Battery Technologies

7.6 The Sodium Nickel Chloride

Zebra Battery

Introduction
The ZEBRA Battery (Zero Emissions Batteries Research Activity) is a
Sodium Nickel Chloride battery, manufactured in limited volume in
Switzerland for EV applications. It is the only dedicated EV battery in
production in the world today.

The technology was first developed in South Africa during the 1970s
and 1980s. The major development then took place at AERE Harwell,
who then entered joint development with AEG. AEG were later bought
by Daimler Benz and then divested.

This technology is only manufactured today by the company MES-DEA

GmbH, located in Stabio, Switzerland. MES-DEA bought the rights to
the technology from AEG in 1999 after Daimler Benz divested itself of
AEG in the late 1990s. MES-DEA built a new $66M factory in 2001 to
manufacture the battery. The factory presently has an annual capacity of
30,000 units.

Figure 40 shows the functioning1 of the Zebra cell.

FIGURE 40 ZEBRA CELL

The -alumina ceramic electrolyte tube has the cross section of a clover
leaf to increase the surface area available for ion transport between
anode and cathode.

The finished battery package with control electronics has a specific

energy density of 90 - 120Wh/kg (depending on format). Volumetric
energy density is 166Wh/l. The theoretical specific energy of a cell is

1. From ZEBRA Battery - Material Cost, Availability and Recycling, Dr. Galloway,
Dr. Dustmann, MES-DEA GmbH, EVS 20, 2003.

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790Wh/kg. The battery is robust, potentially inexpensive, available in a

number of large EV formats and is a well tested technology. This
specific energy density is about the same or better than current
generation LiIon battery packs for EVs, available from SAFT or Sony.
The Sony 32.4kWh LiIon battery pack in the 1999 Nissan Altra had a
specific energy of 89Wh/kg. Existing SAFT LiIon EV modules have a
specific energy of 110Wh/kg.

In comparison, the 9kWh LiIon battery provided by Valence Technology

for retrofit into the Toyota Prius weighs 250 lbs, i.e. an effective specific
energy density of only 80kWh/kg

The Zebra battery will withstand at least 1,000 100% DOD charge/
discharge cycles including any type of partial charge/recharge and is
also marketed by Rolls-Royce for demanding marine applications,
including stand-by power in military submarines and surface vessels. It
is an extremely robust and rugged battery capable of being used in
demanding and harsh environments.

On rapid recharge, the Zebra battery can be 80% recharged in 75

minutes.

BMW used an earlier related technology (Sodium Sulphur) on their

prototype E2 electric car in the early 1990s. Sodium Sulphur technology
was developed by Ford in the 1960s and discontinued in the 1990s due
to corrosion problems. Mercedes Benz announced that they would
launch an electric version of the A Class in 1998 equipped with the
NaNiCl battery. The Electric A Class would have had a range of 120
miles. The vehicle was not marketed. With the latest generation of
Zebra battery, the range of the A Class EV would increase to 180 miles.

Efficiency Comparison
The major perceived drawback of the Sodium Nickel Chloride battery is
that it is a high temperature technology. The battery has to be
maintained at an internal operating temperature of between 270C and
350C for efficient operation. While the battery is being used, this
causes no energy penalty since the internal resistance of the Zebra
battery coverts resistive losses to heat with 100% efficiency. All batteries
have internal resistance and in all batteries, this internally generated
heat has to be removed by a cooling system to prevent overheating.

Therefore in the case of the Zebra battery, the heat generated during
operation can be used to maintain the temperature.

However, when the vehicle is not in use, the battery will start to cool
down. After about 4 hours, external heat has to be applied to maintain
the temperature. The battery contains a heater which can be powered
by the mains or powered by the battery itself. If the vehicle is left
overnight it can be plugged in to both recharge it and to keep the battery
hot. If the vehicle is left for more than 4 hours in a location without
access to a source of mains power, the onboard DC heater switches on
to maintain the temperature.

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The key question in relation to other ambient temperature battery

technologies is therefore:
How much more life-cycle electrical energy does the ZEBRA battery
use than ambient temperature batteries?

The Mendrisio Operating Trial

Between 1995 and the present, the Swiss town of Mendrisio has been
operating an EV trial programme. The programme started with Peugeot
106 EVs equipped with a 14kWh NiCad battery pack, supplied by SAFT.
The electric motor is a 20kW DC motor.

