Batteries from cradle to grave

In the Classroom

Batteries, from Cradle to Grave
Michael J. Smith*
Departamento de Química, Universidade do Minho, 4710-057 Braga, Portugal
*mjsmith@quimica.uminho.pt

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

Employers expect graduates to have an area-specific knowl- perspective of the research, extension, and intended audience
edge and to be able to apply instrumental, interpersonal, were defined, together with a schedule for periodic facilitator
problem-solving, and systematic skills efficiently. To maximize contact for discussion of progress and monitoring of group
the number of students achieving high levels of competence, a activity. After a period of group activity, the students submitted
greater emphasis should be placed on activities intended to the results of their research as a short report with supporting
develop the appropriate skills within the course structure (1). bibliography and also as a poster or oral presentation to an audi-
Problem-based learning (PBL) is a widely applied approach ence of colleagues and instructors during a session at the end of
intended to encourage students to learn through the structured the semester. A short text introducing the research assignment
exploration of a research problem. Small teams of students are and a typical student handout has been provided in the support-
given an open-ended assignment that they research in order to ing information.
present well-supported, evidence-based solutions or strategies in Instructor assessment of student learning in this activity was
written or oral format. This approach effectively combines positive and the overall impression was that students performed
independent learning with written and oral presentation at a level significantly above their average course grade. This
practice. improvement was attributed to the high level of motivation,
Portable electronic equipment has become an essential underlining the importance of authentic problems for students.
component of our everyday lives, and whether the device in Our students showed initiative in fact gathering and in the
question is a remote-controlled toy, a mobile phone, or a laptop proposal of new solutions to existing problems and invested
computer, it relies on batteries as a source of power. In 2008, the significant personal effort in self-directed study. The end pro-
European Union introduced new legislation to regulate the use ducts delivered as reports, posters, and oral presentations made a
of toxic chemicals in batteries and to outline a program for the useful contribution to student skill development, fully vindicat-
obligatory recycling of spent batteries. This legislation is expected ing the PBL approach in undergraduate education.
to have a widespread impact on both industry and the consumer,
and hence, it is timely to look at key issues such as environmental The Chemistry of Batteries
consequences, public awareness and acceptance, current good
practice, challenges and practicalities, and the consequences of Electrochemical power sources or batteries are devices that
legislation that are currently being addressed within Europe, convert energy stored in chemicals into electrical energy. Strictly
North America, and Asia. speaking, a battery is made up of an assembly of two or more cells
We have identified the area of spent-battery recycling as a connected in a series or parallel configuration (2-7), but over
relevant topic on which to build a PBL activity. Evolving battery the last few decades the terms cell and battery have become
design and related disposal issues, relevant to the fields of synonymous. Although credit for the original invention that
electrochemistry, environmental chemistry, materials chemistry, demonstrated the viability of the concept is generally attributed
electrical engineering and technology, and waste management to Alessandro Volta (1800), various, more practical devices were
and recycling, are reviewed to provide key entry points and useful subsequently developed in a sustained effort to improve the
information resources for instructors who wish to adopt this efficiency of energy storage and conversion (7). Since the early
teaching strategy. days of battery science, the development of better portable energy
sources has been driven by the needs of manufacturers in the
Problem-Based Learning electronics sector.
Batteries can be classified as primary (single use) or second-
The problem-based learning (PBL) activity based on battery ary (rechargeable), with further subdivision into household (for
recycling was successfully implemented with a class of students in consumer goods such as telephones, flashlights, radios, watches,
the third year of chemistry. The students were introduced to the or computers), industrial (for reserve network power, local back-
topic through an oral presentation after completing lecture up, or traction), and SLI (for starting, lighting, ignition in
courses on environmental chemistry and applied electrochem- vehicles). The principal commercial battery chemistries are listed
istry. The class was divided into three-member groups, and in Table 1, together with examples of typical applications.
students were assigned problems. Some examples of these Further details of the operational characteristics of these cells
problems are included in the supporting information. A general may be obtained from refs 2-7.

