrolyte to the cathode while the electrons flow through an external circuit and produce electric power. Oxygen, usually in the form of air, is supplied to the cathode and combines with the electrons and the hydrogen ions to produce water. The reactions at the electrodes are as follows: Anode Reactions: Cathode Reactions: 2H2 => 4H+ + 4e O2 + 4H+ + 4e => 2 H2O

Overall Cell Reactions: 2H2 + O2 => 2 H2O Compared to other types of fuel cells, PEMFCs generate more power for a given volume or weight of fuel cell. This high-power density characteristic makes them compact and lightweight. In addition, the operating temperature is less than 100C, which allows rapid start-up. These traits and the ability to rapidly change power output are some of the characteristics that make the PEMFC the top candidate for automotive power applications. Other advantages result from the electrolyte being a solid material, compared to a liquid. The sealing of the anode and cathode gases is simpler with a solid electrolyte, and therefore, less expensive to manufacture. The solid electrolyte is also more immune to difficulties with orientation and has less problems with corrosion, compared to many of the other electrolytes, thus leading to a longer cell and stack life. One of the disadvantages of the PEMFC for some applications is that the operating temperature is low. Temperatures near 100C are not high enough to perform useful cogeneration. Also, since the electrolyte is required to be saturated with water to operate optimally, careful control of the moisture of the anode and cathode streams is important.

49 Molten Carbonate Fuel Cell: (MCFC) MCFCs are high-temperature fuel cells that can operate on a number of fuels from hydrogen to carbon monoxide containing gases including gasified coal and reformed natural gas. Cell components: Nickel containing 10% by weight of chromium as foils of 0.5 to 1.5 mm thickness is used as anode material. Lithiated nickel oxide foils of 0.5 to 0.75 mm thickness are used as cathode material. A mixture of Li2CO3-Na2CO3 (52 48 mol%) is used as melt electrolyte. The cell operates at a temperature range of 873 to 923 K. Matrix support material is the mixture of ceramic particles that forms the capillary network which contains the electrolyte. The support material does not take part in the electrochemical reaction. But the physical properties of the matrix such as thermal cycle strength and differential pressure capability are largely controlled by the support material. The size, shape and distribution of the support particles determine the interparticulate porosity and pore distribution. This in turn governs the electrolyte retention, volume and ohmic resistance of the matrix. The chemical and physical stability of the support particles is an important property for long term electrolyte retention. The matrix support is a mixture of fine and coarse particles as well as fibers. The fine particles which are currently used are -LiAlO2 of 0.1 micron size. The coarse particles are -Al2O3 of 100 micron size. Fibers of -Al2O3 of 5 micron size are added as fibers for additional strength. Electrochemical reactions that occur at the electrodes are as follows: At the cathode: (overall reduction) 1/2 O2 + CO2 + 2e CO32

At the anode: (overall oxidation) 1. If hydrogen is the fuel, the products are water and carbon dioxide. H2 + CO32 H2O + CO2 + 2e The overall cell reaction is H2 + 1/2 O2 + CO2(cathode) H2O + CO2 (anode) Carbon dioxide formed at the anode is recycled and consumed at the cathode. 2. If methane is the fuel it is first transformed to syngas by steam CH4 + H2O CO + 3H2

50 The oxidation reaction is H2 + CO + 2 CO32 H2O + 3CO2 + 2e

Different technologies are available in using methane as fuel. Internal reforming and external reforming are in vogue. External reformers operate at around 1073K and the heat required is obtained from the anode exhaust gases through heat exchangers in MCFC. Internal reformers operate at around 923K and use catalysts.

Methanol Fuel Cell The direct methanol-air fuel cell (DMFC) is highly suitable for portable power sources, electric vehicles and transportation applications. Methanol is cheap, readily available, easily stored and handled. In DMFC it is directly oxidized and in indirect methanol cell it is reformed to hydrogen, which functions as the fuel. The typical design of a DMFC is shown below:

Schematic DMFC This consists of an anode at which methanol is electro-oxidized to carbon dioxide: CH3OH + H2O CO2 + 6H+ + 6e E0 = 0.016V/SHE

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At cathode oxygen is reduced to water or steam: 3/2O2 + 6H+ + 6e 3H2O E0 = 1.229V/SHE

The main advantages of the methanol fuel cell over the other cells are Fuel vaporizer and associated parts are not required. Thermal management systems are not needed. Methanol liquid can be used as a coolant also. Lower size, weight and temperature of this system compared to others.

Despite the above advantages this is not commercially popular because of the high cost of platinum catalyst employed for oxidation. Other difficulties are Carbonate is formed in alkaline solution which precipitates out and to avoid this acid electrolytes are to be used and they cause corrosion. Anode reaction is slow with the catalysts used at present.

The performance of DMFC depends entirely on the extent of electro-oxidation of methanol and the salient features of electro-oxidation are summarized below: Eletrosorption of methanol on bulk platinum is slow at lower potentials with a high activation energy. Subsequent proton stripping from methanol takes place via several intermediates that decrease the overall efficiency. Micro-etched surface of platinum enhances the catalytic activity and increases the rate of oxidation. Anions such as chloride, bromide, iodide, perchlorate and phosphate interfere with the electro-oxidation of methanol.

