HAPTER 8/ELECTE 366 © a ROCHEMISTRY Function involved in cells or batteries. A bat. Conversion chemical energy into electrical energy 1S the 0 EA both, in order to get the required amount of i i rT arallel or cells either in series or P s, the words cell and battery tery is a combination o ‘ ectrical energy: In modern times electrical energy. Ic is a portable source of el are used interchangeably. Wich che increased human activities a have come into existence. Batteries are used in wrist wat en ee flashlight devices, electric calling bells, calculators, alarm signals, space vehicles and missile firing units, “There is a growing trend in the manufacture of consumet-eiendly cells o batteries. In fact, not al the voltaic cells find commercial applications. The general criteria for any cell to be a commercial cell are havea long cycle life and high shelf life; should bea that they should be cheap, light and portable; should | eae a aca stan source of EME over a long incerval of time and should be «rechargeable uni The galvanic cells used to form batteries can be classified as: acd comforts, a numberof batery-dependent appliances or goods ‘ches, emergency sources of light (UPS), hearing aids, is converted into electrical energy as long as the 1. Primary cells: In chese cells, the chemical energy hhemical components are used up, they cannot be chemical components are active. Once the active cl regenerated or reused. These cells are then nor rechargeable, 2. Secondary cells: In these cells, the redox reaction that converts chemical energy into electrical energy can be reversed by passage of current. These cells can be recharged and reused. The electrical tenergy is stored in them in form of chemical energy and hence these are also known as storage cals, ‘These cells behave as a galvanic cell during discharge, converting chemical energy inco electrical and as electrolytic cell during charging, converting electrical energy into chemical. ‘A new class of batteries, known as reserve bacteries has been designed co mect the conditions of long Shelf life and exereme storage. In these bacceries, a key component mainly the electrolyte is separated cell to prevent reaction berween electrolyte is separated from the cell to prevent reaction from th ‘The batteries are cell components are activated by addition between cell components and self-discharge. of active components. ‘The basic components of a battery are: “Anode: Ie contains active materials which spontaneously cake part in the oxidation reactions. Cathode: Ie contains active materials which spontaneously take part in the reduction reactions. Electrolyte: It helps in the migration of the ions leading to the generation of electrical enewBy: Separator: It is a thin polymeric membrane which prevents che mixing of products formed at che electrodes. Usually, polypropylene and polystyrene separators are used. ayers Discharging and Charging of a Battery ‘A cell is a battery that is packed with active materials at anode and cathode. As soon as the anode and the cathode are connected to the load, redox reactions occur spontaneously. The electrons liberated at the shed flow tothe cathode chrough the external wire and take part in the reduetion reaction. This proces in which spontaneous redox reaction occurs is called discharging. During che discharging process as shown in Figure 21(a), active materials are converted into inactive materials. The cell becomes inactive once the active material is consumed. f secondary inter bacevies,the cell reaction is reversed if the external curse fe seal tn che reverse directo? This process of conversion of an inactive materia! back into active ea Cae as shown in Figure 21(b). Ie is a non-spontaneous process. So a Scanned with CamScant367 Flow of otectrons } * Electrolyte «| Anode Cathode Separator —_____] (a) (o) Figure 21 (a) Discharging and (b) charging processes in a batcery. | Characteristics of a Battery Section of battery depends on the condition: signed for this purpose. The suitabilicy of sof working. In fact, cells or batteries are specifically a batcery depends on the following characteristics: 