How to Recycle Batteries
Articla from http://batteryuniversity.com
Lead acid led to the success of early recycling and today more than
97 percent of these batteries are recycled in the USA. The automotive industry
should be given credit for having organized recycling early on. The
recycling process is simple and 70 percent of the battery’s weight is reusable
lead. As a result, over 50 percent of the lead supply comes from recycled
batteries. Other battery types are not being returned as readily as lead
acid, and several organizations are working on programs to make collection of
spent batteries more convenient. Only 20 to 40 percent of cellular phone and
consumer batteries are currently recycled.
The main objective for recycling batteries is to prevent hazardous
materials from entering landfills. Lead acid and nickel-cadmium batteries are
of special concern, and although Li-ion is less harmful, the aim is to include
all batteries in the recycling programs. Do not store old lead acid
batteries in households where children play. Simply touching the lead poles can
be harmful.
Even though they are environmentally unfriendly, lead acid
batteries continue to hold a strong market niche. Wheeled mobility and UPS systems
could not run as economically if it were not for this reliable battery. NiCd
also continues to hold a critical position among rechargeable batteries. Large
flooded NiCds start the Auxiliary Power Unit (APU) of commercial airplanes and
power sightseeing boats in rivers of larger cities, pollution-free.
Toxic batteries will continue to be with us for a while longer
because we have no practical alternatives. There is nothing wrong in using
these batteries as long as we properly dispose of them. Europe banned NiCds in
consumer products because there is a suitable replacement, the NiMH battery.
Controlling the disposal of NiCds from consumer products is difficult because
many users do not know that the retiring equipment includes this battery. The
long-term environmental damage if the world’s NiCds were improperly disposed of
could be devastating.
Let’s look at what happens when NiCds are carelessly disposed of in
landfills. The metallic cylinder of the cell eventually begins to corrode and
the cadmium gradually dissolves, seeping into the water supply. Once such
contamination begins, the authorities have few options to stop the carnage. Our
oceans already show traces of cadmium (along with aspirin, penicillin and
antidepressants) but scientists are not certain of its origin. Regulatory
discipline will lead to a cleaner environment for the next generations.
Nickel-metal-hydride batteries contain nickel and electrolyte,
which are considered semi-toxic. If no disposal service is available in an
area, individual NiMH batteries can be discarded with other household waste.
When accumulating 10 or more batteries, the user should consider disposing of
the packs in a secure waste landfill. The better alternative is bringing the
spent batteries to a neighborhood drop-off bin for recycling.
Primary lithium batteries contain metallic lithium that reacts
violently when in contact with moisture and the batteries must be disposed of
appropriately. If thrown in the landfill in a charged state, heavy equipment
operating on top could crush the cases and the exposed lithium would cause a
fire. Landfill fires are difficult to extinguish and can burn for years
underground. Before recycling, apply a full discharge to consume the lithium
content. Non-rechargeable lithium batteries are used in military combat, as
well as watches, hearing aids and memory backup. Li-ion for cell phones and
laptops do not contain metallic lithium.
In North America,Toxco and Rechargeable Battery Recycling
Corporation (RBRC) collect spent batteries and recycle them. While Toxco has
its own recycling facilities, RBRC is in charge of collecting batteries and
sending them to recycling organizations. Toxco in Trail, British Columbia,
claims to be the only company in the world that recycles large lithium batteries.
They receive spent batteries from oil drilling in Nigeria, Indonesia and other
places. Toxco also recycles retired lithium batteries from the Minuteman
missile silos and tons of Li-ion from the war in Iraq. Other divisions at Toxco
recycle nickel-cadmium, nickel-metal-hydride, lead, mercury, alkaline and more.
Europe and Asia are also active in recycling spent batteries. Among
other recycling companies, Sony and Sumitomo Metal in Japan and Unicore in
Belgium have developed technology to retrieve cobalt and other precious metals
from spent lithium ion batteries. The raw material lithium can also be
retrieved and re-used repeatedly.
