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SAE TECHNICAL PAPER SERIES

2000-01-1528

SAE TECHNICAL PAPER SERIES 2000-01-1528 Advanced Power Sources for a New Generation of Vehicles Steven G.

Advanced Power Sources for a New Generation of Vehicles

Steven G. Chalk

U.S. Department of Energy, Office of Transportation Technologies

H. Jackson Hale

Consultant

Fred W. Wagner

Energetics, Incorporated

Reprinted From: 2000 Future Car Congress Proceedings CD-ROM

Reprinted From: 2000 Future Car Congress Proceedings CD-ROM 2000 Future Car Congress Arlington, Virginia April 2-6,

2000 Future Car Congress Arlington, Virginia April 2-6, 2000

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2000-01-1528

Advanced Power Sources for a New Generation of Vehicles

Steven G. Chalk

U.S. Department of Energy, Office of Transportation Technologies

ABSTRACT

The U.S. Department of Energy (DOE) and the U.S. automotive industry are collaborating on research and development of advanced compression ignition direct injection (CIDI) engine technology and polymer electrolyte membrane (PEM) fuel cells for automotive applications. Under the auspices of the Partnership for a New Generation of Vehicles (PNGV), the partners are developing technologies to power an automobile that can achieve up to 80 miles per gallon (mpg), while meeting customer needs and all safety and emissions requirements. Research on enabling technologies for CIDI engines is focusing on advanced emissions control to meet the proposed stringent Environmental Protection Agency emissions standards for oxides of nitrogen (NO x ) and particulate matter (PM) in 2004, while retaining the high efficiency and other traditional advantages of CIDI engines. DOE is teaming with U.S. diesel engine companies, catalyst manufacturers, and national laboratories to develop integrated emissions control systems. This paper will present emissions and efficiency data for several advanced diesel fuel alternatives when burned in a Daimler Benz Model OM 611 CIDI engine. Progress achieved in lean NO x catalyst and particulate trap emissions control systems will also be discussed. DOE and the automotive industry are also investing heavily in research and development of PEM fuel cells to meet the requirements of the PNGV. Two critical challenges facing fuel cell systems are addressing fuel processing issues including the removal of sulfur from fuel and lowering the overall cost of fuel cell systems. A cost estimate will be presented for a 50-kW PEM fuel cell system for automobiles based on technology available in year 2000. The high risk challenges facing the development of CIDI engine and PEM fuel cell technologies for the PNGV necessitate an active government role. This paper provides a status report on the PNGV program and an overview of the technical accomplishments and challenges facing the Advanced Combustion and Emission Control R&D and

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H. Jackson Hale

Consultant

Fred W. Wagner

Energetics, Incorporated

Fuel Cells for Transportation Programs of the Department of Energy.

INTRODUCTION

The Partnership for a New Generation of Vehicles (PNGV) is presented with the difficult challenge of developing, by the year 2004, a production prototype of an up-to-80-mpg family sedan that will meet customers’ needs for quality, performance, and utility as well as safety and emissions requirements. Key to achieving the goal of 80-mpg is the development of clean, advanced power sources with high energy conversion efficiencies. The PNGV has identified two primary candidates for the energy conversion system on the up-to-80-mpg production prototype vehicle: the compression ignition direct injection (CIDI) diesel engine, and the polymer electrolyte membrane (PEM) fuel cell. To achieve the target of up to 80-mpg, the energy conversion systems are likely to be part of a hybrid electric propulsion system.

likely to be part of a hybrid electric propulsion system. Figure 1. Shows the timetable for

Figure 1.

Shows the timetable for the PNGV Program.

CIDI ENGINES FOR PNGV – The CIDI engine is an attractive candidate for the PNGV because it has a very high energy conversion efficiency, and a technical and manufacturing maturity that is in line with the PNGV program schedule (see Figure 1). The engine also has excellent evaporative and cold start emissions and low

operating hydrocarbon (HC) and carbon monoxide (CO) emissions. However, it does face serious challenges in meeting the Environmental Protection Agency’s (EPA’s) proposed stringent emissions standards for oxides of nitrogen (NO x ) and particulate matter (PM) in 2004, and in reducing the weight and cost of the power plant. One of the critical challenges facing CIDI engines is the trade- off between emissions of NO x and particulates. In today’s diesel engines, strategies to reduce NO x (i.e., exhaust gas recirculation and retarded injection timing) result in increased particulate emissions. Conversely, methods to reduce PM (i.e., higher operating temperatures and more complete in-cylinder mixing) tend to increase NO x emissions. This situation is particularly difficult given that significant reductions are required in both particulate and NO x emissions.

The applicable EPA Tier 2 target for particulates is 0.01 grams/mile (g/mi). Emissions of particulates from today’s CIDI engines exceed this target by more than a factor of six. Current engine-out NO x emissions for CIDI engines are 0.5 g/mi or greater whereas the target is the Tier 2, 120,000-mile standard of 0.07 g/mi. This standard will require emissions control with NO x conversion efficiencies of approximately 90 percent. Technologies currently being demonstrated exhibit NO x conversion efficiencies of about 40 percent and require near sulfur- free fuel. To achieve these ambitious emissions targets will require emissions control for both NO x and PM, as well as significant changes in fuels. Fuel composition can have significant impacts on engine-out emissions and the performance of emissions control systems.

FUEL CELLS FOR PNGV – The PNGV is developing fuel cell technology because of its potential for high efficiency, near-zero emissions, and fuel flexibility. Despite many advances in recent years, it is likely that the timeframe for developing fuel cell technology utilizing conventional type fuels will extend beyond the current 2004 deadline of the PNGV program. Fuel cells are likely to be the long-term replacement for internal combustion engines in automobiles and other transportation systems, but many important technical issues, including cost, remain to be solved before fuel cells can become a viable alternative.

