Batteries

Definition Battery is an electrochemical cell or several electrochemical cells connected in series that can be used as a source of direct electric current at a constant voltage. It stores chemical energy for latter release as electrical energy .i.e., a chemical reaction proceeds spontaneously in an electrochemical cell and its free energy is converted into electrical energy G= -nFE An Electrochemical cell consists of Anode: Oxidation takes place-releases e Cathode: Reduction takes place-accepts e released by anode Electrolyte: Supplies ions to conduct electricity inside the cell. Separator: Physical barrier between the cathode and anode to prevent direct shorting of electrodes. They must be permeable to ions but should not conduct e-s. They are inert to the electrolyte. External Circuit: Through which electrons flow. Types of Batteries 1) Primary battery:Irreversibly transform chemical energy into electrical energy- Discharged only once and then discarded. 2) Secondary Battery:Cell reaction can be reversed by passing direct current in opposite direction during charging. They can be charged again and again. This cycle is repeated until capacity fades or is lost suddenly due to internal short-circuit. 3) Reserve Battery and fuel cell:Active materials are kept separate by special arrangement. When it has to be actually used, an activation device makes it ready. Characteristics of Batteries Voltage Voltage is an electrical measure which describes the potential of a cell to do work. Each cell has an electromotive force (or emf), determined by its ability to drive electric current from the interior to the exterior of the cell. The std electrode pot ential Eo (cell) =Eo (cathodic) Eo (anodic). -The emf of the cell (E cell) is calculated by Nernst equation E=E + RT ln[reactant]/[product] --------------------------------------nF Electrode pot decreases as increase in temp. The nominal voltage of battery depends on the number of cells that have been wired in series. Current Current is a measure of how many electrons flowing through a battery. Current is usually measured in amperes (A). Capacity Capacity is a measure of how much energy the battery can store at nominal voltage and is frequently abbreviated to C. Unit is Amp-hour (Ah): Current flow over time(amp-hours or Ah), a product of the average current and the amount of time it flows. Capacity is additive when batteries are wired in parallel. Storage Density or Energy Density Capacity per unit mass

Power and power density Power is the product of voltage and current and is measured in Watts. P= VI Power delivered in watts per unit mass is power density. Energy Efficiency The energy efficiency denotes how well a battery converts an electrical charge into chemical energy and back again. The higher this factor, the less energy is converted into heat (energy loss) and the faster a battery can be charged without overheating. The lower the internal resistance of a battery, the better its conversion efficiency. conversion efficiency of lead-acid cells is 85%-95% is much higher than Nickel-Cadmium at 65% Charge/discharge cycle Charge The operation of a cell when an external source of current (Electrolytically) reverses the electrochemical reactions of the cell to restore the battery to its original charged state. Discharge-The operation of a cell when current flows spontaneously (Electrochemically) from the battery into an external circuit. State of Charge (SOC) The State of Charge describes the charge condition ie., how full a battery is charged. It depends on measuring changes in the weight of the active chemical, electrodes or electrolyte. The exact voltage to battery charge correlation is dependent on the temperature of the battery Cold batteries will show a lower voltage when full than hot batteries. . Measurements of SOC SOC from Specific Gravity (SG) Measurements This is the customary way of determining the charge condition of lead acid batteries. As the battery discharges the active electrolyte, sulphuric acid, is consumed and the concentration of the sulphuric acid in water is reduced. This in turn reduces the specific gravity of the solution in direct proportion to the state of charge. Voltage Based SOC Estimation This uses the voltage of the battery cell as the basis for calculating SOC or the remaining capacity. Results can vary widely depending on actual voltage level, temperature, discharge rate and the age of the cell and compensation for these factors must be provided to achieve a reasonable accuracy. -A more accurate state-of-charge measurement is possible with a rapid-test instrument that examines the chemical integrity of the battery. Self-Discharge The self-discharge rate is a measure of how much batteries discharge on their own. Due to current produced by side reaction within the cell even if no load is applied. Cycle Life measure of how many charge and discharge cycles a battery can take before its failure. The greater the average depth-of-discharge, the shorter the cycle life. Battery Life Defined as the end-of-life of a battery when it can no longer hold a proper charge or when the available battery capacity is 80% or less than what the battery was rated for Shelf-life -Maximum time for which a given battery can be stored without self-discharge or corrosion or loss of performance. Many batteries can be stored for many years Tolerance to service condition: -The battery should posses tolerance to various service condition like temp, vibration, penetration, shock,etc.,