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162 Journal of Chemical Education Vol. 87 No. 2 February 2010 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.
10.1021/ed800053u Published on Web 01/12/2010

In the Classroom

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 portable
electronic devices; low-cost modest
discharge performance; 1.5 V cell
potential
Alkaline-manganese Zinc powder KOH MnO2, C (mix) Improved performance version of the ZnC
cell, more energy and power but also more
expensive; 1.5 V cell potential
Mercury Zinc powder NaOH or KOH HgO, C (mix) Previously used in hearing aids, cameras,
and calculators, discontinued because of
Hg toxicity; 1.35 V cell potential
Lithium Lithium foil Organic solvent MnOp, C (mix) Available in range of systems with various
and Li salt cathodes with voltages between 1.5 and
about 3.6 V; excellent performance;
expensive
Zinc-air Zinc powder KOH Air, C Principal niche market of hearing aids; good
cell performance with nominal 1.4 V, but
high self-discharge rate
Zinc- Zinc powder KOH Ag2O, C (mix) Typical application in watches or calculators;
silver oxide good discharge performance, but
expensive because of Ag content; nominal
1.55 V cell potential
SECONDARY NiCd Cd KOH NiO(OH) Substantial market presence in portable
devices; high cycle life, but suffers from
memory effect; nominal 1.2 V cell
potential; Cd is toxic
NiMH AB5 or AB2 KOH NiO(OH) Substitute for traditional NiCd cell; improved
Intermetallic in both electrochemical and environmental
compound performance; nominal 1.2 V cell potential
Lead-acid Pb H2SO4 PbO2 Generally used in SLI applications, traction
battery, or as a reserve power source; high
toxicity; nominal 2 V; easy to recycle
Lithium ion C, Lix Organic solvent Li(1-x)MnOp High performance cell widely used in
and Li salt portable electronic equipment; low
environmental impact; nominal 3.6-3.7 V
cell potential
Li-poly or LiPo C, Lix Polymer gel Li(1-x)MnOp Proposed as substitute for Li ion, probably
and Li salt cheaper and safer with comparable
performance; nominal 3.7 V

All commercial batteries are made up of two electrodes, the nickel-metal hydride (NiMH), and lithium ion (Li ion)
anode and the cathode, and an electrolyte. The efficiency of the batteries.
battery chemistry depends on the chemical reactions taking place
at the electrodes and the nature of the electrolyte present. In Batteries and Environmental Issues
addition to these active components, batteries must also contain
inactive components that have support functions and ensure cell Battery components present no threat to human health or
operation. These inactive components include the casings (often to the environment while the battery is in normal use. However,
made of steel) and separators, seals, or labels (typically fabricated when subjected to careless disposal within the household or
from polymers, paperboard, or paper). The active components workplace, inevitable damage and degradation of the battery
that are currently of greatest environmental concern are those housing changes this situation. The environmental impact of
based on cadmium, lead, and mercury, and to a lesser degree batteries in landfills (11-14) depends on the battery chemistry,
copper, nickel, lithium, silver, and zinc (8). the residual capacity of the battery, the local conditions of
Precise up-to-date estimates of the number of household temperature, moisture, and oxygen content, the design and
batteries produced are difficult to obtain (9), but approximate maintenance of the landfill, and the proximity of surface or
annual sales in the United States, Europe, and Japan are about groundwater.
4, 5.5, and 1.9 billion, respectively (6, 10-13). The secondary Batteries identified for household use are mainly zinc-
cell market share is between 10 and 14% of annual sales, and carbon, alkaline-manganese, zinc-air, zinc-silver oxide, and
this is made up of a mixture of nickel-cadmium (NiCd), lithium types. This group of primary batteries continues to make

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r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 2 February 2010 Journal of Chemical Education 163