Gaseous hydrogen (H 2 ) is the ideal fuel for fuel cells, but because of the difficulty of storing H 2 on board the vehicle, the lack of infrastructure for distributing H 2 , and its high cost, its use is not viable in the near term for mass-produced light-duty vehicles. To serve as a transition, it is necessary to use liquid hydrocarbon fuels, which must be reformed to produce hydrogen-rich gas for the fuel cell stack. Reformation of hydrocarbon fuels introduces a host of complex issues.

DOE’S ADVANCED COMBUSTION AND EMISSION CONTROL R&D PROGRAM

In support of the PNGV, DOE’s Office of Advanced Automotive Technologies (OAAT) is sponsoring a

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research and development (R&D) program to develop advanced CIDI-enabling technologies for automobiles and light truck applications. The program works closely with the PNGV’s four-stroke direct injected (4SDI) engines technical team to identify R&D priorities, establish technical targets, and review progress. The focus of the program is on advanced emission-control technologies that will enable CIDI engines to meet future emissions standards while maintaining the high efficiency and other advantages of the diesel engine. The DOE program targets for the CIDI engine system for automobiles and light trucks are shown in Table 1. Emissions targets for the CIDI engine system are especially challenging. The remainder of this section is a discussion of new CIDI program activities and the progress made in meeting the challenges facing fuels and emissions control for CIDI engines.

Table 1. DOE Targets for the CIDI Engine System

engines. Table 1. DOE Targets for the CIDI Engine System NEW CIDI ACTIVITIES – In 1998,

NEW CIDI ACTIVITIES – In 1998, it became clear that to achieve stringent standards for NO x and PM emissions for CIDI engines, emissions reduction must be pursued within the context of an integrated system. That is, improvements in in-cylinder combustion and fuels reformulation must be synergistically combined with emission-control systems. The National Research Council Committee Panel, which is chartered with annually reviewing the progress and direction of the PNGV, stated that considerably more effort and resources should be devoted to exhaust-gas aftertreatment of NO x and particulates. The Panel also stated that the PNGV should consider greatly expanding its efforts to involve catalyst manufacturers.

In October 1998, OAAT released a solicitation and in late 1999 awarded 2 ½ year contracts to teams lead by

Cummins Engine Company and Detroit Diesel Corporation for the development of components for emission-control subsystems. The Cummins-Engelhard team is evaluating parallel prototype hardware combinations for reducing NO x and PM emissions including a lean NO x catalyst, plasma-assisted catalyst, and an adsorber catalyst using intermittent rich conditions. Each system will be coupled with a microwave regenerated catalyzed soot filter to control PM emissions. The Detroit Diesel-Johnson Matthey team is pursuing two parallel approaches to achieve NO x reduction including a NO x catalyst and a lean NO x trap. Their system will be combined with a continuously regenerating trap for PM reduction. Efforts will be closely coordinated with R&D at the national laboratories. Deliverables include the development of complete emission-control subsystems for CIDI engines that are candidates for PNGV. These subsystems will operate on a low sulfur diesel fuel and will meet interim emissions targets of 0.2 g/mi NO x and 0.02 g/mi particulates. Deliverables will be provided to Oak Ridge National Laboratory (ORNL) for independent verification and may be provided to automotive manufacturers for subsequent testing and evaluation. In addition, the emissions control subsystems will be scaled for light-duty truck applications.

FUELS FOR CIDI ENGINES – During the past several years, a substantial research effort has been focused on the evaluation of diesel fuels which appear to have the potential to reduce engine emissions. DOE has funded Southwest Research Institute (SWRI) to conduct diesel fuels tests using one of the worlds most advanced production automotive diesel engines. Daimler Benz provided their Model OM 611 engine which is commercially produced and used in their stock European Class C automobile. This direct injection, 2.2 liter diesel engine includes advanced engineering features such as high-pressure, common-rail injection, turbocharger with

intercooling, variable EGR, variable intake swirl, and electronic controls. This engine is similar in many ways to the designs evolving for the PNGV automobiles. The initial testing at SWRI was conducted without changing the engine tuning from the factory settings, and using a full spectrum of speed load conditions. The fuels tested included the following:

2D

EPA Certification Fuel

CARB

Pseudo California Certification Fuel

LS

Low-Sulfur Low Aromatics Diesel

FT100

Fischer-Tropsch Synthetic Diesel

FT20

Twenty percent blend of Fischer-Tropsch in

B20

LS fuel Twenty percent blend of Biodiesel (produced

DMM15

from soybean feedstock) with the LS fuel Fifteen-percent blend of Methylal in LS fuel

Results from these early tests have been reported by SWRI in their Interim Report TFLRF No. 338, published in November 1998. Further analysis by SWRI has revealed that there is a strong correlation between the reduction of particulate matter (PM) and the hydrogen/ carbon (H/C) ratio and the oxygen content of the fuel (see Figure 2). If tests continue to support this trend, it would appear that selection of diesel fuels for the future should include fuels having the highest practical H/C ratio and

include fuels having the highest practical H/C ratio and Figure 2. PM reduction is correlated with

Figure 2.

PM reduction is correlated with the hydrogen/ carbon ratio and the oxygen content of the fuels.

hydrogen/ carbon ratio and the oxygen content of the fuels. Figure 3. For the same operating

Figure 3.

For the same operating conditions, thermal efficiency varies little for all of the test fuels.

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the maximum practical oxygen content. This trend also appears to indicate that there are some limitations to the reduction of particulate emissions through improvements in fuel composition alone. As shown in Figure 3, these initial tests also show that there are only minor variations in the thermal efficiency for all of the tested fuels when they are burned at the same operating power level (speed and torque) – with the exception of the non-tuned idle conditions.

