BATTERIES:

A device, comprises an electrochemical cell or a series of electrochemical cells which convert chemical energy of a spontaneous redox reaction into direct electric current at constant voltage. Batteries are in continuous demand for power sources as they are compact, dimensionally adaptable, able to operate over a wide temperature range and highly dependable. There are following three types of batteries. A. Primary batteries B. Secondary batteries

C. Reserve batteries

A. Primary Batteries
A primary battery can be defined as a device in which the cell reaction is non-reversible and it cannot be recharged. So, the amount of energy it can deliver is limited to that obtainable from the reactants that were placed in it at the time of manufacture. The most common examples of these types of batteries are leclanche cell, Alkaline cell, button cells, lithium battery. So that electrical energy can be obtained as long as the active materials are still present. Once these have been consumed, the cell can not be profitably or readily rejuvenated and must be discarded. Or in other words, they cannot be recharged and re-used.

B. Secondary batteries/Storage cells /Accumulators

A secondary battery once used can be recharged by passing current through it so that it can be used over and over again. Its electrode reactions are reversible so can proceed in either direction. During charging electrical work is done on the cell to provide the free energy needed to force the reaction in the non-spontaneous direction so that redox reaction gets reversed during recharging. Thus electrical energy is stored in the form of chemical energy and utilized for supplying the current when needed. Whereas, a primary cell acts only as a galvanic or voltaic cell, a secondary cell can act both as galvanic cell and electrolytic cell. During discharging it acts as a galvanic cell, converting chemical energy into electrical energy and during charging it acts as an electrolytic cell converting electrical energy into chemical energy. e.g Lead-acid battery, Nickle-Cadmium battery.

C. RESERVE BATTERIES:
In this type of batteries, a key component is separated from the rest of the battery prior to activation. These batteries designed in such a way that they are capable to store in an inactive state by isolating/inactivating some vital cell components (usually electrolyte) and made ready prior to use by adding/activating that component which capable them for long-term storage e.g thermal batteries are activated by melting solidified electrolyte which then become conductive, water activated batteries, the electrolyte solute is already contained in the cell while only water is added for activation. Batteries which use highly active component material are designed in this form to withstand deterioration in storage and to eliminate self discharge prior to use. They are usually used to deliver high power for relatively short periods of time needed as in missiles, torpedoes and other weapon systems.

A. Primary Batteries
1. Dry Cell or Leclanche cell

Anodic area Anode = Zinc Cylindrical Container Electrolyte/Anolyte =ZnCl2 Additive =NH4Cl

Cathodic area Cathode = Carbon Graphite Rod Electrolyte/Catholyte = MnO2 Additive = C (granular powder)

Cell Configuration MnO2C

Zn ZnCl2,NH4Cl
Anodic cell Cathodic cell

Cell Reactions A. Primary Reactions (Electrode reactions) At Anode Zn Zn2+ + 2e[Oxi Half Reaction] At Cathode 2MnO2 + H2O + 2e-

Mn2O3 + 2OH- [Red Half Reaction]

Net primary cell reaction Zn + 2MnO2 + H2O

Cell Working Mechanism
2e-

Zn2+ + Mn2O3 + 2OH-

2e_

Zn | ZnCl2 , NH4Cl || MnO2 | C Zn2+ 2OH_

As discharging going on In Anolyte Cations become in excess In Catholyte Anions become in excess This Cation and Anion disbalance retards further performance of anodic and cathodic cells so excess cations and anions are removed by secondary reactions. B. Secondary reactions (side reactions)
2NH4Cl + 2OH 2Cl + 2NH3 + 2H2O 2NH4OH

Zn2+ + 2NH3 +2Cl

[Zn(NH3)2Cl2]

NH4Cl is used to convert OH in undissociated form as NH4OH which is a weak base. If NaCl is used than OH would not convert in undissociated form as NaOH is strong base.
As dry cell has low water concentration so most of ammonia do not dissolved in water but this excess ammonia react with ZnCl2 to form a Zinc Complex. NH4Cl in paste of ZnCl2, can attack on Zn metal cylinder to liberate H2 gas as follow Zn + 2NH4Cl [Zn(NH3)2Cl2] + H2 During discharging, in anodic region electrode is consumed while in cathodic region electrolyte is consumed i.e reason they taken in larger quantities as compared to their counterpart for increasing duration of cylinder. Anode take part in redox reaction so undergoes chemical changes while cathode do not undergo chemical changes i.e reason Anode should be of high surface area and more in quantity as compared to cathode.

Characteristic Properties:
Its very cost effective to give voltage of 1.5 volts but have limited shelf life due to self discharge.

2. ALKALINE BATTERY: It is modern version of dry cell. Its called so b/c instead of NH4Cl, an alkaline electrolytic solution (usually KOH & NaOH) is used which permits cell to deliver higher current, avoids corrosive effects of acidic ammonium ion increase shelf life 5-8 times more than dry cell and supply constant voltage of throughout its lifetime as conc of OH- does not change in electrolyte during discharging.

i- Manganese dioxide-Zinc alkaline cell

Anodic Area Cathodic Area

Anode = Powdered zinc in contact with brass rod or foil

Electrolyte = KOH paste

Cathode = Powdered carbon graphite in contact with steel case

Electrolyte= MnO2

Cell Configuration
Zn | KOH || MnO2 | C Anodic cell Cathodic cell

Cell Reactions
At Anode Zn + 2OHAt Cathode 2MnO2 + H2O + 2eNet cell reaction Zn + 2MnO2 Cell Working Mechanism
2e_ 2e_
| KOH || MnO2 | C

ZnO + H2O + 2e-

[Oxi Half Reaction]

