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Development of Sensors for Automotive PEM-based Fuel Cells

Final Report
Reporting Period: 3/2002-9/2005 Principal Authors:

Brian Knight and Tom Clark


With William Buttner, Frank DiMeo, and Scott Swartz Date of Report: December 5, 2005 DOE Contract No. DE-FC04-02AL67616 United Technologies Corporation, Fuel Cells Division Thomas Clark: (860) 727-2287 Brian Knight: (860) 610-7293

Disclaimer This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Refer herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise.

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Table of Contents
Executive Summary ........................................................................................................................ 3 Objective.......................................................................................................................................... 4 Approach ......................................................................................................................................... 4 Objective.......................................................................................................................................... 4 Approach ......................................................................................................................................... 4 Accomplishments............................................................................................................................. 5 Introduction...................................................................................................................................... 5 Requirements for Physical and Chemical Sensors.......................................................................... 7 Initial Technologies Available for Chemical Sensing .................................................................... 9 Electrochemical......................................................................................................................... 11 Micro Electro Mechanical Systems (MEMS) ........................................................................... 12 Current Technology for Physical Sensing ................................................................................ 12 Task List........................................................................................................................................ 13 Performance Metrics ..................................................................................................................... 14 Program Tasks Performed By Team Members ......................................................................... 14 Task 1.1 Selection of Sensors ................................................................................................... 15 Task 1.2 Buildup of Test Facility ............................................................................................. 15 Task 1.3 Physical Sensor Testing ............................................................................................. 15 Task 1.4 Physical Sensor Modification / Retest ....................................................................... 15 Task 2.0 Chemical Sensor Development and Testing .................................................................. 16 Task 2.1.1 Selection of Gas Sensing Materials......................................................................... 16 Task 2.3 Sensor Performance Testing in IIT Benchmark Facility................................................ 19 Task 2.4 Chemical Sensor Evaluation .......................................................................................... 20 Sensor Testing............................................................................................................................ 20 Team Structure .............................................................................................................................. 21 Program Financials ....................................................................................................................... 23 Program Financials ....................................................................................................................... 23 Conclusions ................................................................................................................................... 24 ATMI ............................................................................................................................................ 24 IIT ................................................................................................................................................. 25 NexTech Materials, LTD .............................................................................................................. 25 Acknowledgements ........................................................................................................................ 26 Publications/Presentations ............................................................................................................ 27 Acronyms ...................................................................................................................................... 28 Appendices .................................................................................................................................... 29 4

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Final Report for DOE Sensors Contract DE-FC04-02AL67616

Development of Sensors for Automotive Fuel Cell Systems


Mr. Thomas Clark
UTC Fuel Cells 195 Governor's Highway South Windsor, CT 06074-2419 Phone: (860) 727-2287; Fax: (860) 998-9811; E-mail: tom.clark@utpwr.com

Mr. Brian Knight


United Technologies Research Center 411 Silver Lane East Hartford, CT 06108 Phone: (860) 610-7293; Fax: (860) 660-1204; E-mail: knightba@utrc.utc.com

DOE Technology Development Manager: Donna Ho


Phone: 202-586-5673; Fax: (202); E-mail:Donna.Ho@ee.doe.gov

Subcontractors
ATMI, Inc., Danbury, CT Illinois Institute of Technology (IIT), Chicago, IL NexTechMaterials, LTD, Worthington, OH

Executive Summary
The purpose of this program was to develop a suite of physical and chemical sensors for automotive PEM fuel cell applications that would allow for on-board control of a fuel reformer/PEM cell stack assembly. Average cost of the sensors was to be less than $20 in quantities of 200k/year. The program utilized a team approach, with primary project control through Mr. Tom Clark of United Technologies Corporation, Fuel Cells Division (UTC FC). Under UTC FC leadership, the team utilized the expertise and facilities of four subcontractors. Advanced Technical Materials, Inc. (ATMI) under the direction of Dr. Frank DiMeo, was utilized for their expertise on MEMS sensors. The Illinois Institute of Technology, with task lead by Dr. William J. Buttner, was utilized for sensor testing and sensor technology review. NexTech Materials, LTD, under the lead of Dr. Scott Swartz, was utilized for their expertise in electrochemical sensor development. United Technologies Research Center (UTRC), with program lead from Mr. Brian Knight, was used for overall coordination with the above subcontractors, interface with UTC FC, testing of physical parameter sensors and chemical sensors, and for program reporting and coordination with DOE. This project was performed over the period from April 2002 through September 2005. The total program budget was $3.7 million, with 80% ($3.0 million) provided by DOE, with cost share from ATMI and UTC FC. Initially, the DOE technology development manager was Dr. Nancy Garland (nancy.garland@ee.doe.gov), with technical advice provided by Mr. Robert Sutton (sutton@cmt.anl.gov). Early in the third year of this program, technical management was transferred to Dr. Donna Ho (Donna.Ho@ee.doe.gov). As detailed in the report and Appendices
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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

below, the overall objective of this program was met with great success. ATMI has developed H2 safety and stack sensors that are at the commercialization stage that meet the program goals. NexTech Materials has developed CO sensing technology that can detect 50 ppm level CO in a humid gas stream in the presence of 40% H2. Both ATMI and NexTech have demonstrated H2S detection, with NexTech demonstrating detection at 10 ppb; NexTech in the best position for commercialization of this sensor. Both teams have demonstrated ammonia detection at the 5 ppm level, although NH3 sensing was dropped from the list of required sensors in 2004. IIT tested all sensors as well as developed sensor technology on their own. In addition, IIT provided an extensive literature and vendor review of current sensing technologies that provided guidance throughout this program. In addition to overall coordination of sensor development with these vendors, UTRC evaluated and tested physical and chemical sensors. A final list of physical sensors needed to fulfill the program goals was developed after testing at UTRCs sensor test facility.

Objective
The objective of this effort was to develop technology and a commercial supplier base capable of supplying physical and chemical sensors required to optimize the operation of Proton Exchange Membrane (PEM) fuel cell power plants in automotive applications.

Approach
Two important aspects of DOEs overall fuel cell and hydrogen programs guided the approach used to execute this project. The first aspect is the difference in approach taken for chemical and physical sensors. The sensor state of the art is dramatically different between physical and chemical sensors. Physical sensors, in general, are more highly developed due to their application in a wide variety of industrial and commercial processes. As a result, the focus was on surveying, evaluating and specifying commercial off-the-shelf (COTS) devices suitable for use in PEM fuel cell systems. Chemical sensor technology for the target compounds, environments, operating conditions and cost targets does not exist. As a result, this project focused on development of the required chemical sensing technologies. This also helped drive the second aspect of the approach, which is the teaming arrangement used to conduct the work. UTC manufactures fuel cells, not sensors. To ensure success, a team was formed for this work, comprised of UTC Fuel Cells (along with UTRC), two for profit corporations whose mission is to develop, produce and market sensor technology to industry, ATMI, Inc. and NexTech Materials, and Illinois Institute of Technology (IIT), a technological academic group capable of independent evaluation of sensors developed and identified for PEM fuel cell applications. Each member of the team brings expertise critical to achieving the difficult goals. UTC FC is a world leader in the fuel cell industry, having developed and produced the PC25 and the S200 PEM fuel cell and presently maintains over 300 installed PC25 systems. ATMI and NexTech are leading developers of high performance chemical sensor technologies. IITs Sensor Research Group has a major research commitment in electrochemistry at the center for Electrochemical Science and Engineering, and has expertise in electrochemistry, catalyst preparation, battery technology, fuel cells, electrochemical sensors and electrochemical processes.

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Accomplishments
Designed and constructed physical and chemical sensor test facility for simulated reformer gas stream. Developed lower explosion limit (LEL) sensor for H2 that meets cost and technical goals. H2 (LEL) sensor is ready for commercialization. Developed Stack H2 sensor with dynamic response of less than 2 seconds in humid gas streams containing up to 70% H2. Demonstrated 5 ppm CO sensing in humid gas stream in the presence of 40% H2. Demonstrated H2S sensing at 10 ppb level with new sensing technology. Demonstrated Ammonia sensing technology at 5-ppm level at 75C. Completed physical sensor survey and candidate sensor evaluation.

Introduction
The present state-of-the-art in fuel cell power plant sensor technology is embodied in the United Technologies Corporation, Fuel Cell Division (UTC FC) PAFC PC 25 and PEM S200 power plants. Sensors measuring all of the parameters defined by DOE are utilized in designing and setting up these power plants. However, none of the chemical sensors, and only a very few of the physical sensors are on - board the power plant, and only temperature and stack differential pressure, in the S200, are measured continuously for control purposes. Production automotive fuel cell power plants require all of these sensors to be on board the power plant, and to provide data signals on a continuous basis to optimize fuel cell operation and to protect the cell stack from damage. Table 1 below provides a comparison of the sensor requirement for the PEM power plant versus the requirement for the current baseline products, the PC25 and S200 fuel cell power plants. For each power plant, the first column indicates the location of each sensor and the frequency with which that sensor is utilized. The final column associates a gap, from Table 2 below, between the current state of the art and the PEM systems that are under development. Table 1
Analyte CO H2 Sulfur Compounds Ammonia Oxygen H2 Flow Temp Humidity Diff Pressure PC25/S200 Req. No No No No No No On Board No/Cont. No/Cont. Freq. NA NA NA NA NA NA Cont On Board On Board PEM Req. On Board On Board On Board On Board On Board On Board On Board On Board On Board Freq Cont Cont Cont Cont Cont Cont Cont Cont Cont Gap(s) 1,2,3,4 2,3,4 1,2,3,4 1,2,3,4 3,4 3,4 3,4 3,4 3,4

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Table 2 identifies the nature of the gap that must be overcome to make the measurement in the PEM environment, and summarizes the anticipated difficulty of the associated effort. The gap can range from the need for a totally new measurement principle to adaptation of existing principles to account for various deficiencies, as per the table. An entry of yes in a table element indicates that resources must be directed toward that need. An entry of no means that the basic capability exists in available technology and resources were not to be directed toward that need within the scope of this project. Table 2 Gap 1 2 3 4 Degree of Difficulty 1= Low, 5 = High

Gap Adjustment CO H2 Sulfur Gas Ammonia Oxygen H2 Flow Temp Humidity Diff Pressure

New Measurement Principle Yes No Yes Yes No No No No No

Adapt to Continuous Operation Yes No Yes Yes No No No No No

Adapt for Fuel Environment Yes Yes Yes Yes Yes Yes Yes Yes Yes

Adapt for Cost Yes Yes Yes Yes Yes Yes Yes Yes No 5 3 5 5 2 2 1 2 2

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Requirements for Physical and Chemical Sensors Table 3. Requirements of CO Sensors for Different Operational Regimes
Operational Temperature Response Time Gas Environment Accuracy

Sensor Types 1 100 ppm reformate (pre-stack) 100 1000 ppm (reformer exhaust) 0.1 2 % (inside reformer)

< 150 C

0.1 1 sec

250 C

0.1 1 sec

250 C 800 C

0.1 1 sec

High humidity & reformer exhaust. 2. H2 at 30 75 %. 3. CO2, N2, H2O at 1 3 atm total pressure, trace NH3, H2S, HC.

1.

1 10 % full scale

* based on:DOE Workshop; Sensor Needs and Requirements for Fuel Cells and CIDI/SIDI Engines," Robert S. Glass, Ed., published by LLNL, April, 2000.

Table 4. Requirements for H2 Sensors


Operational Temperature

Sensor Types

Response Time

Gas Environment 1 3 atm total pressure, 10 30 mol % water, total H2 at 30 75 % in CO2, N2 and trace NH3, H2S, HC. Ambient air, 10 98% relative humidity

Accuracy

1 100 % H2 Product gas (prestack)

70 150 C

0.1 1 sec

1 10 % full scale

1 % H2 Safety sensors* (in cabin air)

-30 80 C

< 1 sec

5%

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Table 5. Requirements for Oxygen Sensors


Oxygen Sensor Types Measurement Range Operational Temperature Response Time Accuracy Gas Environment High humidity and reformer exhaust. H2 at 30 75 % with CO2, CO, N2, H2O at 1 3 atm total pressure

Fuel processor reactor control (in reformer just downstream)

0 20 %

200 C 800 C

< 0.5 sec

2 % of full scale

Cathode exit (rear-stack)

0 50 %

30 C 110 C

< 0.5 sec

1 % of full scale

H2, CO2, N2, H2O at 1 3 atm total pressure

* based on:DOE Workshop; Sensor Needs and Requirements for Fuel Cells and CIDI/SIDI Engines," Robert S. Glass, Ed., published by LLNL, April, 2000. Table 6. Requirements for Other Gas Sensors
Measurement Range Operational Temperature Response Time Gas Environment H2, CO, CO2, water vapor and trace NH3, H2S, HC

Sensor Types Sulfur-containing molecules sensors (reformer exhaust or pre-stack)

0.05 0.5 ppm

< 400 C

< 1 min at 0.02 ppm

Ammonia gas sensor (pre-stack)*

1 10 ppm

70 150 C

seconds

High humidity and reformer exhaust, H2 at 30 75 % CO2, CO, N2, H2O at 1 3 atm total pressure and trace NH3, H2S, HC.

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Current Sensing Technology for Other Gases Sulfur-containing compounds. Electrochemical H2S sensors & Spectrometric methods are not designed for the fuel cell environment. Elimination of sulfur in the liquid fuel would reduce the need for this sensor. Ammonia gas. MOS sensor, electrochemical sensor, IR spectroscopy and surface acoustic wave devices are not designed for fuel cell environment and require design and validation. Table 7. Requirements: Physical Parameter Sensors
Sensor Types Measurement Range Operational Temperature Response Time Accuracy Gas Environment

Flow rate sensors (instack)

30 300 L/min

80 C

N/A

N/A 1.5 % at -40 100 C 2% at 100 150 C

Temperature sensors (pre-stack, ambient)

-40C / +150C

N/A

Relative humidity sensors (pre-stack, ambient) Differential pressure sensors* (pre-stack)

20 100 %

30 C 110 C

< 0.5 sec at -40 100 C < 1 sec at 100 150 C

High humidity and reformer exhaust. H2 at 30 75 % with CO2, CO, N2, H2O at 1 3 atm total pressure and trace NH3, H2S, HC.