Testing at SWRI is continuing to determine whether further emissions reductions can be achieved by optimizing the engine for each fuel by electronically tuning exhaust gas recirculation, rail pressure, and injection timing. The procedure includes a set of statistically designed tests which cover the practical limits of the engine operating conditions and the available test variables. For each fuel, the test results are analyzed to generate engine emissions response surfaces as shown in Figure 4. Comparable response surfaces are generated for emissions of PM, NO x , HC, CO, and specific fuel consumption. Further statistical analysis of this data enables the selection of engine operating parameters that should be used to achieve the overall optimum engine performance and criteria emissions. Although various optimization scenarios can be analyzed with this approach, the DOE has initially elected to achieve the minimum NO x and PM, while sacrificing not more than 10 percent of the engine fuel economy. This work will lead to a set of emissions and performance maps which will be used in a vehicle performance model to ascertain the criteria emissions and vehicle performance for a PNGV type vehicle operating under the driving cycles as prescribed by EPA. The automotive companies are evaluating their newly evolving CIDI engines using fuels similar to those being tested at SWRI. They have elected to use a different test and optimization approach; when their test results become available, they will be compared with the SWRI test results.

available, they will be compared with the SWRI test results. Figure 4. Representative NO x emissions

Figure 4.

Representative NO x emissions map shows effect of electronically controlled engine parameters.

The DOE is also sponsoring SWRI to evaluate the tailpipe emissions of a stock European Mercedes C220 automobile which uses the same engine model as the

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one used in the above testing. For the initial testing, three fuels (LS, FT100, and DMM15) were selected from the original group.

All of these fuels had less than 10 ppm of sulfur to avoid damage to the stock emissions control system provided on the vehicle. Each of the fuels were evaluated using the current EPA FTP driving cycle, the European ECE driving cycle and the EPA proposed US06 driving cycle. These tests are continuing, so the results are preliminary and subject to later revision. However, the early results are illustrated in Figure 5, which shows the PM and NO x levels that were achieved for the three driving cycles. For comparison purposes, the proposed EPA Tier 2 Standards are shown in the small box in the lower corner of the chart. This preliminary data shows that the proposed EPA US06 driving cycle results in the highest emissions. For the current EPA FTP driving cycle, the NO x emissions for all three fuels are about half of the results achieved with the US06 driving cycle, and the PM is reduced significantly when using DMM15. Even further reductions of PM and NO x result when using the European ECE driving cycle. Finally, Figure 5 clearly shows that the attainment of the proposed EPA Tier 2 emissions standards will require a major breakthrough in the emissions control systems of the future.

breakthrough in the emissions control systems of the future. Figure 5. Vehicle emissions are strongly influenced

Figure 5.

Vehicle emissions are strongly influenced by selection of the standard driving cycle.

Based on the early test results from SWRI, DOE is also funding additional integrated fuels research at several

National Laboratories and SWRI, in collaboration with the automotive and fuels industries, to gain further understanding of the emissions reductions that can be derived from oxygenated fuels. The industrial participants are working collectively to recommend the most promising and practical oxygenated diesel fuels for CIDI engines. Sandia National Laboratories (SNL) is investigating the in-cylinder processes to determine the importance of oxygen concentrations in reducing soot

formations.

SNL will use these results in the

development of a technological and scientific information base that is needed to optimize in-cylinder combustion processes while using oxygenated fuels. Lawrence Livermore National Laboratory (LLNL) is developing an improved understanding of the chemical kinetics that provide links between the combustion stages in diesel engines; this will lead to an improved understanding of

the effects of oxygenates in diesel fuels. LLNL research to date indicates that the products of rich pre-mixed ignition are strong soot precursors. Laboratory research results also indicate that the total amount of oxygen in the fuel determines the suppression of soot precursors. However, there seems to be little correlation between rich pre-mix conditions and the formation of NO x . In addition, DOE is sponsoring research at the SWRI to determine whether any of these new fuels will generate combustion products that have high levels of toxicity. All of this research information is critically important for the successful transition to CIDI engines in automobiles and light-duty trucks.

EMISSIONS CONTROL SYSTEMS FOR CIDI ENGINES – Conventional NO x reduction catalyst technology used on gasoline engines cannot be applied to CIDI engines due to excess oxygen in the exhaust. As such, OAAT is supporting research focusing on lean NO x catalysts for CIDI engines applicable to the PNGV. New catalyst formulations are being targeted to achieve 1) high NO x conversion over steady-state and transient operation of the FTP cycle, 2) low light-off temperatures that are critical for lower temperature CIDI exhaust applications, and 3) wider operating temperature windows from 100°C to 350°C.

operating temperature windows from 100 ° C to 350 ° C. Figure 6. SNL is comparing

Figure 6.

SNL is comparing NO x reduction results for various Pt-based/HTO:Si catalysts.

Sandia National Laboratories has developed and scaled- up platinum-based hydrous metal-oxide (HMO)- supported catalysts for NO x reduction. As shown in Figure 6, SNL has identified new silica-doped hydrous titanium oxide-supported platinum (Pt/HTO:Si) catalysts which lower light-off temperature and widen the temperature window of appreciable NO x reduction. Material A represents the new dopant added to the baseline Pt/HTO:Si material.

Screening experiments at Los Alamos National Laboratory (LANL) on microporous support materials have resulted in the discovery of a new family of zeolite- based catalysts that exhibit high NO x reduction over a broad temperature range. LANL has undertaken optimization of preparation procedures for the catalysts which involves the choice of zeolite support, support pretreatment, active metal catalyst, and the method of exchange. Figure 7 illustrates the importance of support pretreatment procedures (Treatments A-D) on two

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different zeolite supports used to fabricate catalysts with the same active metal and exchange method. Support 1 prepared by pretreatment method A demonstrates between 100 and 85 percent NO x conversion between 125° and 600°C. Support 2 prepared by pretreatment method C has demonstrated greater than 95 percent NO x conversion between 250°C and 500°C.

percent NO x conversion between 250 ° C and 500 ° C. Figure 7. LANL's choice

Figure 7.