Mn2O3 + 2OH-

[Red Half reaction]

ZnO + Mn2O3

Zn

2OH + Mn2O3 ZnO

ii- Mercuric oxide Zinc alkaline cell / Mercury button or coin cell
It has high electric storage density

Cell output is 1.34 Volts

Anodic Area Anode = Powdered Zinc in contact with steel cell cap Electrolyte = Paste of KOH or aqueous solution of NaOH

Cathodic area
Cathode = Mercury in contact with steel cell casing Electrolyte = HgO

Cell Configuration Zn | KOH || HgO | Hg Anodic cell Cathodic cell

Cell Reactions At Anode: Zn + 2OHAt Cathode: HgO + H2O + 2eNet cell reaction: Zn + HgO Cell Working Mechanism ZnO + H2O + 2e- [Oxi Half Reaction] Hg + 2OH- [Red Half Reaction] ZnO + Hg

2e_

2e_
| KOH || HgO | Hg

Zn

2OH_ + Hg ZnO

iii. Silver Oxide Zinc alkaline cell / Silver button / coin cell
Anodic Area Anode = powdered Zinc in contact with steel cell cap Electrolyte = Paste of KOH or aqueous solution of NaOH Cathodic Area Cathode = silver in contact with steel cell casing Electrolyte = Ag2O

Cell Configuration Zn | KOH || Ag2O | Ag Anodic cell Cathodic cell

Cell Reactions
At Anode: Zn + 2OHZnO + H2O + 2eAt Cathode: Ag2O + H2O + 2e2Ag + 2OHNet cell reaction: Zn + Ag2O Cell Working Mechanism
2e_ 2e_
| KOH || Ag2O | Ag

[Oxi Half reaction] [Red Half reaction]

ZnO + 2Ag

Zn

2OH_ + 2Ag ZnO

This cell gives an emf of 1.6 volts with KOH as an electrolyte.

KOH offers less resistance to cell current flow so make it efficient under higher current drains. Therefore KOH types are better for the short bursts of higher current drain,e.g LCD watches with backlights. On other hand NaOH offers comparatively more resistance to cell current flow so make it suitable for low current drain which last two to three years e.g analog digital watches or digital watches without backlight.

3. Lithium Batteries:
The term lithium battery refers to a large family of batteries with a common feature of having lithium negative electrode (anode). The different lithium battery systems differ in the choice of electrolyte medium and of positive electrode system. Lithium is an ideal anode material owning to its light weight, high oxidation potential and good conductivity. The electrolyte used in lithium batteries can not be aqueous solutions, because of the high reactivity of lithium with water. Following non aqueous solutions are used
LiX + Aprotic polar organic solvent (propylene carbonate, THF, ethers & acetonitrile) LiX + Aprotic inorganic solvent ( thionyl chloride, sulfuryl chloride) An ion conducting Li salt electrolyte (LiI or Li + Al2O3) LiX + Ion conducting organic polymers (Polyethylene Oxide). Molten mixture of Lithium salt (LiCl + KCl)

Li cells have longer shell life for over 10 up to 20 years b/c it have ability to react with its surrounding electrolyte layer to form a stable passivation layer (e.g. lithium chloride, lithium dithoinite, lithium hydroxide & lithium carbonate etc. which depend upon type of electrolyte used) which retard further dissolution of electrode. In spite of passivation film lithium electrode may be activated quickly & easily by applying electrical load. Which break down passivation film quickly within fractions of seconds. Protic solvents are not used in lithium cells b/c they are not able to produce a sufficiently stable and really passivating layer with lithium electrode.

i- Lithium Manganese dioxide Battery

Anodic Area Anode = Lithium metal Electrolyte = KOH paste

Cathodic Area Cathode = Carbon Electrolyte = MnO2

Cell Configuration
Li | KOH || MnO2 | C Anodic cell Cathodic cell

Cell Reactions
At Anode Li + OHAt Cathode MnO2 + 2H2O + eLiOH + e[Oxi Half Reaction] Mn(OH)3 +OH- [Red Half reaction] LiOH + Mn(OH)3

Net cell reaction Li + MnO2 + 2H2O Cell Working Mechanism

e_ e_
| KOH || MnO2 | C

Li

OH_ + Mn(OH)3 LiOH

Advantages of Li- manganese battery iHigh energy density is stored as 1F is release by dissolution of 7g of the metal. ii- Long shelf life. iii- Low self-discharge rate (less than half of Ni based batteries). ivNeeds less maintenance. v- Can provide very high current and voltage (upto 4 v) depend upon cathode material. vi- No memory and scheduled cycling is required to prolong the batterys life. vii- Cause little harm when disposed. viii- Retain constant voltage and resistance throughout discharging process.

Limitations of Li- manganese battery

iiiiiiShow aging effect even if not in use but this can reduce by storing charged battery in a cool space. Air transportation is restricted due to fire hazards Its manufacturing cost is 40% higher than nickelcadmium battery.