1% 0 1 psig (or 0 10 & 1 3 psig) 30 C 100 C with -40 C survivability

< 1 sec

1%

* Size: 1 square inch and without orientation problem * Must be able to withstand and measure both liquid and gas phases Initial Technologies Available for Chemical Sensing CO is routinely measured by taking a gas sample and transporting it to laboratory instruments such as a fast gas chromatograph (GC), an analog non-dispersive infra red analyzer (NDIR), or fast Fourier transform infrared spectrometer (FTIR).

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Hydrogen analysis is often made by taking a gas sample and utilizing a thermal conductivity detector (TCD) on a GC. Hydrogen concentration can be measured by various techniques. DCH Technology makes a continuous hydrogen sensor based on technology developed at Sandia National Labs, which has shown promise for use in the laboratory evaluation, but has not yet been shown to provide continuous operation in this environment or rapid response. A typical time constant of about 20 seconds has been observed by UTC FC laboratory staff with DCH sensors. The team evaluated DCH sensors in the Benchmark Facility, but ATMI developed an H2 sensor during this program that provided better sensitivity, faster response, and better selectivity than the DCH sensor. Sulfur gases are usually measured by FTIR, chemiluminescence and fluorescence methods utilizing laboratory instrumentation. Samples of the gas stream can also be analyzed in a laboratory by means of its reaction with a tape impregnated with lead acetate. Since the infrared absorption of these gases is weak, NDIR methods are difficult to use. Ammonia is difficult to measure via NDIR methods due to the interference with water at the analytical line at 743 cm-1. Instrumentation such as the Thermo Electron Company ammonia analyzer is routinely used in the laboratory work with gas samples. Oxygen is easily measured with paramagnetic analyzers, thermal conductivity analyzers using passivated filaments or zirconia sensors. Zirconia sensors are commonly used in automotive exhaust sensing, but have a narrow operating range near stoichiometric. While the technical capability to make measurements of each of these parameters exists, extension of conventional technology to the PEM fuel cell environment is cost prohibitive. None of the laboratory type instruments is capable of continuous on board operation. All require frequent calibration, well-controlled environmental conditions, and a highly skilled operator. The technologies in most cases are not amenable to modification for the PEM application. Table 2 indicates the sensor technology modification that is required to meet the requirements of Table 3.2 and 3.3 of the SFAA. Low cost sensors for the target species in a pure compound in a pure air situation are available. However, cross sensitivity, or interference, with non-target analytes can either mask or simulate the response to a target analyte. In the case of CO in a hydrogen environment, sensors which might meet the cost target (metal oxide semiconductor sensors, for example) cannot discriminate between the two gases. The measurement of hydrogen, especially in the ambient environment, is also problematic, because many other compounds which might be expected in ambient air will produce a response in a hydrogen sensor. Some, may, in fact, produce an opposite or masking response, such as NO2 in a metal oxide semiconductor sensor. At this time, no fast, sensitive, stable and low cost ($1 $10 per unit in quantity) sensors are available for detection of the contaminant compounds in this environment. The measurement technology used by the PC 25 and S200 off-line chemical analyzers cannot be adapted to provide the basis for on-board, continuously measuring chemical sensors. UTC FC and its team members have identified three candidate technologies that we believe have the potential to achieve these goals.
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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

The sections below discuss each technology that we used to develop the required capability. Each of the team members developing a technology brought with it specific background capability which was used as a platform for advancement. Electrochemical Electrochemical sensing is based on the interaction of an electrically conductive film with a molecular species in its environment. Typically an inorganic film is deposited on a semi conducting film, which, in turn is deposited over a series of interdigitated electrodes. The temperature of the device is maintained at a predetermined temperature to facilitate the desired interaction. As the target compound adsorbs to the sensing film, a change in the conductance of the semi conducting film between the interdigitated electrodes is produced, sensed and a signal is generated for external use. One member of the UTC FC team, NexTech Materials, LTD, was the only group that has demonstrated the detection of ppm CO in a 50% hydrogen stream. Using this technique, NexTech Materials has been pursuing the development of low-cost CO sensors that will meet the requirements of the fuel cell application. NexTech has recently demonstrated this unique capability using CuCl thick films. The sensing approach is based on the change in electrical resistance that occurs when carbon monoxide is selectively adsorbed by an inorganic film of a semi conducting material. The sensing material is deposited onto a substrate with interdigitated electrodes, with temperature being controlled by a thick-film heater deposited on the underside of the substrate. NexTechs results have demonstrated that this resistance change occurs rapidly (with either increasing or decreasing CO content), varies with the amount of CO from the gas stream, is insensitive to the presence of hydrogen, and can be used to detect low carbon monoxide levels. This type of sensor has the potential to be manufactured at a cost of $5 to $10 in volume. However, these sensors were used at a single temperature and CO concentration in the range of 100 1500 ppm. More work was needed to determine the capability of this material for sensing CO at higher temperatures and/or higher CO concentration. Work to explore the range of operation of the sensor was accelerated under this program.

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Micro Electro Mechanical Systems (MEMS) Micro-Electro-Mechanical Systems is a method to produce microscopic three dimensional sensor arrays from a solid substrate. Sensing mechanisms such as the hydrogen-induced transition from a metallic di-hydride to a semi conducting tri-hydride can be deposited on a MEMS substrate. The reduced size, mass, subsequent thermal rise and fall times of the tiny devices, often called microhotplates, makes it possible to pulse the sensor to a desired operating temperature in milliseconds, make a measurement, and step to another measurement condition. Power consumption of such devices can be brought to very low values, response times can be in the sub second range and sensitivity controlled by the actual reaction taking place in the uppermost sensing film. The micro-hotplate gas sensor is a conductometric MEMS based sensor that uses the change in conductance of the sensing layer as a function of temperature and time to measure the gases present. A critical step in developing these gas sensors is the selection of a specific chemiresistive reactive layer for each target gas. ATMI has demonstrated the development of a high performance-low cost MEMS based H2 gas sensor, (US Patent, 09/231277, Allowed 2000). ATMIs MEMS based H2 selective gas sensors use Pd alloy coated metal hydrides as the gas sensitive layer. The sensing mechanism of these films is based on the reversible, hydrogeninduced transition from the metallic di-hydride compound to the semi-conducting tri-hydride compound. These sensors have shown over a 100% change in resistivity to 0.25% H2 in air, at response times of less than 0.5 second. UTC FC and its team members investigated each of these platforms as a technology for part of the chemical-sensing requirement of SFAA Table 3.2. No single platform is believed capable of addressing the entire chemical sensing requirement; therefore each of the team members developed its platform toward the program requirements. The goal was to develop at least one applicable technology for each species. Current Technology for Physical Sensing The state of development of physical sensor technology is dramatically different from that of the chemical sensors. Demand for high performance temperature, humidity and pressure sensors by the automotive and HVAC industries have resulted in a large variety of different sensors for designers to choose from. Consequently, the primary goal of this section of the effort was to evaluate and modify, as necessary, commercial off the shelf sensors to fill the need. The physical sensors used by the PC 25 and S200 physical power plants were used as the basis of onboard continuously measuring sensors. Additionally, it is possible that more recently developed sensors for measuring the same parameters may be a better starting platform than the PC25/S200 sensors. The team continually monitored the evolution of new physical sensors during the performance of this project.

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

The UTC FC team selected a baseline device for each sensor and confirmed its ability to fully meet the DOE specification. If there were any deficiencies we worked with the manufacturer to modify the sensor to conform. The potential limitations of each sensor were carefully evaluated in lab testing and subsequent on line testing if they successfully complete the lab testing phase.

Task List
The team executed the tasks of the WBS below. Each major task was assigned to one team member under the guidance of the UTC FC Principle Investigator as indicated in the WBS. At appropriate stages during the development of each subtask, the individual team met with the UTC FC PI to assess progress toward the milestones. Appropriate decision points were built into the performance schedule at which time, a team effort could be terminated by mutual agreement that the goal was not achievable.

Task
1.0 1.1 1.2 1.3 1.4 2.0 2.1 2.1.1 2.1.2 2.1.3 2.1.4 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.3 2.4 2.5

Table 8. Work Breakdown Structure (WBS) Description Owner


Physical Sensors Selection of Sensors Buildup of Test Facility Physical Sensor Testing Physical Sensor Modification/Retest Chemical Sensors Electrochemical Sensor Development Selection of Gas Sensing Materials Assessment of Transduction Techniques Sensor Response Optimization Prototype Fabrication and Testing MEMS Sensor Development Hydrogen Sensor Development Sulfur Compound Sensor Development Ammonia Sensor Development Sensor Integration and Prototype Fabrication BenchMark Facility Testing Simulated Reformer Stream Testing S300 Gasoline PEM FC Testing Brian A. Knight, UTRC Team Leader

Dr. Scott Swartz, NexTech Materials, Ltd.

ATMI, Inc. Dr. Frank DiMeo

IIT, Dr. William J. Buttner Brian A. Knight Thomas Clark

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Performance Metrics
The team members developed each sensor technology to stepwise levels of readiness. At each step of development where a sensor was constructed, a prototype embodying the then current state of technology was supplied to UTC FC for performance determination. UTC FC evaluated the sensor, initially in the IIT PEM Fuel Cell Benchmark Facility, and if appropriate in the UTRC reformate or cell stack gas simulator facility. Performance data collected in these tests was transmitted to the developer team and a meeting to evaluate results and consider design changes needed, if any, were conducted. When a sensor passed simulator tests and is determined to be robust and reliable enough for on line testing in a breadboard PEM fuel cell, a prototype was supplied to Mr. Thomas Clark at UTC FC or Brian Knight at UTRC. Performance results obtained on the breadboard tests were transmitted to the developer with recommendations for changes, if any. Program Tasks Performed By Team Members

Task 1.0 Physical Sensor Development and Testing, Mr. Brian A. Knight, Team Leader.
Table 9. Physical Sensor Development Tasks
Gap Gap Adjustment Oxygen H2 Flow Temp Humidity Diff Pressure 1 New Measurement Principle No No No No No 2 Adapt to Continuous Operation No No No No No 3 Adapt for Fuel Environment Yes Yes Yes Yes Yes 4 Adapt for Cost Yes Yes Yes Yes Yes 2 2 1 2 2 Degree of Difficulty 1= Low, 5 = High

The tasks below were used to evaluate the baseline technology for physical sensors relevant to the PEM environment. Table 9 above provides a high level summary of the goals and difficulty of achieving those goals for the physical sensors. As noted in the Technical Concept, the oxygen sensor effort is included here.

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

Task 1.1 Selection of Sensors


Physical sensor selection was based upon previous sensor technology that has been used at UTC FC for the PC25, S200 and fuel cell development programs. Selection of sensors required an interactive process with the sensor developers to be sure the starting platform has the highest probability of success.

Task 1.2 Buildup of Test Facility


The sensor testing was conducted in a facility in which gas mixtures could flow with or without humidity at temperatures specified in Table 3-3 of the SFAA. Mass flow meters were used to mix gases or specific custom-manufactured gas mixtures from the vendor were used. A test chamber, capable of operation to 3 atm, was constructed which enabled quick access to the sensors for easy maintenance and substitution. A PC running LabView controlled all aspects of the experiment including gas flows and temperatures and logged the data.

Task 1.3 Physical Sensor Testing


Physical sensors were tested for H2 flow, temperature, humidity, and differential pressure, all at atmospheric pressure. The flowrate of product gas was adjustable up to 300 SLPM. Sensor testing was conducted at low flows, with intervals of high flow to test sensor response and repeatability. Test conditions spanned the range specified in Table 3.3 of the SFAA.

Task 1.4 Physical Sensor Modification / Retest


In the course of testing the physical sensors, design flaws were identified that needed to be addressed. UTRC interfaced with the sensor manufacturer to obtain an appropriate modification. This did include switching to a different sensor manufacturer if the sensor originally chosen cannot be modified to withstand the environment or provide the accuracy needed for this program. A constant dialog between UTRC and the sensor manufacturer was maintained to optimize the sensor performance and minimize impact upon the program schedule if a sensor does not meet the design criteria.

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Task 2.0 Chemical Sensor Development and Testing


Table 10. Chemical Sensor Technology Gaps
Gap 1 2 3 4 Degree of Difficulty 1= Low, 5 = High

Gap Adjustment CO H2 Sulfur Gas Ammonia

New Measurement Principle Yes No Yes Yes

Adapt to Continuous Operation Yes No Yes Yes

Adapt for Fuel Environment Yes Yes Yes Yes

Adapt for Cost Yes Yes Yes Yes 5 3 5 5

In this section, the tasks to develop sensors for the chemical parameters in Table 3.2 of the SFAA are presented. The development of the chemical sensors proceeded along technology based tasks. Each major task proposed a technology which has potential to meet one or more requirements. The table at the beginning of each proposed technology indicates the chemical species that technology attempted to address. More than one technology was proposed to address each compound. These tasks proceeded in a competitive environment to assure that at least one technology would be developed to detect each species. Task 2.1 Electrochemical Sensor Development NexTech Materials, Inc. Principle Investigator, Dr. Scott Swartz Team Member NexTech CO X H2 SO2 X H2S X NH3 X

NexTech had already demonstrated sensitivity for ppm CO in the presence of hydrogen without interference from hydrogen concentration in the flow stream. Task 2.1 expanded the device capability to increase operational range and response speed, as well as to explore resistance to environmental conditions and drive cost down. This same platform was explored for the detection of sulfur gases and ammonia.