In 2001, a fleet of Renault Twingo electric cars powered by a 21.2kWh

ZEBRA battery started operations. The motor is a 36kW AC induction
motor.

The trial has been carried out under the auspices of the Swiss Federal
Office of Energy and monitored independently by the local municipal
authorities.

An important difference between the two vehicles is that the Peugeot

106s are equipped with a small gasoline heater for the passenger cabin,
while the Renault Twingos use a 3kW electric heater powered by the
main drive battery.

Operating results from this trial were presented by MES-DEA at the

latest Electric Vehicle Symposium1 in April 2005.

The table below summarises the characteristics of the two vehicles.

TABLE 15 MENDRISIO VEHICLE COMPARISON

Peugeot 106 Renault

Twingo
Gross Vehicle Weight 1350 kg 1230 kg
Empty Weight 1050 kg 980 kg
Range at 50 mph 50 miles 75 miles
Heater Petrol 3kW electric
Battery 14kWh NiCad 21.2kWh
Motor 20kW DC 36kW AC
Avg. Energy Use 0.41Wh/mile 0.37Wh/mile
Fleet Sample Size 15 5

Over a two year period, the Peugeot 106 used an average of 25.8kWh
of electricity from the mains per 100 km driven, or 0.41Wh/mile. Over a

1. Mendrisio Operating Results using NiCd and ZEBRA Batteries, EVS-21,

Monaco, 2-6 April 2005

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4 year period, the Renault Twingos have used an average of 23.2kWh/

100km delivered from the mains, or 0.37Wh/mile.

These figures for the Renault Twingos equipped with the ZEBRA battery
include use of the battery to heat the car in winter, not a trivial
requirement in Switzerland. In fact, the winter consumption averaged
25kWh/100km versus 20kWh/100km in summer. In addition, the
Twingos were equipped with winter tyres which increase rolling
resistance, while the Peugeot 106s were not. There was no difference
between winter and summer energy use by the Peugeot 106s for these
same reasons.

With both vehicles, energy use per km decreases as the distance

travelled per day increases.

The thermal energy loss of the ZEBRA battery when not in use is about
90W or 2.16kWh per day. However, in normal use the energy loss will
be lower than this. Even if the vehicle was left unused with the battery
plugged in for an extended period of time, the cost of this electricity to
keep the battery at operating temperature would be minimal - less than
20 cents per day in Europe or the USA and would be equivalent to about
5 - 8 miles driving distance per day.

Conclusion
In normal everyday use, it does not appear that the ZEBRA Battery will
use any more electricity than a NiCad system. There is so much
variation in daily driving habits that the extra energy required to keep the
ZEBRA battery hot does not appear to make much difference to overall
energy efficiency.

The ZEBRA may in fact be superior to NiCad, since it has demonstrated

slightly higher efficiency while also supplying cabin heat in winter and
having higher resistance winter tyres.

Cost Potential of the Zebra Battery

MES-DEA believe that the selling price of the ZEBRA battery would be
$240/kWh in low volume production (10,000 units). At 100,000 units per
year it is projected that the price would fall to $109/kWh.

In 2003, MES-DEA published a cost analysis1 to justify these forecasts.

The production cost breakdown of the ZEBRA battery is shown below.

1. ZEBRA Battery - Material Cost Availability and Recycling, RC Galloway, C-H

Dustmann, EVS 20, Nov. 15 - 19 2003, Long Beach, CA.

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TABLE 16 ZEBRA BATTERY COST PROJECTION

$/kWh $/ Battery
(21.2kWh)
Nickel 17.75 376.30
Other Internal 10.53 223.24
Materials
Battery Case 9.37 198.65
Cell Manufacture 13.82 292.98
Case Manufacture 9.37 198.65
Controller - 250
TOTAL $1540

The total production cost is estimated at $1,540 or $73/kWh. MES-DEA

assumed that the production cost would be 2/3rds of the selling price,
giving an end user price of $109/kWh.

The most expensive item in the ZEBRA battery is the Nickel metal used
in the cathode. MES-DEA state that the NaNiCl technology makes much
more efficient use of Nickel than NiMH or NiCd: 1.53kg of Ni is used per
kWh of stored electricity compared to 6.8kg/kWh for NiMH and 3.5kg/
kWh for NiCd. This is partly because the potential of the NaNiCl cell is
2.58V, more than twice the 1.2V of other Nickel systems.