B- Secondary batteries / Storage cells / Accumulators

1- Pb-Acid battery:

Anode = Cathode = Separator = Electrolyte =

Lead frame grids consist of spongy lead Lead frame grids consists of PbO2 Insulating sheet of micro porous polyethylene divider About 4 M H2SO4 solution saturated with PbSO4

Cell Configuration : Pb | PbSO4, H2SO4 || PbSO4, H2SO4 | PbO2 | Pb Anodic cell Cathodic cell

CELL REACTION: 1. Discharging At Anode i. Pb ii. Pb+2 + SO4-2 Net anode reaction Pb + SO4-2 At Cathode Pb+2 + 2ePbSO4 PbSO4 + 2e- Eoanode= - 0.36 V Pb+2 + 2H2O PbSO4 PbSO4 + 2H2O Eocathode = +1.69 V

Net cathode reaction

i. PbO2 + 4H+ + 2eii. Pb+2 + SO4-2 PbO2 + 2H+ + H2SO4 + 2e-

Net cell Pb + PbO2 + 2H2SO4 Discharging reaction

PbSO4 + PbSO4 + 2H2O +Eelectrical

Eocell = Eocathode - Eoanode = +1.69 -(- 0.36) = 2.05 V

As each electrode pair develops a potential of 2 V, a number of cell electrode pairs are connected in series to obtain higher potential. So voltage of Pb-Acid battery is always in multiple of 2 volts. Usually six electrode plates pairs are used to make a battery of 12 volts output. Cell discharging mechanism
2e_ 2e
_

Pb | H2SO4, PbSO4

|| PbSO4, H2SO4 | PbO2 | Pb Reduction

Oxidation

As discharging process consumed H2SO4 and produced water while H2SO4 is about twice dense than water so as the cell is discharge, mass density (specific gravity) of electrolyte solution also decreased therefore voltage of battery drop and it becomes less efficient b/c as H2SO4 concentration decreased, rate of discharging would also decreased. Therefore state of charge or efficiency of a battery can be estimated by measuring the mass density of electrolyte solution through hydrometer. e.g When Conc of H2SO4 is 39.2 %, 21.4%, 7.4% than electrode potential of single pair would be 2.14 V, 2.0 V, 0.9 V respectively.

Recharging:
At Cathode (previous anode): PbSO4 + 2eAt Anode (previous cathode): PbSO4 + 2H2O Net cell recharge reaction: 2PbSO4 + 2H2O Cell recharging mechanism
2e
_

Pb + SO4-2 PbO2 + SO4-2 + 4H+ + 2ePb + PbO2 + 2H2SO4

|_

+|

2e

Pb | H2SO4, Pb2+SO4 || Pb2+SO4, H2SO4 | Pb4+O2 | Pb

2+ Pb Reduction

Pb2+

Oxidation
Discharging Recharging

Overall cell reaction Pb + PbO2 + 2H2SO4

2PbSO4 + 2H2O + Eelectrical

Limitation:
Heavy weight battery due to weight of Pb. In cold weather efficiency decreases b/c as electrolyte solution become more viscous, it inhibit flow of ions b/w plates and reduce current delivery. It have tendency to self discharge. Fast charging of battery cause electrolysis of water molecule hence release H2 gas which can tear off PbO2 from cathode. This will settle down at bottom of battery and can cause short circuit of electrode Some of PbSO4 ppt do not deposited at electrode hence do not converted into PbO2 during charging which decrease battery capacity. Overcharging may damage electrodes which may lead to explosion. These batteries pose a significant danger if leakage occurs, as the electrolyte used in lead-acid batteries is very corrosive sulfuric acid. Full discharge should be avoided as during discharging both electrodes are sulfated and if cell is completely discharged then both lead electrode plates would entirely sulfated and become identical so terminal voltage collapse and reaction become irreversible.

Effect of solubility of electrode discharge product in secondary batteries

It is an important factor which influences stability of electrode structure, hence determined number of discharge /charge cycle that a battery can undergoes. If electrode discharge product is highly soluble then discharging cause loss of electrode initial structure by dissolution of electrode to a larger extent which leads to problems during recharging b/c redeposition of electrode material is fast at bottom where concentration/density of solution is high. Hence deformation/distortion of electrode structure occur which reduce efficiency & cycle life of battery. Moreover during recharging precipitated electrode material can disintegrate to form dendrites which may penetrate into separator and reached the opposite electrode, thus gradually establishing a short circuit e.g. Zn & Li metals discharge electrode product are highly soluble thus not fit to use as an efficient electrode for secondary batteries.

But if discharging electrode product is extremely insoluble (e.g. Cd(OH)2 .PbSO4 etc, Pb+2 ions have solubility in order of 10-6 mole/dm3 in presence of H2SO4 or SO4-2 ions) then it leads to formation of insulating covering layer on electrode surface. Thus discharge reactions come to halt as this passivating layer completely covered electrode surface. So only a thin layer of active material surface can reacts. This passivation problem is encountered by increasing surface area through physical changes in electrode structure i.e. a spongy electrode structure is used which has a large surface area. This will lead to precipitations of reaction product within the pores of active material surface i.e. close to place of their origin hence structure of electrode remain nearly stable.

2. SECONDRY LITHIUM BATTERIES:

Initially lithium batteries were not considered safe for use in secondary modes as they had some safety problems. During discharge lithium anode not only change it oxidation state but also migrates quantitatively to the cathode so that structure of anode completely decomposed. During recharging Lithium metal built up again through uncontrolled granular deposition at anode thus yielding large microscopic surfaces of high lithium reactivity. Moreover if Li deposited as metals within pores of separator then it cause serious cell short circuit. Overcharging of Li batteries also leads to explosion.

i. Li ion battery:
Li ion technology offered advantages of light weight and high energy density in a rechargeable and safe mode.

Chemistry NiCd NiMH Li ion

ED (Wh/L) 120-150 250-300 280-320

ES (Wh/kg) 40-50 70-80 110-130

The lithium-ion technique operates with host lattices for both anode and cathode, between which lithium ions are exchanged during discharge and charge. The anode of carbon in the graphitic or coke form, contains the lithium in the charged state and delivers it to the cathode made from transitional metal oxide MeO2 during discharge where it is able to build in a maximum amount of lithium corresponding to the formula LiMeO2. The lithium ions migrate during cycling forth and back between the two host lattices of Cx and MeO2. The following reaction scheme shows this in a simplified manner: Anode: LiC6 C6 + Li+ + eCathode: Me+4O2 + Li+ + eLiMe + 3O2 Cell LiC6 + MeO2 C6 + LiMeO2 E0 = 4V Where MeO2 = CoO2, NiO2 & Mn2O4
For recharge the arrows have to be reversed. This back and forth of the lithium ions is named rocking chair or swing Principle.