Task 2.1.1 Selection of Gas Sensing Materials Potential inorganic materials such as semi conducting metal halides, or oxides were tested to establish applicability for the detection of various gases within the specified concentration and temperature regime. Materials in pure as well as in composite forms were used in thick film format. Sensing units with candidate materials were set-up and tested for specific gases. Measurements were made in resistive mode during this task.
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Final Report December 5, 2005

Task 2.1.2 Assessment of Other Transduction Techniques Techniques other than resistance change with gas concentration were assessed to effectively screen the signal from one gas in presence of others. To address the need for sensors for many gases, the measurement of current-voltage (I-V) characteristics of suitable p-n junctions made from potential semiconducting oxide materials were evaluated. Enhancement of the signal for target gas(es) were investigated as a function of chemistry and process modification, geometry variation, and temperature modulation.

Task 2.1.3 Sensor Response Optimization Process parameters to deposit thin films of sensor materials (pure or two-phase composites in for resistive sensors or suitable p-n junctions for I-V sensors) onto suitable substrates with interdigitated electrode (IDE) arrays were optimized. The results obtained were used to determine the feasibility of sensor systems to be developed for each gas. These results were used to improve the overall behavior of the chosen materials. The usage of various techniques as well as materials in different formats (thick film, thin film, n-p junction, electrochemical mode, etc.) was exploited to optimize the response for each gas in the stream.

Task 2.1.4 Prototype Fabrication and Testing For each type of sensor, prototypes were developed integrated with the electronics and packaged as an -prototype. The sensor was first tested in the laboratory under simulated conditions, either at the sensor developer and then at IIT or UTRC. Task 2.2 MEMS Sensor Development ATMI, Inc. Dr. Frank DiMeo, Principle Investigator Team Member ATMI CO H2 X SO2 X H2S X NH3 X

ATMI, Inc. has already demonstrated and patented a new platform for hydrogen detection, the micro hotplate. Task 2.2 expanded on the capability of the system, which has been demonstrated, to increase operational range and response speed, to explore resistance to environmental conditions and drive cost down. This same platform was examined to explore capabilities for sensing sulfur gases and ammonia. Task 2.2.1 Hydrogen Sensor Validation

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The platform of the existing hydrogen sensor was used to expand the capability for hydrogen detection to the safety sensor as well as the reformer flow stream concentration measurement. Since the demonstrated technology meets many of these requirements, efforts focused on demonstrating the performance of the sensor under specific conditions. Film modifications to produce unique response as a function of concentration in the 25 75% H2 environment were investigated. To monitor such high levels of H2, the H2 permeable membrane layer required further development. Previous experiments indicated that film thickness and composition are the two most important parameters. They were adjusted to achieve the desired range of sensitivity.

Task 2.2.2 Sulfur Compound Sensor Development We investigated the use of ultra thin metal films (<50 nm) of Rh and Ir to detect gaseous sulfur compounds. These materials have been chosen because they are inert, have very low energies of oxide formation, and are known to form sulfur complexes. In addition, films of Pt, and Pd were investigated either alone or as alloying compounds. ATMI staff investigated metal thickness, morphology and operating temperature in the detection of sulfur compounds. Task 2.2.3 NH3 Sensitive Materials Selection We investigated two materials systems as NH3 specific reactive layers, catalyzed H2 sensors as well as metal sulfides (Cu2S, AgS, and AuS). The first approach was to add a catalyst layer (e.g. W, Pt) to the surface of the Pd/Hydride layers mentioned previously. At the appropriate temperature, the hydrogen disassociated from NH3 molecules should be detected by the underlying hydride layer. The second approach used stable metal sulfides, such as Cu2S, AgS, and AuS as the NH3 sensitive layer. During the third year of the program, ammonia sensor development was determined to be of low importance so work on this sensor was terminated. Task 2.2.4 Sensor Integration and Prototype Fabrication Individual sensors from the previous objectives were developed into and single sensor systems. Fuel-Processor sensors were developed as one package and reformate gas sensors were developed to be integrated into a separate package. Both single chip and multi chip module options were examined to investigate issues of signal interference, space utilization, durability and manufacturability. Prototype sensors were delivered to IIT and UTRC for evaluation.

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Task 2.3 Sensor Performance Testing in IIT Benchmark Facility Task 2.3.1 Analysis of Sensor Technology A thorough review of all sensor technologies that are candidates was performed. This included a paper review of the manufacturer specs, and in-depth analysis of the specs versus the goals of SFAA Table 3.2 and 3.3. The role of IIT was to understand the fundamentals of the candidate technology and methods to make the required screening measurements so that their interpretation
is directly relevant to the goals.

Task 2.3.2 Benchmarking Sensors


The first sensors for benchmarking were identified early in the technology review task and others followed within the first year as task one concluded. Candidate sensors were exposed to steady state environmental conditions up to the operational limits specified in SFAA Tables 3.2 and 3.3. Sensor response were logged versus time and exposure conditions and reported to UTC FC at the end of each test.

Task 2.3.3. Performance Analysis and Interface Design


IIT staff analyzed sensor performance, consulted with the supplier and UTC FC to determine what modifications were needed and possible. IIT analyzed circuit designs to assist the UTC FC team to achieve the optimum performance from sensors passing screening tests.

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Task 2.4 Chemical Sensor Evaluation, Mr. Brian A. Knight, Team Leader. Chemical sensor testing was conducted in the reformate or cell stack gas simulator facility. All candidate sensors resulting from work of team members were tested in this facility under conditions outlined in SFAA Table 3-2. During these tests, the sensors were installed in a chamber through which gases simulating an ATR exhaust stream (created by mixing gases, heating and humidifying as necessary, to obtain the desired composition) flowed. The tests operated continuously for 40 hours during which time a PC controlled and logged all test parameters, including gas composition and sensor output. For all the chemical sensors, the main gas environment flowing through the test chamber consisted of 30 to 75% H2, CO2, N2, H20 and CO at one atm pressure and appropriate temperatures per SFAA Table 3-2. For very low concentrations of test gases of interest, gravimetrically premixed gases were used. For all the chemical sensors, tests were conducted with two types of sensors in the test chamber based upon the operating conditions required. The gas flow was continuous, with intermittent ramps of total flow to check sensor response.

Sensor Testing
UTC FC evaluated the sensors described above in the appropriate test facilities, supplying a synthesized gas stream of known inlet gas composition, and determining the response accuracy of each sensor at the required operating temperature. By controlling the inlet gas composition and mass flow, a fixed reference was established to which the sensor response was compared as a function of time. This effort was conducted in UTRC, IIT, ATMI, and NexTech Materials facilities. Baseline sensor technologies taken from a combination of production PC25, S200 and fuel cell development laboratory applications were subjected to a series of performance, durability and cost reduction studies. Concurrent with this portion of the task, a detailed review of alternate sensors was conducted by IIT. New advanced solid state electrochemical and micro electro-mechanical system (MEMS) sensors were developed at NexTech, Inc and ATMI, which include new transduction principle development, new sensing materials and fabrication development, and sensor prototyping. Sensors were ranked according to their probability of successful test results. Initial qualification tests were conducted by IIT in the PEM Fuel Cell Benchmark Facility. These tests consisted of installation and exposure of baseline sensor technologies to precisely controlled temperature, humidity, pressure, and gas mixture conditions. Sensor response versus these parameters was logged. Second level testing was conducted at UTRC. During these tests, the sensors were installed in a chamber through which gases simulating an autothermal reactor (ATR) exhaust stream flow (created by mixing gases, heating and humidifying as necessary, to obtain the desired composition). The sensors were evaluated for accuracy, speed of response, cross sensitivity to non-target parameters and test gas parameters. The tests operate continuously during which time a PC utilizing National Instruments LabView software controlled and logged all test parameters, including gas composition, sensor output, and control safety systems. In some cases repetition of the above testing cycle was required due to non-performance of some sensors. If baseline sensors could not demonstrate the required performance, alternates were selected.
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H2 Sensors Development The H2 safety sensor was designed to operate in ambient conditions and detect H2 levels up to 4% in air. ATMI utilized their micro-hotplate design, shown in Appendix 3, as a basis for the sensor platform. Tests have validated sensor operation in temperatures from 30 to 80oC, with a response time of < 1 s. Humidity ranged from 10-98%. Selectivity from hydrocarbons was demonstrated with an accuracy of 5%. A five-year lifetime is predicted. Results are shown in Appendix 3. The pre-stack sensor has been tested with H2 concentrations ranging from 1-100% at temperatures ranging from 70-150oC. Response time (T90 ) demonstrated ranged from 0.1-1 s at 1-3 atm total pressure, 10-30 mole % water, with CO2 and N2 ranging from 30-75%, and an accuracy ranging from 1-10 % full scale. Sensor performance is discussed in Appendix III. CO Sensors Development NexTech Materials has developed SOFC-based sensor technology with electrodes engineered to respond to CO that shows reversible and quantitative response to CO in wet N2/H2 gas streams. Development is discussed in Appendix IV. Part of their sensor development focused on schemes to improve sensitivity for CO in the 0-100ppm range and testing cross-sensitivity to alternate syngas components. H2S Sensor Development NexTech Materials and ATMI have developed a metal oxide based chemi-resistor (not electrochemical) sensor that shows reversible and quantitative response to H2S as demonstrated in Appendix III and IV. NexTech evaluated various dopant schemes to reduce the temperature of operation. Their work focused on measuring lower sulfur concentrations and cross-sensitivity to individual syngas components. Team Structure A team was assembled to address the development and evaluation of physical and chemical sensors meeting the requirements listed above. Table 11 shows the breakdown of responsibilities for each of the team members.

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Team Member UTC FC UTRC ATMI IIT NexTech

T X X

P X X

RH flow O2 X X X X X X

CO H2 X X X X X

SO2 X X X X X

H 2S X X X X X

X X

NH3 Technological Expertise / Responsibility X Testing on S300 Breadboard X Testing in reformate simulator X Develop Using MEMS Silicon Microhotplate X Testing in Benchmark Facility X Develop Using Solid State Electrochemical

Table 11. Sensor Development Team Responsibilities The interaction of all team members can be shown graphically as below:

Figure 1. Sensor Program Team and Interactions UTRC has constructed a physical and chemical sensor test facility capable of subjecting candidate sensors to gas compositions simulating operation in a gasoline/natural gas-fueled reformer based fuel cell system. IIT is evaluating all sensors developed during execution of this project in their PEM fuel cell test facility. The UTRC facility design is shown in Figure 1 in Appendix I. NexTech Materials, Inc has multiple test platforms for development of

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electrochemical and solid-state sensors. ATMI has developed H2 safety and pre-stack sensors using a micro-hotplate design. Table 6 in Appendix I summarizes the results of the physical sensor survey and testing conducted at UTRC. The results shown indicate the candidate physical sensor technologies that have been selected that will meet the technical goals of the program. UTRC continued to search for new sensing technologies as the program progressed, and interacted with Honeywell Corporation in their sensor development efforts under their DOE-funded program.

Program Financials Project duration: 42 months (Apr 2002 September 2005) Total cost: $3.7MM; DOE cost: $3.0MM (80%) UTC Cost Share: $0.7MM (20%)

Figure 2. Overall Program Financial Status

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Conclusions
During the execution of this program, the following accomplishments have been made. They are summarized here by subcontractor.

ATMI
The goal of this project was to develop MEMS based solid state sensors for gas detection in the multi-component environments found in fuel cell applications. This project was initially divided into three tasks, based on the chemical composition of the detected gases: the development of H2 sensors (for both life safety and fuel cell stacks) using metal hydride systems; the development of sensors for sulfur compounds using ultra-thin metal films; and the demonstration sensors for NH3 using metal hydride and metal sulfide thin films. During the course of the program, the NH3 sensor became less critical to the overall objectives the larger fuel cell program, and was deemphasized. This project has achieved substantial success in each of its primary tasks

Life Safety Hydrogen Sensors


Multiple generations of rare earth hydride MEMS sensors were developed and successfully. As shown in this report, these sensors substantially meet the performance targets, especially with respect to speed and sensitivity of response.

Fuel Cell Stack Hydrogen Sensors


Much of the knowledge gained in the development of life safety sensors was readily applied to the development of fuel stack sensors, and multiple generations of new sensors were investigated. This included new sensor materials stacks consisting of Pd, Ir, and Rh quad-layer sensors. Of these new designs, the Pd quad stack operated at a temperature that is elevated with respect to the life safety sensor has been recommended as the leading candidate. This configuration substantial meet the performance targets

H2S Sensors
Similarly, the knowledge gained in the development of hydrogen sensors was readily applied to the development of H2S sensors, and multiple generations of new sensors were investigated. Through the use of ultra thin films of Rh, we have demonstrated the detection of 10 ppb H2S. This exceeded the original program goals, and even exceeded the new target of 50 ppb that was suggested during one of our program review meetings.

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IIT
The IIT Sensor Research Group developed a sensor test facility for evaluation of sensors in simulated fuel cell environments, and invited commercial manufacturers of sensor technology to submit sensors for testing. This testing was performed in confidentiality, and results reported to both the manufacturer and UTC. In addition, the IIT-SRG collaborated with several commercial groups in evaluation of sensor technology and development of new sensors for hydrogen as well as potential contaminants in the fuel stream sulfur gases and carbon monoxide. Several technologies were moved along in the development cycle as a result of this testing and collaboration, and at least one manufacturer is introducing a hydrogen detector which benefited from testing at IIT. The status of chemical sensors for fuel cell safety applications is encouraging. There are several sensors commercially available which meet the requirements for safety applications. In the area of fuel reformer and fuel streams, however, substantial work needs to be done. None of the sensors tested for reformer applications met all the specified requirements as packaged. There are several sensors, however, that have the performance criteria, if it can be packaged to meet the temperature range. The RKI sensor exhibits excellent performance over the range of conditions for which it was tested (0-2% Hydrogen, ambient-750C, 0- 95% RH [non-condensing], and 1-4 atmospheres). There were no visible effects of temperature, humidity, or pressure over this range, and no response to CO or hydrogen sulfide. This sensor should perform as an excellent safety sensor. For reformate and in-stream applications, the sensor in principle should be able to be made suitable: The ceramic catalyst is amenable to high temperatures. The packaging could be redone to replace the plastic and other ambient condition materials with materials compatible with high temperatures, and the linear range could be extended by appropriate geometry of the exposure/diffusion path. Several other sensors provided suitable performance for safety applications of hydrogen, but none were designed to handle the higher temperatures and low oxygen levels of the fuel stream. No sensors were found to be ready for OTC-use for H2S or CO measurements. The Peak Laboratories GC yielded excellent results for CO in a high hydrogen background, but this was a complete instrument requiring carrier gas, not a sensor.