Alkaline Primary Battery The alkaline battery gets its name because it has an alkaline electrolyte Anode: Zn powder is mixed with KOH to get a gel. Cathode: Graphite rod is surrounded by pastes containing MnO2. Electrolyte: KOH Cell voltage: 1.5V The cell reactions Anode: Zn (s) + 2OH (aq) ZnO (s) + H2O (l) + 2e Mn2O3 (s) + 2OH ZnO(s) + Mn2O3(s)

Cathode: 2MnO2 (s) + H2O (l) + 2e Net Reaction: Zn(s) + 2MnO2(s)

Merits: They have good capacity retention on long term storage. Life of battery is higher than other primary batteries as zinc does not dissolve as readily in basic medium. Limitation: Over time, alkaline batteries are prone to leaking KOH, a caustic agent that can cause respiratory, eye and skin irritation. Uses: Cameras, audio, calculators, watches, toy devices

Secondary Batteries
Other names are accumulators,, storage batteries, rechargeable batteries Types Acid Batteries or lead acid accumulators. Alkaline storage batteries Ex.. nickel cadmium (Ni-Cd),, nickel metal hydride (Ni-MH). Others including lithium/lithium ion batteries. LEAD ACID BATTERY COMPONENTS Container: Plastic container made up of polyethylene, co-polymers or reinforced polyethylene or metallic or a synthetic rubber.. Electrodes:: The positive electrode (cathode) consists of pure lead dioxide supported on a metallic grid. The negative electrode (anode) consists of a spongy lead plate or grid of metallic lead alloy containing various elemental additives, antimony, calcium, arsenic, copper, tin, strontium, aluminum, selenium and more recently bismuth and silver to change grid strength, corrosion resistance, reduce overpotential or maintenance and internal resistance. Separator : Porous synthetic plate separators are made from reinforced polyethylene, but are also available in PVC and fiber glass. Electrolyte: Liquid electrolyte consisting of 35% sulfuric acid and 65% watter. Terminal : The positive and negative lead terminals used to connect the battery to load.

Discharging

The Cell Reactions: Pb + PbO2 + 2SO4 2- + 4H+

2 PbSO4+2H2O
Charging

During Discharging The battery is assembled in the charged state and is ready for discharge At anode Pb Pb2+ + 2ePb2+ + SO4 2- PbSO4 At cathode PbO2 + 2e- + 4H+ Pb2+ +2H2O Pb2+ + SO4 2- PbSO4 Net reaction Pb + PbO2 + 2SO4 2- + 4H+ 2 PbSO4+2H2O PbSO4 precipitated at both electrodes and H2SO4 is consumed

During Charging At cathode PbSO4 Pb2+ + SO4 2At anode: PbSO4 + 2H2O PbO2 + SO4 2- + 4H+ Net reaction 2 PbSO4+2H2O Pb + PbO2 + 2SO4 2- + 4H+ H2SO4 is regenerated

Classification of lead acid batteries 1. Sealed Maintenance Free (SMF) or Valve Regulated Lead Acid (VRLA) Batteries remain under constant pressure of 1-4 psi. This pressure helps the recombination process under which 99% of the Hydrogen and Oxygen generated during charging are turned back into water. VRLA batteries will not leak if inverted, pierced, etc. and will continue to operate even under water. 2. Open: Stored/ used in vertical position. It needs regular routine maintenance. Properties Energy/size: 60-75 Wh/LL Power/weight: 180 W/kg Charge/discharge efficiency: 70%-92% Self-discharge rate: 3%-20%/month Cycle durability: 500-800 cycles Nominal Cell Voltage: 2.0 V Automobile battery:6 cells are connected to produce 12v. SOC: It is relatively simple to determine the state of charge by merely measuring the specific gravity (S.G.) of the electrolyte, the S.G. falling as the battery discharges.. State of Charge Specific gravity Voltage 12V 6V 100% 1.265 12.7 6.3 75% 1.225 12.4 6.2 50% 1.190 12.2 6.1 25% 1.155 12.0 6.0 Discharged 1.120 11.9 6.0 electronic flash units, have a simple hydrometer built in using coloured floating balls of differing density Cell Configuration: Pb|PbSO4(s)||H2SO4 (aq)||PbSO4(s)|PbO2(s)|Pb or Pb|P 2+||H2SO4 ||Pb4+|Pb2+|Pb Nominal Cell Voltage :2.0 V

