1、LITHIUM ION BATTERY RECYCLING:A REVIEW OF THE CURRENT METHODS AND GLOBAL DEVELOPMENTS First commercially introduced in 1991,lithium ion batteries(LIBs)(Figure 1)have become an indispensable part of modern technology,being used in vehicles,consumer electronics,power tools,medical devices,and backup p

2、ower systems.However,the manufacturing and disposal of lithium ion batteries has had a wide range of political,economic,and environmental concerns.The explosion in popularity of electric cars with ever-increasing battery sizes,in tandem with the rapid disposal of smartphones and other electronics to

3、 landfill,has increased energy waste and reliance on non-renewable resources.The increasing use of LIBs and their high disposability supports a rationale for increased recycling and their components and materials.Currently,LIB recycling methods are associated with financial incentives.The benefits o

4、f recycling batteries are dependent upon the component materials and their value.While batteries at end-of-life are likely to contain materials of value,this is not uniformly the case.Significant battery design variability and the lack of technological convergence contribute to the challenges faced

5、with recycling.Design variability makes automation of recycling processes difficult and contributes to higher costs.Furthermore,many recycling benefits are public goods and so do not reward individuals or companies directly.However,there are both material security and environmental benefits of recyc

6、ling LIBs,such as:a decrease in water consumption and pollution from mining,reduced energy consumption and greenhouse gas emissions,as well as reduced pollution and safety risks.These benefits are not easily monetized.The costs of battery recycling are highly dependent on the capacity and technologi

7、cal capabilities of facilities.These limitations suggest that regulation is required to standardize practices for LIB recycling being implemented broadly to minimize costs.Government policies play a role in developing recycling capabilities,but it is important to note the economics of recycling and

8、the material requirements for manufacture should also contribute to the construction of recycling facilities.IntroductionLITHIUM-ION BATTERY RECYCLING|3Throughout this white paper,discuss the methods for LIB recycling,namely hydrometallurgy,pyrometallurgy,and direct recycling,with a focus on the rec

9、ycling of cathode materials.Figure 2 describes the processes involved for each of these 3 methods.Using data from CAS Content Collection,we analyzed LIB recycling methods and materials in both academic and patent literature from 20102021 to provide a holistic view of how LIB recycling is progressing

10、 in industry and academia.The economic and regulatory benefits,and challenges of LIB recycling,alongside an overview of established and planned global recycling facilities and reported capacities are also discussed.Figure 1.Schematic diagram of lithium ion battery.The battery is charged via the appl

11、ication of current,which causes s to pass from the cathode to the anode via the electrolyte.Upon discharge,the ions spontaneously deintercalates from the anode with concomitant transfer of an electron to drive current through an external loadFigure 2.An outline of the three methods used for LIB recy

12、cling LIB Recycling TechniquesHydrometallurgyHydrometallurgy uses solutions(primarily aqueous solutions)to extract(leach)and separate metals from battery(cathode)materials.Pyrometallurgy Pyrometallurgy uses heat to convert the metal oxides used in battery materials to either metals or metal compound

13、s.Direct RecyclingDirect recycling is the removal of cathode material for reuse or reconditioning.ChargeChargeDischargeAnodeLi+Li+LiCoO2DischargeNon-aqueouselectrolyteCathodee-e-SeparatorLIB recycling around the worldIn most cases,combinations of hydrometallurgical and pyrometallurgical methods are

14、used to process LIBs(Figure 3).For example,Retriev(originally Toxco)(4500 tons batteries/year),Sumitomo/Sony(150 tons/year),and Inmetco(6000 tons/year)use primarily pyrometallurgical methods;Recupyl(110 tons/year)uses a hydrometallurgical method;Akkuser(4000 tons/year),Umicore Valeas(7000 tons/year)

15、,and Glencore(3000 tons/year)use both pyrometallurgy and hydrometallurgy as parts of their recycling methods.Pyrometallurgical methods are likely used because they allow flexibility in battery feedstock(the Umicore method is used for both lithium ion and nickel metal hydride batteries)and because th

16、ey have significant fixed investment in facilities.Methods in development,on the other hand,rely on hydrometallurgy to a larger degree,at least in part because the cost of facilities to implement these methods are smaller.Lithorec and Aalto University(Finland)both have devised hydrometallurgical met