Recycling Process
Recycling begins by sorting the batteries into chemistries.
Collection centers place lead acid, nickel-cadmium, nickel-metal-hydride and
lithium‑ion into designated drums, sacks or boxes. Battery recyclers claim that
if a steady stream of batteries, sorted by chemistry, were available at no
charge, recycling would be profitable.
The recycling process generally begins by removing the combustible
material, such as plastics and insulation, with a gas-fired thermal oxidizer. The
plant’s scrubber eliminates the polluting particles created by a burning
process before releasing them into the atmosphere. This leaves the clean and
naked cells with their valuable metal content. The cells are then chopped into
small pieces and heated until the metal liquefies. Non-metallic substances are
burned off; leaving a black slag on top that a slag arm removes. The alloys
settle according to weight and are skimmed off like cream from raw milk while
in liquid form.
Cadmium is relatively light and vaporizes at high temperatures. In
a process that appears like a pan of water boiling over, a fan blows the
cadmium vapor into a large tube cooled with water mist, and the vapors condense
to produce cadmium that is 99.95 percent pure.
Some recyclers do not separate the metals on site but pour the
liquid metals directly into what the industry refers to as “pigs” (65 pounds,
24kg) or “hogs” (2,000 pounds, 746kg). Other battery recyclers use the 7-pound
nuggets (3.17kg). The pigs, hogs and nuggets are then shipped to metal recovery
plants where they are used to produce nickel, chromium and iron for stainless
steel and other high-end products.
Toxco uses liquid nitrogen to freeze lithium-based batteries before
shredding, crushing and removal of the lithium, as well as other battery
components. The lithium is dissolved in a solution to make the metal
non-reactive and is sold for producing lubricating greases. Similarly, the
cobalt is separated, collected and sold.
Battery recycling is energy-intensive, and it takes 6 to 10 times
more energy to reclaim metals from recycled batteries as it does to produce the
materials through other means, including mining. Let’s explore who pays for the
recycling of batteries.
Each country imposes their own rules and fees to make recycling
feasible. In North America, some recycling plants invoice on weight, and the
rates vary according to chemistry. Nickel-metal-hydride yields the best return,
as recycling produces enough nickel to pay for the process. The highest
recycling fees apply to nickel-cadmium and lithium‑ion, because the demand for
cadmium is low and lithium‑ion contains little in retrievable metal.
Rather than calculate the cost according to battery chemistry, some
countries deal in tonnage. The flat cost to recycle a ton of batteries is
$1,000 to $2,000, and Europe hopes to achieve a cost per ton of $300. Ideally,
this would include transportation, but moving and handling the goods is
expected to double the overall cost. To simplify transportation, Europe is
setting up several smaller processing plants in strategic geographic locations.
Manufacturers, agencies and governments still must provide
subsidies to support the battery recycling programs. This is underwritten by a
tax added to each manufactured cell. RBRC receives funding from such a program.
Battery Recycling as a Business
Lithium-ion batteries are expensive to manufacture and this is
mainly due to the high raw material cost and complex preparation processes. The
most costly metal of most Li-ion is cobalt, a hard lustrous gray
material that’s also used to manufacture magnets and high-strength alloys.
The first commercial Li-ion battery of the early 1990s was lithium
iron cobalt. The high specific energy made this battery popular for
mobile phones, laptops and digital cameras. Other lithium-ion systems soon
emerged, in part to substitute cobalt with the lower-cost manganese and nickel,
as well as to gain better load capability, improve safety and prolong service
life. Then came lithium iron phosphate, a lithium-based battery that
uses no cobalt. This system delivers excellent load capability and offers high
stability, but comes at the cost of lower specific energy. See Types of Lithium-ion Batteries. Table 1 lists the
material value per ton of lithium-ion batteries. The table also includes lead
acid, the easiest and most profitable battery to recycle.