In the Classroom

up the majority of batteries consumed, accounting for about 90% batteries that contest the commercial terrain occupied by
of the portable battery market (6, 11-14). The commercial lead-acid batteries. However, the highly toxic cadmium anode,
success of aqueous electrolyte-based batteries (zinc-carbon, along with the nickel oxide hydroxide cathode and the concen-
alkaline-manganese, zinc-air, and zinc-silver oxide) is due trated potassium hydroxide electrolyte, present an environmen-
to low material costs, ease of manufacture, and performance tal dilemma.
characteristics that are suitable for a wide range of electronic In 1990, NiMH cells with their improved electrochemical
devices with modest energy and power requirements. Although performance became available commercially and also occupied a
these batteries are based on some of the oldest chemistries, they more favorable environmental position. While the electrolyte
have been subjected to continuous improvement. It is note- and cathode compositions are similar to those of a NiCd cell, a
worthy that the alkaline-manganese, zinc-air, and zinc-silver hydrogen storage anode of nickel-cobalt-rare-earth metal alloy
oxide miniature batteries (coin or button format) may contain replaced the toxic cadmium electrode.
small quantities of mercury as a corrosion-suppressing additive NiMH technology is generally viewed as being a stopgap, to
for the anode. In Europe, for example, the marketing of button be superseded by lithium-based battery technology. There has
batteries containing more than 2% of mercury by mass and other been significant electrochemical development in this sector; first
batteries containing more than 0.0005% of mercury has with the launch of the lithium-ion cell and more recently with
been prohibited since January 2000. In addition, silver oxide, the lithium polymer (Li-poly) cell. A move to lithium-based
zinc-air, and alkaline button batteries that contain between batteries (both primary and secondary) represents an advance in
0.0005% and 2% per cell must also be labeled as not for house- terms of environmental impact. Although the anodic materials
hold waste disposal. The mercury-content restrictions have are nontoxic, lithium-ion cells contain flammable electrolytes
motivated structural changes: the introduction of zinc alloy and may also contain moderately toxic composite cathodes.
powder anodes, the development of new corrosion suppressors, Li-poly cells contain similar anode and cathode constituents
and modified cathode formulations to maintain prelegislation but incorporate a polymeric gel electrolyte. The advantages of
performance. this new cell format, such as high electrochemical and safety
The lithium nonaqueous primary-battery technology has performance and a thin-cell profile that allows manufacturers to
also progressed significantly since the early 1970s (15, 16). adapt cells to fit available space in new devices, will lead to
Although substantial market growth has been observed, the cost significant growth of this battery in the market and will require
of lithium-based primary batteries is only justified in specific alterations in disposal strategies.
applications where high cell performance is essential.
Of all the systems under consideration here, it is the Legislation
lead-acid battery predominantly used in SLI, traction, and
industrial energy storage that is the most successfully recycled Although there are differences in the way countries ap-
(Figure 1). The greatest contribution to this situation lies in proach health and environmental issues, the content of the
factors such as the inherent value of the scrap metal, the effective regulations applied to industry is similar. In Europe (17-19),
spent-battery collecting procedure, the relatively simple structure Asia (19, 20), and North America (21-25), the first stages of
of the battery, and the straightforward nature of the lead- regulation involved limitation of dangerous substance content in
smelting process. household batteries. Subsequent legislation regulated the collec-
The NiCd secondary battery has been commercially avail- tion and disposal or recycling of industrial and household
able since 1950 and effectively dominated the household sec- batteries. Representation of the battery manufacturing industry
ondary-battery market until about 1990. It is still produced from the outset has permitted consensual positions to be estab-
in the standard battery packaging (cylindrical, button, and flat lished and resulted in the associations of manufacturers and
prismatic formats) for household use and in industrial, large-scale importers (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 regulate the mass of batteries sold for any given financial year, can be
disposal and recycling, poor public knowledge of the legislation, achieved. In Belgium (27), for example, the collection rate per
lack of enforcement, and insufficient budget allocation to person is the highest in the world. To achieve this, it was
regulation (33, 34) have been the major contributors to ineffec- necessary to invest in an intense and continuous public-aware-
tive application of these new laws. ness campaign to inform the population about national laws, to
motivate participation in collection programs, and to change
The Disposal Option battery disposal habits. The Belgian program involves schools,
public and private services, civic associations, point-of-sale out-
Many batteries still end up in landfills or are incinerated lets (supermarkets, jewelers, photographic shops, pharmacies, toy
because of inefficient national collection and recycling schemes. stores), and municipal ecoyards.
This is undesirable because of the risk of hazardous chemicals Most collection programs are intended for all types of
contributing to leachate from landfill (a 25 g NiCd phone household batteries, with sorting taking place at the recycling
battery can contaminate 750,000 L of groundwater to the installation. As most recycling treatments are sensitive to battery-
maximum acceptable concentration limit) or to emissions from type purity, the sorting is a critical phase in the process. Various
incineration plants. For incineration, the quantities of hazardous types of automatic sorting equipment have been developed based
emissions depend on furnace temperature, the volatility of the on magnetic, photographic, UV label detection, and X-ray
battery elements, and the efficiency of local treatments applied to fingerprinting. Improvements in sorting rates over the last 10
the furnace emissions. Some heavy elements may be concentrated years mean that identification and selection can now be achieved
in the furnace slag and require specific and expensive secondary at rates of up to 24 batteries per second with a recognition
treatment. efficiency of about 99%. This phase of battery treatment no
Where disposal is the only end-of-life option, it is possible to longer represents the limiting step of the recycling process.
treat heavy metals by stabilization and inertization to avoid
leaching. These processes reduce the toxicity by making insoluble
or immobilizing the hazardous waste and involve chemical Recycling Procedures for Batteries
reactions between constituents in the waste or with species in a The diversity of battery chemistries has led to a correspond-
solid matrix added to the residue. Inertization is generally ingly wide range of recycling treatments. Regardless of the
considered to be financially nonviable. It requires a battery treatment method undertaken, the preliminary processing stage
collection scheme, and unlike recycling, the inertized materials involves removal of labels, opening of cell casings, and destroying
have no residual commercial value. seals and separators by procedures based on mechanical cutting,
Battery Collection and Sorting Strategies chopping, or pounding, vacuum milling, cryogrinding, or pyro-
lysis (Figure 2). The secondary stages of recycling are broadly
Although certain segments of the battery market benefit classified as hydrometallurgic or pyrometallurgic.
from specific collection routines (for example the lead-acid Hydrometallurgic techniques applied to the cell fragments
batteries or large capacity installations of industrial batteries), the include acid, alkaline, or solvent extraction. These procedures
most challenging market segment is that of household batteries. yield metal solutions that are subsequently subjected to precipi-
These batteries are widely dispersed, use a broad variety of tation, selective reactions, electrolysis, or electrodialysis to isolate
chemistries, and represent a large portion of the overall cell the purified materials.
market. Efficient collection of household batteries depends on Pyrometallurgic procedures, using high temperatures to
legislation and the willingness of the population to recycle spent separate metals, may be subdivided by the final destiny of the
cells. Recent studies (32) confirm that high recycling rates, recycled material. One subdivision relates to treatments that
measured as a percentage of the mass of recycled batteries to ultimately incorporate the processed battery material as a

