Automotive development

V. Hacker and K. Kordesch Volume 4, Part 11, pp 12171223 in Handbook of Fuel Cells Fundamentals, Technology and Applications (ISBN: 0-471-49926-9) Edited by Wolf Vielstich Arnold Lamm Hubert A. Gasteiger
John Wiley & Sons, Ltd, Chichester, 2003

Chapter 89 Automotive development

V. Hacker and K. Kordesch
Graz University of Technology, Graz, Austria

1 INTRODUCTION
Corporate activities in the year 2001 are almost exclusively related to ZeTek Corporation. ZeTek is the parent organization of three companies involved in developing products for transportation (ZEVCO plc.), marine (ZeMar Ltd.) and stationary power (ZeGen Ltd.) applications. On a smaller scale, Astris Energi in Canada has developed fully integrated portable fuel cell generators. The company produces in the Czech Republic. Prototypes of Astris Energi are equipped with a compressed hydrogen tank and efciencies of 50% at full load were demonstrated. A golf car was equipped with fuel cell Model E6 in March 2001. Apollo Energy Systems in Fort Lauderdale, FL, have researched alkaline systems and mainly improved electrode performance. The work was done in co-operation with Graz University of Technology and resulted in the design of new alkaline fuel cell modules.[14] The research work at Graz University of Technology includes modeling and construction of a laboratory vehicle. The whole system comprises of fuel storage, fuel cracker, alkaline fuel cell, buffer battery, system control, materials and heat management, and simulation of electric load. Ammonia is used as fuel for the alkaline fuel cell system. Compared to hydrogen, ammonia offers signicant advantages in cost and convenience as a vehicular fuel due to its higher density and the ease of storage and distribution. A catalyst for cracking of ammonia into nitrogen and hydrogen was developed and a laboratory-scale ammonia cracker, providing hydrogen for an approximately 1 kW fuel cell, was built.[5] Apollo Energy System is planning to enter

the commercial market in 2003, specializing on alkaline systems using rechargeable batteries in hybrid modes. The cost of these systems should be lowered by mass production through the adaptation of high-volume battery producing machinery for fuel cell production.[69]

2 ZeTek CORPORATION TECHNOLOGY

ZeTek launched its rst prototype taxi in London, UK, which used a 5 kW alkaline fuel cell with circulating electrolyte. Following that, ZeTek has introduced a series of commercial vehicles including airport tow-tugs and fuel-cell-powered boats. Two delivery vans, one with a maximum power of 63 kW and one (an Iveco Daily 35C11) with 68 kW, were built. The fuel cell power of the vans is 5 kW and 7 kW respectively. In 2000, ZeTek introduced a new taxi, the Millennium Taxi. Unfortunately in early 2002 the company went into bankruptcy proceedings and ceased to exist as a commercial entity. The continuation of the manufacturing facilities in Geel, Belgium is not assured. It is, however, expected that they will resume. Fuel cells used in the prototypes are based on the Mk2 module (Figure 1) with a power output of 432 W. The basic module contains 24 cells (48 electrodes), connected in series/parallel to give an operating voltage of 4 V at a current of 108 A. Stacks are guaranteed for 3000 h, over which time a 10% reduction in performance is expected. Published values on degradation of the stack range from 12 to 14 mV 1000 h1[10, 11] up to 30% power loss after 6000 h.[12]

Handbook of Fuel Cells Fundamentals, Technology and Applications, Edited by Wolf Vielstich, Hubert A. Gasteiger, Arnold Lamm. Volume 4: Fuel Cell Technology and Applications. 2003 John Wiley & Sons, Ltd. ISBN: 0-471-49926-9.

1218

Part 11: Current fuel cell propulsion systems

H2

KOH AIR

AIR H2 KOH

Figure 1. Working schematic of fuel cell module [ZeTek, 1999].