Battery Chemistry
|
Metal value (per ton)
|
Table 1: Metal value
per
ton of battery
Lead acid remains the
most suitable battery to recycle; 70% of its weight contains reusable lead.
|
Lithium cobalt oxide
|
$25,000
|
|
Lithium iron phosphate
|
$400
|
|
Lead acid
|
$1,500
|
Knowing that billions of Li-ion batteries are discarded every year,
and given the high cost of cobalt, one wonders why so few companies recycle
these batteries. The reason becomes clear when examining the complexity and low
yield. The retrieved raw material barely pays for labor, which includes
collection, transport, sorting into batteries chemistries, shredding,
separation of metallic and non-metallic materials, neutralizing hazardous
substances, smelting, and purifying the recovered metals. See How to Recycle Batteries.
Consumers return 20–40 percent of spent household batteries for
recycling. Many are faded laptop batteries, their life if known to be short,
but one of the highest numbers comes from mobile phones. Since the battery is
the only replaceable part of most mobile phones, service providers replace them
as a way to solve an apparent phone problem. Most times, the fault lies
elsewhere and examining the returned batteries reveal that 90 percent of these
returned packs are good or can be restored with a simple service.
Ingenious entrepreneurs have discovered a business opportunity to
test and recirculate batteries that have been collected in overflowing boxes
under the counters of mobile phone stores. Battery service centers have sprung
up in the USA, UK and Israel. They purchase surplus batteries by the ton and
check them with Cadex battery analyzers. This is made possible with QuickSort™,
a technology that assesses the battery state-of-health in 30 seconds. Read more
about Testing Lithium-based Batteries.
Some service centers handle as many as 400,000 batteries per month.
Customers receiving restored B-Class batteries offer the same performance as
new packs with no increased returns. Figure 2 shows a box of unwanted mobile
phone batteries for testing and recirculation. Restoring discarded batteries
offers a profitable and clean alternative to recycling.
|
Figure 2: Discarded
mobile phone
batteries for service and redistribution
90% of warranty returns
can be serviced. Modern battery rapid-test technologies
make rapid sorting possible.
Courtesy of Cadex
|
Larger batteries can also be tested and reused. Several companies,
including ABB, are studying the redeployment of reclaimed batteries from
electric vehicles. EV batteries have a longer life than packs used in mobile
phones and laptops. EV manufacturers estimate up to 70 percent remaining
capacity after 10 years of service when the car may be worn out. This presents
sufficient reserve performance for less demanding application such as
residential and commercial energy storage systems. An effective rapid-test
method to check these larger batteries does not yet exist and would help the
business case.
Lead acid are the most widely recycled batteries and the automotive
industry receives credit for making this possible early on. Recycling programs
are believed to have started soon after Cadillac introduced the cranking motor
in 1912. The process is simple and up to 70 percent of the battery’s weight
yields reusable lead. In the USA, recycled batteries provide over 50 percent of
the lead supply, and leading lead-acid battery manufacturers, including Johnson
Controls and Exide Technologies, run profitable recycling operations. There are
over 100 million e-bikes on Chinese roads and the mostly lead acid batteries
are responsible for 20 percent of China’s 3.7 tons of lead refining.
Recycling can be dirty and the EPA (Environmental Protection
Agency) has imposed strict guidelines to recycle lead acid batteries. The
plants must be sealed and the smokestacks fitted with scrubbers. To check for
possible lead escape, the perimeters must be surrounded by lead-monitoring
devices.
However, people find loopholes. Lead is gold and many batteries end
up in Mexico and other developing countries with lax regulations. This puts
workers and residents at risk of lead poisoning. Lead can enter the body by
inhaling lead dust or ingestion by touching the mouth with lead-contaminated
hands. Children are most vulnerable; excessive lead can affect growth, cause
brain damage, harm kidneys, impair hearing and induce behavioral problems. Read
more about Health Concerns with Batteries.
Nickel-based batteries can also be recycled and the retrieved
materials are iron and nickel, materials used in stainless steel production. Nickel-metal-hydride
(NiMH) yields the highest return in nickel and with enough supply, the
recycling process is said to make money. The lower demand for cadmium has a
reduced profitability for NiCd batteries. Furthermore the difficulty to
retrieve precious metals from Li-ion makes this battery less attractive and a
financial breakeven may not be possible. Although alkaline and carbon zinc
amount to over 90 percent of batteries consumed in the United States, the
precious metals content is low, so is the toxicity. Nevertheless, organizations
are seeking ways to recycle them also. Table 3 lists the typical metals content
of commonly recycles batteries.
|
Fe
Iron |
Mn Manganese
|
Ni
Nickel |
Zn
Zinc |
Li
Lithium |
Cd
Cadmium |
Co
Cobalt |
Al
Aluminum |
Pb
Lead |
Lead acid
|
|
|
|
|
|
|
|
|
65
|
NiCd
|
35
|
|
22
|
|
|
15
|
|
|
|
NiMH
|
20
|
1
|
35
|
1
|
|
|
4
|
|
|
Li-ion
|
22
|
|
|
|
3
|
|
18
|
5
|
|
Alkaline
|
24
|
22
|
|
15
|
|
|
|
|
|
Table 3: Metals in commonly recycled batteries as a percentage of
the overall content. The metal content may vary according to battery type.
Battery recycling is energy-intensive and it takes 6–10 times more
energy to reclaim metals from recycled batteries than through other sources,
including mining. Efficient logistics to get the batteries is important, and
recyclers claim that the business could be profitable if a steady stream of
batteries, sorted by chemistry, were available at no charge. See also How to Recycle Batteries.
Recycling Lithium
Some lobby groups warn about an imminent lithium shortage; they
compare lithium to fossil oil as the future commodity of high demand. The need
for Li-ion batteries is indeed increasing, and finding sufficient lithium as a
raw material could be a challenge for the mining industry. A compact EV battery
(Nissan Leaf) uses about 4kg (9lb) of lithium. If every man, woman and teenager
were to drive an electric car, a lithium shortage could indeed develop.
Lithium is named after the Greek word “lithos” meaning “stone.”
About 70 percent of the world’s supply comes from brine (salt lakes); the
remainder is derived from hard rock. Scientists are developing technology to
draw lithium from seawater. China is the largest consumer of lithium; they
believe that future cars will run on Li-ion batteries and an unbridled supply
of lithium is important to them. The total demand for lithium in 2009 reached
almost 92,000 metric tons, of which batteries consumed 26 percent. Figure 4
illustrates uses of lithium that also include lubricants, glass, ceramics,
pharmaceuticals and refrigeration.
|
Figure 4: Lithium consumption (2008)
Batteries consume the highest percentage of lithium. With the
advent of the electric vehicle, the demand could skyrocket but for now the
world has enough proven reserve.
Courtesy of Talison MineralsMost of the known lithium sources are
in Bolivia, Argentina, Chile, Australia and China. The supply is ample and
concerns of global shortages are speculative. It takes 750 tons of brine, the
base of lithium, and 24 months of preparation to get one ton of lithium in
Latin America. Lithium can also be recycled an unlimited number of times; 20
tons of spent Li-ion batteries yield one ton of lithium, but recycling could
be more expensive than harvesting new supply through mining. The recycled
lithium is contaminated and has a quality similar to raw material that needs
much processing.
|
Lithium is inexpensive. The raw material costs a fraction of one
cent per watt, or less than 0.1 percent of the battery cost. A $10,000 battery
for a plug-in hybrid contains less than $100 worth of lithium. Rather than
worrying about a lack of lithium, graphite, the anode material, could be
in short supply. A large EV battery uses about 25kg (55lb) of anode material.
The process to make anode-grade graphite with 99.99 percent purity is expensive
and produces much waste.
