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Current trends and future perspectives in the recycling of spent lead acid batteries in India Kalpna Varshney a Pradeep K Varshneyb Kajal Gautamc Monika Tanwarc Meghna Chaudharyc aDepartment of Chemistry Faculty of Engineering 10 Power storage device in electrical vehicles EV 11 Power source in hybrid electrical vehicles and grid scale energy storage component of electricity generated by renewable sources solar wind etc 12 Mobile applications Automotive or vehicular batteries used for starting in vehicle lighting and ignition SLI 13 14 If immobile application of lead acid batteries would not be there the power outages nearly be every day as lead acid bat teries has come for rescue supplying large amounts of electric ity for a short duration of time until supplementary power is added to the grid In the growing electricity networks the need of energy stor age is very important because more generating capacity is using renewable resources of energy The best way of steadying elec tricity networks is batteries Electricity storage will be an impor tant tool to empower the subsequent segment of the energy transition Along with enhancing solar and wind power genera tion it will be helpful in decarbonisation issue of the energy market LABs are well known device for automobiles Industries and is also consuming for utility energy storage 15 The ability of spinning reserve to maintain the quality of power is decreased with the increase of renewable inputs and there is a need to develop new strategies to improve renewable inputs without deduction or mutilation 16 As the consumption of batteries increased day by day India become third biggest market of vehi cles till 2020 Lead acid batteries cover up the whole market by their widely used power back up systems because it has portable applications and has the ability of recycling as compare to other batteries After 3 to 4 years of using these batteries can be recy cled and reused If recycling cannot be handled properly it leads to hazardous issues to the environment There are various tech nologies by which we recover lead from the lead acid batteries these schemes are hydrometallurgy and pyro metallurgy All waste disposals and their cost should be done in such a way so that Environment is not harmed The waste management cost can be reduced changing the design of products 1 1 Battery types and its applications A battery is a package of one more galvanic cell where the chemical energy transforms into electrical energy The process by which this conversion of energy change takes place is known as an electro chemical redox reaction of its active material The basic electrochemical unit is cell The number of cells in a battery can be increased or decreased depending upon the required output voltage Batteries are further divided into three categories depend ing upon their function and working 1 1 1 Primary batteries Primary batteries are those which can provide charge only once and continuously discharge During discharge the chemical compo nents of the battery are changed irreversibly and electrical energy is obtained from chemical energy They can neither be recharged nor re use as a source of DC direct current power Typical exam ples of primary batteries are mentioned Table 1 along with their applications 17 18 1 1 2 Secondary batteries Secondary batteries are those which are made up of various chemicals and basic materials During charging and discharging this material can change reversibly The most common secondary battery is lead acid battery Typical examples of secondary batter ies are mentioned in Table 2 along with their application 19 24 1 1 3 Tertiary batteries A tertiary battery is commonly known as a reserve cell It is dif ferent from primary and secondary cell as the main chemical com ponent of the cell is separated from the remaining materials while waiting for initiation In general the isolated component is elec trolyte Such type of assembly in battery is used generally in ther mal batteries where the solid electrolyte is inactive for usage until the battery is activated by ionic conduction when electrolyte is melted and forms ionic state The reserve batteries are not refi ll able they are discarded after single use 25 These batteries appre ciably reduce the probability of self discharge and reduce chemical deterioration Tertiary batteries are operated in explosion devices such as in missiles torpedoes and other weapon systems which are based on timing temperature and pressure sensitiveness These are majorly categorized into four types based on their activa tion methods By water activation By Gas activation Electrolyte activated batteries By Heat activation Fig 1 Mining Data of Lead with top mining countries in the world Source Global Data Mining Intelligence Center Table 1 Typical examples and applications of primary batteries S No Common NameApplication 1 Zinc carbonTorches radios toys power drain application fl ashlights electronic equipment remote controller table watches 2 Zinc chlorideRecorders clocks calculator remote controllers 3 Alkaline zinc manganese dioxide Digital camera portable CD player battery saver 4 Lithium manganese dioxide Watches cameras test instruments 5 Zinc mercuric oxideCalculators pagers hearing aids 6 Zinc silver oxidePagers hearing aids watches military submarines 7 Zinc oxygenHearing aids pagers 2K Varshney et al Materials Today Proceedings xxx xxxx xxx Please cite this article as K Varshney P K Varshney K Gautam et al Current trends and future perspectives in the recycling of spent lead acid batteries in India Materials Today Proceedings https doi org 10 1016 j matpr 2019 12 168 The fourth class of batteries are the fuel cells These are just like batteries except that electrolyte is not a vital part of the system as in a battery In fuel cells electrolytes are supplied into batteries from an external source The fuel cell differs from normal battery as it can harvest electrical energy