Current densities for the existing Mark 2 electrodes, can reach 120 mA cm2 at 70 C, though the normal operating point is 100 mA cm2 at 0.67 V per cell. A current density of 400 mA cm2 seems to be a realistic goal. The performance of a fuel module is shown in Figure 2. The overall efciency of the complete system is shown in Figure 3. The low-pressure alkaline fuel cell (AFC) system achieves a high overall efciency due to less energy demand, particularly in compressing the air. The high efciency of the partial load is especially important for car applications to achieve sufcient consumption for the New European Driving Cycle (NEDC). The peripheral system and the three principal uid loops (hydrogen, air and electrolyte) are shown in Figure 4. The gas systems control and direct the pressure and ow of the gases to the fuel cell stack. The hydrogen, fed from a pressurised supply and additional energy, used to promote a vigorous ow across the active surface of the electrode, is minimal. The pump for the air circuit requires only 350 W for a 5 kW system. Electrolyte is circulated using a 50 W pump. This lead to an efciency for about 90% of electrical consumers.

7 6

Voltage d.c. (V)

5 4 3 2 1 0 0 25 50 75 100 125 150

Load current (A)

Figure 2. Performance Mk2 module [ZeTek, 1999].

Limitations in the allowable stack voltage are caused by the potential power loss due to parasitic electric circulating currents in the KOH electrolyte. As an electrolyte an aqueous solution of KOH with a nominal concentration of 6.6 M and pH > 14 is used. The electrolyte is very corrosive and has the ability to penetrate through seals and joints, where it appears as white powder of potassium carbonate as it

Automotive development 1219 circuits and in the hydrogen circuits due to small internal seepage, and the material used in these circuits must be similarly resistant. Suitable materials include polypropylene, polytetrauoroethylene (PTFE), nickel and nickel alloys. The fuel cell generator system has to create the conditions to keep the temperature of the electrolyte at the stack inlets between 15 and 70 C, the gas supply temperatures to the stack range between 10 and +55 C, the gas humidity between 50 and 90% and to operate the stacks at the pressures stated in the normal operating condition of the application. The specication of Mk2 module is shown in Table 1. The anodes and cathodes are multi-layer gas diffusion electrodes. The active layer consists of an organic powder and carbon-catalyst mixture. Electrodes are manufactured in a dry process, requiring no heat treatment and modest pressures. Catalyst powders for anode and cathode, comprised of graphite, carry the anode and cathode catalyst. Teon powder is required to achieve a hydrophobic electrode structure. The layers are pressed onto a conducting metal mesh with the active layer in the mesh and the

60 50

Efficiency (%)

40 30 20 10 0 0 25 50 75 100

% of nominal power

Figure 3. Efciency of the Zevco fuel cell system [ZeTek, 1999].

dries out. The electrolyte spreads as a liquid lm across all the internal surfaces in the electrolyte circuit and can form solid carbonates and/or KOH crystals under some conditions. The electrolyte has the potential to appear in the air
Air

CO2 Scrubber Blower Filter KOH Ejector

H2

PIC

N2 KOH tank Purge Fuel cell stack Ventilator H 2O Condenser Heater

Heat exchanger Hydrogen loop ATM Air loop KOH loop H2O tank H2O tank

Pump

Liquid outlets

Figure 4. Fluid ows in the AFC system (AVL list). (Reproduced from De Geeter et al., J. Power Sources, 80, 210 (1999) by permission of Elsevier Science.)

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Part 11: Current fuel cell propulsion systems Cost comparisons with conventional combustion engines have been carried out by several institutions (Deutsche Forschungsanstalt f r Luft- und Raumfahrt (DLR), u Germany, L-B-Systemtechnik (LBST), Germany, Zentrum f r Sonnenenergie (ZSW), Germany, Hoechst, Germany, u Royal Institute of Technology, Sweden). The calculations show that stack costs are similar to all other low temperature systems. The production costs for the AFC system seem to be the lowest. With todays technology the costs were calculated to be approx. US$400500 per kilowatt in large scale production.[11, 1316]