Anodic material: Carbon is a candidate for anodic host lattice due to its ability to build up stable, highly Porous particles of graphitic-layered structure which consist of parallel staggered layers of carbon hexagons units arranged in two dimensional network like structure as honey comb. Each carbon layer consists of sigma bond skeleton mounted by bond structure. Two adjacent carbon planes are held together by weak Vander waal forces i.e. no chemical bond cross linking is present. Hence normal distance b/w adjacent carbon layer of 3.35 Angstrom may be widened easily by incorporation of foreign atoms/ions. This behavior of graphite enables it to use as intercalating electrodes for intercalation of lithium. Moreover incorporation of lithium cations b/w graphitic carbon layers means accumulation of positive charges which than compensated by intake of electrons into conducting band of -bonding system. of lithium ions for incorporation is limited to formula LiC6 to LiC2 As lithium cations are of very smaller size(A0) so a slight increase in distance b/w carbon layers is required for incorporation of lithium ions. This thing justified by x-rays analysis of pure graphite and lithium containing graphite. So only a little activation energy is needed for ion-out migration i.e in-excorporaton of Li due to this a small over voltage is needed is for recharge when Li ions are inserted again in graphite. Therefore redox potential for lithium incorporation is near to potential of electrochemical solution for deposition of pure metallic lithium. Consequently lithium ion cells deliver high CCV values similar to Li primary cells, which are based on a pure lithium metal anode.

Cathodic Material:
In Li ion batteries that substances should be used as cathode which, can intercalate and discharge lithium ions at a highly positive potential compared to the intercalations into carbon cathode. Offers low kinetic hindrance for insertion and release of Li ions. Can hold & release electrons to compensate for Li-cation in-excorporation.

These requirements fulfilled by transitional metal oxides MeO2 like CoO2, NiO2
& Mn2O4 etc. Crystals of these metal oxides have layered structure with cubic closet packages. During discharge of the cell, Li+ ions are inserted b/w these layers whereas geometry of their crystal is changed only slightly by Li in-and excorporations. Thus offering low kinetic hindrance. Transitional metal atoms of these compounds can easily change their oxidation state due to easy transactions of valence electrons in their 3dn valence bands, which is necessary to compensate for simultaneous intake or release of Li ions. Although transitional metal halides and sulfides have above mentioned Properties but they are poor electronic conductor than oxides, so not used as a cathode material. Whereas Mn2O4 fulfilled all cathodic material requirements but practically it is not in use b/c in the case of Mn2O4 cathode over discharging make battery irreversible a/c to following discharging step mechanism.

(i) Discharging Mn2O4 + Li+ + e LiMn2O4 This Li ion incorporation takes place at a cell voltage of about 4V and it is reversible (ii) Over discharging LiMn2O4 + Li+ + e Li2Mn2O4 This Li incorporation takes place at a cell voltage of about 3V but it is irreversible.

Electrolyte for Li-ion batteries:

Electrolyte consists of electrolytic salt and solvents which should have following quality criteria. The quality criteria for electrolyte solvent are high dielectric constant for good solvation of salt. Low viscosity for increasing ionic mobility or conductance. Low freezing point for good low temperature performance. Inert to electrodes thus avoid exfoliation.

(Exfoliation is the destruction of anode graphite structure by incorporation of solvent molecules thus destroying cohesion of carbon layers during discharge-charge cycles. Cyclic esters like propylene carbonate (PC) and Ethylene carbonate (EC) are used as electrolyte solvent due to high dielectric constant but they are highly viscous b/c of their polarity. To compensate for it, low viscous straight alkyl esters like dimethyl carbonate (DMC) & diethyl carbonate (DEC) are added. Today lithium-ion batteries with electrolyte mixture of PC + DEC and EC + DMC are found in the market. Lithium salts with voluminous anions are used as electrolyte salts, to kinetically retard anions mobility e.g Li ClO4, LiBF4, LiAsF6, LiPF6 and LiAlCl4

Protection against overcharging: As overcharging may deposit metallic Lithium at anodes which is dangerous b/c of its high reactivity. As a protective measure a slight charging at voltage over to 4.8 V. Thus creates overpressure in hermetically sealed cell by its gaseous reaction products. A suitably designed membrane bulges consequently and interrupts the contact b/w cathode and batterys positive pole.

Protection against overheating:

One substantial problem of Li technology is lower Melting point of Li metal at 180oC. In contrast to solid state, molten Li metal strongly react with cathode and electrolyte material, releasing huge amount of heat which leads to blast of cell case. Cell lid contains positive electrode which has outer contact through thermo switch foil (polyswith ). Polyswith is made of polymer foil which is conductive at normal temperature but becomes non-conductive at a defined threshold temperature. Thus gives protection against overheating. These cells also comprises thermally soft or weak separators which close their pores at a defined high temperature and stop any further discharge reactions which hinders thermal runaway if the cell is shortened. In new secondary Li-ion systems, safety is controlled by electronic charge and discharge control devices to avoid any damage by faulty operation. This achieve by limitation of charge and discharge voltages, thermo control devices, switches and membranes to avoid overpressure due to overheating.

ii. Lithium ion polymer battery.

