Batteries from cradle to grave

162 Journal of Chemical Education

_Vol. 87 No. 2 February 2010

_pubs.acs.org/jchemeduc

_r2010 American Chemical Society and Division of Chemical Education, Inc.

10.1021/ed800053u Published on Web 01/12/2010

In the Classroom

Batteries, from Cradle to GraveMichael J. Smith*Departamento de Química, Universidade do Minho, 4710-057 Braga, Portugal*[email protected]

Fiona M. GraySchool of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, Scotland

Employers expect graduates to have an area-specific knowl-edge and to be able to apply instrumental, interpersonal,problem-solving, and systematic skills efficiently. To maximizethe number of students achieving high levels of competence, agreater emphasis should be placed on activities intended todevelop the appropriate skills within the course structure (1).Problem-based learning (PBL) is a widely applied approachintended to encourage students to learn through the structuredexploration of a research problem. Small teams of students aregiven an open-ended assignment that they research in order topresent well-supported, evidence-based solutions or strategies inwritten or oral format. This approach effectively combinesindependent learning with written and oral presentationpractice.

Portable electronic equipment has become an essentialcomponent of our everyday lives, and whether the device inquestion is a remote-controlled toy, a mobile phone, or a laptopcomputer, it relies on batteries as a source of power. In 2008, theEuropean Union introduced new legislation to regulate the useof toxic chemicals in batteries and to outline a program for theobligatory recycling of spent batteries. This legislation is expectedto have a widespread impact on both industry and the consumer,and hence, it is timely to look at key issues such as environmentalconsequences, public awareness and acceptance, current goodpractice, challenges and practicalities, and the consequences oflegislation that are currently being addressed within Europe,North America, and Asia.

We have identified the area of spent-battery recycling as arelevant topic on which to build a PBL activity. Evolving batterydesign and related disposal issues, relevant to the fields ofelectrochemistry, environmental chemistry, materials chemistry,electrical engineering and technology, and waste managementand recycling, are reviewed to provide key entry points and usefulinformation resources for instructors who wish to adopt thisteaching strategy.

Problem-Based Learning

The problem-based learning (PBL) activity based on batteryrecycling was successfully implemented with a class of students inthe third year of chemistry. The students were introduced to thetopic through an oral presentation after completing lecturecourses on environmental chemistry and applied electrochem-istry. The class was divided into three-member groups, andstudents were assigned problems. Some examples of theseproblems are included in the supporting information. A general

perspective of the research, extension, and intended audiencewere defined, together with a schedule for periodic facilitatorcontact for discussion of progress and monitoring of groupactivity. After a period of group activity, the students submittedthe results of their research as a short report with supportingbibliography and also as a poster or oral presentation to an audi-ence of colleagues and instructors during a session at the end ofthe semester. A short text introducing the research assignmentand a typical student handout has been provided in the support-ing information.

Instructor assessment of student learning in this activity waspositive and the overall impression was that students performedat a level significantly above their average course grade. Thisimprovement was attributed to the high level of motivation,underlining the importance of authentic problems for students.Our students showed initiative in fact gathering and in theproposal of new solutions to existing problems and investedsignificant personal effort in self-directed study. The end pro-ducts delivered as reports, posters, and oral presentations made auseful contribution to student skill development, fully vindicat-ing the PBL approach in undergraduate education.

The Chemistry of Batteries

Electrochemical power sources or batteries are devices thatconvert energy stored in chemicals into electrical energy. Strictlyspeaking, a battery is made up of an assembly of two or more cellsconnected in a series or parallel configuration (2-7), but overthe last few decades the terms cell and battery have becomesynonymous. Although credit for the original invention thatdemonstrated the viability of the concept is generally attributedto Alessandro Volta (1800), various, more practical devices weresubsequently developed in a sustained effort to improve theefficiency of energy storage and conversion (7). Since the earlydays of battery science, the development of better portable energysources has been driven by the needs of manufacturers in theelectronics sector.