Table 1. Specication of Mk2 module.[1] Module conguration Cells per group connected in parallel Cell groups connected in series Cells in total Nominal dimensions Length/width/height Weight excluding electrolyte Weight including electrolyte Volume Construction materials Module Casing Nominal operating conditions Reaction temperature Reaction pressure Hydrogen quality Air quality Nitrogen quality Electrolyte Electrolyte concentration Hydrogen supply pressure Air supply pressure Electrolyte supply pressure Electrical output at nominal operating conditions Open circuit voltage Nominal voltage Nominal current Nominal power Maximum allowable current Fluid ows at full power Hydrogen consumption Air consumption Nitrogen consumption Electrolyte ow rate Max. water production rate Electrical efciency 4 6 24 98 mm/250 mm/310 mm 4.7 kg 6 kg 8l ABS (Acrilo-nitrile butadiene styrene)

3 ALKALINE FUEL CELL LABCAR

A test stand for alkaline fuel cells with control systems enabling dynamic load simulation (e.g., power demand of passenger cars in the NEDC) was developed and assembled under the co-operation of Graz University of Technology and AVL List GmbH, Austria. The prototype fuel cell was provided by ZeTek, UK, and the ammonia cracker was contributed by Apollo Energy Systems, USA. Figure 5 shows the schematic diagram of the test bench. The test bench is subdivided into three main areas: (1) the reformer with ammonia storage and initial fuel supply; (2) the AFC with KOH storage and gas supply; and (3) the electrical load. Hydrogen is used for the start-up of the ammonia dissociator. In a heat exchanger hot cracked gas containing hydrogen, nitrogen and traces of ammonia is cooled down to the working temperature of the AFC (anode in) and ammonia is preheated. A second heat exchanger heats up air for the burner using exhaust gas of the ammonia dissociator. The CO2 content in the air (cathode in) is reduced to below 10 ppm by using a soda-lime lter. Anode exhaust gas is partly recirculated and mixed with cracked ammonia gas and partly serves the burner of the ammonia dissociator as fuel. Cathode exhaust gas might be recirculated to the ammonia dissociator as well. Due to the gas mixture, the concentration of nitrogen increases in the anode loop as hydrogen is consumed. Therefore a much higher gas ow in the anode channel occurs than at systems with only hydrogen supply. The KOH storage is equipped with a heating device to keep the fuel cell at operating temperature. This is necessary because of the small output power of the AFC. At more powerful cells, a cooling system would be necessary. The electrolyte can be drained to an external reservoir when the fuel cell is shut off. It is absolutely necessary to keep the fuel cell lled with KOH during start-up and during operation to avoid damage of electrodes (if no electrolyte

70 C Atmospheric Industrial grade Max 50 ppm CO2 Industrial grade Potassium hydroxide 6.6 mol l1 (30% by weight.) Ambient + 30 mbar 5 mbar Ambient + 30 mbar 5 mbar Ambient + 70 mbar up to 100 mbar

min 5.5 V(d.c.) = 10% 4 V(d.c.) 5% 107 A 5% 410 W 5% 120 A 0.27 Nm3 h1 2.4 Nm3 h1 0.0 Nm3 per on/of cycle 50 l h1 at t of 2.5 C 0.24 l h1 4555% (subject to load, excluding heat recovery)

hydrophobic layer on the gas side of the electrodes. Total electrode thickness is approx. 0.4 mm and the active area of each electrode is 170 170 mm. The stacks are assembled manually. Each half cell is inserted inside a plastic frame and the stack is built up by further half cells in a cathode-anode-cathode sequence.

Automotive development 1221

Heater Ammonia (N2, H2, H2O) MV N2

2

(KOH)1 T6 P6

KOH O2, N2 N2, H2, P3 NH3 T3 M2 T5 P5 MV

N2, H2, NH3 T1 T2 P2 NH3 dissociator Burner Air T9 MV N2, H2, NH3 M6 P1 Blower 300 mbar

Fuel cell

O2, N2

T8 P8

Electrolyte pump KOH

CO2 filter

T4 P4 UD

T7 P7 UD

Ball valve H 2O N2, H2, H2O, NH3

T10

Exhaust

H2 Air Start-up

Figure 5. Schematic diagram of test bench.