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

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In the Classroom

component in steel production; the other subdivision involves chemical energy from a quick-fill reservoir outside the cell (or
specific processes designed to yield purified elements for reentry stack) structure. As the source of chemical energy is not part of
into a variety of industrial feedstocks. While the nickel, chro- the cell, the task of recycling these units is greatly simplified. The
mium, and manganese residues from recycled batteries are use of precious-metal catalysts in the composite electrode com-
acceptable components in steel production, the quantities of ponent of these cells also provides a strong economic motivation
cadmium, copper, and zinc must be carefully monitored to avoid for end-of-life collection and recycling treatment. Even before
deterioration of the steel's properties. At the extremely high the routines for end-of-life processing of current primary and
furnace temperatures used in steel production, any residual zinc secondary cells have become well established and before wide-
and cadmium (and mercury, should it be present) will evaporate, spread collection strategies have been implemented at a local
oxidize, and be emitted from fume stacks as flyash loaded with level, there are clear indications that a new fuel cell-based power
hazardous dust. Although useful, this strategy for battery waste source is gaining commercial viability and that the portable
treatment carries certain limitations. Various companies specia- electronics industry is prepared to welcome this innovation.
lize in the production of purified zinc, cadmium, lead, mercury,
and nickel using batteries as feedstock. These pure elements are
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In the Classroom

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Batteries from cradle to grave

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