Batteries can be classified as primary (single use) or second-ary (rechargeable), with further subdivision into household (forconsumer goods such as telephones, flashlights, radios, watches,or computers), industrial (for reserve network power, local back-up, or traction), and SLI (for starting, lighting, ignition invehicles). The principal commercial battery chemistries are listedin Table 1, together with examples of typical applications.Further details of the operational characteristics of these cellsmay be obtained from refs 2-7.

r2010 American Chemical Society and Division of Chemical Education, Inc.



_Journal of Chemical Education 163

In the Classroom

All commercial batteries are made up of two electrodes, theanode and the cathode, and an electrolyte. The efficiency of thebattery chemistry depends on the chemical reactions taking placeat the electrodes and the nature of the electrolyte present. Inaddition to these active components, batteries must also containinactive components that have support functions and ensure celloperation. These inactive components include the casings (oftenmade of steel) and separators, seals, or labels (typically fabricatedfrom polymers, paperboard, or paper). The active componentsthat are currently of greatest environmental concern are thosebased on cadmium, lead, and mercury, and to a lesser degreecopper, nickel, lithium, silver, and zinc (8).

Precise up-to-date estimates of the number of householdbatteries produced are difficult to obtain (9), but approximateannual sales in the United States, Europe, and Japan are about4, 5.5, and 1.9 billion, respectively (6, 10-13). The secondarycell market share is between 10 and 14% of annual sales, andthis is made up of a mixture of nickel-cadmium (NiCd),

nickel-metal hydride (NiMH), and lithium ion (Li ion)batteries.

Batteries and Environmental Issues

Battery components present no threat to human health orto the environment while the battery is in normal use. However,when subjected to careless disposal within the household orworkplace, inevitable damage and degradation of the batteryhousing changes this situation. The environmental impact ofbatteries in landfills (11-14) depends on the battery chemistry,the residual capacity of the battery, the local conditions oftemperature, moisture, and oxygen content, the design andmaintenance of the landfill, and the proximity of surface orgroundwater.

Batteries identified for household use are mainly zinc-carbon, alkaline-manganese, zinc-air, zinc-silver oxide, andlithium types. This group of primary batteries continues to make

Table 1. Chemistry Present in Household, Industrial and SLI Batteries

Principal Components

Designation Anode/Negative Electrolyte Cathode/Positive Typical Applications

PRIMARY Zinc-carbon Zinc sheet NH4Cl or ZnCl2 MnO2, C (mix) Used in a wide range of small portableelectronic devices; low-cost modestdischarge performance; 1.5 V cellpotential

Alkaline-manganese Zinc powder KOH MnO2, C (mix) Improved performance version of the ZnCcell, more energy and power but also moreexpensive; 1.5 V cell potential

Mercury Zinc powder NaOH or KOH HgO, C (mix) Previously used in hearing aids, cameras,and calculators, discontinued because ofHg toxicity; 1.35 V cell potential

Lithium Lithium foil Organic solventand Li salt

MnOp, C (mix) Available in range of systems with variouscathodes with voltages between 1.5 andabout 3.6 V; excellent performance;expensive

Zinc-air Zinc powder KOH Air, C Principal niche market of hearing aids; goodcell performance with nominal 1.4 V, buthigh self-discharge rate

Zinc-silver oxide

Zinc powder KOH Ag2O, C (mix) Typical application in watches or calculators;good discharge performance, butexpensive because of Ag content; nominal1.55 V cell potential

SECONDARY NiCd Cd KOH NiO(OH) Substantial market presence in portabledevices; high cycle life, but suffers frommemory effect; nominal 1.2 V cellpotential; Cd is toxic

NiMH AB5 or AB2Intermetalliccompound

KOH NiO(OH) Substitute for traditional NiCd cell; improvedin both electrochemical and environmentalperformance; nominal 1.2 V cell potential

Lead-acid Pb H2SO4 PbO2 Generally used in SLI applications, tractionbattery, or as a reserve power source; hightoxicity; nominal 2 V; easy to recycle