Thermal management Hardware Waste heat Electric load

Fuel supply

Fuel processor

Stack

d.c./d.c. converter power electronics

Inverter motor

Transmission

Vehicle

Battery S-cap.

Power supply

Air management, fuel management, sensors, electronic controls

Control electronics d.c./d.c. converter, electric load, power supply

V Vehicle management system Vref

Figure 6. HIL-System of fuel cell-powered vehicle for Labcar test stand (Graz University of Technology, AVL List GmbH).

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Part 11: Current fuel cell propulsion systems 1. 2. 3. 4. 5. 6. 7. 8. 9. start-up and shutdown of the system; safety routines running in the background; watchdog of module voltage of each fuel cell stack; watchdog of pressure difference between KOH inlet and each gas outlet; watchdog to detect if burner ame is out; watchdog to detect if cracked gas temperature is too high; keep reformer temperature constant; keep hydrogen stoichiometry at ve, independent of the electrical load; limit the current ow if hydrogen stoichiometry is smaller than two.

is in the chamber during operation hydrogen reacts directly with air on the electrode). The electrical load enables the dynamic real-time simulation of a down-scaled vehicle in a driving cycle. No buffer battery was included in the set-up. The principle of the control system is a hardware in the loop (HIL) system as shown in Figure 6. The grey block covers the hardware components: fuel supply, reformer, fuel cell stack, converter, battery, load, etc. This block is surrounded by control software: thermal management, vehicle management, etc. Powertrain and vehicle models are also part of the software system. The dynamic electrical load for the fuel cell system is calculated with the simulated powertrain. In the labcar test stand the electrical load is directly connected to the fuel cell (without direct current d.c./d.c. converter) and acts as load only and not as power supply in case of recuperative braking. The controller used in the labcar has the following tasks:

The fuel cell stack shows a very good dynamic response in the NEDC (under consideration of the manufacturers restriction of a maximum current gradient of 20 A s1 ). Figure 7 shows stack voltage, current and power within the NEDC (each diagram shows the NEDC prole in dashed

Stack voltage
8

Voltage (V)

6 4 2 0

700

800

900

1000

1100

1200

Stack current
30

Current (A)

20

10

700

800

900

1000

1100

1200

Stack power
100

Power (W)

50

700

800

900

1000

1100

1200

Time (s)

Figure 7. Voltage, current and power measurements of AFC-stacks in the NEDC.

Automotive development 1223 line). The cracker shows a slow dynamic response, due to temperature drop under dynamic load. The layout of the heat exchanger systems and the gas channels have therefore to be further optimised.[17] The tests showed that cracked ammonia (nitrogen/hydrogen mixture) can be used in an alkaline fuel cell, and that the fuel cell is still able to respond to the NEDC.