LANL's choice of zeolite support and support pretreatment procedure significantly impacts NO x conversion efficiency.

significantly impacts NO x conversion efficiency. Figure 8. Zeolite based catalyst activity is largely

Figure 8.

Zeolite based catalyst activity is largely unaffected below 300 °C despite progressively severe treatments of the catalyst power.

Figure 8 presents the results of LANL’s progressive treatment process on a single zeolite-based catalyst. This catalyst was initially tested fresh, then pretreated for 8 hours at 650°C with 5 percent steam (tested), steam pretreated for 4 hours at 750°C (tested), and steam pretreated for 2 hours at 850°C prior to final testing. Results indicate that the 8-hour steam pretreatment has little effect on catalytic properties; subsequent steam pretreatments progressively diminish activity above 300°C. Throughout the pretreatments, low temperature activity (below 300°C) remains largely unchanged within experimental error (±5 percent conversion at high conversion levels). Figure 9 presents data obtained from catalysts prepared by placing the pretreated support on a cordierite monolith by slurrying the support in either water or alumina (Disperal). The active metal component was then ion-exchanged onto the coated monolith, dried, and calcined prior to testing. Both slurrying methods lead to NO x conversion results similar to the unsupported catalyst. 1

Figure 9. The effectiveness of a zeolite based catalyst prepared by slurrying a pretreated support

Figure 9.

The effectiveness of a zeolite based catalyst prepared by slurrying a pretreated support on a cordierite monolith is similar to the unsupported catalyst.

While it is generally agreed that achieving the emission

target for NO x is the greatest barrier facing CIDI engines, targets for particulates are also very demanding. This situation is made worse by the fact that many CIDI engines may have to employ in-cylinder NO x reducing strategies such as exhaust gas recirculation that tend to exacerbate particulate emissions. To achieve the target

of 0.01 g/mile for particulates will require particulate

reduction close to 90 percent. While particulate traps are

a relatively well-proven technology, they must still

demonstrate better efficiency, reduced pressure drops

across the filter, and improved regeneration methods, and must be made more durable and cost-effective.

Industrial Ceramic Solutions, LLC (ICS) has developed silicon carbide fibers highly efficient in converting microwaves to heat energy for regeneration of particulate traps (see Figure 10). ICS, in conjunction with Oak Ridge National Laboratory and other industrial suppliers, has demonstrated an exhaust filter system that can achieve regeneration temperatures of greater than 600°C at engine idle conditions. Experimental results indicate the filter removes between 80 and 90 percent of diesel particulates. Efficiency can be improved to greater than 90 percent by reducing pore size through the media papermaking process. Three microwave cleanings of the filter cartridge (at engine idle speed) subsequent to each of three one-hour particulate loadings has resulted in a 97 percent regeneration efficiency. Additionally, test cell results show the pressure drop across the ceramic paper cartridge is significantly lower (approximately 0.4 kPa) than that experienced by existing extruded cordierite wall-flow filters (approximately 2 kPa). 2

cordierite wall-flow filters (approximately 2 kPa). 2 Figure 10. In less than one minute, ICS’s silicon

Figure 10. In less than one minute, ICS’s silicon carbide fibers can reach 800°C in a 2.45 GHz microwave field (under ambient air conditions).

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Table 2. Ambitious Program Targets for the PNGV’s Integrated Fuel Cell Power Systems

Targets for the PNGV’s Integrated Fuel Cell Power Systems The emissions challenges facing the use of

The emissions challenges facing the use of CIDI engines in light-duty vehicle applications are daunting, requiring an approximately 90 percent reduction in both particulates and NO x as compared to the current state- of-the-art. It is clear that fuel modification can only go part of the way and that highly effective emissions control systems are required. As discussed earlier, progress is being made in these areas, however significant challenges remain before the CIDI engine can become a viable future option for mass produced automobiles and light trucks.

DOE’S FUEL CELLS FOR TRANSPORTATION PROGRAM

Under the auspices of the PNGV, the U.S. Department of Energy is a major participant in an ambitious, cost- shared, government-industry R&D program to develop automotive fuel cell power system technologies. These technologies are expected to be highly efficient with low or zero emissions, cost-competitive, and to operate on conventional and alternative fuels. The program targets

for integrated fuel cell power systems are shown in Table

2. The following sections present an overview of the

progress made and challenges for fuel cells in several key areas, including improving their efficiency, fuels, and lowering overall system costs.

EFFICIENCIES OF FUEL CELL SYSTEMS – Table 3 presents an analysis by Argonne National Laboratory (ANL) of the challenges to meeting efficiency targets for

fuel cell systems. The program’s target efficiencies of 48 percent at 25 percent power (12.5 kW) and 38 percent at full power (50 kW) will require fuel cell stack voltages of approximately 0.9 volts and 0.77 volts, respectively. Fuel cell stacks typically operate at cell voltages of about 0.6-

0.7 volts, at higher voltages power density and cost

become significant challenges. Additionally, this requires

the fuel processor to achieve an overall efficiency of 80 percent, which is a major challenge when using petroleum-based fuels.