NexTech Materials, LTD


During the course of this program, NexTech developed multiple techniques and materials sets for measuring ammonia, CO, and H2S in syngas environments. Numerous sensing platforms were developed for monitoring carbon monoxide. These included, mixed potential, chemical capacitor and resistor, and fuel cell sensors which all showed changes in signal output with changes in various CO concentrations. With proper selection of electrodes, the fuel cell and mixed potential sensors enabled the measurement of CO in simulated syngas environments
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between 250 and 500C. Chemical resistors and capacitors based on copper chlorides, bromides and alloys thereof were used to detect CO in dry nitrogen, hydrogen and syngas mixtures at temperatures between 40-100C. By compositing the metal-halides with high surface area metaloxides, enhancements in the sensitivity were achieved. However, all measurements in humid hydrogen, nitrogen and syngas mixtures resulted in a loss of sensitivity. Since the UTRC application required the detection of CO in humid syngas environments and removal of the water from the system would result in an increase in system complexity, all work with metal-halides was abandoned early in the program. However, during the later stages of research, it was suggested that it may be necessary to monitor CO in dry hydrogen due to the reactive nature of the most feasible hydrogen storage media. Thus, it appears that the metal-halide sensors may play a role in future hydrogen filling stations. Results from the mixed potential and fuel cell CO sensor development were much more promising. NexTech identified two key electrodes which exhibited a quantitative and reversible response to carbon monoxide in humid reducing environments. The lower limit detection limit of the mixed potential sensor was found to be 5 ppm, which is well within the required detection range for the PEM protection application. The fuel cell sensor while showing a high change in voltage with introduction of carbon monoxide actually has lower sensitivity when normalized to the baseline voltage. The use of YSZ requires a higher temperature of operation, but leads to issues of baseline drift due to electrode sintering. The critical issues with the carbon monoxide mixed-potential sensors include: o Response time, which may be improved through device miniaturization and electrode optimization (small crystallite size). o Baseline drift issues during device operation, possibly due to electrode sintering. o Poisoning issues with multiple cycles at high CO concentration. As noted above, the miniaturization of the CO sensor and reduction of the electrode size may result in faster response times. However, it is important to optimize crystallite size such that issues of baseline drift related to electrode sintering do not adversely affect the sensor performance. The poisoning issue is believed to be a result of the multiple exposures to high concentrations of CO. It is expected that the sensor will not be required to monitor this range of CO concentrations (500ppm) for the PEM fuel cell protection application since concentrations as a high as 10 ppm are known to poison the cell. Cross-sensitivity tests to methane and CO2 showed the sensor to be impervious to coking, making its use in the fuel processing application a real possibility.

Acknowledgements
The authors would like to acknowledge the financial and technical support of DOE during execution of this program. In addition, the efforts of the following persons are recognized as being invaluable to the successful completion of this program: ATMI Dr. Frank DiMeo, Philip S. Chen, James Welch, Jeffrey W. Neuner, Ing-Shin Chen.
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IIT Dr. William J. Buttner, Mel Findlay, Joseph R. Stetter, Nathan Schattke and Gu Hyun Chung. NexTech Materials Dr. Scott Swartz, Chris Holt, and Steve Cummings. UTRC Jeffrey Benoit, Lei Chen, John Hawkins, Heidi Hollick, Jim MacLeod, Gayle Marigliani, William Rioux, Salvatore Saitta, and Bernard Woody.

Publications/Presentations
1. DOE Sensor Program 4th Quarter Review, submitted March 5, 2003. 2. DOE Hydrogen & Fuel Cells Annual Program Review, May 19-22, 2003. 3. Development of Sensors for Automotive Fuel Cell Systems 2003 4th Quarter Report, submitted December 8, 2003. 4. DOE Hydrogen & Fuel Cells Annual Program Review, May 26, 2004. 5. FreedomCAR Fuel Cell Tech Team Meeting September 15, 2004, Detroit, MI 6. Development of Sensors for Automotive Fuel Cell Systems 2004 4th Quarter Report, submitted December 8, 2004. 7. DOE Sensor Program 4th Quarter Review, presented March 8, 2005. 8. DOE Sensor Program 4th Quarter Review, presented March 23, 2005. 9. DOE Hydrogen & Fuel Cells Annual Program Review, May 26, 2005. 10. DOE End-of-Program Review September 28, 2005 Washington D.C. 11. FreedomCAR Fuel Cell Tech Team Meeting, October 19, 2005 Detroit, MI.

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Acronyms AgS Silver Sulfide ATMI Advanced Technical Materials Incorporated ATR Auto-thermal Reformer AuS Gold Sulfide CO Carbon Monoxide CO2 Carbon Dioxide Cu2S Copper Sulfide H2 Hydrogen Water H2O H2S Hydrogen Sulfide IIT Illinois Institute of Technology Ir Iridium kW Kilowatt MEMS Micro Electromechanical System N2 Nitrogen NH3 Ammonia PAFC Phosphoric Acid Fuel Cell PEM Proton Exchange Membrane Psi Pounds per square inch Rh Rhodium RH Relative Humidity S300 Series 300 Fuel Processing and PEM Cell System Sulfur Dioxide SO2 UTC FC United Technologies Corporation Fuel Cells Division W Tungsten

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Appendices
I. II. III. IV. UTRC IIT ATMI NexTech Materials, LTD

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Appendix I Physical and Chemical Sensor Testing at UTRC


Reporting Period: 3/2002-9/2005 Principal Author: Brian Knight Date of Report: December 5, 2005 DOE Contract No. DE-FC04-02AL67616 United Technologies Corporation, Research Center Brian Knight: (860) 610-7293 knightba@utrc.utc.com

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Appendix I Table of Contents


UTRC Role ....................................................................................................................... 32 UTRC Test Facility ........................................................................................................... 32 Test Conditions from UTC FC and DOE ..................................................................... 33 Physical Sensors................................................................................................................ 34 Sensor Program Deliverables ............................................................................................ 37 Chemical Sensors Testing at UTRC ................................................................................. 38 Tests of H2Scan Hydrogen Sensor at UTRC ................................................................ 39 Results and discussion for the H2Scan Sensor ............................................................. 40 Initial H2 Sensing Technologies ................................................................................... 44 Hydrogen Sensor for anode exhaust: Tests and findings .................................................. 44 Semiconductor (MOS) Hydrogen Sensor ..................................................................... 49 Catalytic Bead Sensor ................................................................................................... 52 Electrochemical Sensor ................................................................................................. 53 Hydrogen Field Effect Transistor ................................................................................. 54 Fiber Optic Hydrogen Sensor (Chemo chromatic Type) .............................................. 55 Conclusion and Recommendation for alternate H2 Sensing Technologies ...................... 56 Hydrogen Sensor for Anode Exhaust: Tests and Findings ............................................... 57

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UTRC Role
During execution of this program, UTRC performed as a subcontractor to UTC FC. In its role, UTRC was responsible for physical and chemical sensor testing, as well as coordination of activities of the other subcontractors on the program. UTRC provided guidance to the sensor developers (ATMI and NexTech Materials) and interacted with IIT on sensor testing. All team members provided input for quarterly and annual reports, but UTRC was responsible for report assembly and submission. As a sister division of UTC FC, UTRC worked in concert with the program director to present all material as requested at technical reviews and program reviews with DOE.

UTRC Test Facility


Figure 1 shows a schematic of the test facility constructed at UTRC. With this test rig, we were able to mix gases to a precise concentration, heat the gas stream to a desired temperature, humidify the gas stream, and expose the test sensor to that gas. In order to provide for rapid or transient response testing, gas was flowed through a dummy chamber in order to establish flow stability. The chamber containing the sensor had a dry syngas flowing through it to establish a stable temperature with the appropriate H2/CH4/N2 background gas. Once stable conditions were established, the 4-way valve was switched and the sensor being tested was exposed to the species being evaluated. This allowed us to see sensor response time with minimal influence of the test facility dead volume on the sensor response. To perform repetitive sensor response tests, the 4-way valve was switched back and forth between the background syngas and the gas flow that contained the species to be sensed. This was all controlled via the LabView program that also acquired flow data and sensor response.

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MFC0 Metha ne N2+S O2 C O CO2 House H2 House N2 Water D.I. Exces s valve s To vent To vent NDIR MFC1 MFC3 MFC4 MFC5 MFC6 LFC

100 psi relief valve To vent Steam generat or NH3/SO2 generator 100 psi relief valve

Flow meter To vent Blower/ circulate

In vented cabinet

NH3 analyzer Back Ar House pressu H2 re regulat or GC

Condens er

Sensor chamb er

Switch valve

To vent Computer 2 (Analysis)

D/A , GPIB, data acquisition House Computer 1N2 (Control and data acquisition)

Dumm y chamb er To vent

Chamber temperature: 0~250C. Chamber pressure: 1~3atm

Figure 1. Test Facility used at UTRC

Test Conditions from UTC FC and DOE Operating temperatures: up to 150 C or 250 C; 800 C - maximum Gas environment: high humidity steam/autothermal / partial oxidation reformer gas H2, 30-75%, CO2, CO, N2, H2O at 1-3 atm total pressure Accuracy of the sensors: 1-10% full scale Response time test: 0.1-1 sec High Flow Rates up to 300 slpm

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Physical Sensors
Table 1. Overall Physical Sensor Status at Program Start Sensor
Humidity

Meet DOE/FC tech. specs


Most

Further effort
Validate new technologies (MEMS sensors) to improve the condensation recovery time. Collaborate with vendors to improve stability. Identify new technologies. Collaborate with vendor for miniaturization and significant cost reduction. Needs major development and modifications. Identify inexpensive thermistor for high temp. Improve response time.

Technical gap/stretch
Medium

Flow rate Differential pressure

Most Most

High High

Temperature

Most

Low

Table 2. Overview of Humidity Sensors Available Operating principle


Polymer capacitive Polymer capacitive

Vendor
Honeywell Sensirion

Operating specs
0 to 85 C, 0-100% RH 0 to 70 C continuous, to 120 C intermittent, 0100% RH 0 to 180 C, 0100% RH 0 to 85 C, 0-100% RH

Meet DOE/FC tech. specs


Most Most

Comments
Improve recovery from condensing and temp. range Improve recovery from condensing and temp. range Improve recovery from condensing Improve recovery from condensing and temp. range

Polymer capacitive MEMS strain gauge

Panametrics Hygrometrix

Most Most

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Table 3. Overview of Flow Sensors Available Operating principle


Ultrasonic vortex shedding Turbine

Disadvantages
Electrical noise can affect reading. Rotating machine, corrosion in the deionized water. Response fluctuation due to water condensation / evaporation Pressure drop too small to give needed accuracy

Meet DOE/FC tech. specs


Most Most

Comments
Improve electrical noise performance. Somewhat cost effective. Improve tolerance to DI water to improve life. Most cost effective. Improve tolerance to water droplets. Not applicable due to ambient operation.

Thermal dissipation

Most

Differential pressure

No

Table 4. Overview of Differential Pressure Sensors Available Operating principle


Strain gauge

Technology
Silicon based IC compatible fabrication. Can measure wide range differential pressure. Current dimension is big.

Meet DOE/FC tech. specs


Most

Comments
May be mass produced and miniaturized. Orientation is not a problem. Current application is not designed for fuel cells and thus price is high. Needs major development. Measurable pressure range is too low for fuel cells. Not applicable due to ambient operation.

Flow rate based Differential pressure

Can measure very small differential pressure from 100 Pa up to 1 psi.

No

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Table 5. Overview of Temperature Sensors Available Sensor technology


Thermocouple

Operating specs
40 to 1300 C

Meet DOE/FC tech. specs


Yes

Comments
Cost effective. Being used extensively in FCs for other applications. Accuracy does not meet spec. Response time needs improvement. More expensive than thermistors. Response time needs improvement Cost-effective. Need higher temp. (>=800C) for fuel processing system. Response time needs improvement.

RTD

-196 to 480 C

Yes

Thermistor

0 to 250 C, -40 to 750 C

Yes

Table 6. List of Physical Sensors Determined to Meet Program Requirements

Sensor Temperature

Operating Principle
Thermistor

Positive Attributes
0 to 250 C, -40 to 750 C Silicon based IC compatible fabrication. 0 to 180 C, 0100% RH Most cost effective

Development Needs
Response time needs improvement May be mass produced and miniaturized Improve recovery from condensing flow regime Response fluctuation due to condensation

Pressure RH Flow

Strain gauge (Druck) Polymer capacitive (Panametrics) Thermal dissipation

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Sensor Program Deliverables Physical Sensors Develop prototype flow measuring devices for measuring the flow rate of reformate or hydrogen into the fuel cell at 1-3 atm. total pressure. Develop prototype fast-response temperature sensors that operate in high humidity reformate streams that are insensitive to flow velocity. Develop prototype sensors to measure the relative humidity for the anode and cathode gas streams.

All physical sensors were purchased or borrowed from the vendors after a comprehensive survey was conducted and vendor interactions were pursued. The physical sensor evaluation was prioritized to address the issues concerning UTC FC. The validation work for flow meters and differential pressure transducers was emphasized. This was a continuing effort. In summary, the design proposed by GE Duck has the best potential for cost reduction from more than $1000 to about $150 each in the near term. The turbine flow meter will still be the most cost effective option and used dominantly against other types of meters. Thermal dissipation flow meters are also suitable for the fuel cell applications where humidified streams need not be measured. Among all the flow meters the costs are stable without much space for reduction in the near future.