This class of battery is similar to Li-ion battery except having dry solid gelled Polymer electrolyte, which replaces conventional porous separator soaked with electrolyte. Solid electrolyte does not conduct electricity but allows ionic conductance lower than fluid electrolyte b/c of low ionic mobility. Hence these cells tolerate very low load b/c of higher cell resistance. On other hand solid electrolyte reduced side reactions (like self discharge) to negligible. Therefore this battery system shows high reliability during shelf lives and operational times for many years. This cell fit best only for low rate long time applications with A current for a number of years e.g cardiac pacemaker battery. These batteries are smaller in size and light weight as gelled electrolytes enable Simplified packaging by eliminating metal shell in battery structure hence make it fit for portable use. It has less safety hazards as chances for electrolyte leakage are rear.

Limitations:
They have low energy density storage Manufacturing cost is higher Cost to energy ratio is also higher than Lithium-ion

Example: Lithium Iodide solid state cell

Anode: Lithium Cathode: Iodine absorbed in dry solid polymer gel of Poly-2-Vinyl Pyridine. P2VP acts as conducting agent and absorber for Iodine so that vapour pressure of Iodine reduced. Electrolyte: Li I Cell configuration: Li | Li I || I2 (in polymer) Cell reactions: At anode 2Li discharging recharging

2Li+ + 2e-

At Cathode

discharging At cathode P2VP. nI 2 + 2erecharging P2VP. (n-1)I 2 + 2I - At Anode

Net reactions

2Li + P2VP. nI 2

discharging
recharging

P2VP. (n-1)I 2

+ 2Li I

Cell working Mechanism:

During discharging During recharging

2e_

2e_

2e_
Cathode

|_

+|

2e_

Anode

2Li | 2LiI 2Li+

||

I2
2I-

2Li | 2LiI 2Li+

||

I2
2I
-

Anode

3. Ni-Cd battery
Anodic cell Anode = grid covered with Cd Electrolyte = Cd(OH)2, KOH Cathodic cell Cathode =Ni frame grids Electrolyte = Mixture of NiO2 & Ni(OH)2

Cell configuration: Cd | Cd(OH)2, KOH || NiO2, Ni(OH)2 | Ni 2NiO(OH)

Cathodic cell electrolyte is not an exactly defined chemical compound but a mixture of Ni2+, Ni3+ and Ni4+. Thus 2.NiO(OH) in the charged state more precisely can be written as u.NiO2v.NiOOHw.H2O where u,v and w are factors that describe the share of three components.

Ni ions remain in their solid crystalline state structure in spite their oxidation /reduction during charging & discharging cycle respectively. To preserve electrical neutrality, a corresponding number of H+ ions (proton) must migrate into crystal lattice during discharge. When nickel electrode is charged (oxidized) these protons must leave the crystal lattice otherwise local space charges would immediately bring the reaction to a standstill. Small H+ ions have high mobility which facilitates such migrations but requires a large surface area of the electrode active material in order to keep penetration distance low i.e. spongy electrode is used. An important feature of Ni-Cd battery is that no KOH is consumed during charging or discharging except small amount of K+ ions that are incorporated into nickel hydroxide during overcharging.

Cell reactions: At anode: Cd + 2OHdischarging

recharging discharging

Cd (OH)2 + 2e-

At Cathode

At Cathode: 2NiO(OH) + 2H2O + 2e-

recharging

2Ni(OH)2 + 2OH-

At Anode

Net Cell reaction 2Ni+3O(OH) +2H2O + Cd

discharging recharging

2Ni+2(OH)2 + Cd+2(OH)2

Cell working mechanism:

Discharging
2e_ 2e_
Cathode

Anode

Cd | Cd(OH)2,KOH || 2NiO(OH) | Ni Cd++ 2OH - + 2Ni(OH)2

Recharging
2e_

|_

+|

2e_

Cathode

Cd | Cd(OH)2, KOH || 2NiO(OH) | Ni Cd++ 2OH 2OH - + 2Ni(OH)2

Anode

This has cell nominal potential 1.2V so12V NiCd batteries are made up of 10 cells connected in series. This is compact way of storing electrical energy reversibly thus have lower weight for a given quantity of stored energy. It used in small consumer devices. They have good charging efficiency(as charging is endothermic reaction so cause cooling of NiCd batteries), small variation in terminal voltage during discharge (It is consider drawback b/c it is difficult to detect when the battery charge is low), low internal resistance and non critical charging conditions. They can deliver higher surge current and undergoes hundred of charge & discharge cycles but their use is being discouraged b/c Cd is an environmental toxin more over it show sever memory effect and mAh rating is not high enough to keep device running for a long period. The alkaline electrolyte (KOH) is not consumed in cell reactions and therefore it specific gravity is not a guide to its state of charge as in lead acid batteries.

4. Nickel Metal hydride cells (Ni - MH Cells)

Cell Configuration: MH | KOH || NiOH | Ni

Ni MH cell is similar to Ni-Cd Cell except it uses hydrogen, adsorbed in a metal alloy for active negative material in place of Cd in Ni-Cd cell. Anodic cell Cathodic cell

Anode = Ni wire gauze grid frame coated With highly purpose & spongy metal alloys of AB2 & AB5 class like LaNi5, ZrNi2 etc. Which hold H2 gas as their hydrides
Electrolyte = conc. KOH solution absorbed in non woven synthetic material separator.