17、hods,while Accurec,Battery Resources,and OnTo use both hydrometallurgical and pyrometallurgical methods.PretreatmentDischargeIf the potential can be retrieved and stored economically,LIB can be electrically discharged.InactivationIf not,then the batteries need to be deactivated so the battery materi

18、als can be removed.This is often achieved by immersing LIB in an aqueous salt solution,allowing the charge and heat from discharge to be removed rapidly and preventing combustion of organic byproducts.An inert atmosphere can be used to prevent combustion as well,and liquid nitrogen is also used both

19、 to inhibit combustion and to cool LIB so that they are less likely to overheat and catch fire.Carbon dioxide is used in some processes as an unreactive gas for battery inactivation.Disassembly manualManually disassembled batteries then require further processes to obtain battery material;either sol

20、vent treatment,calcination,dissolution in aqueous NaOH,or ultrasonication yield the battery materials.Disassembly shredding The simplest method is to shred,crush,or break apart the batteries into small pieces;performing the shredding under an inert atmosphere allows the deactivation and disassembly

21、steps to be combined.LITHIUM-ION BATTERY RECYCLING|5SeparationBattery materials can be sorted by size using screens,by density using solutions or airflows,or using filtration.Direct recyclingDirect recycling is the removal of cathode material for reuse or reconditioning.To directly recycle LIBs,batt

22、eries must be disassembled to obtain the separated components.PyrometallurgyPyrometallurgy is the use of heating(most often using a furnace)to convert the metal oxides used in battery materials to either metals or metal compounds.SmeltingIn reductive roasting(smelting),the battery materials(after pr

23、etreatment)are heated under vacuum or inert atmosphere to convert the metal oxides to a mixed metal alloy containing(depending on the battery composition)cobalt,nickel,copper,and iron and slag containing lithium and aluminum.Reductive roasting then requires leaching of the mixed metal alloy to yield

24、 the separated metals,while the slag containing the lithium has to be processed if recycling lithium is desired.Salt roastingAlternatively,addition of salts such as aluminum chloride to the battery materials is used for salt roasting,allowing the metal oxides to be converted to salts such as cobalt

25、chloride.HydrometallurgyHydrometallurgical methods use solutions(primarily aqueous solutions)to extract(leach)and separate metals from battery(cathode)materials.The pretreated battery materials(with aluminum and copper removed earlier)are most often extracted with acidic aqueous solutions.The most c

26、ommon combination of inorganic leaching reagents used is sulfuric acid and hydrogen peroxide(with hydrogen peroxide acting as a reductant),while hydrochloric and nitric acid are also commonly used.Organic acids can be used,with citric and oxalic acids being most commonly used.Alternatively,base solu

27、tions of ammonia with either ammonium sulfate or ammonium carbonate can be used for extraction.Once the metals have been extracted into solution,they need to be selectively removed from solution;either the metal salts are precipitated selectively using pH variation or extracted using organic solvent

28、s containing extractants such as dialkyl phosphates or phosphinates.Metal extraction using bacteria or other organisms(bioleaching)has been studied.Figure 3.Flowchart of common recycling methods.In most cases,LIBs must be pretreated,after which they can be subjected to pyrometallurgy,hydrometallurgy

29、,direct recycling,or a combination of methods.Pretreatment includes three sets of processes discharge or inactivation,disassembly,and separationCosts and benefits of LIB recyclingRecycling LIBs can be beneficial from an economic and environmental standpoint.In addition,the specific processes used in

30、 the recycling pathway may modify these costs and benefits(Table 1).Table 1.Advantages and limitations of common recycling methods.The specific processes used in the recycling pathway carry different advantages and limitations from practical,economic,and environmental standpointsProcessAdvantagesLim

31、itationsDisassembly shredding Simplest method for disassembly Does not allow the current collectors or casing to be separated intactDisassembly manual Allows intact separation of components Exposes the workers to the battery materials Labor-intensivePyrometallurgical Requires simpler pretreatment me

32、thods to prepare batteries for recycling and requires fewer different methods to recycle LIB of differing compositions,shapes and sizes Likely(but not certain)to require lower amounts of reagents than hydrometallurgical methods Many of the components of LIB cannot be recovered at all using pyrometal