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Chemical Sensors Testing at UTRC


Approach UTC FC evaluated the sensors described above in the appropriate test facilities, supplying a synthesized gas stream of known inlet gas composition, and determined the response accuracy of each sensor at the required operating temperature. By controlling the inlet gas composition and mass flow, a fixed reference was established to which the sensor response was compared as a function of time. This effort was conducted in UTRC, IIT and UTC FC facilities. Baseline sensor technology taken from a combination of production PC25, S200 and fuel cell development laboratory applications were subjected to a series of performance, durability and cost reduction studies. Concurrent with this portion of the task, a detailed review of alternate sensors was conducted. New advanced solid state electrochemical and MEMS sensors were developed at NexTech, Inc and ATMI, which include new transduction principle development, new sensing materials and fabrication development, and sensor prototyping. Appropriate sensors were ranked according to the probability of successful test outcome. Initial qualification tests were conducted by IIT in the PEM Fuel Cell Benchmark Facility. These tests consisted of installation and exposure of baseline sensor technologies to precisely controlled temperature, humidity, pressure, and gas mixture conditions. Sensor response versus these parameters was logged. Second level testing was conducted at UTRC. During these tests, the sensors were installed in a chamber through which gases simulating an ATR exhaust stream (created by mixing gases, heating and humidifying as necessary, to obtain the desired composition) flowed. The sensors were evaluated for accuracy, speed of response, cross sensitivity to non-target parameters and test gas parameters. The tests operated continuously during which time a PC utilizing National Instruments LabView software controlled and logged all test parameters, including gas composition, sensor output, and control safety systems.

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Figure 2. UTRC PEM Fuel Cell Gas Stream Simulator: Gas flow control system, steam generator, and test chamber Tests of H2Scan Hydrogen Sensor at UTRC Testing was conducted on an H2 sensor manufactured by H2Scan, Inc. The sensor was subjected to both dry and moisturized gas stream consisting of the same species (H2, CO, CO2, CH4, H2O, and N2); these tests were conducted for quantifying accuracy, repeatability and response time. In order to improve the system response time to minimize the interference of unsteady gas steam on the sensor response time determination, a four-way valve was used to divert the gas streams to the sensor adapter only after steady concentration and flow have been established. According to a CSTR (complete stirring tank reactor) model, the response time of the system is related to the gas flow rate and the volume of the vessel that the gas flows through. This relationship is given as

t 90 = 2.303

V m

where V is the volume of the vessel that the gas flows through, and m is the volumetric flow rate of the gas. The typical values for V and m are 16 cm3 and 600 to 800 sccm, respectively. Therefore the system response time is less than 3 seconds, which is

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negligible compared with the sensor response time required. The hydrogen concentration is roughly 3% for dry and moisturized tests (for dry gas its concentration is 3 % and the same flow rates for each gas was used for moisturized test and thus the hydrogen concentration is a little less than 3% due to the water added in the gas matrix). Among all tests, the metallic filter on the sensor head was not removed.
Results and discussion for the H2Scan Sensor

The sensor response time tested in dry gas stream show inconsistent results for two series of tests. The response time evaluated in the test shown in Figure 3 is between 40 to 50 seconds. In Figure 4, the sensor response in a wet gas stream is nearly 90 seconds. Compared with the sensor exposed to dry gas stream the sensor responds more slowly to the change in hydrogen concentration in moisturized gas mixture. Based on the most recent tests, however, the decrease in response time is marginal. The response time measured in the tests shown in Figure 4 is 103 seconds in average. Neither of them is acceptable based upon the specifications for the anode exhaust sensor defined by UTC FC. Ultimately, the H2 sensor developed by ATMI met the program goals and was the recommended sensor.
7 6 Sensor response (mA) 5 4 3 2 1 1500 H2 sensor

2500

3500

4500

5500

6500

Response time test in dry gas

Elapsed time (s)

Figure 3. H2Scan sensor response to 3% hydrogen in dry gas stream

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7 6.5 Sensor response (mA) 6 5.5 5 4.5 4 3.5 3 0 200 400 600 800 1000 1200 Elapsed tim e (s) response

Figure 4. H2Scan sensor response to ~3% hydrogen in humid gas stream (With average response time of 94 s) The sensor response time in dry gas mixture was tested again to check the reproducibility of the results. The porous metallic filter on the sensor head also was removed to identify the cause of the sluggish response time found in the past tests. According to the results, it seems that the sensor response time does not vary noticeably for the scenarios with and without the porous filter. This may eliminate the possibility that the filter can block the gas flow to the extent affecting the sensor response time. Interestingly, the sensor responds slightly more slowly for lower hydrogen concentration than for a little higher concentration. This is likely to result from the diffusion of hydrogen atoms in the sensing alloy. When the hydrogen concentration is higher, there is a higher concentration gradient. The greater concentration gradient results in faster mass transfer in the solid phase and thus shorter response time. However, for the hydrogen concentration that may be often encountered in the anode exhaust (0 to 4%), the variation of response time due to the difference of concentration gradient is not too high, and it may fall in the range of several seconds to 10 seconds range.

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8 H2Scan 7 H2 %

9 8 7 6 5

Sensor response (mA)

4 3

2 1 0

2 0 2000 In dry gas filter on, purge 480s/ 7-11-03 4000 6000 8000

-1 10000

Elapsed time (s)

Figure 5. H2Scan Response in Dry Gas with Filter On


8 H2Scan 7 H2 % 9 8 7

Sensor response (mA)

6 66s

50s

6 5

5 4

4 3 2 1 0

2 4000 4500 In dry gas filter on, purge 480s / 7-11-03

5000

5500

-1 6000

Elapsed time (s)

Figure 6. H2Scan Sensor Response with filter in place

H2 concentration (%)

H2 concentration (%)

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8 reference H2 cal %

10 9 8 7 6

7 Sensor response (mA)

5 4

3 2 1

2 0 2000 Filter removed in dry gas purge 480s 4000 6000 8000 Elapsed time (s)

0 10000

Figure 7. H2Scan Sensor Response with Filter Removed The sensor was subjected to both dry and moisturized gas streams consisting of similar species (H2, CO, CO2, CH4, H2O, and N2) for tests quantifying accuracy, repeatability and response time. Compared with the sensor exposed to dry gas stream the sensor responds more slowly to the change in hydrogen concentration in moisturized gas mixture. Based on the most recent tests, the decrease in response time is noticeable; it was measured as 103 seconds on average. This is not acceptable based upon the specifications for the anode exhaust sensor defined by UTC FC. The recovery time for the foregoing tests is roughly 140 seconds, which is obviously too long. The sensor was deemed not acceptable for this program. The dependence of sensor response to temperature was investigated. If the hydrogen atom diffusion in the solid-state film is the rate-determining step, both temperature and hydrogen concentration would affect the response time. However, the magnitude of this influence may vary with the range of the operating parameters. As far as the temperature variation encountered in the anode exhaust is concerned (60 degree C at most), the temperature dependent response time variation is negligible. We investigated the effect of the hydrogen concentration on the response time. This is complicated by both diffusion and the accumulated effect of the resistance change. Qualitatively, a greater concentration gradient may lead to faster response due to the greater driving force.

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Initial H2 Sensing Technologies Metal oxide semiconductors sensors, electrochemical sensors, thermal conductance, palladium thin film resistance sensors and acoustic sensors. Technologies need evaluation and validation. Operating temperature, cross sensitivity lifetime, accuracy, and cost not well known in automobile application. Integration of this sensor development program with the Commercial Beta Operability/Control Simplification program was designed to leverage the DOE funding with UTC FC sensor requirements. The objective of the control simplification task was to redesign the PC35 Beta control system to reduce the cost of sensors (e.g. pressure sensors) and actuators (e.g. control valves) and to improve power plant performance and operability (e.g. reduce the potential for plant shutdown during sudden load transients). The focus is on the FPS where controls and sensors are estimated to account for $10,582 (17%) of the total FPS cost.
Hydrogen Sensor for anode exhaust: Tests and findings

The candidate sensor consists of a palladium-nickel (Pd/Ni) thin film deposited on a silicon substrate. The lattice inherent in the Pd/Ni absorbs hydrogen atoms. As a result, the resistance of the Pd/Ni increases in direct correlation to the amount of hydrogen present. The durability of this sensor needs to be verified for this application.

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H2scan sensor calibration curve 5/13/2003

16 14 H2 concentration (%) 12 10 8 6 4 2 0 0 2 4 6 8 Current (mA) 10 12 y = 2.3935x - 9.3781 R = 0.9993


H2scan calibration
2

Figure 8 a, b. H2Scan Sensor Calibration and Photograph of Unit The factorial-design tests in a dry gas environment show temperature has a slight effect (-0.54) on the sensor response followed by flow rate (0.53) and methane concentration (0.08). The influences of temperature and flow may be caused by the exothermic effect of metal hydride formation. The flow rates investigated varied from 81 to 250 SCCM. Wide sensor response variation is expected when operating this sensor in an actual fuel cell power plant due to large flow variations. This needs to be investigated in the actual power plant. Temperature (26-62 C) and methane concentration investigated cover the most likely values to be encountered in the PC35 power plant and thus the influences of temperature and methane are not likely to be problematic.
12 10 H2 concentration (%) 8
Dry gas factorial design tests

6 26 C 4 2 0 0 1000 2000 3000 4000 5000 Elapsed time (s) 62 C

Figure 9. Dry Gas Factorial Design Test Program for H2Scan Sensor

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Condition A B C D

Flow rate + + -

CH4 conc. + +

The relative error of the sensor response in a dry gas stream is +/- 3.1% which meets the 0.2% absolute accuracy requirement for typical operations of PC35 defined by UTC FC . Durability test is performed by cycling hydrogen concentration and temperature to which the sensor is exposed.
45 40 H2 concentration (%) 35 30 25 20 15 10 5 0 0 20 40 60 80 100 120 140 Elapsed time (min)
sensor response actual (calculation)

31 C

68 C

31 C

Figure 10. H2Scan Sensor Response to Multiple Exposures to Test Gas Stream We then tested the alpha prototype hydrogen sensor fabricated by one of the subcontractors, ATMI, The hydrogen sensor was designed as a monitor to detect concentrations near the lower flammability limit. The actual detectable concentration range is from 0 to 2%. (Less than the 0 to 10% requirement specified in the DOE contract) It was found that the sensor did respond to the change in hydrogen concentration, however; the electronic noise was markedly large such that the sensor response was not valid for quantifying hydrogen concentration. These finds were communicated to Dr. Barry Chen and Frank DiMeo. They provided a solution by changing a microprocessor on the sensor signal conditioning board.

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To accommodate a critical request on the selection and qualification of a hydrogen sensor for PEM fuel cells, in substitution of a catalytic burner that was eliminated, we evaluated the sensors from H2Scan Inc. and Applied Sensor Inc. Based on the experiment results it was found that the H2Scan meets most of the requirements for this application except an unsatisfactory response time. As a result, a meeting with Dennis Reid of H2Scan and UTC FC engineers and managers was arranged and held at UTC FC. The people working on the bus program were particularly interested in the sensor and our findings. (The bus fuel cell power system utilizes the stored hydrogen as its fuel; hydrogen with high concentration in the exhaust is circulated for reuse). The discussion on this meeting motivated the modification of the sensor by the vendor. The response time of the H2Scan hydrogen sensor was improved to less than 15 seconds from this modification. This improvement qualified the sensor for fuel cell application. The sensor was adopted by UTC FC and installed on one fuel cell power plant. The cost of such sensor is still high (>$2000 each) though. Therefore, other less expensive sensors were investigated at the same time. Applied Sensor provides a field effect transistor (FET) prototype sensor for the measurement of hydrogen in the range of 0 to 5%. These sensors were tested in late 2003. The sensor package is small and convenient for installation. The sensor has an impressive response time (<15 seconds), but it suffers from poor resolution. The Applied Sensor unit seems to be not susceptible to the water content in the gas stream, which is a major problem for other sensors. Its response time is not compromised in a humidified gas stream relative to in a dry stream. The Applied Sensor unit costs much less than the H2Scan sensor (CMOS technology) to manufacture. The quoted price is around $250 each (not in volume, not a rigorous quotation), which offers a great potential in cost reduction in the future for our fuel cell application as long as its performance can be improved to address the current issues. We coordinated our efforts with the UTC FC bus program on the hydrogen sensor via consulting and specifically, helping build the simulated bus exhaust loop into our sensor-testing rig to evaluate the dynamic performance of the hydrogen sensor under a simulated bus operating condition.

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16 14 12 H2 conc. (%) 10 8 6 4 2 0 0 500 1000

H2 % (sensor) H2 % (calculation) Methane %

8 7 6 5 4 3 2 1 0 Methane conc. (%)

1500

2000

2500

Elpased time (sec)

Figure 11. Applied Sensor H2 Sensor Test Results in H2 and CH4 stream The tests show the H2 sensor has a linear response to the concentration of H2 present in the gas stream. The sensor indicates no cross-sensitivity to methane under the conditions investigated. The sensor shows excellent repeatability among the tests conducted so far. Due to the gas residence time in the present test apparatus, the response time for the sensor to reach full scale varies from 90 seconds to 126 seconds depending on the flow rates (indicated as the curved step changes). This does not necessarily mean the response time measured as such can be translated to be the response time of the sensor itself. The test rig was modified to reduce the system response time such that more reliable response or recovery time of the sensor could be measured.