Argonne National Laboratory estimated1 in 2000 that the Nickel content

per kWh of a LiIon high energy EV battery (using a nickelate LiNiO2
cathode) would be 2.5kg/kWh.

TABLE 17 COMPARATIVE NICKEL USE BY BATTERY

Battery Nickel Use per kWh

NaNiCl 1.53 kg/kWh
LiNiO2 2.5 kg/kWh
NiMH 6.8 kg/kWh
NiCad 3.5 kg/kWh

In practice, future Mixed Oxide cathodes using Mn, Ni and Co for LiIon
EV batteries will probably use less Nickel than 2.5kg/kWh but it may still
be the second metal in the cathode after Manganese, so it could be
present in similar quantities to that used in ZEBRA technology.

1. Costs of Lithium-Ion Batteries, Linda Gaines, Roy Cuenca, Argonne National

Laboratory, May 2000

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The current price of Nickel is between $7 and $8 per lb ($17.6/kg),

which is $6/kg more than the cost used above in Table 16 by MES-DEA
in 2003. This price increase will affect all Nickel based battery
technologies1 but there is no shortage of Nickel resources for increasing
production in future if required. Global Nickel production is currently
about 1.2M tonnes per annum with many new mines scheduled to open
over the next 5 years. Global Nickel production would currently be
sufficient to manufacture 37 million 21.2kWh ZEBRA batteries per year.

At current Nickel prices, the cost of the 21.2kWh NaNiCl battery above
would increase to US$1,735, i.e. an end user selling price of $123/kWh.

The other main chemicals used in the ZEBRA battery are Iron, common
salt (NaCl) and the inert mineral boehmite, a form of alumina. These
substances are cheap and available in unlimited quantities. The total
material cost is less than $40 per kWh.

The cost of the case is quite significant, since the battery requires good
thermal insulation. The case is made of a double walled stainless steel
box, containing a vacuum like a Dewar flask to minimise thermal
conduction. However, the cost of the case rises at a lower rate than the
size of the battery, so larger capacity batteries have a proportionately
lower casing cost.

The cost of the controller is also independent of battery size, adding to

the economy of scale as battery size increases.

Using MES-DEAs methodology, a ZEBRA battery with a capacity of

42.4kWh would cost about US$3,640 to produce, based on a Nickel
price of $18 per kg. Taking MES-DEAs assumption that the production
cost would be 2/3rds of the selling price, the price of a 42.4kWh ZEBRA
battery would therefore be $5,461 or about $130 per kWh.

Even at todays high Nickel prices, $130/kWh would be far cheaper than
any competing battery technology, with the possible exception of Lead
Acid.

If Nickel availability or price became an issue, the battery will work

almost equally well with Iron instead of or partially replacing the nickel.
In this case, the battery becomes a Sodium Iron Chloride battery. The
cell potential is slightly lower (2.35V instead of 2.58V) but the operating
temperature can be reduced from 300C to 250C. The cost of the
battery could be reduced even further if iron was used instead of nickel.
There would of course be no material supply issues at all with a
NaFeCl2 battery: practically unlimited quantities of this battery could be
manufactured from iron and common salt. In fact, starting in 1998, later
versions of the ZEBRA battery already used a 4:1 nickel to iron mix,
along with some aluminium to improve overdischarge capability.

1. For comparison with the cost of NiMH batteries, See Cost Analysis on page 80.

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Safety
The ZEBRA battery must maintain an internal operating temperature of
between 270C and 350C. In operation, the anode consists of molten
sodium. The cathode consists of nickel chloride (or a mixture of nickel
chloride and ferrous chloride) combined with molten sodium
tetrachloroaluminate (NaAlCl4).

Safety concerns are therefore frequently raised with regard to this

technology, particularly since it contains molten sodium metal.

In 1998, the National Renewable Energy Research Laboratory (NREL)

published1 an independent safety study on the Zebra battery.

The report found that when subjected to extreme external influences

simulating vehicle accidents, batteries do not appear likely to add
additional significant hazards to occupants or emergency response
personnel. The cells are fail-safe to overcharging or overdischarging
and are fabricated without the use of metallic sodium. Failure from
exposure to high temperatures results in small hazards and they can be
safely and legally shipped in the cold state.