REFERENCES
1. K. Kordesch, V. Hacker, J. Gsellmann, P. Enzinger, M. Cifrain, R. Aronson, G. Faleschini, M. Muhr and K. Friedrich, J. Power Sources, 86(12), 163 (2000). 2. V. Hacker, P. Enzinger, M. Muhr, K. Kordesch, J. Gsellmann, M. Cifrain, P. Prenninger, K. Meitz and R. Aronsson, Advantages of Alkaline Fuel Cells for Mobile Applications, Fuel Cell Seminar 2000, Portland, USA, pp. 655658, Oct. 30Nov. 2 (2000). 3. K. Kordesch, V. Hacker, J. Gsellmann, M. Muhr, P. Enzinger, M. Cifrain and R. Aronson, Alkaline Fuel Cells for Electric Vehicles, 3rd IFCC, Nagoya, Japan, pp. 165168, Nov. (1999). 4. K. Kordesch, J. Gsellmann, M. Cifrain, S. Voss, V. Hacker, R. Aronson, C. Fabjan, T. Hejze and J. Daniel-Ivad, J. Power Sources, 80, 190 (1998). 5. G. Faleschini, V. Hacker, K. Kordesch, R. Aronsson and M. Muhr, Ammonia for High Density Hydrogen Storage, Fuel Cell Seminar 2000, Portland, OR, Oct. 30Nov. 2 (2000). 6. P. Kalal and J. K. Nor, Carbon Dioxide Tolerant Hydrogen and Methanol Fuel Cell with an Aqueous Carbonate Electrolyte, Proc. of 1990 Fuel Cell Seminar, Phoenix, AR, p. 471 (1999). 7. Apollo Energy Systems, Exhibitor at Fuel Cell Seminar, Portland, OR (2000). 8. K. Kordesch and G. Simader, Fuel Cells and their Applications, VCH, Weinheim (1996). 9. K. Kordesch, Brennstoffbatterien, Springer Verlag, Wien (1984). 10. H. van den Broeck, Status of Elencos Alkaline Fuel Cell Technology, Intersociety Energy conversion Engineering Conference Proceedings, Philadelphia (1987). 11. G. McLean, T. Niet, S. Prince-Richard and N. Djiali, Int. J. Hydrog. Energy, 27, 507 (2002). 12. P. Michael, An Assessment of the Prospects for Fuel Cell Powered Cars, ETSU, UK (2000). 13. E. G lzow, J. Power Sources, 61, 99 (1996). u 14. K. H. Tetzlaff, R. Walz and C. Gossen, J. Power Sources, 50, 311 (1994). 15. H. B hnisch, E. Dienhart, J. G lzow and J. Nitsch, Bedeuo u tung, Einsatzbereiche und technisch- konomische Entwicko lungspotentiale von Wasserstoffnutzungstechniken, Ottobrunn, Stuttgart (1992). 16. O. Lindstr m, Fuel Cell Seminar, San Diego, CA, pp. 194 o (1994). 17. K. Meitz, P. Prenninger, V. Hacker and K. Kordesch, Alkalische Brennstoffzellensysteme f r Fahrzeugantriebe u eine m gliche Antwort auf offene Problemstellungen?, o VDI-Veranstaltung Innovative Fahrzeugantriebe, Oct. 2627 (2000).

4 SUMMARY AND OUTLOOK

The AFC has often proven in the long history of research and development that it can compete with other fuel cells on the basis of performance and costs. In order to reach the goal of higher power density for mobile applications, the current density has to be increased as well as further developed to simplify the system, for example new techniques for CO2 removal, an efcient electrolyte management and bipolar cell systems, are necessary. Although alkaline technology has been largely neglected in the past 10 years, interesting developments have been demonstrated, for example by Hoechst with the falling lm fuel cell. The electrolyte ows from the top to the bottom through the cell. The pressure difference between the electrolyte on the front-side of the electrode and the gas on the other side remains constant over the whole area of the electrode. DLR have developed low-cost electrodes with an operation time of over 5000 h and have demonstrated CO2 resistant electrodes. Considering the experience gathered by space applications and prototypes, newly available materials and production techniques and new and innovative solutions, it would be premature to say that the choice of the fuel cell type is already nal. The alkaline fuel cell is suitable for mobile applications and might be an interesting option in the future, since alkaline fuel cells do not require noble metal catalysts and use a reasonably inexpensive electrolyte.

ACKNOWLEDGEMENTS
The authors appreciate the nancial support received from the Austrian government (Bundesministerium fuer Verkehr, Innovation und Technologie (BMVIT)). Special thanks to Josef Gsellmann, Robert R. Aronsson, Peter Prenninger, Klaus Meitz, Gottfried Faleschini, Peter Enzinger, Martin Cifrain, Michael Muhr and Juergen Besenhard.