Lithium ion C, Lix Organic solventand Li salt

Li(1-x)MnOp High performance cell widely used inportable electronic equipment; lowenvironmental impact; nominal 3.6-3.7 Vcell potential

Li-poly or LiPo C, Lix Polymer geland Li salt

Li(1-x)MnOp Proposed as substitute for Li ion, probablycheaper and safer with comparableperformance; nominal 3.7 V





In the Classroom

up themajority of batteries consumed, accounting for about 90%of the portable battery market (6, 11-14). The commercialsuccess of aqueous electrolyte-based batteries (zinc-carbon,alkaline-manganese, zinc-air, and zinc-silver oxide) is dueto low material costs, ease of manufacture, and performancecharacteristics that are suitable for a wide range of electronicdevices with modest energy and power requirements. Althoughthese batteries are based on some of the oldest chemistries, theyhave been subjected to continuous improvement. It is note-worthy that the alkaline-manganese, zinc-air, and zinc-silveroxide miniature batteries (coin or button format) may containsmall quantities of mercury as a corrosion-suppressing additivefor the anode. In Europe, for example, the marketing of buttonbatteries containing more than 2% of mercury by mass and otherbatteries containing more than 0.0005% of mercury hasbeen prohibited since January 2000. In addition, silver oxide,zinc-air, and alkaline button batteries that contain between0.0005% and 2% per cell must also be labeled as not for house-hold waste disposal. The mercury-content restrictions havemotivated structural changes: the introduction of zinc alloypowder anodes, the development of new corrosion suppressors,and modified cathode formulations to maintain prelegislationperformance.

The lithium nonaqueous primary-battery technology hasalso progressed significantly since the early 1970s (15, 16).Although substantial market growth has been observed, the costof lithium-based primary batteries is only justified in specificapplications where high cell performance is essential.

Of all the systems under consideration here, it is thelead-acid battery predominantly used in SLI, traction, andindustrial energy storage that is the most successfully recycled(Figure 1). The greatest contribution to this situation lies infactors such as the inherent value of the scrap metal, the effectivespent-battery collecting procedure, the relatively simple structureof the battery, and the straightforward nature of the lead-smelting process.

The NiCd secondary battery has been commercially avail-able since 1950 and effectively dominated the household sec-ondary-battery market until about 1990. It is still producedin the standard battery packaging (cylindrical, button, and flatprismatic formats) for household use and in industrial, large-scale

batteries that contest the commercial terrain occupied bylead-acid batteries. However, the highly toxic cadmium anode,along with the nickel oxide hydroxide cathode and the concen-trated potassium hydroxide electrolyte, present an environmen-tal dilemma.

In 1990, NiMH cells with their improved electrochemicalperformance became available commercially and also occupied amore favorable environmental position. While the electrolyteand cathode compositions are similar to those of a NiCd cell, ahydrogen storage anode of nickel-cobalt-rare-earth metal alloyreplaced the toxic cadmium electrode.

NiMH technology is generally viewed as being a stopgap, tobe superseded by lithium-based battery technology. There hasbeen significant electrochemical development in this sector; firstwith the launch of the lithium-ion cell and more recently withthe lithium polymer (Li-poly) cell. A move to lithium-basedbatteries (both primary and secondary) represents an advance interms of environmental impact. Although the anodic materialsare nontoxic, lithium-ion cells contain flammable electrolytesand may also contain moderately toxic composite cathodes.Li-poly cells contain similar anode and cathode constituentsbut incorporate a polymeric gel electrolyte. The advantages ofthis new cell format, such as high electrochemical and safetyperformance and a thin-cell profile that allows manufacturers toadapt cells to fit available space in new devices, will lead tosignificant growth of this battery in the market and will requirealterations in disposal strategies.