The NREL commented that AEG Zebra (as it was then) felt that a
breached cell was very unlikely to release sodium, since any trauma
capable of breaching the cell would also break the ceramic electrolyte,
binding all of the sodium into sodium chloride. No sodium had been
released in any safety tests. However, the report did recommend that
tests should be undertaken to determine if there were circumstances in
which sodium could be released and what the effects would be.

The use of the battery in military and civilian submarines, including its
proposal by Rolls Royce for nuclear submarines, indicates that any
safety concerns have been satisfactorily resolved.

In March 2005, the UK oil well logging equipment company Sondex

bought the rights to advanced Zebra battery technology under
development by Beta R&D in the UK. They are using NaNiCl batteries to
replace Lithium Ion in downhole equipment - a very harsh operating
environment. They see Zebra batteries as being a more robust, reliable
and cost effective alternative to LiIon. This also indicates that any
reliability or safety issues with the technology have been resolved.

High Temperature
Being a high temperature battery, the Zebra battery uses 90W of power
to maintain its operating temperature if it is not used. The battery is
plugged in to the mains to power an onboard mains heater when not in
use and has a small onboard DC heater for use where mains power is
not available. This requirement to keep the battery hot is not a problem

1. Current Status of Health and Safety Issues of Sodium Metal Chloride (Zebra)
Batteries, D. Trickett, NREL, WW171000, November 1998.

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in fleet utility or public transport operations and would not be a

significant cost for private drivers. The battery heats up during operation
so external heating only needs to start a few hours after shutdown.

On the other hand, the high temperature of the Zebra battery has the
advantage that the poor cold weather performance of ambient
temperature batteries, especially LiIon, is avoided. The Electric A Class
developed by Mercedes used an oil cooled Zebra battery that could also
provide instant cabin heating in winter. The Zebra Battery was found by
Mercedes to perform equally well in an outside temperature range from
minus 40C to +40C. Standard LiIon batteries are down to 50%
capacity at -20C and experience a further sharp drop off in
performance below that temperature.

If the battery is not required for an extended period, the heater can be
switched off and the battery allowed to solidify. This freezes in the state
of charge and no charge is lost while the battery is frozen. Unlike the
earlier Sodium Sulphur battery, an unlimited number of freeze-thaw
cycles can be performed without damage or loss of capacity. On
thawing the full charge that was in the battery at time of freezing
becomes available again. Therefore there is no self-discharge during
idle periods, unlike NiMH. The battery takes 12 - 15 hours to heat up
after it has frozen.

Recent Developments
In September 2004, MES-DEA started an active commercial
programme to convert the Renault Twingo and Smart Car to electric
propulsion, equipped with the Zebra battery. These vehicles can be
purchased from MES-DEA for about 18,000 euros. The Italian
Government provide a 65% subsidy to people who buy an EV, which
makes the vehicle an attractive proposition for the Italian market.

The Zebra battery has been selected by Th!nk Nordic for their new
Th!nk Public 4 seater EV. The Indian electric car manufacturer Reva
have also selected it for their proposed NXG city electric car. A number
of US bus manufacturers also offer it as an option for hybrid or pure
electric buses. The 3 UK Commercial EV programmes have all selected
the Zebra battery.

The city of Lyon in France is operating 5 electric buses (45 passengers),

each equipped with 8 Zebra batteries. As of July 2005, the city of Rome
in Italy has ordered 36 electric buses equipped with the Zebra battery
and has tendered for 400 electric taxis also to be equipped with this
battery. Italy is particularly vulnerable to oil supply shortages since 73%
of its electricity comes from thermal power stations, the majority of
which are oil fired - not coal or natural gas.

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Conclusion
The ZEBRA battery has many advantages:
1. Energy density higher or equal to LiIon
2. Lowest Cost of any modern EV battery technology
3. Available, cheap and plentiful materials
4. Resistant to Overcharge and Overdischarge
5. Fail-safe to cell failure
6. Ruggedness
7. High calendar life
8. Undiminished low temperature performance

Its disadvantages:
1. 12 - 15 hours to thaw out after freezing
2. 90W energy loss while not in use

The battery is therefore finding particular application in public transport

and utility operations where it can be put into continuous use and
energy losses are minimised. However, the much lower cost of the
NaNiCl technology compared to NiMH or LiIon means that for a 20kWh
Zebra battery, it would take more than 50 years for the energy losses of
the Zebra battery if kept permanently on stand-by to equal the extra cost
of the other batteries.

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