1, Voltage or EMF: A good cell is one which offers large and almost constant EME. + Ic depends on the change in free energy of the reaction, A —nFE ce, Larger the change in free energy, higher will be the EME * According co Nernst’s equation, 2:303RT |, (Products) mE tReactants} Exe = Eee = where E°,) = ER - EP. ; 5 (a) Larger the potential difference between the electrodes, higher is EQ, and hence Egat. (b) As temperature increases, the EMF decreases. (0) As the value of [Products}/{Reactants} increases, EMF of che cell marginally decreases. * A good battery is one which has a flac discharge rate (constant EMF) (Figure 22). Dead stato of the cell EMF of the cell Time for which the coll Is used . Figure 22, Flac discharge rate, Scanned with CamScantR8/ 368 . CHAPTER B/ELECTROCHEMIS iy c reactions of the cell. It depends on the amount of 2. sicisenes f discharg F Current: It is a measure of the rate of 8 ill be the time for which EM'y : ger wi active materials. Higher the amount of active materials, long generated. 3. Current capacity: Ic is defined as the amount of eae cerms of ampere-hour (A h) and depends on the discharge conditions. Capacity is inversely propor. tional co the average molar mass of the active materials. A good battery should have higher curreng capacity. 4. Power density: current generated in unit time. It is measured in a measure of the power generated in a cell per unit weight of the bactery ‘Amount of power generated in a cell _ iEcet Foner densi Weight ofthe cell wv where and Eo, are current and EMF generated in a cell, respectively. Lesser the weight of the cell, higher would be the power density. 5. Energy density: It is measure of the energy av: he of the cell lable in che cell per unit w FRt _ HEcettiavg) Xt Amount of energy generated in the cell w Ww Weight of the cell Energy density = ance offered by the cell and time for where i, R and 1 are the currene generated by cell, re which the current generated is measured. Always, cells or batceries with higher enei are preferred 6. Energy efficiency: Ic is applicable only to secondary cells. During discharging, electrical energy is released while electrical energy is utilized when the cell is being charged. A good cell is that which liberates more electrical energy chan ic uses during charging process. The rates of electrical energy released and used in discharging and charging, respectively, is known as zy densities . Amount of electrical energy released during dischar, Percentage energy efficiency = TOU % electrical energy released during discharg Amount of electrical energy used during charging 7. Cycle life: Ic is applicable only to rechargeable (secondary) cells. The EME of cell decreases during discharging. If ic is followed by charging process, the amount of active materials in the cell increase and hence the EMF. The discharging and charging processes cannot be repeated perpetually. A discharging followed by charging is referred co as a cycle. The number of times it can be repeated is called cycle life. In other words, cycle life is defined as che number of times the discharging, and charging operations can be alternated cill such time ie performs as designed A good cell should have high cycle life. Sometimes, the cycle life would be lower than expected Ie may be due to che following reasons, + The active materials at the electrodes may whither off due to rapid charging conditions * There may be irregular deposition of the products during discharging. It may result in short circuiting. * Due co overcharging, the corrosion may occur resulting contact wire and the active materials. 