Several metals and alloys were tried as anode materials. At present unsupported Pt-Ru of high surface area is the preferred anode which has demonstrated highest cell performance. Next to this is Pt-Sn catalyst system. The ternary alloy Pt-Ru-Os has been shown to be better than the binary alloy Pt-Ru. At 363 K 0.4V, 360mA/cm2 for the ternary and 260mA for the binary has been reported. The current research is in the direction of oxidation of methanol on supported systems. For this micro/nano particles of noble metals are dispersed on high surface area materials such as carbon and conducting polymers. The support plays a major role determining the mechanical and thermal stability of the particles. The individual dispersed metal particles are physically separated from each other thereby decreasing the rate of agglomeration. This is responsible for the increased activity of the anode material. The most intensively studied electrolyte is sulphuric acid. Performance of the catalyst varies with the

52 nature of the electrolyte, its ionic activity and corrosivity. Other acids such as sulphonic acid and its derivatives have also been explored. Biochemical Fuel Cell Microorganisms are able to utilize a vast range of organic and inorganic substances, which can be regarded as potential fuels for combustion in a fuel cell. The direct combustion of these substances cannot be performed due to lack of suitable electro catalysts. Microorganisms dispose of a large set of enzymes for the highly efficient and controlled oxidation of different substrates with concomitant electron transfer by way of a sequence of reactions to a terminal electron acceptor (oxygen for aerobic catabolism). The key enzymes for these processes are the oxidoreductases, which catalyze the electron transfer for the redox reactions involved, a property that is highly desirable for good fuel cell performance. The concept of bioelectrochemical fuel cells was extremely popular in the early 1960s when it was taken up by NASA (National Aeronautics and Space Administration, USA). NASAs interest in studying the production of electricity by means of biochemical reactions stemmed from the problems of waste management in the closed system of a space shuttle during longer space flights: human waste should be reprocessed in the spacecraft. Therefore, algae and bacteria were among the first organisms used in this phase of experiments with bioelectrochemical fuel cells. The first experiments in the field of bioelectrochemical fuel cells were performed in 1911. It was POTTER who first postulated a relationship between electrode potentials and microbial activity. He measured the potential difference between two electrodes, one of which was inserted into a bacterial culture and the other into a sterile culture medium. He actually made what can be considered to be the first biochemical fuel cell battery by assembling six cells, each of which consisted of a yeastglucose half-cell and a glucose half-cell without microorganisms. Such an experimental set-up is shown below. The potential difference of a vigorously growing bacterial culture amounted to 0.51 V over the control medium. The greatest deficiency of the microbial half-cell was that its current output was generally very low (105106 A).

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Early Bioelectrochemical Cell

A microbial fuel cell (MFC) or biological fuel cell is a bio-electrochemical system that drives a current by mimicking bacterial interactions found in nature. Micro-organisms catabolize compounds such as glucose, acetate, butyrate or wastewater. The electrons gained from this oxidation are transferred to an anode, where they depart through an electrical circuit before reaching the cathode. Here they are transferred to a high potential electron acceptor such as oxygen. As current now flows over a potential difference, power is generated directly from biofuel by the catalytic activity of bacteria. A microbial fuel cell is a device that converts chemical energy to electrical energy by the catalytic reaction of microorganisms. A typical microbial fuel cell consists of anode and cathode compartments separated by a cation specific membrane. In the anode compartment, fuel is oxidized by microorganisms, generating electrons and protons. Electrons are transferred to the cathode compartment through an external electric circuit, and the protons are transferred to the cathode compartment through the membrane. Electrons and protons are consumed in the cathode compartment, combining with oxygen to form water. In general, there are two types of microbial fuel cells, mediator and mediator-less microbial fuel cells. The electron transfer from microbial cells to the electrode is facilitated by mediators such as thionine, methyl viologen, methyl blue, humic acid, neutral red etc., Most of the mediators available are expensive and toxic.

54 A mediator-less microbial fuel cell does not require a mediator but uses electrochemically active bacteria to transfer electrons to the electrode (electrons are carried directly from the bacterial respiratory enzyme to the electrode). Among the electrochemically active bacteria are Shewanella putrefaciens and Aeromonas hydrophila. Some bacteria, which have pili on their external membrane, are able to transfer their electron production via these pili. Bacteria in mediator-less MFCs typically have electrochemically-active redox enzymes such as cytochromes on their outer membrane that can transfer electrons to external materials. In a bioelectrochemical fuel cell the electrode reactions are similar to those in the hydrogenoxygen fuel cell, except for the fact that the fuel is not hydrogen gas but a form of carrier-bonded hydrogen, produced by physiological redox reactions. The overall reaction of a hydrogenoxygen fuel cell and a bio electrochemical fuel cell [with the coenzyme NAD (nicotine adenine dinucleotide) as the assumed hydrogen carrier] are: Hydrogenoxygen fuel cell:

Bioelectrochemical fuel cell: