EE543 Rechargeable batteries

1. Introduction to Rechargeable Batteries

In this section we evaluate the strengths and limitations of various battery chemistries.
Each battery system offers unique advantages but none provides a fully satisfactory
solution. With the increased selection of battery chemistries available today, better
choices can be made to address specific battery needs. A careful evaluation of each
battery's attribute is important.

1.1 The lead-acid battery

Invented by the French physician Gaston Planté in 1859, lead-acid was the first
rechargeable battery for commercial use. Driven by different market needs, two lead-
acid systems emerged: the small sealed lead-acid (SLA), also known under the brand
name of Gelcell, and the large valve-regulated-lead-acid (VRLA). Both SLA and
VRLA are designed with a low over-voltage potential to prohibit the battery from
reaching its gas-generating potential during charge. Lead-acid is not subject to
memory. Leaving the battery on float charge for a prolonged time does not cause
damage. Lead-acid is relatively inexpensive to purchase but the operational costs can
be more expensive than the nickel-cadmium if full cycles are required on a repetitive
basis. Depending on the depth of discharge and operating temperature, the sealed
lead-acid provides 200 to 300 discharge/charge cycles.

Among modern rechargeable batteries, the lead-acid battery family has the lowest
energy density, making it unsuitable for handheld devices that demand compact size.
In addition, performance at low temperatures is poor. In terms of disposal, the lead-
acid is less harmful than nickel-cadmium but the high lead content and the electrolyte
make the lead-acid environmentally unfriendly.

Fig 1: Lead-acid battery

1.2 The nickel-cadmium battery

Nickel-cadmium prefers fast charge to slow charge and pulse charge to DC charge. It
is a strong and silent worker; hard labor poses little problem. In fact, nickel-cadmium
is the only battery type that performs well under rigorous working conditions. All
other chemistries prefer a shallow discharge and moderate load currents. A periodic
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full discharge is so important for Nickel-cadmium that, if omitted, large crystals will
be formed on the cell plates (also referred to as memory) and the nickel-cadmium will
gradually lose its performance.

Among rechargeable batteries, nickel-cadmium remains a popular choice for two-way

radios, emergency medical equipment and power tools. There is shift towards
batteries with higher energy densities and less toxic metals but alternative chemistries
cannot always match the superior durability and low cost of nickel-cadmium.

Fig 2: Ni-Cad battery

1.3 The nickel-metal-hydride battery

Nickel hydrogen batteries are bulky, require high-pressure steel canisters and cost
thousands of dollars per cell. The success of nickel-metal hydride has been driven by
high energy density and the use of environmentally friendly metals. The modern
nickel-metal hydride offers up to 40% higher energy density compared to the standard
nickel-cadmium. Nickel-metal hydride is less durable than nickel-cadmium. Cycling
under heavy load and storage at high temperature reduces the service life. Nickel-
metal hydride suffers from high self-discharge, which is higher than that of nickel-
cadmium.

Nickel-metal hydride has been replacing nickel-cadmium in markets such as wireless

communications and mobile computing. It is widely accepted that nickel-metal
hydride is an interim step to lithium-based battery technology.

Fig 3: NiMH battery

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1.4 The lithium-ion battery

Lithium-ion battery stores more energy and hence has larger power density compared
to other technologies. The energy density of lithium-ion is typically twice that of the
standard nickel-cadmium. The chemical composition enables greater chargeable
characteristics. Li-ion type requires sophisticated technology to charge and provide
safety environment to the user. Therefore, the charger for Li-ion should be able to
provide protection against over voltage, excessive current under voltage and excessive
thermal conditions.

Li-ion batteries with solid electrolytes have high impedance and as a result are best
suited for low power applications. The batteries with liquid electrolyte can be
discharged at a higher rate but the application of which is limited to memory-retention
and battery backup.

Lithium-ion is a low maintenance battery, an advantage that most other chemistries

cannot claim. There is no memory and no scheduled cycling is required to prolong the
battery's life. In addition, the self-discharge is less than half compared to nickel-
cadmium, making lithium-ion well suited for modern fuel gauge applications.
Lithium-ion cells cause little harm when disposed.

Despite its overall advantages, lithium-ion has its drawbacks. It is fragile and requires
a protection circuit to maintain safe operation. Built into each pack, the protection
circuit limits the peak voltage of each cell during charge and prevents the cell voltage
from dropping too low on discharge. In addition, the cell temperature is monitored to
prevent temperature extremes. The maximum charge and discharge current on most
packs are is limited to between 1C and 2C. With these precautions in place, the
possibility of metallic lithium plating occurring due to overcharge is virtually
eliminated. Aging is a concern with most lithium-ion batteries and many
manufacturers remain silent about this issue. Some capacity deterioration is noticeable
after one year, whether the battery is in use or not. The battery frequently fails after
two or three years. It should be noted that other chemistries also have age-related
degenerative effects.

Fig 4: Li-ion Battery

Table 1.1 Comparison of Lithium based cells

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From: Chan, C.C. The Present Status and Future Trends of Electric vehicles, Science and Technology
Review, Vol. 23, NO. 4, Feb 2005.

1.5 The lithium Polymer battery

The lithium-polymer differentiates itself from conventional battery systems in the

type of electrolyte used. The polymer electrolyte replaces the traditional porous
separator, which is soaked with electrolyte.

The commercial cells use a separator/ electrolyte membrane prepared from the same
traditional porous polyethylene or polypropylene separator filled with a polymer,
which gels upon filling with the liquid electrolyte. Thus the commercial lithium-ion
polymer cells are very similar in chemistry and materials to their liquid electrolyte
counter parts.

Lithium-ion-polymer has not caught on as quickly as some analysts had expected. Its
superiority to other systems and low manufacturing costs has not been realized. No
improvements in capacity gains are achieved - in fact, the capacity is slightly less than
that of the standard lithium-ion battery.

1.6 What's the best battery for Electric Vehicle?

The electric vehicle will gain public acceptance as soon as a battery emerges that is
inexpensive and provides 10 years of reliable service. The high cost and limited cycle
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life of the batteries used in hybrid vehicles negate the savings achieved in burning less
fuel. The benefits are more environmental in nature rather than in cost savings. Higher
fuel prices could change this equilibrium.

Table 1.2 Comparison of different chemistries

From: Chan, C.C. The Present Status and Future Trends of Electric vehicles, Science and Technology
Review, Vol. 23, NO. 4, Feb 2005.
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Table 1.3 Advantages and limitations of batteries of different chemistries

From: Chan, C.C. The Present Status and Future Trends of Electric vehicles, Science and Technology
Review, Vol. 23, NO. 4, Feb 2005.

It should be noted that lithium-ion systems have the potential of higher energy
densities but at the cost of lower safety and reduced cycle life. The Lithium-ion
systems are promising candidates for both the EV and plug-in HEV but require more
research. Here are some of the roadblocks that need to be removed:

Durability: The buyer requests a warranty of ten years and more. Currently, the
battery manufacturer for hybrid electric vehicles can only give eight years on NiMH.
The longevity of lithium-ion has not yet been proven and honoring eight years will be
a challenge.

Cost: If the $2,000 to $3,000 replacement cost of a nickel-metal-hydride pack is

prohibitive, lithium-ion will be higher. These systems are more expensive to produce
than most other chemistries but have the potential for price reductions through
improved manufacturing methods. NiMH has reached the low cost plateau and cannot
be reduced further because of high nickel prices.

Safety: Manganese and phosphate-based lithium-ion batteries are inherently safer than
cobalt. Cobalt gets thermally unstable at a moderate temperature of 150°C (300°F).
Manganese and phosphate cells can reach 250°C (480°F) before becoming unsafe. In
spite of the increased thermal stability, the battery requires expensive protection
circuits to supervise the cell voltages and limit the current in fail conditions. The
safety circuit will also need to compensate for cell mismatch that occurs naturally
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with age. The recent reliability problems with lithium-ion batteries in portable devices
may delay entry into the EV market.

Availability: Manufacturers of manganese and phosphate cells can hardly keep up

with the demand. A rapid increase of lithium for EV batteries would put a squeeze on
battery production. With 7 kg (15 lb) of lithium per battery, there is talk of raw
material shortages. Most of the known supplies of lithium are in South America,
Argentina, Chile and Bolivia.

1.7 Conclusion

We anticipate that lithium-ion will eventually replace nickel-metal-hydride in hybrid

electric vehicles but short service life, high manufacturing costs and safety issues will
stand in its way today. We need to remind ourselves that the automotive market can
only tolerate a marginal cost increase for a new battery technology. In terms of added
capacity, lithium-ion offers only a 20% increase in energy density per weight over
nickel-based systems. The nickel-metal-hydride has proven to work well in current
EVs and a new chemistry would need to offer definite advantages over present
systems to find buyers.

Toyota, Honda and Ford are leading in HEV technology. Other major automakers are
expected to offer competitive models by 2010. Currently, Panasonic EV Energy and
Sanyo supply over 90% of the EV batteries. Both companies are also developing
lithium-ion batteries.

While Japan and Korea are focusing on manganese systems, the USA is
experimenting with phosphate, the chemistry that made the A123 Systems famous.
Europe is relying on clean-burning diesel. These engines are so clean that they won't
even stain a tissue that is placed on the exhaust pipe. BMW is working on a zero
emission hydrogen car.

In this project, LiFePO4 battery is chosen for its excellent safety performance and
high energy density. We expect LiFePO4 to become the dominant battery for EV and
HEV in the foreseeable future. We also noticed some emerging technologies in Li-ion
battery such as nano-titanate Li-ion battery which promises much improved overall
performance and safety over the matured Li-ion batteries. However, it is immature as
a trusted technology and its cost is prohibitive for mass production at the moment.
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Fig 5: Typical charging characteristics for batteries.