8. Sete be dual of tome under specified conditions at the end of which the cell still ha ci id oe Pe Pertormance. A good battery should possess a long shelf life 9. Self-discharge: Sometimes, che discharge reactions may occur even though the cell is not 19 us Ic is due to the local acti = zh the cell 1s ne is due co che local actions that occur in the cell. It is defined as the loss of active materials of the in severing connections between the ocanned witn LamscaniJATIERIES qassicAL - 369 jue to localized action on th cell dt —_ ¢ clectrode even when the cell d Longer the self-discharge, lower would be the shelf life is not in discharge mode. Long acs ss riveria for a commercial battery? a 1 tare Ux . Phat ; What is meant by the energy efficiency of a arc reserve b | How 8 " attery? per types of Dat tcrics Pipi the essential components of a battery * pants the process of charging and discharg- ofa battery teries more efficient than * What are the reasons for the lowering of cycle life of a battery? Classical Batteries primary Cells Dy Cell ‘seell, also known as Leclanche cell, consists of a cylindrical zinc container which acts as the anode. rod surrounded by a paste of manganese dioxide acts as the cathode. These are in contact wi hl iste of ammonium chloride and zinc chloride which acts as the electrolyte (Figure 23). Seal Zine(-) NHCI(aq) Carbon(+) Powdered C + MnO. Insulator Figure 23 Leclanche cell. The cell reactions are: Atthe anode: Zn > Zn? + 267 At the cathode: MnO, + H20 + 2 Ot 4 Mng0s-+OH™ The ove eo 02 + H20 > Zn in203 ' - Omni feaccion: 20 a oF he ells which do nor contribute ro de EME of che cll 5 ehey ono day reactions take Pract yl ions generaced a ee cho et wih NEC beac egret efectos, Th yon complex (ZaQNHT)ICly These processes dseupe ee flow ich reacts wi current > Mn,03 + 20H” Scanned with CamScanCHAPTER 8/ELECTROCH — lEMISTRY ch usage due to accumu, A dry cell develops a potential of 1.5 Vand the voleage ae ee ane curmlation of products at the electrodes. Even when the cell is not in use, the HIGE indefinite Je. Dry cells are most commonly used batteries that fing because acidic NH ,Cl corrodes the zine cathode. Dry 7 use in flash lights, radios, tape recorders, transistors, et. "Alkaline Dry Cell This cell is same in construction as the dry cell but modified to replace NHjCl as electrolyte by sodium hydroxide or potassium hydroxide, hence the name alkaline dry cell. Replacing NH,Cl with NaOH/KOH prevents corrosion of zinc cathode since it does not dissolve in basic medium. The cel] reactions are: At the anode: Zn + 2OH™ — ZnO + H20 + 2e— Ac the cathode: 2MnO2 + 2e7 + HO — Mn203 + 20H” The overall cell reaction: Zn +2MnQ2 — ZnO + Mn203 Mercury Cell This cell, also known as Ruben—Mallory cell after the inventors, consists of amalgamated zinc powder that functions as the anode. The cathode comprises paste of mercuric oxide with some amount of graphi A paste of zinc oxide and potassium hydroxide forms the eleccrolyce (Figure 24), Insulation Steel (+) S ZLLILILIS Zino(-) Solution of HgO in KOH and Zn(OH)y oa: = Oz zs x EX Figure 24 Mercury cell. The cell reactions are: Ac the anode: Zn ++ 20H” ~> ZnO +H,0 +267 Ac the cathode: HgO + H20 + 2e" > Hg + 20H™ The overall cell reaction: Zn + HgO > ZnO + Hg The zinc cell develops a potential of 1.35 V. It is compact in size because the zinc anode can be compressed into pellee form; the cathode material, mercury oxide, is dense; and the eleccrolyte KOH is non-variane and thus required in minimal amount. Ie gives constant potential throughout is lifetime and shows good performance at high temperatures. Ic is however, expensive due to the high cost of mercury oxide. These cells are used in electronic watches, heating aids, microphones, cameras, tC. Silver Button Cell This cell consists of silver oxide as cathode and zinc metal as the anode. These electrodes are separated by semi-permeable membranes and potassi ; : ' ; a Bs nes and potassium hydroxide and sodium hydroxide is used as an electrolyte Scanned with CamScanLASSICAL BATTERIES a I 87 Can |—> Anode cap |—> Anode » Gasket * Separator > Cathode Figure 25 Silver button cell. pecell eactions are: rine anode: Zn + 20H” ~ Zn0-+ 1130 + 267 acthe cathode: Ag2O + HzO + 2c" 9 2Ag +20H7 verl cell reaction: Za-+ AgsO > Zn0-+2Ag The cell reaction shows that che amount of electrolyte does not change or is non-variant. The cell gives a voltage of 1.31.5 V, which remains fairly constant during the cell discharge. The cell is compact and finds use in electronic watches, hearing aids, pacemaker, etc. Secondary (Storage) Cells lead Storage Cell (Lead-Acid Battery) This