Table 3. ANL’s System Analysis Identifying Component and Operating Challenges to Achieve Program Targets

and Operating Challenges to Achieve Program Targets Epyx is developing fuel-flexible partial oxidation (POX)

Epyx is developing fuel-flexible partial oxidation (POX) fuel processing technologies for automotive PEM fuel cell systems. Figure 11 presents the thermal conversion efficiency and percent hydrogen (dry) in the reformate of Epyx’s fuel processor when operating on California Phase II gasoline. The efficiency shown is at the exit of the preferential oxidation (PROX) carbon monoxide (CO) clean up system which functions to maintain CO levels in the reformate at less than 10 ppm. The Epyx reformer demonstrates efficiencies in excess of 70 percent over a turndown of four to one; similar efficiencies have been demonstrated at higher turndown. These efficiencies are close to the maximum theoretical efficiency indicating a highly optimized reformer design. 3

efficiency indicating a highly optimized reformer design. 3 Figure 11. Epyx's multifuel processor demonstrates high

Figure 11. Epyx's multifuel processor demonstrates high thermal conversion efficiency and hydrogen concentrations when operating on gasoline.

Current state-of-the-art fuel processing subsystems combined with fuel cell stack subsystems lead to an efficiency around 35 percent. Presently, these systems consist of experimental units made up of components which have yet to be integrated into a complete system; no automotive size system operating on petroleum-based fuels currently exists. DOE’s current focus is to develop this system and to improve overall functionality while achieving a total system efficiency of 30 to 35 percent. Once the system has been fully integrated and is operating, work will commence to increase overall system efficiency to 40 percent.

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to increase overall system efficiency to 40 percent. 7 Figure 12. PNNL is using engineered microstructures

Figure 12. PNNL is using engineered microstructures in its fuel processing technology.

Pacific Northwest National Laboratory (PNNL) is using engineered microstructures to develop ultra-compact reactors, separators, and heat exchangers to facilitate the reforming of liquid hydrocarbon fuels (see Figure 12). PNNL has developed a 50-kW e -capacity microchannel gasoline vaporizer for partial oxidation (POX) and/or autothermal reformers, which has met performance goals at a volume of only 0.3 liters. This technology has been transferred for testing to the industry fuel processor developers Epyx and Hydrogen Burner Technology. PNNL is also developing and testing the first proof-of- principle, single-cell, microchannel steam reformer. Steam reforming operates at lower temperatures (650°C) than POX or autothermal reforming and at greater than atmospheric pressure without a compressor, while producing higher concentrations of hydrogen in the product stream. Fuel cells can operate more efficiently with a pure hydrogen feed. Figure 13 illustrates PNNL’s success in using an integral microchannel reactor/heat exchanger leading to fast kinetics for steam reforming. The conversion of iso-octane (a surrogate for gasoline) and selectivity to hydrogen are both about 90 percent with a reactor residence time of just 2.3 milliseconds. The drygas content of hydrogen is between 65 and 70 percent compared to a drygas content of 35 to 40 percent traditionally obtained with POX and autothermal reactors.

traditionally obtained with POX and autothermal reactors. Figure 13. Data obtained from PNNL’s microchannel steam

Figure 13. Data obtained from PNNL’s microchannel steam reforming system using iso-octane demonstrates conversion and selectivity of about 90 percent.

In the future, the DOE Fuel Cells for Transportation Program will target higher-risk development of high-

catalysts. Typically, fuel cell stack operating temperatures are limited to 80°C. Key advantages would be obtained from the development of an inexpensive, high- temperature membrane operating at 100°C-150°C that sustains current densities comparable to today’s membranes and does not require significant humidification. This membrane would enhance CO tolerance and facilitate heat rejection permitting a dramatic reduction in the size of the condenser and radiator. As mentioned earlier, higher operating voltages are required to meet efficiency targets for fuel cell systems. The development of improved oxygen reduction electrocatalysts with greater kinetics would be beneficial because the most significant contributor to cell voltage loss is polarization on the cathode. Additionally, advanced oxygen catalysts could reduce air compressor requirements in fuel cell systems, thereby improving efficiency through reduced parasitics. 4

FUELS FOR FUEL CELLS – The DOE Fuel Cells for Transportation program is pursuing a fuel-flexible strategy enabling the conversion of petroleum-based fuels, ethanol, methanol, and natural gas into hydrogen-rich streams for fuel cells (see Figure 14). This fuels strategy accepts the reality of today’s fuel infrastructure while creating pathways for alternative fuels. Today and for perhaps the next 50 years, petroleum-based fuels are a primary focus because of their easy availability and low cost. Although from a vehicle perspective it is less environmentally compatible than a zero-emissions, direct-hydrogen fuel cell vehicle, a petroleum-based gasoline-like PEM fuel cell vehicle is expected to have much greater efficiency and far lower emissions than are allowable under the strictest California standards proposed. Ethanol and methanol are part of the DOE fuels strategy because they are renewable and can be made from domestic energy sources, providing the most oil displacement. Natural gas is included in the fuels strategy to maintain synergism with DOE stationary and portable power applications and for potential heavy vehicle applications. These alternative fuels provide a transition to a hydrogen-based refueling system.

provide a transition to a hydrogen-based refueling system. Figure 14. DOE’s fuel strategy for fuel cells

Figure 14. DOE’s fuel strategy for fuel cells is fuel- flexible and emphasizes domestic energy sources.

Desirable characteristics of fuels for fuel cells include high hydrogen to carbon ratios which lead to high conversion efficiencies (see Table 4) and high hydrogen content in the fuel stream. High oxygenate concentra-

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tions and low aromatics tend to reduce coke formation and fuels containing no sulfur eliminate the requirement for on-board removal systems. Another important consideration is that the type and size of hydrocarbon molecules in the fuel can influence the ease of reforming. 5

Fuel cells do not require pure hydrogen to operate efficiently and it is acceptable for reformate to contain substantial carbon dioxide, water, and nitrogen concentrations. However, reformate cannot contain impurities or contaminants that poison the anode. As a result, fuels for fuel cells must contain very low levels of contaminants and must be sufficient to preserve catalyst activity for more than 100,000 miles.