till the electrolytes are supplied to the electrodes but stop functioning in the absence of such mate rials 22 25 1 2 Lead acid battery Since the discovery of Lead acid battery in 1859 a great applica tions are being identifi ed in the area of batteries The best applica tions of LABs are their usage as genuine rechargeable energy storage ideal way out for most of four wheelers and other automo biles It is also widely used in yachts submarines uninterruptible power supplies UPS and several other house hold and medium rage applications Rechargeable Lead acid battery is having the best cost to performance ratio for storage of energy Generally the anode in lead acid battery is made up of lead Pb and cathode is of lead oxide PbO These electrodes are dipped in an aqueous solution of sulphuric acid which is the electrolyte for transfer of electron from anode to cathode When the battery produces elec tricity energy the lead ions migrate into the solution and combi nes with electrolyte to form lead sulphate PbSO4 and the PbO reacts to produce lead sulphate and water This process is called discharging of battery 25 see Fig 2 During discharging process there is accumulation of lead sulphate on the electrode and water in the electrolyte During charging the process gets reversed and the lead sulphate gets combined with water there by producing lead and lead oxide 26 Charging 2PbSO4 2H2O PbO2 Pb H2SO4 Discharging PbO2 Pb H2S04 2PbSO4 2H2O There are different types of batteries available in the market among these batteries lead acid batteries provides a reliable and economic solution for energy storage 16 27 32 Among these renewable battery systems lead acid and nickel batteries are most popular one Nickel batteries NiCd NiMH are being obsolete because of its high cost and environmental factors For portable electronics Lithium ion battery is a well well known tool but large scale application of it is still questionable it may challenge many immobile applications where volume weight temperature sensi tivity and low maintenance is more vital than preliminary costing Lead acid batteries are well established option in market from last 150 years and in the upcoming future also due to its low cost recy clability and conventional industrial base 16 33 The usage of LABs can be of two types for smaller duration of time the stored charge in battery can control frequency and stability and for longer duration they can bring about energy management Lead acid bat teries are used as an energy storage system because they are com pact deployable and inexpensive and provide prompt response both to incoming and outgoing current to battery 1 2 1 Types of lead acid battery 34 1 Flooded battery Electrolyte is open a Lead Calcium Battery b Lead Antimony Battery c Lead Carbon Battery 2 VRLA LAB Electrolyte is in closed chambers a Gel based Lead Acid Battery b Deep Cycle Lead Acid Batteries 1 3 Consumption of lead acid battery The demand of lead is fulfi lled by either primary mining or secondary refi ning and recycling lead sources Nearly 80 of lead is used to produce lead acid batteries 35 and out of this approx 99 100 of the lead is recovered recycled and reprocessed world wide China being the top most producer and consumer of lead is also having highest refi ning rates and over 67 1 92 billion kg of its total lead usage is utilized for producing LABs 36 As per the statistics data the total lead production in US was 1507 000 metric tonnes in Europe it is 16181 000 metric tonnes and in China which is again at the top with 6602 000 metric tonnes in 2017 37 38 see Table 3 Fig 2 Schematic representation of components of lead acid battery Table 2 Typical examples and applications of secondary batteries S No Common Name Applications 1 Lead acidMotor vehicle engine starting backup power supplies electric motors ignition system of automobiles computer telephone exchange inventors portable emergency lights submarines lawn mowers wheel chairs Robots spinning reverse peak shaving load leveling UPS remote station communication base station 2 Alkaline rechargeable In remotes of various electronic gadgets fl ash lights portable radios clocks cameras hand held games MP3 players toys power tools T V mobiles video recorders computers memory stimulating instruments cordless devices emergency beacons 3 Nickel IronBackup power supply off grid power supplies mining equipment 4 Ni Cd Portable electronics toys emergency lightings fl ash light power tools portable radios T V cell phones camcorders computer instruments emergency beacons wireless peripherals 5 Nickel Metal Hybrid Electric vehicles consumer electronics satellites Roberts emergency power fuel cell water activated batteries hybrid electric vehicles plug in hybrid electric automobiles fork lift trucks milk folks locomotive fl ash lights toys T V power tools portable radios mobile phones camcorders laptop computer memory uplifting equipments cordless devices and peripherals emergency beacons 6 Lithium IonPortable electronics electric vehicles aerospace application IPods wrist watches artifi cial place makers digital dairies stop watches cameras clocks spinning reverse peak shaving load levelling fork fl it trucks milk folks locomotive 7 Lithium ion polymer Mobile phones laptops radio control equipment and air soft electric vehicles power banks tablets electronic cigarette wireless controller for video game consoles portable media player K Varshney et al Materials Today Proceedings xxx xxxx xxx3 Please cite this article as K Varshney P K Varshney K Gautam et al Current trends and future perspectives in the recycling of spent lead acid batteries in India Materials Today Proceedings https doi org 10 1016 j matpr 2019 12 168 India Energy Storage Alliance IESA estimates that lead acid battery market in India at around INR 27 000 Crore USD 4 2 bil lion in 2015 16 In this the contribution to of batteries in station ary and movable function is roughly INR 12 650 crore USD1 9 billion As per IESA the the future