There is also a concern about shortages of rare earth materials for
permanent magnets. Electric motors with permanent magnets are among the most
energy efficient and they are found in many EV powertrains. China controls
about 95 percent of the global market for rare earth metals and they expect to
use most of these resources for its own production. High prices of these metals
may encourage more recycling in the future but current methods are difficult
because the material tends to oxidize. Returning these elements to their
metallic state requires special procedures that may not be economical with
current technologies.
Summary
Batteries are made for good performance and long life at a low
price. Recycling is an afterthought and manufacturers invest little to simplify
retrieving precious metals. The recycling business is small compared to the
vast battery industry, and to this day only lead acid can be recycled
profitably. Nickel-based batteries might make money with good logistics, but
Li-ion and most other chemistries yield too little in precious metals to make
recycling a viable business without subsidies. The true cost to manufacture a
modern battery is not only in raw materials alone but in preparation,
purification and processing into micro- and nano-structures. Recycling brings
the metal to ground zero from which the preparations must start anew.
To make the recycling business feasible, subsidies are needed by
adding a tax to each cell sold. Perhaps more important than earning a profit is
preventing toxic batteries from entering landfills. Soil contamination can be
harmful to health and is difficult to reverse.
The key in reducing the battery wasteland, however, is to respect
batteries by treating them well and only discard them when no salvage remedy
exists. Better charge methods, clever battery monitoring systems (BMS) and
advanced battery test devices help in getting the full life out of a battery.
Too many batteries are being replaced as a way to troubleshoot an apparent
problem. Advanced diagnostic devices help in eliminating trial-by-error so that
only batteries with valid deficiencies are being exchanged.
Summary of Do’s and Don’ts
Table 1 provides suggestions on how to extend battery life by
following simple guidelines. Because of similarities within systems, the
chemistries are limited to lead, nickel and lithium.
Table 1: Dos and don’ts summary how to use, maintain and dispose of batteries.
Table 1: Dos and don’ts summary how to use, maintain and dispose of batteries.
Battery care
|
Lead acid: Flooded, sealed, AGM
|
Nickel-based:
NiCd, NiMH |
Lithium-ion: Cobalt, manganese, phosphate
|
Best way
to charge |
Apply a saturated charge to prevent sulfation; can stay on charge
with correct float charge.
|
Avoid getting battery too hot on charge. Do not leave battery in
charger for more than a few days (memory!).
|
Partial and random charge is fine; does not need full charge;
lower voltage limit preferred; keep battery cool.
|
Charge methods
|
Constant voltage to 2.40–2.45/cell, float
at 2.25–2.30V/cell; battery stays cool; no fast charge possible. Charge = 14h |
Constant current, trickle charge at 0.05C, fast charge preferred.
Slow charge = 14h Rapid charge = 3h Fast charge = 1h |
Constant voltage to 4.20V/cell; no trickle charge; battery can
stay in charger Rapid charge = 3h Fast charge = 1h |
Discharge
|
Do not cycle starter batteries; avoid full discharges; always
charge after use.
|
Do not over-discharge under heavy load; cell reversal causes
short. Avoid full discharges.
|
Prevent full cycles, apply some charge after a full discharge to
keep the protection circuit alive.
|
How to prolong battery
|
Limit deep cycling, apply topping charge every 6 months while in
storage to prevent sulfation, keep cells at or above 2.10V
|
Do not keep battery in charger for more than a few days,
discharge to 1V/cell every 1–3 months to prevent memory (NiCd)
|
Keep cool, battery lasts longest when operating in mid
state-of-charge of 20–80%. Prevent ultra-fast charging and high loads.
|
Storage
|
Do not store below 2.10V/cell; keep fully charged if possible
|
Store in cool place; NiCd stores for 5 years; prime before use
|
Store at 40% charge in cool place (40% SoC reads 3.75–3.80V/cell)
|
Disposal
|
Do not dispose. Lead is a toxic metal
|
NiCd: Do not dispose.
NiMH: Can be disposed in low volume |
Can be disposed of in low volume
|