Legislation

Although there are differences in the way countries ap-proach health and environmental issues, the content of theregulations applied to industry is similar. In Europe (17-19),Asia (19, 20), and North America (21-25), the first stages ofregulation involved limitation of dangerous substance content inhousehold batteries. Subsequent legislation regulated the collec-tion and disposal or recycling of industrial and householdbatteries. Representation of the battery manufacturing industryfrom the outset has permitted consensual positions to be estab-lished and resulted in the associations of manufacturers andimporters (26-32) that assume responsibility for coordination

Figure 1. Recycling procedure of lead-acid batteries. (UPS is uninterruptible power supply.)





In the Classroom

of battery elimination or recycling. Despite legislation to regulatedisposal and recycling, poor public knowledge of the legislation,lack of enforcement, and insufficient budget allocation toregulation (33, 34) have been the major contributors to ineffec-tive application of these new laws.

The Disposal Option

Many batteries still end up in landfills or are incineratedbecause of inefficient national collection and recycling schemes.This is undesirable because of the risk of hazardous chemicalscontributing to leachate from landfill (a 25 g NiCd phonebattery can contaminate 750,000 L of groundwater to themaximum acceptable concentration limit) or to emissions fromincineration plants. For incineration, the quantities of hazardousemissions depend on furnace temperature, the volatility of thebattery elements, and the efficiency of local treatments applied tothe furnace emissions. Some heavy elements may be concentratedin the furnace slag and require specific and expensive secondarytreatment.

Where disposal is the only end-of-life option, it is possible totreat heavy metals by stabilization and inertization to avoidleaching. These processes reduce the toxicity by making insolubleor immobilizing the hazardous waste and involve chemicalreactions between constituents in the waste or with species in asolid matrix added to the residue. Inertization is generallyconsidered to be financially nonviable. It requires a batterycollection scheme, and unlike recycling, the inertized materialshave no residual commercial value.

Battery Collection and Sorting Strategies

Although certain segments of the battery market benefitfrom specific collection routines (for example the lead-acidbatteries or large capacity installations of industrial batteries), themost challenging market segment is that of household batteries.These batteries are widely dispersed, use a broad variety ofchemistries, and represent a large portion of the overall cellmarket. Efficient collection of household batteries depends onlegislation and the willingness of the population to recycle spentcells. Recent studies (32) confirm that high recycling rates,measured as a percentage of the mass of recycled batteries to

the mass of batteries sold for any given financial year, can beachieved. In Belgium (27), for example, the collection rate perperson is the highest in the world. To achieve this, it wasnecessary to invest in an intense and continuous public-aware-ness campaign to inform the population about national laws, tomotivate participation in collection programs, and to changebattery disposal habits. The Belgian program involves schools,public and private services, civic associations, point-of-sale out-lets (supermarkets, jewelers, photographic shops, pharmacies, toystores), and municipal ecoyards.

Most collection programs are intended for all types ofhousehold batteries, with sorting taking place at the recyclinginstallation. As most recycling treatments are sensitive to battery-type purity, the sorting is a critical phase in the process. Varioustypes of automatic sorting equipment have been developed basedon magnetic, photographic, UV label detection, and X-rayfingerprinting. Improvements in sorting rates over the last 10years mean that identification and selection can now be achievedat rates of up to 24 batteries per second with a recognitionefficiency of about 99%. This phase of battery treatment nolonger represents the limiting step of the recycling process.

Recycling Procedures for Batteries

The diversity of battery chemistries has led to a correspond-ingly wide range of recycling treatments. Regardless of thetreatment method undertaken, the preliminary processing stageinvolves removal of labels, opening of cell casings, and destroyingseals and separators by procedures based on mechanical cutting,chopping, or pounding, vacuum milling, cryogrinding, or pyro-lysis (Figure 2). The secondary stages of recycling are broadlyclassified as hydrometallurgic or pyrometallurgic.

Hydrometallurgic techniques applied to the cell fragmentsinclude acid, alkaline, or solvent extraction. These proceduresyield metal solutions that are subsequently subjected to precipi-tation, selective reactions, electrolysis, or electrodialysis to isolatethe purified materials.