33、lurgy Burning the organic components of LIB requires pollution mitigation measures Requires larger investments in facilities than hydrometallurgy or direct recycling Requires far higher temperatures and energy consumption than other battery recycling methodsHydrometallurgical organic acids More rene

34、wable than inorganic reagents and so are likely to be preferred Require more energy from reagent use and manufacture,cost more,and generate more carbon dioxide than inorganic reagentsHydrometallurgy Provides metals in forms that can easily be manipulated or used in producing new LIB,and more of the

35、materials from batteries can be easily recovered by hydrometallurgy than by pyrometallurgy.The lower temperatures required for hydrometallurgy reduce its energy intensity.Hydrometallurgical facilities also require less capital than pyrometallurgical ones Requires large amounts of water(and,when solv

36、ent extraction is used to separate the metal compounds,organic solvents).The wastewater treatment requirements(including neutralization)for hydrometallurgy are significant.The pretreatment methods needed for hydrometallurgical methods are more labor-intensive than for pyrometallurgical methods.Final

37、ly,the methods for metal separation from the need to be selective to avoid cross-contamination of battery materialsHydrometallurgy-bioleaching(metal extraction using bacteria or other organisms)has been studied Likely to require less water,reagents,and energy than other hydrometallurgical methods Re

38、quires more time to extract metals,thus requiring larger facilities for equal metal outputDirect recycling Likely to have lower energy costs and reagent costs than other methods Energy requirements are likely to be lower than for either pyrometallurgical or hydrometallurgical methods Lower fixed fac

39、ility costs than other methods Likely less reagent and solvent use than what is required for hydrometallurgy Allows recyclers to recover all components from LIB and may allow the cathode material to be retrieved with intact crystal structure appropriate for use in LIB Requires that LIB be in good co

40、ndition for recycling Different methods are required to reconstitute batteries based on the battery type and composition Requires that either the selection of acceptable batteries be reduced to a smaller selection to reduce the facility and complexity costs for multiple battery types,or increased fa

41、cilities and labor must be available to recycle input LIB Larger labor costs will be required than other methodsLITHIUM-ION BATTERY RECYCLING|7Economic benefitsThe worlds reserves of LIB components are limited,and their mining is energy-and labor-intensive.Many of them are found or produced only in

42、specific regions meaning materials may be subject to significant price fluctuations.In addition,natural disasters,war,or resource allocation decisions may also reduce availability.Earlier battery designs that are now due for recycling are likely to contain more cobalt,one of the key battery material

43、s with supply limitations.Recycling can provide domestic security for battery components and limits the ability of suppliers to control the pricing.Providing alternative sources,particularly sources which are unlikely to coordinate their production and pricing,recycling should insulate manufacturers

44、 against short-term price variation.From the estimated 500,000 tons of batteries which could be recycled from global production in 2019,15,000 tons of aluminum,35,000 tons of phosphorus,45,000 tons of copper,60,000 tons of cobalt,75,000 tons of lithium,and 90,000 tons of iron could be recovered.Recy

45、cling can reduce the need to mine new materials and dependence on imports.Overall,the current LIB recycling market is estimated to be worth approximately$1,700 million and is expected to increase significantly over the next ten years.Mining virgin materials and recycling used batteries does exact an

46、 environmental cost.For example,some environmental costs of producing one ton of virgin lithium are shown in Figure 4.While refining brine requires less energy than refining spodumene,it requires 1824 months,yields lower grade lithium,and recovers less of the lithium present in brine than is recover

47、ed from ore.In addition,refining brine consumes water.In Chile,where mining represents over half its export market,most of the countrys water is consumed by the mining industry.LITHIUM ION BATTERY RECYCLING|7If battery recycling has a potential economic benefit,then the likelihood of battery recycli

48、ng on a large scale is improved.The value of materials obtained from battery recycling determines its economic benefit.Environmental benefitsAssessments of the environmental benefits of LIB recycling such as greenhouse gas emissions saved are highly variable.They tend to differ over time with variat

49、ions in the methods used,changes in energy costs,battery composition,and improvements in modelling efforts.A key factor that determines the environmental benefit of LIB recycling is technology.One assessment found that using older technology combined with a lower fraction of capacity can use ten tim