Cathode = A highly porous sintered or felt Ni substrate

Electrolyte = Nickel oxyhydroixide impregnate into cathode

Cell Configuration:

MH | KOH || NiOH | Ni

Ni MH cell is similar to Ni-Cd Cell except it uses hydrogen, adsorbed in a metal alloy for active negative material in place of Cd in Ni-Cd cell. Anodic material: In this cell H2 is not stored as a gas but hold by Anode at low internal pressure so do not required a cell container that can with stand high pressure. There are two types of transitional metals which formed metallic hydrides or Interstitial hydrides. Strong-hydride forming metals e.g lanthanum, Titanium, Zirconium & Vanadium etc. A + H2 AH (most of Hydrogen exist in hydride form)

Weak-hydride forming metals Ni, Pd, Pt, Al etc. B + H2 B.H2 (most of Hydrogen exist in diatomic molecule form)

If any one material used as anode it make cell irreversible so inter metallic compounds are formed by making alloys of both metals in AB2 & AB5 system while A is strong hydride forming metals and B is weak hydride forming metals. e.g LaNi5.ZrNi2, TiNi2, LaNi4.1Al0.3 etc A + B. H2
absorption desorption

AH + B

This intermetallic anode absorbed H2 gas as hydride during charging while desorbed H2 gas during discharging. So both metals A& B also acts as catalytic electrode surface for absorption & desorption of H2 gas respectively.

Cell Reactions Discharging At anode i) ii) At Cathode MxH

desorption absorption

XM + H2 H2O + eNi (OH)2 + OHxM0 + Ni2+(OH)2

H2 + OHNiO(OH) + H2O + e-

Net cell discharge MxH + Ni3+O(OH) reactions is

Discharging mechanism:
Hydrogen desorption is an endothermic process so cooling effect is observed when cell is discharge. Nominal cell discharge voltage is 1.3V

Recharging: At Anode At Cathode Ni(OH)2 + OH i) H2O + eii) xM + H2 Net cell recharging Reaction is Ni+2(OH)2 + xM0 Discharging mechanism: NiO(OH) + H2O + e H2 +OHMxH Mx+1 H + Ni+3O(OH)

5. Zinc-Air cell
Zinc-Air battery has very compact size catalytic cathode which used oxygen directly from atmosphere as an active material of cathode to produce electrochemical energy by delivering electrons for reduction of oxygen (O2 + 4e2O2-). A very thin cathode of the cell (about 0.5 mm) permits the use of very large zinc anode. This reduce volume requirement for cathodic half cell so more space is available for anodic part while cell capacity now depend open anodic part. As Zn is used as anode which is light weight metal and offers a very negative reduction potential so weight & volume of battery are reduced while cell capacity & energy density are increased. Anode = granulated powder of Zn

Electrolyte = Aqueous alkaline electrolyte (30%KOH)

Cathode =Gas diffusion electrode (GDE). It consist of catalyst layer contains carbon blended with oxides of manganese which mixed with wet proofing agent coated on Ni plated steel mesh support to form conducting medium an outer layer of gas permeable Teflon. A number of holes which provides a path for oxygen to enter the cell and diffuse to cathode catalyst site. Both electrodes are separated by an electrolyte absorbent separator. Cell Configuration Zn| KOH || O2 | Cathode Catalyst

Cell reactions:
At anode i) ii) Net anode Reaction Zn Zn2+ + 2OH Zn + 2OH Zn2+ + 2eZnO + H2O ZnO + H2O + 2e-

At cathode O2 + H2O + 2e2OHNet cell reactions Zn + O2 ZnO During cell reaction, alkaline electrolyte and cathode remain invariant.
2e_ 2e_ KOH 2OH_ || O2 | Cathode Catalyst

Zn | Zn2+

ZnO

H2O

Zn-air cell has OCV of 1.4V. Although it has high energy density, longer shelf life if sealed, no environmental hazards and lower cost but has limited power out put and short operational life. Znair cells are rechargeable but two problems arise in respect to recharging. High solubility of Zn causes shape distortion in each cycle Intensive oxygen evolution that occurs during charge which may harm the positive electrode. Due to this, Zn electrode can stand only a very limited number of cycles (<10). This problem over come by replacing used Zn electrodes after each /some discharge by new ones i.e mechanical recharging. The zinc oxide of removed negative electrode is regenerated in central electrolysis unit that operates for a whole fleet of cars, equipped with Zinc/Air batteries.

1. Phosphoric acid fuel cell (FAFC)

Electrolyte: Concentrated phosphoric acid absorbed into a solid matrix of silicon carbide. Operating temperature: 150 200oC Intermediate high operating temperature b/c at low temperature phosphoric acid has poor ionic conductivity and carbon monoxide poisoning of platinum electro-catalyst becomes sever at anode. Anode Reaction: Cathode Reaction: H2 O2 + 2H+ + 2e2H+ + 2eH2O

Net cell reaction :

H2 + O2

H2O

Advantages:
Its most mature & commercially available fuel cell technology. PAFCs generate electricity at more than 40% efficiency while 85 % of produced steam can economically used for co-generation. Excellent thermal, chemical and electro chemical stability of electrolyte. Relatively low volatility of phosphoric acid above 150 0C compared to other acid, so It has very low water vaporization rate so steady state water removal by reactant gases will always equal to water production rate so managing water level is not a problem. Due to intermediate high temperature CO is catalytically oxidized by water CO + H2O CO2 + H2 so it can use impure hydrogen fuel containing CO up to 1.5% so broadens the fuels choice range.

Disadvantages It generate low power and current Larger size and weight In this cathode performance is sluggish.