cell, also known as acid storage cell, is the common automobile battery. Its present form is a sariant of lead-acid accumulator first designed in 1859. Lead storage cell consists of lead grid filled vith spongy lead which acts as the anode and a lead grid packed with lead oxide that acts as the cathode. ‘Anumber of (generally six) such electrode pairs are dipped in sulphuric acid solution (2096) which acts asthe electrolyte and these are separated by inert and porous partitions (Figure 26). Figure 26 Lead-acid battery: The cell reactions are: Acthe anode: Ph +SO%” 9 PbSO4 +2" Ath cathode: PbO» + 4H* + SO4 +24 The overall cell reaction: Pb + PbO2 + 2H ~ 5 PbSO4 + 2420 9804 —> 2PbSO4 +2H20 ocanned witn Lamscani372. CHAPTER 8/ELECTROCHEMISTay consumed during the reaction, so as the p The cell reaction shows that the electrolyte HO, is consu is Proceeds, the concentration of H SO, dec permissible le action Once the concentration of H$O, has fallen toa cerain cl, the battery needs to be recharged by reversing the discharge reaction. For this. external potential higher than the cell potential is applied. The cell then operates like an electro] and the PbSO, depo Lyte cell red on the electrodes is reverted to Pb and PbO, by the following reactions: + 4 s0- At the anode: PbSO4 +2 H30 > PbO» + 4H* +S07 Acthe cathode: PbSO4 +2e” — Pb +$07” . 7 The overall cell reaction: 2PbSO4 +2H20 + Pb-+PbO2 + 4H* +2807 The cell reactions show that the concentration of HS, increases during recharging of the cell, The potential developed by each electrode pair is about 2V and higher potential can be obtained by con. necting a number of electrode pairs in series. These batteries find extensive use as automobile batteries, besides being used for electrical supply in trains, hospitals, etc. Nickel-Cadmium Cell This cell, also known as alkaline storage battery, with cadmium hydroxide. The cathode graphite and other compounds. (Figure 27). consists of anode grid which contains spongy cadmium grid contains nickel oxyhydroxide along with small amounts of A concentrated solution of potassium hydroxide acts as an electrolyte (+) Positive terminal }— Separator Cadmium anode [— NiO (OH) cathode By Figure 27 Nickel—cadmium cell, Ac the anode: Cd + 20H™ 3 Cad (OH); +2e7 Ac the cathode: 2NiO(OH) + 2H20 +2” + 2Ni( ‘The overall cell reaction: Cd + 2NiO(OH) + 2H. As the reaction proceeds, the products NiOH), and Ca(OH), The cell can be recharged by reversing the reactions. This cell gi made into compact button cell type battery and finds use in Pp emergency lights, portable electronics, toys, etc, OH), +2 OH™ 20 > 2Ni(OH), + C4OH)> stick to the surface of the electrode. &ives potential of about 1.4 V. It can be ocket calculators, electronic flash lights, ocanned witn Lamscaniane ithium Batteries fam isa light metal wich low electrode potential and iereal for batteries, and can be expected to have high po siburteries where lithium is used as an anode are known as lithium batteries and they were commercial- jal in 1990. A large number of lithium batteries are available which have lithium as anode but differ inchoice of cathode and electrolyte. These may also be classified as primary or secondary. The most sell-known of lithium batteries, lithium—manganese dioxide cell is discussed here. ‘The construction of Li-MnO, battery is as follows: good conductivity. Ic is, therefore, a good ential and high energy density. The group 1, Anode is composed of lithium. 1, Cathode is composed of heat treated MnO,. 3, Electrolyte contains a mixture of LiCl, LiBr, LiAlO, and LiClO, dissolved in organic solvents like propylene carbonate and is 2-dimethoxyethane. The cell reactions are as follows: | Arthe anode: Li Li* +7 Wm Atthe cathode: MnOp + Li* +” > LiMnO, i +MnO2 — LiMnO2 The battery offers an EMF of 3.0 V. These batteries have the following characteristics: The overall cell reaction is: |. The batteries are light in weight and compact. 2. They are known for low maintenance and have high energy density. These batteries find application in memory backups, automatic cameras and calculators. Pee Scanned with CamScant