50、es more energy compared with maximum capacity facilities using more recent technology.However,savings to emissions and energy could be significant:the same assessment found that recycling the cathode material and current collectors could reduce energy use by more than 50%,while recycling LCO could r

51、educe carbon dioxide emissions by up to 75%.One argument questions whether the environmental costs of LIB manufacture,use,and recycling outweigh the reduction in fossil fuel use they enable.Benefits of LIB batteries in plug-in electric vehicles depend on the source of the electricity used to charge

52、them.When coal-heavy electricity sources are used,the benefits of electric cars are lower than when electricity generated using renewable sources is used.For example,one assessment concluded that internal combustion engine(ICE)-driven vehicles use 20-25%more energy and generate 15-50%more greenhouse

53、 gas emissions than either plug-in or hybrid electric vehicles.However,electric vehicles are not without limitation,since battery manufacturing can cause them to emit up to 3-fold more sulfur oxides than ICE-driven vehicles,a situation that LIB recycling would be likely to ameliorate.Transportation

54、of end-of-life batteries from disposal sites to a recycling facility can be a significant cost,particularly when long distance or international transport is required.The magnitude of these costs is highly variable and depends on several factors,including distance and cost of labor.The different proc

55、ess employed can also strongly impact costs;see Table 1.Figure 4:Some environmental costs of producing one ton of virgin lithiumLITHIUM-ION BATTERY RECYCLING|9LIB recycling research trends Li-ion battery recycling publicationsPublications related to lithium ion battery recycling were searched for in

56、 the CAS Content Collection,and these were analyzed based on their publication type and publication year(Figure 5).While the global scientific publication volume has been steadily increasing in the past decade,we found that the annual volume growth in publication on this topic(32%)far exceeds that o

57、f overall scientific publications(4%annually),suggesting an emerging interest on this topic,especially in the last four years.We also found that patent applications account for 74%of the entire pool,whereas patents count for 33%in the entire CAS Content Collection.This indicates the high commercial

58、value of the technologies and discoveries around LIB recycling.An analysis of the countries and regions associated with the affiliated organization of these documents shows that China has the highest publication volume in both journals and patents(Figure 6).Figure 5.Journal articles and patent publi

59、cations on Li-ion battery recycling(Data for 2021 is partial)Number of Publications8007006005004003002001000201020112012201320142015201620172018201920202021JournalPatentDocument TypeJournals and Patents in CAS Content CollectionLi-ion batteryrecyclingOverallNumber of Publications26002400220020001800

60、1600140012008006004002000BelguimBrazilCanadaChinaFinlandFranceGermanyIndiaIndonesiaIranItalyJapanOtherSouth KoreaSwedenTaiwanUnited KingdomUnited StatesJournalPatentDocument TypeWe also assessed the publication trends in different recycling methods,as ranked by the annual numbers of publications inv

61、olving hydrometallurgy,pyrometallurgy,and direct recycling over the past decade.Consistent with overall observations seen in Figure 5,publications involving all three methods increased overall and have grown significantly in the past few years(Figure 7).Hydrometallurgy has outgrown pyrometallurgy co

62、nsiderably after 2015,likely because hydrometallurgy is favored in new developments due to lower facility costs.Direct recycling has also grown substantially in most recent years.Li-ion battery recycling publications by country/regionFigure 6.Li-ion battery recycling publications by country/region d

63、uring the years 2010-2021LITHIUM-ION BATTERY RECYCLING|11To gain a more in-depth perspective,we also assessed the popularity of the extraction of different metals and the recycling methods employed(hydrometallurgy or pyrometallurgy),as ranked by the numbers of publications in the past decade.We foun

64、d that lithium tends to be most frequently recovered,which can likely be partly attributed to the prevalence of lithium in all LIB cathodes(Figure 8).In terms of recycling methods,all metals broadly shared a similar pattern with a combination of methods used in most studies(Figure 8).Li-ion battery

65、recycling methods by yearNumber of PublicationsPublication Year450400350300250200150100500201020112012201320142015201620172018201920202021Direct RecyclingHydrometallurgyPyrometallurgyMeasure NamesFigure 7.Publication volume for each respective recycling method during the years 2010-2021LITHIUM ION B