Advantages Lead-acid batteries are the most commonly used because of their low maintenance requirements, low initial cost, and their availability across the globe. pollution-free emergency power. It is relatively simple to determine the state of charge by merely measuring the specific gravity (S.G.) of the electrolyte, the S.G. falling as the battery discharges.. conversion efficiency of lead-acid cells is 85%-95% is much higher than Nickel-Cadmium at 65%, or other inexpensive battery technologies. Disadvantages Ageing affects batteries as the chemistry inside them attacks the lead plates. Weather capability is poor: People living in cold climate have trouble starting their car the battery has apparently gone dead. The electrolyte is not fully conducting as viscosity increases as temp decreases which leads to voltage drop and the lead-acid batteries will freeze. By warm up the battery or dilute the electrolyte by adding water can help recover the battery. Overcharging with excessive charging voltages will generate oxygen and hydrogen gas by electrolysis of water, forming an explosive mix. Caution must also be observed because of the extremely corrosive nature of sulfuric acid. Uses of Lead Acid battery Starter Battery: They power the majority of mobile vehicles both on land and sea. They start engines, back up critical systems in submarines, and power navigational signals and devices in boats. Back-up power (UPS): Ensure our safety by providing necessary for everything from computers to hospital emergency lighting. Lead acid batteries, back up interruptible operations like hospitals, railroad signals, weapons systems, and air traffic controls, and help electric utilities shift loads among grids. Pollution-free emergency power: They also provide quiet, pollution-free emergency power for critical operations in facilities like air traffic control towers, hospitals, railroad crossings, military installations, submarines, and weapons systems. Lead-acid batteries and alternative energy : Solar energy and wind-powered systems would be subject to constant power fluctuations as the wind speed increased, dropped or disappeared entirely. As storage batteries, lead-acid batteries are what enable a home power system to deliver a constant level of power to the electrical system. Secondary Alkaline battery: Ni-Cd batteries Usually pronounced "Ni-Cad-this abbreviation NiCad is a registered trademark of SAFT. Cell Components Anode: Cadmium rod or spongy Cd. Cathode: NiO(OH) paste -(Ni is mixed with NiO) Separator: Porous polymer (Polypropylene).The positive and negative electrode plates are isolated from each other by the separator and rolled in a spiral shape inside the case Electrolyte: Alkaline NaOH or KOH 2+ 3+ 2+ Cell representation: Cd|Cd || KOH || Ni |Ni |Ni Ni-Cd batteries usually have a metal case with a sealing plate equipped with a self-sealing safety valve to permit gas transport when pressure build-up across the cell Assembled in the discharged state Cell Reactions At anode:
Discharge