Table 4. Theoretical Fuel Conversion Efficiencies as a Function of Hydrogen-to-Carbon Ratios.

Efficiencies as a Function of Hydrogen-to-Carbon Ratios. An important new aspect of the DOE Fuel Cells

An important new aspect of the DOE Fuel Cells for Transportation program is determining the effects of fuel constituents, additives, and impurities on the performance and durability of fuel processors and fuel cell stacks. ANL and LANL are examining petroleum- based and alternative fuels (methanol, ethanol, dimethyl ether, and Fischer-Tropsch liquids) to identify appropriate fuel compositions for use with fuel cells. ANL is conducting autothermal reforming of major constituents in a microreactor to examine by-product formation, catalyst deactivation, and the dependence of hydrogen yield and conversion efficiency on reactor temperature and residence time. LANL is exploring fuel processing reactions with reacting (catalyzed) surfaces and with homogenous (non-catalyzed) mixtures. LANL has also successfully completed its studies on mitigating the effect of certain impurities and constituents on fuel cell stacks, including ammonia, methane, hydrogen sulfide, chloride, aromatics, and olefins.

Sulfur poisoning is one of the biggest issues facing the use of petroleum-based fuels in fuel cell systems. Gasoline sold at the present time in the United States has an average sulfur content of 347 ppm with spikes as high as 1000 ppm. In December 1999, the Environmental Protection Agency announced that the sulfur content of gasoline must be reduced to 30 ppm with a maximum of 80 ppm by year 2004. In the reducing environment of the fuel reformer, the organic sulfur in

gasoline is converted primarily to hydrogen sulfide (H 2 S). For autothermal reforming, the concentration of H 2 S resulting in reformate is approximately one-tenth the sulfur content of the fuel. However, even 3 ppm of sulfur poisons many catalysts, including many envisioned for the fuel processing chain. For example, a maximum concentration of 50 ppb is recommended for copper-zinc oxide catalysts for the water-gas shift reaction.

oxide catalysts for the water-gas shift reaction. Figure 15. The graph illustrates the weight of ZnO

Figure 15. The graph illustrates the weight of ZnO required to lower H 2 S concentration in reformate to less than 1 ppm based solely on ZnO loading capacity.

Tests at ANL are demonstrating that catalysts for autothermal reforming do have some tolerance to sulfur. Initial tests with premium gasoline and diesel fuel show no degradation during short-term testing (of 8 to 20 hours); 20-hour testing with iso-octane containing 300 ppm and 1000 ppm sulfur support these earlier results. However, H 2 S is known to irreversibly poison the platinum anode in fuel cell stacks at concentrations of 1 ppm. Therefore, it may be necessary to remove H 2 S from reformate even when using low sulfur gasoline.

ANL is investigating adsorption with chemical reaction for reducing H 2 S concentrations to below 1 ppm in reformate. Here, H 2 S is reacted with a solid, generally a metal oxide, which “traps” the sulfur by converting it into a stable metal sulfide. Zinc oxide (ZnO) is a candidate adsorbent due to favorable equilibrium thermodynamics for zinc sulfide (ZnS) formation with a H 2 S equilibrium partial pressure of less than 1 ppm under typical fuel processing conditions. ZnO is used in many industrial processes, including ammonia synthesis, to reduce H 2 S concentrations to as low as 50 ppb.

Based solely on the loading capacity of ZnO, Figure15 illustrates the weight of ZnO required for a sulfur adsorption bed for an automotive PEM fuel cell processor using gasoline with different sulfur concentrations. However, to appropriately size an adsorption bed, mass transfer and chemical reaction rates that depend upon space velocity and power rating must also be considered (see Table 5). For a bed based on peak power (50 kW e ), approximately 10 times more ZnO is required than based solely on loading capacity. When sized for average power (10kW e ), ZnO requirements are approximately the

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same as those when based on loading capacity. At the present time, long-term performance has not been established for a sulfur adsorption bed based on average power with periodic operation at peak power. In response, ANL is researching ways to improve the rate of H 2 S uptake by ZnO and is determining the optimal power rating on which to base the size of the absorbent bed while still meeting size and weight constraints established for fuel processors for automotive PEM fuel cell systems.

Table 5. The Weight of ZnO Required to Lower H 2 S Concentration in Reformate to less than 1 ppm for Commercial ZnO Adsorbents Based on Power and Space Velocity

Commercial ZnO Adsorbents Based on Power and Space Velocity COSTS OF FUEL CELL SYSTEMS – Another

COSTS OF FUEL CELL SYSTEMS – Another prime challenge for fuel cells is to reduce the cost of components and subsequently of integrated fuel cell power systems from today’s $300/kW to the program target of $50/kW for high volume production. Membrane electrode assemblies (MEAs) are the core of the fuel cell stack and require very high quality and production yields to achieve automotive cost and performance targets. The 3M Company is developing novel MEAs based on nanostructured thin film catalysts and support systems. Figure 16 shows a scanning electron micrograph of the company’s high-surface-area, catalyst-coated nanostructure supports before transfer to a PEM surface to form a 3-layer MEA. Most importantly, the 3M Company is developing MEAs in parallel with high volume process development to meet the PNGV cost target of $10/kW. 3M is also developing proprietary catalysts based on the nanostructured films for optimized CO tolerance. Figure 17 illustrates the performance comparison of a platinum ruthenium (PtRu)-based system operating on pure hydrogen and 50 ppm carbon monoxide with a 0.5 percent air bleed.

and 50 ppm carbon monoxide with a 0.5 percent air bleed. Figure 16. A scanning electron

Figure 16. A scanning electron micrograph shows 3M’s nano-structured catalyst-coated film.