1- ALKALINE FUEL CELL

Electrolyte : 30 45 % w/v aq. KOH Operating temperature : 100 250oC In alkaline fuel cell Ionic conductance provided by hydroxyl (OH-) ions. Rather than acid electrolyte, alkaline electrolyte cause more rapid reduction of oxygen at cathode and feasibly allow use of wide range of non noble metals electro-catalyst at cathode such as nickel, silver, metal oxides, spinals and noble metals. Anode reaction: H2 2H+ + 2e2H+ + 2OH2H2O H2 + 2OH2H2O + 2eCathode reaction: O2 + H2O + 2e2OHNet cell reaction: H 2 + O2 H2O

Advantages It gives highest cell voltage of all fuel cells due to enhancement of cathode performance It tends to be low cost as choice for electrode material widen to non noble metals. It used in space crafts & submarines for generating electricity & drinking water. Limitations: Fuel & oxidant must be free from CO2 as it from K2CO3 ppt with alkaline electrolyte which severely limits the cells performance by blocking electrolyte pathways and electrode pores. CO2 + 2KOH K2CO3 + H2O Therefore carbonaceous fuels and atmospheric air cannot used in it as final redox products would contain CO2 so it only restricted to pure H2 & O2 gases. In alkaline electrolyte ionic conductor is OH- ion & water is produced at anode, while in acid electrolyte ionic conductor is H+ ion & water is produced at cathode.

Electrode Material: Expensive pt based catalyst seem to be the only catalyst capable of accelerating late of both electrode half reactions platinum is unique b/c it is sufficiently reactive in bonding H and O intermediate as required to facilitate the electorate process and also capable of effectively releasing the intermediate to form the final product. This requires optimized bonding to H & O atoms, not too weak and not too strong, which is unique feature of Pt catalyst e.g. when hydrogen gas diffused at anode through tortuous prose & carbonaceous pathways until a platinum particle encountered which catalytically dissociate H2 molecule into two hydrogen atoms (H), bonded them to two neighboring pt atoms them each H atom release an electron to form a hydrogen ion (H+) current flow in circuit as there H+ ions are conducted to cathode through electrolyte. H2 + 2pt 2pt H 2pt H 2pt + 2H 2pt H 2pt + 2H+ + 2e-

Realizing that the pt (best catalytic material for electrode) is very expensive, lowering pt catalyst levels in electrode is an on-going effort to reduce cost of fuel cell. This accomplish by constructing catalyst layers with the highest possible surface area by impregnating porous carbon with very small size Pt particles, about 2 nanometers in diameter. So enormously large surface area of Pt is accessible to gas molecules while small amount of Pt used. This allow electrode reactions to proceed at many Pt surface sites simultaneously, which generate significant electron flow i.e current in a fuel cell. As both Pt & C are good conductor so current is conducted to external circuit.

Water management:
Effective operation of fuel cell depends upon ionic mobility/ conductance b/w both electrodes through electrolyte which in turn depends upon hydration level of Anode-Electrolyte-cathode assembly b/c solvation of ions by H2O molecules increased ionic mobility. Although water is produced during cell operation but due to high operating temperature it is carried out with some additional water from electrolyte in form of steam which adversely loose ionic conductivity in electrolyte and cell current drop. This thing rectify by prehumidifying both fuel & air, entering the fuel cell. On other hand if fuel / air pass slowly through their respective electrodes than it cannot carryout all H2O produced at electrode hence electrode floods. Cell performance is hurt b/c no enough fuel/air is able to penetrate the excess liquid water to reach electrode catalyst sites.

3. Proton Exchange/Polymer Electrolyte Membrane Fuel Cell (PEMFC)

Electrolyte used is a solid organic polymer Poly-Perflouro Sulfonic Acid. It consists of fluorocarbon polymer backbone (similar to Teflon) to which sulfonic acid groups are attached. These acid groups are fixed to the polymer and can not leak out but protons on these groups are free to migrate though membrane. Therefore although this membrane is an electronic insulator due to organic nature but an excellent conductor of hydrogen ions. So it acts as electrolyte which provides efficient hydrogen ions communication b/w anode & cathode thus increased power density range from 50 to 250 kw. Being a solid electrolyte based on teflon it is stable and can not change, move about or vaporize from the system and also serves as a good separator for the both reactant gases, even can withstand elevated pressure, thus cell can vary their out put quickly to meet shifts in power demand.

Proper water management in PEM is crucial for efficient fuel cell operation as dehydration of membrane reduces proton conductivity and excess of water can lead to flooding of electrodes. This thing encounter by using prehumidified reactant gases and adjusting low operating temperature at 80oC so that water does not vaporize into reaction air steam faster than it is produced. Low operating temperatures can not eliminate lethal effect of CO therefore fuel should be free from CO. Thus choice of fuel limited to pure hydrogen and hydrogen rich gases obtained by decomposition of hydrides. PEM freezes at about 0oC and undergoes a freeze-drying phenomena which make PEMFC non operational at lower temperature. The only liquid in PEMFC is water, which minimize corrosion thus increases cell life. Due to solid electrolyte, cell is simple to fabricate but electrolyte is very expensive which increased cell cost.

4.