Pyrometallurgic procedures, using high temperatures toseparate metals, may be subdivided by the final destiny of therecycled material. One subdivision relates to treatments thatultimately incorporate the processed battery material as a

Figure 2. General recycling procedure for all types of batteries.





In the Classroom

component in steel production; the other subdivision involvesspecific processes designed to yield purified elements for reentryinto a variety of industrial feedstocks. While the nickel, chro-mium, and manganese residues from recycled batteries areacceptable components in steel production, the quantities ofcadmium, copper, and zinc must be carefully monitored to avoiddeterioration of the steel's properties. At the extremely highfurnace temperatures used in steel production, any residual zincand cadmium (and mercury, should it be present) will evaporate,oxidize, and be emitted from fume stacks as flyash loaded withhazardous dust. Although useful, this strategy for battery wastetreatment carries certain limitations. Various companies specia-lize in the production of purified zinc, cadmium, lead, mercury,and nickel using batteries as feedstock. These pure elements aresupplied to other metallurgic companies as raw material, and theslag or bottom-ash containing unwanted residues is separated foruse in road or building foundations.

Procedures for recycling lithium battery feedstocks, alsorepresented in Figure 2, have been developed by various compa-nies. In the Toxco (hydrometallurgic) treatment (35), lithium isrecovered as the metal or lithium hydroxide. Initial processing ofbattery feedstock involves cryogrinding and reacting with waterto produce hydrogen, which can be burnt off above the reactionliquid. In pyrometallurgic procedures, component recovery islimited to cobalt and steel-making residues. Other treatments(not shown) involve a combined pyro-hydrometallurgical pro-cess where punctured cells are subjected to incineration andcobalt is subsequently recovered from metallic waste through theapplication of standard hydrometallurgical procedures. Withalternative, less vigorous, purely hydrometallurgical procedures(36), electrolyte and electrode material may also be recoveredfrom the disassembled cells. This latter option is more attractive,and even with fluctuations in the market value of recycledmaterials, the fundamental profitability of the process is sup-ported by the sale of products rather than from charges levied onbattery end-users.

Future of Battery Technology and Recycling

Information provided by manufacturers and recyclingagencies confirms that treatment of battery residues has arrivedat a critical moment when old responsibilities are being addressedwith new strategies. More than ever before, the current consumergeneration is being made aware of its duty to adopt a socially andscientifically correct response to preserve the quality of ourenvironment.

An ever-increasing number of equipment manufacturers areusing high-performance lithium-based secondary cells in theirproducts. Such cells are increasingly of the Li-poly class and posean interesting conundrum.With foil-bag containers substitutingthe traditional steel casing, they have minimal recyclable contentand combine competitive electrochemical performance withnegligible environmental impact. Future versions of Li-polysecondary cells may represent a truly ecological choice of a powersource in which the toxic chemical content is so low that they cansafely be disposed of as municipal solid waste.

Significant advances are also being made in fuel-cell tech-nology with several companies involved in the design andmanufacture of high-performance fuel cells adapted to theportable electronics, back-up energy, and traction markets(37-41). These hydrogen or methanol-fuelled cells draw their

chemical energy from a quick-fill reservoir outside the cell (orstack) structure. As the source of chemical energy is not part ofthe cell, the task of recycling these units is greatly simplified. Theuse of precious-metal catalysts in the composite electrode com-ponent of these cells also provides a strong economic motivationfor end-of-life collection and recycling treatment. Even beforethe routines for end-of-life processing of current primary andsecondary cells have become well established and before wide-spread collection strategies have been implemented at a locallevel, there are clear indications that a new fuel cell-based powersource is gaining commercial viability and that the portableelectronics industry is prepared to welcome this innovation.

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In the Classroom

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Supporting Information Available

Examples of student research problems; text introducing theresearch assignment and a typical student handout. This material isavailable via the Internet at http://pubs.acs.org.

Batteries from cradle to grave

Education

class of students

battery recycling

environmental chemistry

research problem

small teams of students

materials chemistry

grayschool of chemistry

year of chemistry