Figure 17. This chart shows the performance comparison of 3M CO tolerant anode catalyst based

Figure 17. This chart shows the performance comparison of 3M CO tolerant anode catalyst based on microstructured films using pilot production processes.

One of the most expensive components in the fuel cell stack system is the solid graphite, bipolar separator plates. The Institute of Gas Technology (IGT) is developing low-cost, compression-molded, carbon composite bipolar separator plates and a conceptual design for their mass production. IGT has successfully selected, blended, and optimized inexpensive raw materials to meet or exceed all electrical, chemical, and physical property targets. As shown in Figure 18, the performance of the molded composite bipolar separator plates (300 cm 2 ) is comparable to state-of-the-art machined graphite plates. At a production level of 500,000 units per year, the program goal of $10/kW is expected to be met. The raw material cost is estimated at $1.46 per pound accounting for $4/kW. IGT has transferred this bipolar plate technology to Stimsonite, which has fabricated molds for pilot production and joined with ENDESCO in a joint venture called PEM Plates, LLC.

with ENDESCO in a joint venture called PEM Plates, LLC. Figure 18. The performance of an

Figure 18. The performance of an IGT molded graphite bipolar separator plate is similar to that of a machined graphite plate.

In 1999, Arthur D. Little developed a comprehensive cost estimate for a 50 kW PEM fuel cell system for passenger vehicles based on technology available in year 2000 and assuming high production volumes (500,000 units per year). This cost estimate for the baseline system is the first part of a multi-year effort to assess the impact and progress of technology advances on overall system

costs. The first step in the process was to define a plausible configuration for the fuel cell system and realistic operating parameters on which to base the cost estimate. An overall system efficiency of 35-40 percent and water self-sufficiency were required, which had a strong influence on the design and specification of the system (see Figure 19). Table 6 presents the system parameters chosen which led to a projected overall system efficiency of 37.1 percent at peak power based on lower heating value. The actual drive cycle efficiency could be higher depending on the efficiency of the compressor/expander at partial load. Table 7 shows the allocation of components to the fuel processing and fuel cell sub-systems, as well as balance-of-plant.

and fuel cell sub-systems, as well as balance-of-plant. Figure 19. PNGV requirements for high system efficiency

Figure 19. PNGV requirements for high system efficiency and water self sufficiency impacted the configuration of the fuel cell system.

Table 6. PNGV Requirements and DOE Specifications Established Many System Parameters and Design Goals for the Cost Model

System

System

Requirements

Requirements

Fuel Cell

Fuel Cell

Module

Module

Fuel Cell Stack

Fuel Cell Stack

Fuel Fuel flexible flexible

(gasoline) (gasoline)

50kW 50kW

net net

e

e

0.8 volts per

0.8 volts per

cell

cell

System System efficiency efficiency

35-40% 35-40%

Water Water self- self-

sufficiency sufficiency

3 3 atmosphere atmosphere

operation operation

Turbocompressor Turbocompressor / /

expander expander

300

300

volts @

volts @

full

full

power

power

80°C

80°C

Reforma

Reforma

te fuel

te fuel

310 mA/cm 2

310 mA/cm

2

current

current

density

density

One cooling

One cooling

plate per cell

plate per cell

Total power

Total power

56

56

kW

kW

e

e

85% H 2

85% H

2

utilization

utilization

Specified by DOE

Specified by DOE

Established during

Established during

technology assessment

technology assessment

The factory cost estimate of the fuel cell system and components includes fixed and variable manufacturing costs, but excludes corporate expenses (e.g. R&D, sales, marketing, G&A) and profits. A bottom-up manufacturing model identifying critical manufacturing operations was used to estimate the cost of major fuel processor and fuel cell components. The cost of the balance of the system components (e.g. heat exchangers, control valves, sensors) is based on discussions with suppliers. The cost of components such as valves and sensors not readily available nor currently suitable for high-volume production are based on best estimates by Arthur D. Little.

10

Table 7. The Allocation of Components to the Various Subsystems for Estimating Fuel Cell Costs

Fuel Fuel Processor Processor Subsystem Subsystem

Fuel Fuel Cell Cell Subsystem Subsystem

Balance-of-Plant Balance-of-Plant

Reformate Reformate Generator Generator

Autothermal Reformer

Autothermal Reformer

Hi gh

Hi gh

Shift

Shift

Temperature

Temperature

Sulfur Removal

Sulfur Removal

Low Temperature Shift

Low Temperature Shift

Steam Generator

Steam Generator

Air Preheater

Air Preheater

Steam Superheater

Steam Superheater

Reformate Humidifer

Reformate Humidifer

Fuel Supply

Fuel Supply

Fuel Pump

Fuel Pump

Fuel Vaporizer

Fuel Vaporizer

Fuel Cell Stack (Unit

Fuel Cell Stack (Unit

Cells)

Cells)

Stack Hardware

Stack Hardware

Fuel Cell Heat

Fuel Cell Heat

Exchanger

Exchanger

Compressor/

Compressor/

Expander

Expander

Anode Tailgas Burner

Anode Tailgas Burner

Sensors & Control

Sensors & Control

Valves

Valves

Startup Battery

Startup Battery

System

System

Controller

Controller

System

System

Packaging

Packaging

Electrical

Electrical

Safety

Safety

Reformate Conditioner

Reformate Conditioner

NH 3 Removal

NH

Removal

3

PROX

PROX

Anode Gas Coller

Anode Gas Coller

Economizers (2)

Economizers (2)

Anode Inlet Knockout

Anode Inlet Knockout

Drum

Drum

Water Supply

Water Supply

Water

Water

Separators (2)