66、ATTERY RECYCLING|11Direct recycling,that is the removal of cathode material for reuse or reconditioning,is likely to have lower energy and reagent costs than other methods(see Table 1).While the most value can be gained from cathode recycling,a more holistic,sustainability-minded approach considers

67、all components of the Li-ion batteryrepresenting an opportunity to reduce environmental impact by recovering more waste materials from end-of-life batteries.We quantified publications focusing on the lesser-studied components obtained via direct recycling to gain insight into research progress in th

68、is area(Figure 9).The most studied non-cathode component is the anode,followed by the electrolyte,current collectors,and separator.We also assessed the specific processes involved in the recycling of LIBs.To maximize the amount of recyclable material,disassembly is preferable to comminution of the w

69、hole LIB;our findings are encouraging,showing that considerable research effort has been made towards disassembly (Figure 9).Recovery of metals from Li-ion batteriesFigure 8.Prevalence of metals recovered in documents discussing hydrometallurgy and/or pyrometallurgy8007006005004003002001000LiCoNumbe

70、r of PublicationsHydro onlyHydro+PyroPyro onlyMethodFeMnNiLITHIUM-ION BATTERY RECYCLING|13Recycling of other components and process studiesPublications on Component or Process1501401301201101009080706050403020100AnodeElectrolyteCurrent CollectorSeparatorDisassemblyProcessComponentComminutionDischarg

71、eFigure 9.Publications studying recovery of non-cathode materials and process optimization for recyclingGlobal regulations and policiesLIB recycling regulations are increasing.Many countries fund research into LIB recycling methods,and a variety of countries have LIB recycling laws,with China and th

72、e European Union having or enacting comprehensive regulatory frameworks for LIB recycling(Figure 10).EUROPE No regulations governing LIB recycling,but a draft regulation has been proposed This provides a comprehensive framework for the design,sale,use,and recycling of batteries,particularly LIB They

73、 are intended to provide both environmental and material security for the EU;however,some requirements may disadvantage battery manufacturersUK No explicit regulations for LIBsUSA The federal,state,and local governments have authority At the federal level,no policies directly address battery energy

74、storage system decommissining,or mandate or incentivize reuse/recovery of LIBs(as of 2020)The recycling of lead-acid batteries may be a potential template for future LIB recycling regulations The contents of LIBs are likely to be subject to hazardous waste regulations At the federal level,there are

75、no state or local laws specifically addressing LIB recyclingCountries with LIB recycling regulationsCountries without LIB recycling regulationsCountries developing LIB recycling regulationsFigure 10:Key LIB recycling frameworks around the worldLITHIUM-ION BATTERY RECYCLING|15LITHIUM ION BATTERY RECY

76、CLING|15AUSTRALIA No LIB recycling policyGERMANY The Recycling Law,Battery Recycling Act,and Scrap Automotive Recycling Act define the LIB recycling responsibility of manufacturers,consumers,and recyclersINDIA Regulations for electronic waste,but no framework for LIB recyclingJAPAN Basic,comprehensi

77、ve,and special laws all regulate battery recycling New vehicle manufacturers are assigned responsibility for batteries and must maintain knowledge of battery recycling technology so that it can be incorporated into the recycling process A nonprofit organization manages battery recycling There is an

78、active program to re-use batteries for home emergency powerCHINA A variety of laws determine the national operational standards for battery recycling,some of which directly relevant to LIB Various laws specify battery outcomes,including safety measures,procedures,storage,management,appearance,polari

79、ty,methods for determining voltage,charge and discharge current,and residual energy,uniquely identification and specifications In 2018,China instituted the Notice on the Pilot Work of Power Battery Recycling on New Energy Vehicles(2018),a pilot plan for battery recycling The Law of the Peoples Repub

80、lic of China on the Prevention and Control of Solid Waste Pollution enacted a system in 2020 for the prevention and control of solid waste pollution,including LIB An important caveat is suboptimal compliance with recycliing laws,based on historical compliance with lead-acid batteriesFigure 11.Establ

81、ished and planned global Li-ion battery recycling facilities as of November 2021Current LIB recycling capacity is concentrated in East Asia,with China possessing more than half of the worlds current recycling capacity.Europe possesses most of the remaining LIB recycling capacity.Proposed LIB recycli