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12

sensor response H2 conc. calculated % humidity %

120

Sensor response (mA)/H2 conc. (%)

10

100 Relative humidity (%)

80

60

40

20

0 0
7-2-03 wet test

2000

4000

6000

8000

0 10000

Elapsed time (s)

Figure 12. Resistive Hydrogen Sensor (DCH Robust Hydrogen Sensor) This sensor consists of a thin film of palladium-nickel (Pd/Ni) deposited on a silicon substrate that acts like a resistor in the presence of hydrogen. The lattice inherent in the Pd/Ni absorbs hydrogen molecules. As the number of hydrogen molecules increases in the lattice, the resistance of the Pd/Ni increases in direct correlation to the amount of hydrogen present. The thin film is embedded into an integrated circuit, which interprets this resistance and displays the hydrogen concentration to the operator. It also generates a voltage signal in direct correlation to the amount of hydrogen that can be interpreted by an external monitoring/control system. Since palladium only behaves in this manner in the presence of hydrogen, there is no cross-sensitivity of the sensor with any other elemental or compound gas. In addition to the Pd/Ni thin film, the sensor includes a temperature sensing diode and two on-board FET heaters, which maintain the sensor substrate at a constant temperature. This elevated, controlled temperature assures that sensor operation is unaffected by the environmental temperature. Semiconductor (MOS) Hydrogen Sensor The resistance of the sensing semiconductor material (usually metal oxide) varies with the concentration of the reactants (either oxidizing or reducing) present in the environment. The determination of hydrogen in the environment is achieved by measuring the change in resistance of the sensing material. The sensing materials (WO3,

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SnO2 etc.) is usually heated to several hundred C by an embedded micro-heater (normally made of Pt). The selectivity is a major issue for this type of sensor. By doping with catalysts such as palladium and platinum the selectivity of these sensors could be somewhat improved. OEM manufacturers: Figaro Engineering. Nanomaterials, www.fisinc.co.jp. The Nanomaterials sensors below are capable of detecting hydrogen from ppm level to LEL (Lowest Explosive Level). The pictures below show the products from Nanomaterials and the sensitivity comparison for different gases.

Figure 13 a, b. H2 Sensor from Nanomaterials, Inc. Sensor module (includes electronics) for LEL detection from Fuel Cell Safety System. www.fuelcellSS.com. Price: $200. Measures 100ppm to 1% H2. Contact point: Dan Gauthier. Ph: 616.530.6540. (Uses a Figaro TGS2613). Figaro TGS821: Figaro gas sensors use a tin dioxide (SnO2) sensing element, which has low conductivity in clean air. The conductivity increases in the presence of a reducing gas. Cross sensitivity could be mitigated by choosing the right sensing materials. The maximum detection range is unknown. In general, MOS H2 sensors are very cheap. ($10 each in large quantity). Contact Mr. Taro Amamoto Ph: 847-832-1701. www.figarosensor.com. Figaro TGS821 information shown below.

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Rs = (

Vc 1) RL VRL

Figure 14. Figaro Sensor Response to Various Species including Hydrogen

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Catalytic Bead Sensor

Theory of operation: A coil of wire (or other form) is coated with glass or ceramic material, which is in turn coated with a catalyst. The coil is electrically heated to a temperature that will allow it to catalytically oxidize the combustible gas being monitored. The heat released is proportional to the concentration of the gas present. This heat increases the temperature of the wire coil thereby increasing its resistance, which is then measured electrically. Advantages: Sensors are small, inexpensive and can be made mechanically rugged; long life - usually 2 to 4 years; simple to calibrate and maintain. Disadvantages: Can be poisoned by trace amounts of silicone, halocarbons and metalloorganic substances; may be sensitive to flowrate; some sensors can be permanently damaged when exposed to high or continuous concentrations of gases being measured. Able to measure 1 to 5% H2. Response time is 10 to 30s. Cost is $500 per sensor and $1200 per control unit (estimate). www.delphian.com. RKI price: OEM sensor $10~20, single transmitter $2000, large quantity $200. Measure 0~5000, 0~10000, 0~50000 ppm. Contact point: Jay Fitzgerald, 800-873-0456, jfitzgerald@argus-group.com. RKI H2 sensor (through Argus-group)

Figure 15. Catalytic Thick Film Sensor (From DCH) A thick-film composition paste was used to fabricate the sensor (shown above). An electrical signal runs through the Wheatstone bridge created with the paste. When hydrogen molecules come into contact with the paste (which is fired on a ceramic base), there is a change in the electrical signal. The resistance of this exposed area is compared with that of the passivated area and the resulting difference gives the concentration of hydrogen. 52

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This sensor may be flow rate dependent, which would require flow rate input in order to compensate the H2 measurement. This compensation could be complicated by an environment with a wide range of flow rates and gas temperatures. Developed by DCH, This technology was granted a license by Oak Ridge National Lab.

Figure 16. The layout of the catalytic thick film sensor from DCH The "green" blocks represent a protected area that the hydrogen molecules cannot penetrate.
Electrochemical Sensor

An electrochemical sensor consists of a diffusion barrier, a sensing-electrode containing a noble metal, a counter-electrode and an electrolyte. The electrolyte is normally an aqueous solution of strong inorganic acids. When a gas is detected, the cell generates a small current associated with the concentration of the gas. Concentration output needs temperature input for compensation. Oxygen is required, which implies that the sensor is not environmentally independent. Freezing could block this type of sensor. Can detect 100 to 1000 ppm of H2. Response time < 30 s. An electrochemical sensor consists of a diffusion barrier, a sensing-electrode containing a noble metal, a counter-electrode and an electrolyte. The electrolyte is normally an aqueous solution of strong inorganic acids. When a gas is detected, the cell generates a small current associated with the concentration of the gas. Concentration output needs temperature input for compensation. Oxygen is required, which implies that the sensor is not environmentally independent. Freezing could block this type of sensor. Can detect 100 to 1000 ppm of H2. Response time < 30 s.

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Hydrogen Field Effect Transistor

The MOSFET sensor device is based on a field effect transistor with a catalytic metal as the gate contact. The gate voltage controls the current through the MOSFET device. The gas molecules will affect the voltage to the gate contact and thus change the current through the transistor. For the MOSFET sensor, the gate and drain may be connected to operate the sensor as a two-terminal device. The operating temperature range is 100-200C for Si-based FE sensors and 200600C for SiC-based FE sensors. Testing is needed to confirm proper functioning in the lower temperature range in the exhaust gas from a cell stack as well as in the harsher environment of the fuel reformer. No comparable market price available but it should be very cheap if mass produced. Manufacturer: AppliedSensor Inc. www.appliedsensor.com, 973-887-6900.

Gas molecule drain gate source

Si/SiC

Charge carrier channel

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Figure 17. MOSFET Type Sensor for H2 Hydrogen in the air causes changes in the reflection spectra of interferometric film stacks that are interrogated via optical fibers. One of the films in the stack in each such sensor contains palladium, which reacts with hydrogen to form palladium hydride. The differences between the optical absorbance and indices of refraction of palladium and palladium hydride give rise to observable changes in the spectra. The impetus of using the fiber optic sensor is that it can be mounted away from the electronic circuitry and be immune from damage and ignition risk. This could be advantageous in situations in which the circuitry would be vulnerable to electromagnetic interference or to damage if it were placed at the sensor location. Ongoing research is mostly for space use (NASA). The sensor is complex and expensive and there are few products in the market. This sensor should not be considered only if other alternatives are not available.

Figure 18. Two configurations of the fiber-optic hydrogen sensor utilizing gradientindex-of-refraction (GRIN)
Fiber Optic Hydrogen Sensor (Chemo chromatic Type)

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This sensor is based on a reversible, hydrogen-induced change in the optical absorption of a thin film (transition metal compounds) at the termination of an optical fiber. This chemo chromatic effect associated with hydrogen concentration can be transmitted via another optical fiber and determined using a photo detector. Fiber optic sensor demonstrates the flexibility of sensor placement by using fiber splitter and multi-sensor based control capability with shared signal processing electronics. Its reliability is closely related to the chemical composition of the sensing film. Has not been commercialized. Under development by DCH, IOS Inc. Prototypes may have been shown by Intelligent Optical Systems Inc. www. Intopsys.com. They claimed the price can be reduced, but this will require further work.

Figure 19. Schematic of the working principle of chemo chromatic fiber optic sensor
Conclusion and Recommendation for alternate H2 Sensing Technologies

Resistive hydrogen sensors and catalytic sensors are recommended for further investigation and experimental validation for hydrogen detection in the electrolysis apparatus. They might be the most mature and robust sensors in this field currently. Both resistive and catalytic sensors need to be validated in similar gas environments for long term exposure effects, water condensation effects, flow rate dependence and span (long term) drift investigation. The response of MOS (metal oxide resistive type sensor not metal oxide semiconductor transistor) sensor is quite susceptible to the environment parameters such as temperature and humidity. This makes them not very stable. Also, the measurable range for these sensors is typically less than 1%.

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Electrochemical hydrogen sensors could be treated as an alternative and as a laboratory reference tool. The device using liquid electrolyte is not as robust as the solid devices. Hydrogen field effect transistors are good for higher temperature (>100C) application. Response time as fast as five seconds has been demonstrated by Applied Sensor. Fiber optic sensors are suitable for distributed detection for multi-target mission and spatial distribution sensing. They are not mature and require significant development effort.

Hydrogen Sensor for Anode Exhaust: Tests and Findings


The factorial-design tests in a dry gas environment show temperature has a slight effect (-0.54) on the sensor response followed by flow rate (0.53) and methane concentration (0.08). The influences of temp. and flow may be caused by the exothermic effect of metal hydride formation. The flow rates investigated varied from 81 to 250 SCCM. Wide sensor response variation is expected when operating this sensor in an actual fuel cell power plant due to large flow variations. This needs to be investigated in the actual power plant. Temperature (26-62 C) and methane concentration investigated cover the most likely values to be encountered in the PC35 power plant and thus the influences of temperature and methane are not likely to be problematic. The relative error of the sensor response in a dry gas stream is +/- 3.1% which meets the 0.2% absolute accuracy requirement for typical operations of PC35 defined by UTC FC. Durability test is performed by cycling hydrogen concentration and temperature to which the sensor is exposed.

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14 12 10 H2 conc. (%) 8

1.3 1.25 1.2 1.15 1.1 AppliedSensor response (V)

6 1.05 4 2 0 0.5 1.5 2.5 Time (Hrs) 3.5


H2 % H2Scan sensor AppliedSensor #4

1 0.95 0.9

12-12-03, dry

Figure 20. The response of AppliedSensor #4 to hydrogen concentration indicated


14 12 H2 concentration (%) 10 8 Calibration 6 4 2 0 1.04 y = -174.94x + 196.23 R2 = 0.9609

1.05

1.06

1.07

1.08

1.09

1.1

1.11

Sensor response (V)

Figure 21. Calibration data of AppliedSensor #4 show poor resolution for H2 concentration greater than 10%

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12 H2 % H2Scan sensor 11 10 H2 conc. (%) 9 8 7 6 5 4 1000 1.1 1.08 1.06 1.04 1.02 1 2000 3000 4000 Time (s) 5000 6000 7000 AppliedSensor #4 AppliedSensor response (V) 1.12 1.14

12-12-03, dry

Figure 22. Response of AppliedSensor #4


12 H2 % H2Scan sensor 11 10 H 2 conc. (%) 9 8 7 6 5 4 1000 0.3 0.6 AppliedSensor #3 0.7 AppliedSensor response (V) 0.8

0.5

0.4

0.2 2000 3000 4000 Time (s) 5000 6000 7000

12-12-03, dry

Figure 23. The response of AppliedSensor #3 shows a good deal of noise. The tests for the unit from AppliedSensor in a humidified gas mixture stream shows that the sensor responds to the change in hydrogen concentration quickly and a stable response is achieved immediately, however; the sensitivity and/or resolution of the sensor is very poor at least in the range of 2.2% to 4.4% of hydrogen that was investigated. The response time of the sensor by AppliedSensor is far shorter than that of the H2Scan sensor. This indicates some very attractive prospect for the FET sensor as long as its sensitivity and resolution is improved to meet a specific requirement. This result is presented in Figure 24.

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8 H2 concentration (%)

H2 conc. (%) H2Scan appliedSensor #4


fast/stable response, but poor resolution

1.8 1.6 AppliedSensor response (V) 1.4 1.2 1

Final Report December 5, 2005

4 0.8 2 0.6 0.4 0 5000 -2 6500 8000 Time (s) 9500 0.2 0

AppliedSensor, wet test, 12-10-03

Figure 24. The response of AppliedSensor #4 in a humidified gas stream shows fast/stable response but poor resolution.

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Appendix II Chemical Sensors for Automotive Fuel Cells

by

William J. Buttner, Mel Findlay, and Joseph R. Stetter


with

Nathan Schattke and Gu Hyun Chung

Sensor Research Group BCPS Department Illinois Institute of Technology 3101 S. Dearborn Street Chicago, IL 60616

Final Report delivered to

Brian Knight
United Technology Research Corporation October, 2005

In Support of the Subcontract Award to IIT from UTRC Through DOE Contract Number DE-FC04-01AL67616

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Final Report: Chemical Sensors for Automotive Fuel Cells

Table of Contents
1. INTRODUCTION/EXECUTIVE SUMMARY APPENDICES APPENDIX 1: Market Survey APPENDIX 2: SSTUF Documentation APPENDIX 3: Compendium of Test Reports

2. BACKGROUND 2.1. DOE Fuel Cell program goals 2.2. Summary of Priorities and Technical Hurdles 2.3. IIT Project Outline

3. SENSOR REQUIREMENTS
3.1. Requirements for Hydrogen Sensing 3.2. Requirements for Carbon Monoxide Sensing 3.3. Requirements for Hydrogen Sulfide Sensing

4. SELECTION OF CANDIDATE SENSORS 4.1. Hydrogen Sensors 4.1.1. Market Survey 4.1.2. Commercial Technology Review 4.1.3. Manufacturer Review 4.2. Carbon Monoxide Sensors 4.3. Hydrogen Sulfide Sensors 5. BENCHMARK TEST FACILITY Shared Sensor Test Users Facility (SSTUF)

1
1 2 3 3 4 4 4 4 5 5 5 5 6 9 9 9 10 10 11 62

6. METHODOLOOGY 6.1. Develop Test Protocols 6.1.1. Hydrogen Safety Sensors 6.1.2. Reformer Hydrogen Sensors 6.1.3. Special Test Protocols for CO and Sulfur Gas Technology 6.2. Sensor Development Collaborations 7. SUMMARY OF PROGRESS 7.1. Companies Contacted 7.2. Summary of Sensor Test Results 7.3. Sensor Development Results
8. CONCLUDING COMMENTS

9. REFERENCES

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Final Report: Chemical Sensors for Automotive Fuel Cells


Subcontract Award from UTRC through DOE Contract # DE-FC04-01AL67616

1. INTRODUCTION/EXECUTIVE SUMMARY
This Report presents the results of work performed at Illinois Institute of Technology under a subcontract from United Technology Corporation, on DOE Contract # DE-FC0401AL67616.