Separators (2)

Heat Exchanger

Heat Exchanger

Steam Drum

Steam Drum

Process Water

Process Water

Reservoir

Reservoir

Sensors & Control Valves for each section

Sensors & Control Valves for each section

The cost modeling indicates that the overall system cost for baseline year 2000 is $14,700 or $294/kW. The cost of the fuel cell subsystem represents 60 percent of the overall system cost and the fuel processor subsystem about 30 percent, while the balance-of-plant and assembly account for the rest (see Table 8). The fuel cell stack represents approximately 80 percent of the fuel cell sub-system cost, with the integrated tailgas burner ($465), compressed air supply ($860), and stack cooling system ($480) accounting for the remainder. The tailgas burner incorporates emissions control, steam generation, and fuel vaporization. The membrane electrode assemblies account for 75 percent of the total fuel cell stack cost (see Table 9). The precious metal content in the membrane electrode assemblies (Anode – Ru/Pt 0.2/ 0.4 mg/cm 2 ; Cathode – Pt 0.4 mg/cm 2 ; total of 180 grams of Pt per stack) accounts for 75 percent of the cost of the membrane electrode assemblies. The cost projection for the perfluorosulfonic acid membrane 6 is $50/m 2 , while the cost for injection molded bipolar interconnect plates 7 was estimated at $20/kW. Requirements for high efficiency operation leading to modest power density (250 mW/cm 2 ) is a major factor in the high stack cost. If optimized for high power output, the stack cost would be reduced by up to half. High power lowers the unit cell voltage but increases the current density resulting in a net decrease in fuel cell materials. The active volume is approximately inversely proportional to the power density.

Table 10 presents the cost break down for the fuel processing subsystem. Thermal, water, and steam management; controls; and packaging contribute 70 percent to the overall cost of this subsystem. Consequently, improved system design and engineering will be required to reduce the cost of peripheral systems in fuel processors, as well as improved catalyst technology to reduce bed size and extend life.

The Domination of Fuel Cell and Fuel

Processing Subsystems on the Total Cost of Fuel Cell

Systems

Table 8.

Subsystems on the Total Cost of Fuel Cell Systems Table 8. Table 9. Membrane Electrode Assemblies

Table 9. Membrane Electrode Assemblies are 75 Percent of Fuel Cell Stack Cost

Total Cost of Fuel Cell Systems Table 8. Table 9. Membrane Electrode Assemblies are 75 Percent

11

Table 10.

The Cost of Thermal, Water, and Steam

CONCLUSION

Management,

Processing Subsystem

Controls,

and

Packaging

for

the

Fuel

Processing Subsystem Controls, and Packaging for the Fuel Cost modeling indicates that materials and purchased

Cost modeling indicates that materials and purchased components make up approximately 80 percent of the total factory cost of the fuel cell system (based on high production volumes). Table 11 breaks down these components and materials by categories. Catalysts for stacks and fuel processing represent the largest material cost and are dominated by platinum (total Pt=210 g). Purchased components such as heat exchangers, sensors, valves, controllers, the compressor/expander, pumps, and motors contribute 20 percent to the total system cost. Simplifications in design and alternative technologies could potentially lower these component costs. The next phase of the cost modeling will focus on opportunities for cost reduction achievable through technology improvements such as reduced precious metal loadings, increased fuel cell power density and fuel processing catalyst activities, and higher temperature membranes.

Table 11. The Cost of Purchased Materials and Components for the Fuel Cell System

Purchased Materials and Components for the Fuel Cell System The Department of Energy is working cooperatively

The Department of Energy is working cooperatively to address key challenges facing the development of technologies for CIDI engines and PEM fuel cells for the up-to-80 mpg production prototype vehicle of the PNGV. The most significant challenge facing CIDI engines is to reduce emissions of both particulates and NO x by up to 90 percent. Research data indicates that aggressive fuel modifications have the potential to reduce particulate emissions by up to 50 percent. As such, it has become clear that fuel modifications must be synergistically combined with emissions control systems (such as particulate traps) to achieve targeted particulate levels. With regards to lean NO x catalysis, recent research data indicates significant progress is being achieved. This data shows the potential for 80 to 100 percent NO x conversion over a broad temperature range applicable to CIDI engines for light duty vehicles.

Improving fuel processing and reducing overall system costs are two primary challenges facing the use of PEM fuel cell technology in mass produced light duty vehicles. Researchers are closing in on achieving the targeted efficiency of 80 percent for fuel processors when operating on petroleum-based fuel. However, the effects of fuel constituents, additives, and impurities on the performance and durability of fuel processors and fuel cell stacks remains an issue, with sulfur poisoning being a primary challenge. A multi-year effort is underway to assess the impact and progress of technology advances on overall fuel cell system costs. Based on the results of the cost analyses, the DOE program will target technology improvements in those areas with the greatest potential for long-term cost reduction.

ACKNOWLEDGMENTS

The authors of this paper would like to recognize the significant contribution made by Eric Carlson of Arthur D. Little Corporation in providing the information and narrative on the cost estimate for the 50-kW PEM fuel cell system for passenger vehicles. The authors would also like to recognize the contribution of John P. Kopasz and Theodore Krause of Argonne National Laboratory for their information on Challenges of Working with Gasoline Fuels – The Sulfur Issue.

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Sutton, R., P. Davis, N. Vanderborgh, and S. Ahmed, Fuel Issues for Fuel Cell Systems, Windsor Workshop, Toronto, Ontario, Canada, June 8, 1999.

6. Bartelt, J. Satisfying the Commercial Requirements for Alternative Energy Applications, Workshop on Advanced PEM Fuel Cell Membranes and Membrane Electrode Assemblies for Non- Conventional Fuels, Clemson University, April 28,

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