market size will around INR 24 900 crore USD 4 billion by 2020 which shows a CAGR of 13 in the next 5 year of time 39 1 4 Automobiles Starting lighting ignition SLI lead acid batteries are majorly used in automobiles such as passenger vehicles commercial vehi cles tractors two wheelers etc Growing automotive industries have increased the demand of SLI lead acid battery Two wheelers are the major consumers of SLI batteries According to the society of automobile manufacturers in India the domestic sale of two wheelers is around 16 46 million units which are expected to increase in the upcoming future so there will be signifi cant growth of SLI batteries by 2022 40 The market requirement of LABs for electric bikes has been increased by 0 8 for other automotive 12 8 for electric tricycle and low speed electric vehicle both over 40 and for communication devices around 14 In the next one decade the demand for the automotive switching battery and LABs and modifi ed LABs is likely to increase by 30 40 The demand may increase to 25 30 for low speed electric vehicle battery and for electric tricycle and ATV special purpose electric vehicle around 10 15 41 In India the largest end user of LABs is automobiles and this sec tor has achieved a growth rate of 13 03 from 2008 to 2012 even tually a pressure pull to the growth and demand for automotive batteries Moreover India is growing as the third largest automo tive market in the world that may results in the increasing demand for LABs by 2025 42 In India the market growth in lead acid battery market is expected to grow to 7 6 billion by 2023 According to one research the lead acid battery market in is expected to nurture at a CAGR of more than 9 in the period of 2018 24 SLI battery sector was having the highest returns share in 2017 followed by stationary battery segment SLI battery is pro jected to lead the market during the forecast period owing to its high utilization in automobiles Moreover automobile sales regis tered an increase of around 14 in 2017 vehicle production in India registered a CAGR of nearly 6 during 2011 17 contributing towards the demand of SLI lead acid batteries in the country 43 1 5 Energy storage devices Common municipal lighting system like solar devices generates demand for lead acid batteries solar power systems stores energy in the battery and used for lighting at night This is about 60 of the market share Another sector is outdoor wind and solar power station due to instability in current and power The fl uctuation problem is completely removed by lead acid batteries LABs are expected to account for 75 of the solar and wind power system together because of their low cost and good performance It is pro jected that 1 3 million kWh batteries will be employed in 100 mil lion kW generators The requirement in power plant for lead batteries is very much as a general power plant needs to change batteries two to fi ve times during their operational life of approx imately 20 years 44 49 1 6 Electric vehicles For sustainable development the transportation should be clean and effi cient and this is possible only by electrifi cation of vehicles Various Electric vehicles for example hybrid electric vehi cles HEVs plug in hybrid electric vehicle PHEVs and battery electric vehicles BEVs will go in front in the market in upcoming years And it is predictable that global manufacture of plug in hybrid electric vehicles will increase up to 10 5 million units in 2025 which will increase the demand of lead acid batteries in the market 50 52 1 7 Recycling of spent lead acid battery Issues and aspects Sustainability is the most important and much required aspect in today s world for any technology Recycling of lead acid battery provides a path of sustainable development and is a well established tradition since they were fi rst used Approximately 100 recycling rates have been achieved in western countries and very high recycling rate have been achieved elsewhere Nearly 85 of lead is used in battery production and 60 of the total lead is produced by recycling Lead acid battery is treated so that lead containing components of the battery can be detached from plastic coverings and electrolyte acid all components of battery are reclaimed by further treatments Almost all components of lead acid battery can be completely recycled and re utilized via imple mentation of low energy input processes 16 It is estimated that the demand of automobiles telecommunication tower electric vehicles energy storage devices and solar power systems is going to increase rapidly in the upcoming years but the source of lead ore is limited so there is need to develop new and ecofriendly tech niques to recycle lead from lead acid batteries and other lead con taining scrap It will not only decrease our dependence on lead mining to fulfi ll the world wide lead demand but also reduce the amount of lead waste in the landfi lls Recycling rate of LABs is very much higher than any major con sumer product see Fig 1 Even in United States many advertising programs and educational promos cannot increase the recycling of other consumer products on the other hand lead acid batteries have achieved excellent recycling rates In the United States about 99 of lead acid batteries are recycled 11 Lead acid Pb acid battery recycling is also working well in Europe and Japan 17 Several countries have developed different recycling techniques to recycle lead from the lead acid batteries In United State and European countries nearly 100 recycling rates have achieved Table 3 Global lead production and usage metric tonnes in 2012 S NoCountryPrimary production lead mine production in thousand tonnes Secondary production recycled lead in thousand tonnes Consumption in thousand tonnes 1China2 600 0001 462 0004 629 000 2United States346 0001 110 0001 499 000 3India100 000341 000521 000 4Mexico237 000205 000230 000 5Other countries1 714 0002 681 0003 590 000 The total production globally is 4 997 000 MT against the consumpti