The IIT Sensor Research Group developed a sensor test facility for evaluation of sensors in simulated fuel cell environments, and invited commercial manufacturers of sensor technology to submit sensors for testing. This testing was performed in confidentiality, and results reported to both the manufacturer and UTC.

In addition, the IIT-SRG collaborated with several commercial groups in evaluation of sensor technology and development of new sensors for hydrogen as well as potential contaminants in the fuel stream sulfur gases and carbon monoxide. Several technologies were moved along in the development cycle as a result of this testing and collaboration, and at least one manufacturer is introducing a hydrogen detector which benefited from testing at IIT.

2. BACKGROUND 2.1. DOE Fuel Cell program goals

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This Project is a part of a major DOE initiative with United Technology Research Corporation (UTRC) to develop reformer-based fuel cells for automotive applications. Hydrogen is currently the favored candidate for fuel cell fuel. There are numerous obstacles to overcome before direct, on-board generation of hydrogen is feasible in the meantime, the hydrogen is generated from a hydrogen-rich conventional fuel such as methanol, gasoline, diesel, or gasified coal. A reformer is typically used to convert hydrocarbons into a gas mixture of hydrogen and carbon compounds called "reformate." In many cases, the reformate is then sent to another reactor to remove impurities, such as carbon oxides or sulfur, before it is sent to the fuel cell stack. This prevents impurities in the gas from binding with the fuel cell catalysts. This binding process is also called "poisoning" since it reduces the efficiency and life expectancy of the fuel cell.

The Department of Energy has sponsored workshops and symposia on various aspects of the fuel cell initiative. One area of interest is sensor needs for automotive fuel cell systems. A workshop was held at Lawrence Livermore National Laboratory in 2000 to identify sensor priorities and requirements [1]. This workshop covered both PEM fuel cell systems, as well as advanced compression-ignition, direct injection (CIDI) and spark-ignition, direct injection (SIDI) internal combustion engines. There are two broad areas of concern in the hydrogen fuel cell process: i) concentrations in the fuel processor (reformer) stream. Sensors for process control (hydrogen concentration, CO, sulfur compounds, temperature, flow, RH, pressure.) ii) Hydrogen concentrations in ambient air Safety sensor. Sensor technologies for carbon monoxide, hydrogen, and hydrogen sulfide were identified as the highest priorities. The performance requirements for sensors needed in fuel cell applications were developed by DOE and were based on operating parameters that prevail in functional fuel cells.
2.2. Summary of Priorities and Technical Hurdles

Initial program priorities were identified as [1]:

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PRIORITY #1 CO: For fuel cells, the highest priority was originally assigned to CO sensors for the fuel stream, to prevent poisoning of the catalyst which can occur when 5-100 ppm CO is present in the fuel stream. This was assigned high priority because there is currently no available CO sensor for the fuel stream; each technology has its limitation. The primary hurdles are the harsh environment and cross-sensitivity to high concentrations of hydrogen in the fuel stream. But there is not universal agreement among the fuel cell manufacturers on the requirements for a CO sensor. The LLNL workshop summarized this situation, and offered general discussion on potential solutions that might be employed to improve the usefulness of the different technologies. PRIORITY #2: 1-100% Hydrogen in product stream: Hydrogen sensors for process (performance) control was also assigned high priority. There are a number of sensor technologies available for hydrogen (thermal conductivity, MOS sensors, palladium film resistor and gate sensors, acoustic sensors) and a number of companies are promoting sensors for this application. The major technical hurdles for this application are the operating temperature, cross sensitivity, and sensor cost. There are several technologies which may meet the requirements, but validation in the fuel cell environment difficult, but is required. [This is a major task of the IIT project.] PRIORITY #3 - 0.1-10% Hydrogen safety monitor: in addition to feasibility of providing a clean, cost competitve hydrogen supply, the second major issue is safety. Hydrogen is flammable in air over a concentration range of 4%-75%, making it a very hazardous fuel. A reliable hydrogen sensor is required, with long-term stability and insensitivity to other combustible gases like hydrocarbon vapors. PRIORITY #4- sensor for Sulfur compounds: extremely low concentrations of sulfur can poison or irreversibly affect the performance of the fuel cell catalyst. A sulfur detector is needed upstream of the fuel cell, either in the fuel line, or in the inlet to the reformer. Current sulfur compound detectors are either electrochemical or optical (fluorescence, spectroscopy), and not designed for the fuel process environment. This sensor need was originally assigned fourth priority, as the program evolved it was realized this was a prime need, as trace levels of sulfur gases may permanently 2.3. IIT Project Outline The Illinois Institute of Technology was tasked by UTRC to identify and evaluate potential sensors for hydrogen, CO, and hydrogen sulfide for the fuel stream, as well as hydrogen sensors for safety. This was to be accomplished in three tasks: 2.3.1. Market Survey a review was conducted of commercially available sensors, as well as sensors far enough into development that they could be anticipated to be available in the near term. 3

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2.3.2. Sensor Test Facility - develop a test chamber to permit testing of candidate sensors under environments simulating fuel cell conditions as well as conditions of safety applications 2.3.3. Sensor Evaluation as potential sensors are identified, invite manufacturers to submit representative samples for confidential testing. 2.3.4. Support New Sensor Development IIT, jointly with several manufacturers, conducted sensor development improvement efforts for Hydrogen, as well as CO and sulfur gases.

3. SENSOR REQUIREMENTS 3.1. Requirements for Hydrogen Sensing

The sensor requirements for PEM fuel cells have been specified by the [1]. Through interaction with UTRC and DOE personnel, the requirements for the hydrogen and CO sensors were defined [2]. Two major applications exist for hydrogen sensors. A feedback control sensor is required for use in the reformer of the fuel cell. This sensor must operate internal to the fuel process stream. In addition, a second critical application is the need for an ambient air monitor for use as a safety monitor. Table 1 specifies the hydrogen sensor requirements for fuel cell application.
Specifications
H2 Concentration Range Operational Temperature Response Time (sec) Environment

Fuel Processor
(inside the fuel cell) 1 100% 70 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS

Ambient Air (safety)


(for passenger chamber) 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed) 5% FS 5 year lifetime

Accuracy

Table 1: Performance specifications for deployment of hydrogen sensors in reformer based fuel cells.

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3.2. Requirements for Carbon Monoxide Sensing Specification


CO Concentration Range Operational Temperature Response Time (sec) Environment

Reformate
1 100 ppm <150oC 0.1 - 1 high humid 30-75% H2 CO2 CO N2 H2O 1-3 ATM 1-10% FS

Application Medium Conc.


100 1000ppm 250oC 0.1 1 high humid 30-75% H2 CO2 CO N2 H2O 1-3 ATM 1-10% FS

Low Conc.
0.1 2% 250-800oC 0.1 1 high humid 30-75% H2 CO2 CO N2 H2O 1-3 ATM 1-10% FS

Accuracy

Table 2: Performance specifications for deployment of CO sensors in reformer based fuel cells

3.3. Requirements for Hydrogen Sulfide Sensing Specifications


H2S Concentration Range Operational Temperature Response Time (sec) Environment Accuracy

Fuel Processor (inside the


fuel cell) 0.05-0.5 ppm <400oC <1 min at 0.05 ppm See table for CO sensors 1-10% FS

Table 3: Performance specifications for sulfur compound sensors in fossil fuel reformer based fuel cells

4. SELECTION OF CANDIDATE SENSORS

4.1.

Hydrogen Sensor

4.1.1. Market Survey Sensor technologies for carbon monoxide and hydrogen were addressed. The focus was on sensor types currently commercially available or those devices at a mature level of development such that production could be expected in the near future. In the original survey, vender-supplied sensor specifications were compared to performance requirements for use in fuel cells. The fuel cell requirements were developed by DOE and were based on operating parameters that prevail

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in functional fuel cells. As other sensor types entered the market place, or beta-test prototypes were identified, their specifications were reviewed and the candidate list updated. The results of this market survey and the follow-up benchmarking performance testing by the SRG were to be used by the primary DOE contractor (UTRC) in the design and optimization of reformer-based fuel cell systems. It should be noted that manufacturers are hesitant to participate in such studies without the provision for confidentiality of data. While every attempt was made to include all possible vendors for this technology, some were missed initially and added as the study progressed. Others appeared late in the project, and were not always able to be included in this current program. In these cases, we identified the key technology and possibilities for future evaluation. Although the focus for this work is on sensors that can contribute in the near term, our intent was to provide positive feedback [in confidence] to the vendors about the performance of their sensors so they can be improved, as well as validate one or more sensors for use in current fuel cell applications. 4.1.2. Commercial Technology Review there are currently five general sensing technologies for hydrogen (excluding lab instrumentation), described briefly below: 4.1.2.1. Pd-film and Pd-alloy films one technology which appears promising for reformer streams is the Pd- and Pd-alloy resistor films. The film resistance changes with adsorption of hydrogen; the devices are typically chemisistors or Pd gate FETs. 4.1.2.2. MOS sensors tin oxide type combustible gas sensors and MOSFETs manufacturers have been refining MOS sensors for many years, both in packaging/power requirements, and in selectivity. 4.1.2.3. Pellistor-type combustible gas sensors (heated ceramic with Pt or other noble metal coating. These sensors have been used for more than 20 years in confined space and safety applications, for combustible gas detection. 4.1.2.4. Thermal conductivity hydrogen has a thermal conductivity much different than any other component of a fuel stream, and with semipermeable barriers, selectivity for hydrogen can be very high. 4.1.2.5. Electrochemical Sensors hydrogen, CO, and most sulfur gases are easily detected by electrochemical means. Limitations including been selectivity (eg CO in a hydrogen matrix) and limited temperature range have historically limited this technology to safety applications.
4.1.3. Manufacturer Review Industrial providers of sensor technology were identified through a search of the internet, open literature, personal contacts, and technical publications. Over 70 commercial sensors (or mature developing technologies) were identified for hydrogen. Of these, five commercial hydrogen sensor designs were initially identified that meet or most closely meet deployment requirements for fuel cells. Additionally, several technologies were identified that were near beta-test or production stage, and were included on the list of potential sensor candidates. This is discussed in more detail in Section 7. 4.2. Carbon Monoxide Sensors

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A comparable number of carbon monoxide sensor types were surveyed, but, of these, only two developing technologies met the deployment requirement. The most common reasons for failing to meet criteria were the inability to selectively measure trace carbon monoxide in the presence of hydrogen and the inability to meet temperature specifications over the expected temperature range.
4.3. Hydrogen Sulfide Sensors

The initial survey did not cover sulfur gas sensors, as the priorities originally were defined as carbon monoxide and hydrogen. Sulfur compounds in general, and H2S specifically, are recognized as potentially critical contaminants, as they may poison the fuel cell catalyst irreversibly. As the project progressed, candidates for sulfur compound detection were pursued; this will be discussed later, in Section 8.
5. DEVELOP BENCHMARK TEST FACILITY Shared Sensor Test Users Facility (SSTUF): The sensor testing facility at IIT was developed by the Illinois Institute of Technology Sensor Research Group to facilitate sensor evaluation under non-ambient pressure and temperature conditions similar to what would be encountered in fuel cell applications. This test facility consists of six modules capable of mixing up to four different gases under controlled temperature, relative humidity, and pressure (Figure 1.6).

Module A: Gas Composition Control


The gas-mixing module includes four mass flow controllers (MFC, numbered as MFC 1 to 4) (model GFC 171, Aalborg, Orangeburg, NY, USA) (Figure 1.6 and Figure 1.7). Each MFC connects to a gas cylinder such as air, 10% H2/N2, 100 ppm CO/air or other as specified. Gases at the specified flow pass through inch copper tubing and then feed into the gas inlet of the heated sensor test chamber. The maximum output for the MFC is 500 scc/min at 5V full range control voltage. The flow rate out from the MFC is accurately proportional to the control voltage down to 5% level. Typically the total flow rate was maintained at 500 scc/min throughout an experiment. Gas composition was set by the volume-to-volume ratio of the flow rates from each MFC. A 20% dilution is a combination of 100 scc/min component gas and 400 scc/min make-up gas, which would typically be air or N2. The mixing ratio can be translated into the required flow rates, which then be used to select the control voltages for each MFC. The control voltages parameters are written into the script applied to the Labview virtual instrument. A sample control script is shown in the Table 5.1. In general, the gas matrix (the background gas) is air but it can be varied according to the test conditions specified as required such as high level of hydrogen, low level of oxygen, or high level of carbon monoxide.

Module B: Relative Humidity Control


The relative humidity (RH) for the sample gas is controlled by a commercial water saturator (BekkTech LLC, Longmont, Colorado USA). The saturator consisted of a water chamber with bottom heater to vaporize the water. The test gas did not bubble though the water, but 7

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instead mixed with the water vapor above the liquid water. The liquid water temperature controlled the water vapor concentration. The mixing volume of the test vapor and water vapor determined final humidity of the test vapor. The heater was controlled by the feedback signal of a RH sensor installed inside the sensor chamber which would adjust the temperature of the water heated to reach the desired RH set point. To maintain the water level inside the chamber, an optical level sensor was also installed to activate an auto-fill system. This system consisted of an electronic solenoid which when activate connected the chamber to a pressurized reservoir of water.

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Time (min) 0-10 10-15 15-25 25-30 30-40 40-45 45-55 55-60 60-70 70-75 75-85 85-90 90-100

MFC 2 Target MFC 1 Sample Flow (scc/min)Control Voltage (V)Flow (scc/min)Control Voltage (V) Air 500 5 0 0 0.5% H2 475 4.75 25 0.25 Air 500 5 0 0 1% H2 450 4.5 50 0.5 Air 500 5 0 0 2% H2 400 4 100 1 Air 500 5 0 0 4% H2 300 3 200 2 Air 500 5 0 0 6% H2 200 2 300 3 Air 500 5 0 0 8% H2 100 1 400 4 Air 500 5 0 0

Table 5.1: Sample MFC Control Voltage for Gas Dilution in SSTUF, illustrating the blending of air and 10% hydrogen/N2 to yield a range of hydrogen concentrations.