Cd (s)+ 2 OH - (aq)
Charge

Cd(OH) 2 +2e -

At cathode:
Discharge

2 NiO(OH)(s)+ 2 H2O + 2e Charge

2 Ni(OH)2 (s)+2OH -(aq)

Discharge

Net reaction Cd(s) + 2NiO(OH)(s)+ 2 H2O charge Properties Energy/size: 50150 Wh/L Power/weight : 150W/kg Charge/discharge efficiency:70%90% Self-discharge rate: 10%/month Cycle durability : 2000 cycles Nominal Cell Voltage : 1.4 V Advantages Tolerating deep discharge for long periods- minimal loss off capacity even at high discharge rates Long-term storage without any appreciable deterioration Good cycleablity. Stable cell voltage Portable-can be packed in a sealed container Limitations of Ni-Cd Batteries Toxicity due to Cd : Cd is a toxic heavy metal and therefore requires special care during battery disposal. High cost Overcharging: Overcharging with excessive charging voltages will generate oxygen and hydrogen gas by electrolysis of water, forming an explosive mix. Sealed type: Designed in such a way that adequate porosity is provided within the electrodes and separator to permit gas transport, and venting system is activated when pressure build-up across the cell Memory and lazy battery effects: When recharging if a Ni-Cd battery that has not been fully discharged, it "remembers" the point and during subsequent use, suffers a sudden drop in voltage at that point. Hence the battery can not be discharged fully. The memory effect is caused by crystallization of the battery's substances and can permanently reduce battery's lifetime, even make it useless.. To avoid it, the battery should completely discharged every time. Dendrite shorting: Ni-Cd batteries, when not used regularly, tend to develop dendrites which are thin, conductive crystals which may penetrate the separator membrane between electrodes. Application Small Ni-Cd dry cells are used for portables electronics and toys. Ni-Cd batteries have a niche market in the area off cordless and wireless telephones, emergency lighting, model airplanes, as well as power tools. Larger flooded cells are used for aircraft startling batteries,, electric vehicles,, and standby power. Sealed cells used for space applications in conjunction with solar cells. Cd(OH)2 (s) + 2 Ni(OH)2 (s)

Lithium Batteries
Introduction Due highly electro active nature, Li reacts with water vigorously and produces flammable hydrogen. Hence aqueous electrolyte can not be used in lithium batteries. Non aqueous electrolyte is prepared by dissolving lithium salt (LiPF6 or LiClO4) in an organic solvent, (Propylene carbonate, PC or ethylene carbonate, EC). It is used either in the form of a liquid or immobilized within a polymer (Lithium polymer battery). The first commercial Li-ion cell introduced by Sony in the 90's used a polymeric gel electrolyte, swollen by a high proportion of organic solvent with Li salt. Lithium battery chemistry differs from other types of batteries as lithium ions are exchanged back (intercalated) and forth (deintercalated) between the anode and cathode along with change in the oxidation state of the transition metal present in the cathode during discharging and charging. Intercalation: Incorporation of a foreign atom into some crystal lattice (usually in the interstitial spaces) without changing the structure. It is a reversible process.

Lithium Ion Batteries : Lithium ions rock back and forth between anode and cathode.

Types of Rechargeable(Secondary) lithium batteries Lithium Secondary Batteries Anode: Lithium metal Cathode: Transition metal oxides or sulphides. Electrolyte: Li salt in non aqueous solvent: Ex LiPF6 in PC or non aqueous electrolyte is immobilized in polymer like PVdF(Li polymer battery) Current Collector: Ni, Al or Cu mesh Cell Reactions At anode: Deposition/dissolution of lithium.
Discharge

Lithium ion batteries (Li-ion) This type of battery is known as rocking chair battery or swing battery as the Lithium ions rock back and forth between anode and cathode. Both electrodes have layered structure or spinal structure and so lithium ion can be incorporated into their crystal lattice, usually in the interstitial spaces. Anode: Li insertion material which can store and exchange lithium ions. Ex., C(graphite-layered structure) Cathode: Lithiated transition metal oxide from which lithium can be extracted(charging) can be inserted (discharging) . Ex.LiCoO2, LiTiO2, LiMn2O4. Electrolyte: Li salt in nonaqueous solvent Ex LiPF6 in PC or polymer electrolyte (Li ion polymer battery) Current Collector: Ni,Al or Cu mesh Cell Reactions At Cathode
Charge

Li
Charge

Li + + e -

At Cathode
Discharge

Li + e + Ti O2
Charge

4+

Li Ti 3+ O2

Net Reaction
Discharge

Li + Ti 4+O2
Charge

Li Ti 3+ O2

Cell Configuration Ni|Li|Li+||Li salt in nonaq solvent||LiMO2|Li+ |Ni or polymer electrolyte Li Co O2 Assembled in the charged state.