Molten carbonate fuel cell (MCFC)

Electrolyte is the mixture of alkali metal carbonates (32% Li2CO3 + 28% K2CO3/Na2CO3 absorbed in molten state in a porous inorganic matrix of 40% LiAlO2). MCFC operational temperature is 600700oC which is above than M.P of these carbonates, hence all alkali metal carbonates would be melted and cause ionic conductance by carbonate anions. High operational temperature increases efficiency & gives flexibility to feasibly employed inexpensive non noble metal catalysts and to use more type of fuels as breaking of carbon bonds in larger hydrocarbon fuels occur much faster as temperature is increased. Porous Ni or Ni-Cr alloy serve as anode while cathode is porous NiO. High operating temperature convert any CO in fuel into hydrogen at anode via water gas shift reaction. CO + H2O CO2 + H2

 Therefore MCFC have been operated on H2, CO, CH4, propane, landfill gas, marine Diesel and simulated coal gasification products but have low tolerance to sulfur & chloride compounds. On other hand high operating temperature enhance corrosion and impose severe constraints on cell components hence shortened cell life. Anode reactions: 2H2 + 2CO3-2 2CO2 + 2H2O + 4eIf CO is present CO + CO3-2 2CO2 + 2eor CO + H2O CO2 + H2 Cathode reaction O2 + 2CO2 + 4e2CO3-2 2H2 + O2 2H2O It can gives voltage as high as 0.9 V while CO2 recycled from anode exhaust to cathode inlet. They gives high fuel to electricity efficiencies, about 60% normally and 85% with cogeneration b/c waste heat is available at a relatively high temperature(~500oC), enabling its use in bottoming or industrial heating cycles.

5. Solid oxide fuel cell (SOFC)

It employed a solid, nonporous metal oxide electrolyte which usually consist of hard ceramic material of Zirconium oxide (Zirconia/ZrO2) doped with small amount of yttrium oxide (Y2O3/ ytrria). The cell operates at about 1000oC where ionic conduction takes place by migration of O2- anion across the electrolyte through vacant lattice sites. High operating temperature avoids expensive catalyst. Anode is made up of Co-ZrO2 or Ni-ZrO2 cermets while cathode consists of praseodymium oxide or indium oxide or Sr doped with LaMnO3. It has high tolerance to impurities so it can be operated by using hydrogen or carbonaceous reformed fuels consist of CO. Anode reactions: H2 + O2H2O If CO is present CO + O2CO2 + 2eCathode reaction: O2 + 2eO2Net cell reaction: H2 + O2 H2O It does not require CO2 recycle to the cathode. Power generating efficiencies could reach 60-85 % with cogeneration but cell output relatively less efficient up to 100 KW.

5. Protonic Ceramic Fuel Cell (PCFC)

Most PEM (proton exchange membrane) fuel cells use a polymer membrane, such as Nafion which requires humidity and a low operating temperature to operate efficiently. As the temperature rises, the polymer becomes unstable and the membrane dehydrates, leading to loss of performance. However, operation of PEM fuel cells at higher temperatures would be more desirable, as the reaction rates at the catalysts are increased while potential poisoning of the catalysts is reduced. Ceramics electrolyte material that exhibit high protonic conductively at elevated temperatures have been proposed as good candidates for use in PEM fuel cells because of their thermal, chemical, and mechanical stability, and lower material costs. Although protonic conductivity of mineral membranes(ceramics) is low in comparison with the perfluorosulfonatebased membranes but the chemical reactions that create the electricity are more efficient at higher temperatures.

Proton conducting ceramic membranes consist of metal-oxane e.g ferroxane which consist of iron nanoparticles stabilized by carboxylic acid with lepidocrocite. Another ceramic membrane consists of ferroxane-derived with PVA (polyvinyl alcohol) calcined at 500C (PVA Fe500) showed the best performance. PCFCs share the thermal and kinetic advantages of high temperature operation at 700oC with molten carbonate and solid oxide fuel cells, while exhibiting all of the intrinsic benefits of proton conduction in polymer electrolyte and phosphoric acid fuel cells moreover PCFCs have a solid electrolyte so the membrane can not dry out as with PEMFC or liquid cant leak out as with PAFCs. PCFCs can operate at more high temperature for hydrocarbon fossil fuels to electrochemically oxidize them directly at anode. This eliminates the intermediate step of producing hydrogen through costly reforming process.

B. Zn Air Fuel Cell (ZAFC) It has similar operations as Zn Air cell but additionally has a closedloop system consist of Zinc fuel tank and a Zinc regenerator that automatically & silently, replace & regenerate Zinc fuel. As fuel is used up, the system is connected to the grid source and process is reversed to once again give pure Zinc fuel pellets. This reversing process takes only about 5 minute to complete, so the battery recharging time hang up is not an issue.

C. DIRECT METHANOL FUEL CELL (DMCF) 1. alkaline type:

Anode: Pt or Pd catalyst doped on porous nickel sheet.
Cathode: Silver impregnated in porous nickel sheet. Electrolyte: KOH aqueous solution Fuel: Humidified methanol Oxidant: Air Operating temperature: ~100oC In DMFC, large amount of expensive Pt catalyst is used at anode so that it can itself draw hydrogen from liquid methanol thus eliminating the need for a fuel reforming sub system and a bulky & heavy hydrogen storage system

Electrode reactions: At anode: CH3OH + 6OHAt Cathode: 3/2O2 + 2H2O + 6e-

CO2 + 5H2O + 6e6OH-

Fuel cell reaction:

CH3OH + 3/2O2

CO2 + 2H2O

Alkaline electrolyte has a disadvantage that CO2 release at anode, absorbed & converted into K2CO3 by alkaline electrolyte. 2KOH + CO2 K2CO3 + H2O which decrease ionic conductivity of electrolyte & increase concentration polarization at the electrode surface thus decrease cell efficiency to 40%. The major problem is fuel crossing over from anode to cathode through electrolyte without producing electricity which wastes fuel and decreases the performance of the air electrode i.e cathode. Therefore acid polymer electrolyte membrane is better option.

2. Acid type:
Electrolyte: Proton (H+) conductivity solid polymer membrane. Electrode reactions At anode: CH3OH + H2O CO2 + 6H+ + 6eAt cathode: 6H+ + 6e- + 3/2O2 3H2O Fuel cell reaction: CH3OH + 3/2O2 CO2 + 2H2O