82、ng facilities will increase their recycling capacity by approximately 25%,with most of the(defined)new capacity concentrated in North America(Figure 11).The location of current recycling capacity is consistent with the effect of LIB recycling regulations,while the location of future capacity is more

83、 consistent with economic motivations.12345678United States19AustraliaIndonesia329161718NorwayFinlandPolandItalyGermanyFrance101114151312202523212226243130292827MongoliaChinaJapanEstablishedPlannedStatusCapacity/tonunknown20000400006000080000100000LITHIUM-ION BATTERY RECYCLING|17Is current and futur

84、e LIB recycling capacity consistent with the regulatory outlook?Based on current recycling capacity and stated future capacity,East Asia(particularly China)has the largest concentration of recycling capacity,followed by Europe.The concentration of current capacity is consistent with the level of reg

85、ulation(or with the government priorities that the regulations reflect);China has a significant structure of regulation for LIBs,while members of the EU have significant recycling rules in place and in the process of developing a comprehensive framework LIB recycling in the EU.The largest portion of

86、 future recycling capacity(of that with stated capacity)is proposed for North America,particularly in the United States,where little in the way of national regulation for LIB recycling has been enacted.LIB recycling development in the United States may be driven by the potential for future regulatio

87、n but is more likely to be driven by increases in electric vehicle sales,battery manufacture,and the disposal costs and benefits they may entail.The limited recycling capacity in North America justifies the addition of more capacity within this region rather than elsewhere.While government policies

88、clearly play a role in developing LIB recycling capabilities,other factors(such as the economics of recycling or material requirements for LIB manufacturing)must also play a factor in the construction of LIB recycling facilities.LITHIUM ION BATTERY RECYCLING|17ConclusionIn this white paper,weve been

89、 able to identify several trends in LIB recycling using data from the CAS Content Collection:Consistent with overall observations,publications involving all three methods of LIB recycling increased overall in the last decade and have grown significantly in recent years.China has the highest publicat

90、ion volumes in both journals and patents(roughly 90%of publications).Hydrometallurgy has outgrown pyrometallurgy considerably after 2015,and direct recycling has also seen substantial recent growth.Lithium tends to be the most frequently recovered metal from recycled LIBs while all extracted metals

91、show similar patterns in the recycling methods used.Considerable research effort has been made towards previously lesser-studied LIB components(suggestive of an emerging,more holistic recycling management view)and towards LIB disassembly,which is preferable due to maximizing the amount of recyclable

92、 material.We supplemented our research with an assessment of current and future LIB recycling management globally.In most cases,combinations of hydrometallurgical and pyrometallurgical methods are used to process LIBs.Current LIB recycling capacity is concentrated in East Asia,with China possessing

93、more than half of the worlds current recycling capacity,and Europe possessing most of the remaining capacity.Proposed LIB recycling facilities will increase LIB recycling capacity by approximately 25%,with most of the defined new capacity concentrated in North America.The location of current recycli

94、ng capacity is consistent with the effect of LIB recycling regulations,while the location of future capacity is more consistent with economic motivations.Overall,LIB recycling regulations are increasing;many countries fund research into LIB recycling methods,and a variety of countries have LIB recyc

95、ling laws,with China and the European Union having or enacting comprehensive regulatory frameworks.Coupled with the increasing interest in LIB recycling management as seen in our review,these findings are encouraging for the future of LIB management in a world punctuated by explosively growing numbe

96、rs of LIB applications.LITHIUM-ION BATTERY RECYCLING|19LITHIUM ION BATTERY RECYCLING|19For a detailed review on the developments of lithium ion battery recycling,see our publication in https:/pubs.acs.org/doi/full/10.1021/acsenergylett.1c02602)CAS is a leader in scientific information solutions,part

97、nering with innovators around the world to accelerate scientific breakthroughs.CAS employs over 1,400 experts who curate,connect,and analyze scientific knowledge to reveal unseen connections.For over 100 years,scientists,patent professionals,and business leaders have relied on CAS solutions and expe

98、rtise to provide the hindsight,insight,and foresight they need so they can build upon the learnings of the past to discover a better future.CAS is a division of the American Chemical Society.Connect with us at cas.orgcas.org 2022 American Chemical Society.All rights reserved.CASGENENGWHP100560220120