xLi + + xe - + Li(1-x) CoO2

Discharge Charge
+ -

C 6 + xLi + x e Problems with lithium anodes Handling of lithium metal is difficult due its high reactivity. It should be handled inside the glove box maintained at very low humidity. During charging the lithium does not deposit smoothly over lithium anode but formation of dendrite takes place which penetrates the separator and leads to explosion. Advantage: Energy and power density is higher than lithium ion batteries. Net reaction

LixC6
Discharge Charge

LiCoO2 + C 6
Discharge

Li(1-x) CoO2+ LixC6

Cell Configuration
Ni|C6| LixC6 ||Li salt in nonaq solvent||LiMO2|Li+|Ni or polymer electrolyte

Assembled in the Discharged state. Properties Cell voltage: 3.0 -4.0V Energy/weight :160 Wh/kg Power/weight :1800 Wkg Charge/discharge efficiency :99.9% Self-discharge rate :5%-10%/month Cycle durability :~1200 cycles

Lithium polymer Battery or Plastic lithium battery (PLI) Electrolyte is in the form of polymer film which is prepared by immobilizing non aqueous electrolyte into polymer network. Polymer electrolyte can be used in both types of lithium batteries.(Lithium secondary and lithium ion batteries) All solid state battery. Polymer Electrolyte does a dual job as electrolyte and separator. Advantages No leakage Light weight Available in different shape and size Demerits: Ionic Conductivity of polymer electrolyte is very low and hence the internal resistance of the cell is very high. Advantages of Lithium batteries Lithium is the lightest of all metals, has the greatest electrochemical potential and provides the largest energy density for weight. Li-ion batteries are lighter than other equivalent secondary batteries. 0 Since Li has the most negative E (-3.0V), it generates a higher voltage than any other types of cell. Its cell voltage is higher than 3.0V Since all constituents of the battery are solids (PLI), there is no risk of leakage from the battery. Can be made in a variety of sizes and shapes. Li-ion batteries do not suffer from the memory effect. They also have a low self-discharge rate of approximately 5% per month, compared with over 30% per month in common nickel metal hydride Excellent Discharge Characteristics High Performance & Reliability Ultra-thin, Ultra-light, Ultra-tough (Lipoly) Disadvantages Aging: An older battery will not last as long as a new battery due solely to its age. Exposure to high temp shorten their life .For ex., a battery stored inside a poorly ventilated laptop may be subjected to a prolonged exposure to much higher temperatures which will significantly shorten its life. They are usually more expensive control methods needed for charge/discharge Batteries can be extremely dangerous if mistreated. Application of Lithium batteries I) In portable information & communication devices-Cellular Phones, Audio systems, PHS PDAs (personal digital assistants) Notebook Computers, Personal Transceivers, Camcorders, Digital Cameras Portable CD players, Mini Disc Players II) In Heavy Electric vehicles: Zero emission vehicles- no messy oil, no hazardous coolants, no noisy internal combustion engine, no air pollution

Fuel Cell
Introduction Fuel cell is an electrochemical cell, produces electricity from fuel and an oxidant. The fuel (on the anode side)and the oxidant (on the cathode side).are continuously and separately supplied into the cell, the reaction products flow out of the cell, while the electrolyte remains within it. The electrodes catalyze the cell reaction. When fuel and oxidant passes over the electrodes, they are dissociated catalytically into ions and electrons. The electrons go through an external electrical circuit to provide power while the ions move through the electrolyte toward the oppositely charged electrode where they combined to produce water as by-product. As long as fuel is supplied, the fuel cell will continue to generate power. Since no combustion takes place, fuel cells are clean, quiet, and efficient. Basic Arrangement in a fuel cell: Electrode| Fuel||Electrolyte||Oxidant|Electrode In Fuel systems, chemical energy of the fuel is directly converted into electrical energy its theoretical efficiency of 100%. Components of fuel cell. Fuel: Can be either gaseous or liquid fuels Ex., Gaseous: Hydrogen , CO, alkanes, Liquid fuels:Methanol/ethanol, hyadrazine , formaldehyde Oxidants: O2 or air that are cheap and readily available. Electrodes: Must be good catalysts to promote rate of electrode processes. Ex Pt, porous PVC, Raney Ni etc. impregnated in graphite. Electrolyte:Different electrolytes are used such as solid mixed oxide, acids, alkali etc., and it determines the kind of chemical reaction takes place in the cell. Hydrogen-Oxygen Fuel Cell Fuel is hydrogen and oxidant is oxygen. Types: Based on the electrolyte 1. Alkaline fuel cells (AFC)-KOH is the electrolyte. 2.Phosphoric acid fuel cells (PAFC): Phosphoric acid is the electrolyte 3.Proton exchange membrane fuel cells (PEMFC)- Cation exchange resin membrane is used as an electrolyte. 1) Alkaline Fuel cell (AFC) Electrodes: Graphite impregnated with finely divided Pt, Ag or Ni Electrolyte: An aqueous (water-based) solution of potassium hydroxide (25%KOH) retained in a porous stabilized matrix. The concentration of KOH can be varied with the fuel cell operating temperature, which ranges from 65C to 220C. The charge carrier for an AFC is the hydroxyl ion (OH-) that migrates from the cathode to the anode Thus the fuel cell produces electricity and water as byproduct. Cell Reactions At Anode 2 H2 (g) 4H + (aq)+ 4e + 4H (aq) + 4 OH -(aq) 4H 2 O (aq)

At Cathode O 2 (g) + 2 H2 O (aq) + 4e - 4 OH- (aq) Overall Net Reaction: 2 H2 (g) + O 2 (g) 2 H2 O (aq) Nominal cell Voltage: 0.8-1.0V Advantages: AFCs are the cheapest fuel cells to manufacture. This is because the catalyst that is required on the electrodes can be any materials that are relatively inexpensive compared to the catalysts required for other types of fuel cells. AFCs operate at relatively low temperatures and are among the most efficient fuel cells, that would enable a quick starting power source and high fuel efficiency. Disadvantages: AFCs is very sensitive to CO2 that may be present in the fuel or oxidant The CO2 reacts with the electrolyte, poisoning it rapidly, and severely degrading the fuel cell performance. Therefore, AFCs are limited to closed environments, such as space and undersea vehicle. Purification of hydrogen and oxygen is very expensive. Applications Fuel cells are very useful as power sources in remote locations, such as spacecraft, remote weather stations, large parks, rural locations, and in certain military applications. Alkaline fuel cells (AFC) are one of the most developed technologies and have been used as energy source and source of drinking water for manned space craft. 2)Phosphoric acid Fuel Cell Electrodes: Noble metals impregnated into a PTFE bonded carbon matrix Electrolyte:Phosphoric acid Temp: 170-200C Cell Reactions At Anode 2H2 (g) 4H+ (aq) +4e At Cathode O2(g) + 4H+(aq) +4e - 2H 2O(aq) Overall Net Reaction: 2 H2 (g) + O 2 (g) 2 H2 O (aq) Nominal cell Voltage: 0.8-1.0V Limitation: Operating Temperature is high Advantages: CO2 does not affect the electrolyte or cell performance Low electrolyte volatility and long-term stability are additional advantages. Due to high operating temperature of PAFCs, the waste heat is used for heating hot water or generating steam at atmospheric pressure. Application: Generate electricity in remote areas (40KW-100kW).

3)Ion- Exchange(Proton exchange membrane cell) membrane fuel cell The cation exchange membrane in the H-form is used as electrolytes. Solid polymer electrolyte membrane, Sulphonated poly-tetrafluoroelthylene polymer is used as cation exchange membrane. The resin membrane is sandwiched between two porous metal electrodes At Anode 2H2 (g) 4H+ (aq) + 4e At Cathode O2 (g)+ 4H+ (aq) + 4e - 2H2O(aq) Overall Net Reaction: 2 H2 (g) + O 2 (g) 2 H2 O (aq) Electrodes: Carbon electrodes containing pt as a catalyst. Operating temperature :Low (80C) Limitations: Fuel should be free from CO2-easily poisoned Application: Fuel system for space state applications During shady periods fuel cell provides energy and during sunny days, the output of solar cells electrolyse the water formed in the fuel cell into H2 and O2 which are used as fuel again.