Module C: Heated Test Chamber


Automotive fuel cell specifications require that the sensors must be able to operate at absolute pressures from 1 to 3 atmospheres. The SSTUF test chamber was designed to be able to test sensors under such conditions: it consists of a 4D x 6 L stainless steel tube, sealed with end plates (Model 402006 and model 110025, MDC Vacuum Products Corp., Hayward, CA, USA). One end plate was fitted with a port for a 20-conductor sealed electrical feed-through designed for high-temperature applications under vacuum. The same plate has bulkhead pneumatic connectors for 1/8 tubing to carry gas in and out of the chamber. Thus, sensors can be exposed in either diffusion or pumped mode. A thread hole for a thermocouple is available on the same end plate. The other end plate serves as the access for sensors. This chamber is pneumatically isolated from the outside environment except for a gas inlet and outlet pneumatic system. The internal atmosphere in SSTUF can be subjected to controlled and elevated temperature, pressure, and humidity. The inlet gas passes through a coil of 1/8 inch stainless steel tubing in contact with the inside wall of the test chamber. This coil facilitates thermal equilibrium of the test gas with the heated chamber. A probe thermocouple was inserted into the chamber without contacting the inside wall which measured the temperature of the test gas at the surface of the sensor.

Module D: Temperature Control


Temperature control was achieved via a ceramic fiber radiant heater (model CRWS-64/120A, OMEGA Engineering, INC., Stamford, CT, USA) wrapped around the test chamber and connected to two digital temperature controllers (model TCS-5011, Dwyer Instruments, Inc., 9

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Michigan City, IN, USA). Temperature controller 1 (TC1) was connected to a thermocouple (Model SC-GG-K-30-36, OMEGA Engineering, INC., Stamford, CT, USA) embedded in the ceramic heater and temperature controller 2 (TC2) was connected to the thermocouple (model KMTSS-125U-6, OMEGA Engineering, Inc., Stamford, CT, USA) inserted to the test chamber. TC1 monitored the heater temperature while TC2 monitored the gas temperature inside the test chamber. The inside gas temperature will be lower than the external heater temperature because of thermal losses through the wall of the test chamber. There are three contacts on the switch of the temperature controllers: COM (common), NO (normally open) and NC (normally closed). The thermocouple was connected to the temperature controller input to monitor the temperature, and provide the feedback signal to the controller. When the chamber temperature is lower than the set point, the switch will be at the NC position. The COM on TC1 was connected to the NO on TC2 so that the heater will be on only when both controllers were at the NC position. The sensor test temperature will be set on TC2 and the equilibrium time is approximately 30 minutes. The temperature profile figure, set point of TC2 vs. reading from TC1, is shown below. The temperature vs. time is also shown below. Although TC1 had to be set to a higher temperature than TC2, the TC1 set point was typically set close to TC2 so as to allow better control the internal test temperature without temperature overshoot. (Figure 2.6, Figure 2.7)

Module E: Chamber Pressure Control


An upstream pressure controller (model 5866E, Brooks Instrument, Hatfield, PA, USA; configured for 14.5-72.5 psia full scale) was connected at the gas out line of the sensor test chamber and was used to control the pressure within the chamber. The effluent gas from the chamber was carried to the pressure controller, which measured the pressure and released the gas at a controlled rate to maintain a set pressure inside the chamber. The setpoint pressure is controlled by a serial command from the computer. Careful pressurization of SSTUF was performed in small increment steps with enough stabilization time at each incremental step preventing from the pressure shock on the sensors to cause damages in the seal, membrane, and the porous electrode structures. Once the desired test pressure was achieved, the sensor was allowed to stabilize for an additional 30 minutes prior to testing. Following each test, the incremental pressurization process was repeated to get to the next pressure setting.

Depressurizing was also performed in a similar way but with longer stabilization time to assure that outgassing of absorbed vapors from the sensor proceeded in a controlled manner without causing sensor damage. At each step of pressurization and depressurization processes, the flow rate was continuously maintained as a constant after the pressures was stabilized. As with all flow and gas composition parameters, the pressurization and depressurization of SSTUF were controlled remotely via the computer interface. A pressure gauge was installed between the sensor chamber exit and the pressure controller to manually read the actual pressure Figure 2.8. The output pressure in units of psi gauge (psig) was found to be linear with the control voltage in the range of 1.2 5 volts. 10

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Module F: Data Acquisition and Control Experimental parameters for the mass flow controller and pressure controller were set either manually or through a computer interface using a National Instrument data acquisition system (Labview version 6.0, DAQ PCI card, model PCI-MIO-16XE-10 and PCI-6713, shield connection box model SCB-68, National Instruments, Austin, TX, USA). Detailed in section 2.4. There are 8 output channels on the PCI-6713 card named as output CH 0-7. Output CH 0 to 3 were connected to the mass flow controllers to send out control voltage to set the flow to the desired value for each MFC. Output CH 4 was connected to the pressure controller which set the pressure to the required value. The other output channels were reserved for temperature and humidifier modules. 16 input channels are available on PCIMIO-16XE-10 card and named as input CH 0-15. Input CH 0-4 were set to collect the feedback signals from MFC and pressure controller to confirm the proper behavior of these devices. Input CH 5-8 were set to collect data from four sensors. The rest of the input channels are now not in use but can be set for any other types of analog signals.

6. TEST METHODS

6.1. Develop Test Protocols: Standard test protocols were developed to characterize sensors for: 6.1.1. Hydrogen Safety Sensors sensors tested for suitability as safety sensors were subjected to a series of tests under conditions that simulate the conditions encountered in a typical automotive cabin and fueling environment: ambient temperature and pressure, RH from 5% to >80%. Functionality: A rapid sensor test to confirm that the device is operational and compatible with the IIT DAQ and SSTUF system. Effect of Oxygen on the Hydrogen Response Most hydrogen sensing technologies require oxygen for stable operation. The oxygen concentration in most safety applications should be near ambient, but it is possible that the O2 level could be low in the case of a serious leak, or in confined spaces. The oxygen requirement test is not REQUIRED for the Hydrogen Safety Sensor application and will not be necessarily performed on all devices. Sensitivity at ambient P, T, dry conditions: The sensitivity test determines the sensor response to various hydrogen concentrations. Although the exact test sequence may vary, the basic test sequence (for the Hydrogen Safety Application) is illustrated in Table III.c 1. Exposure times of 10 minutes are used to assure steady state response (many devices reach steady state much quicker) and the test allows for 15 minutes to recover following exposure.

The test data that is obtained for this test will provide: - Sensitivity and lower detection limit, - linear and dynamic range of device accuracy and precision of device RH Effects if the sensor performance under the above tests was acceptable, the sensor was also tested for RH effects on baseline and span. 11

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6.1.2. Reformer Hydrogen Sensors the conditions for sensors in the fuel stream of reformer are much more severe than the safety application. Oxygen Requirement Test - Many but not all of the sensors under evaluation may require oxygen, and this test is designed to verify the minimal oxygen requirement that is necessary for adequate sensor performance. The test consists of a series of exposure to 2% hydrogen with varying levels of oxygen. Temperature Effects for this testing, selected sensors were tested at temperatures from ambient to 750C. None of the sensors received were packaged to withstand higher temperatures. Pressure Effects The pressure in the reformer may be as high as 3 atmospheres. Testing
FLOW Time (min) 0-10 10-20 20-35 40-50 50-65 65-75 75-90 90-100 100-115 115-125 125-140 140-150 150-165 Total 500 500 500 500 500 500 500 500 500 500 500 500 500 AIR 500 475 500 450 500 400 500 300 500 200 500 100 500 N2 0 0 0 0 0 0 0 0 0 0 0 0 0 10% H2 in N2 0 25 0 50 0 100 0 200 0 300 0 400 0 Air 5 4.75 5 4.5 5 4 5 3 5 2 5 1 5 MFC Voltage N2 0 0 0 0 0 0 0 0 0 0 0 0 0 10%H2 0 0.25 0 0.5 0 1 0 2 0 3 0 4 0 %O2 21 19.95 21 18.9 21 16.8 21 12.6 21 8.4 21 4.2 21 VAPOR %N2 79 79.55 79 80.1 79 81.2 79 83.4 79 85.6 79 87.8 79 %H2 0 0.5 0 1 0 2 0 4 0 6 0 8 0

will be performed from 1-3 atmospheres.


Table III-c 1: Test sequence for sensitivity testing (safety application)

6.1.3. Special Test Protocols for CO and Sulfur Gas Technology

6.1.3.1.NexTech H2S Sensor the requirements for sulfur gas detection are very stringent: the sulfur compounds may irreversibly bind to the fuel cell catalyst, reducing efficiency even at sub-ppm levels. The sensor is thus required to detect as low as 10 ppb H2S, for example, in the reformer stream, where temperatures may be 4000C or higher. The only sensor found which claimed to be designed for this application is in development by NexTech. An alpha-prototype was obtained and tested in the STTUF apparatus. To test the sensor, a sample cylinder was used to prepare a 1 ppm standard by serial dilution. This 1 ppm source was then supplied to the SSTUF sample inlet and diluted to levels as low as 20 ppb using mass flow control. Original plans were to test the sensor at elevated temperatures, pressures, and moisture, but the ambient tests results were very poor, it was felt there must be a problem with the sensor. 6.1.3.2.Peak Analytical CO in Hydrogen Process Monitor there is currently no commercial sensor that can detect ppm level CO in a hydrogen matrix. A unique gas chromatograph was identified, which would be suitable for fixed locations, for example bulk reformers, points of custody transfer. 12

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This instrument was tested at concentrations ranging from low ppm to 1% CO, in a background of 10% hydrogen. 6.2.SENSOR DEVELOPMENT COLLABORATIONS 6.2.1. Electrochemical Hydrogen Sensor (IIT/TTI): With a standard reference electrode in an electrochemical sensor, potential drift of the reference due to adsorbed H2 causes signal drift as the sensor is used for H2 sensing. Additionally, there is typically a severe interference from carbon monoxide. 6.2.2. Hydrogen Sulfide Sensor (IIT): Monitoring of sulfur gases at ppb levels 6.2.3. CO sensor for Reformer Stream Application (NexTech): NexTech is developing a solidstate (ceramic) sensor for measurement of carbon monoxide in the harsh conditions encountered in the fuel stream after the cleanup process. 6.2.4. H2S Sensor for Reformer Stream Application (NexTech): NexTech is also working to develop a solid-state (ceramic) sensor for measurement of sulfur gases in this same application, as well as the even harsher conditions encountered in reformer streams and feeds to solid oxide fuel cells.
7. SUMMARY OF PROGRESS 7.1.Companies Contacted Information on the various sensor manufacturers was tabulated from the questionnaires returned. (See Appendix 10.1 for complete Market Survey Report.) Based on the claimed performance specifications, companies were targeted for followup discussions, and potential sensor evaluation. The following companies were contacted and invited to provide sensors for evaluation:

7.1.1. Hydrogen: The following companies were contacted and invited to participate in the hydrogen sensor evaluation, initially by responding to the questionnaire.
Specified Application Technology Reformer Safety

Pd or Pd Alloy H2 Scan Makel Engineering ATMI Metal Oxide: Applied Sensors Nemoto, Japan 13 X X X X X X X

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Figaro, Japan NGK, Japan Synkera Scott-Bacharach Catalytic Diffusion (Pellistor): City Technology, Ltd. FuelCellSensor (Partners of Argus and RKI group) Electrochemical: Transducer Technology, Inc. Drager Safety Inc City Technology Ltd Emerging Technology (Nanoparticle-based sensors): Nano-propriety Nanomix Applied Nanotech Transducer Technology, Inc. X X X X

X X X X X X X X X

7.1.2. Carbon Monoxide: The following CO sensor manufacturers were contacted concerning their products and potential application for CO measurements in the fuel cell applications: Comag IR NDIR sensor, claims to be sensitive to 10 ppm CO. TTI electrochemical sensor, 0-100% H2 range, but cant meet temperature requirements without conditioning. Fluke Fluke manufactures low cost CO detectors using electrochemical sensors. They are intended primarily for health and safety applications Figaro Metal oxide sensor, also responds to hydrogen and combustibles. None of these products suit the requirements for measuring CO in the fuel stream, and none were tested as part of this project. Late in the Project (February, 2005), Peak Scientific presented their gas chromatograph as a possible tool for measuring CO and hydrogen in the presence of each other. While outside the direction of identifying and evaluating in-situ sensors, no strong candidates for CO in hydrogen, so it was decided to have the vendor come out and demonstrate the instrument. 7.1.3. Hydrogen Sulfide although initially assigned a lower priority than CO and hydrogen, it was recognized that monitoring of sulfur compounds such as H2S in the reformer and fuel 14

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stream was critical, as these compounds can poison the fuel cell catalyst irreversibly, at very low ppb-levels. There are no commercially available sulfur compound sensors designed to operate in the extreme temperature and moisture environment encountered in this application. Nextech, another subcontractor on this project, has been developing high temperature sensors for CO and H2S, and during the summer of 2005, supplied IIT with two alphaprototypes to evaluate in SSTUF. This will be discussed in more detail in Section 8.3, and the full test report is included in Appendix 3. 7.2.Sensor Test Results the test results are reported in detail in the test reports that were submitted periodally to UTRC and the manufacturer. Copies of these reports are included in Appendix 3 at the end of this document. Table 7.2.1 summarizes the results of the testing to date. Several companies who expressed interest in participating by submitting sensors for evaluation were not able to do so during the time frame of this project. IIT is currently attempting to find out from these companies what the status of the proposed sensors is, and whether the technology is mature enough that they would be interested in participating in any possible continuations of this evaluation effort. 7.3.Sensor Development Results: 7.3.1. Electrochemical Hydrogen Sensor (IIT/TTI): With a standard Pt/air reference electrode in an electrochemical sensor, potential drift of the reference due to adsorbed H2 causes signal drift as the sensor is used for H2 sensing. Additionally, there is typically a severe interference from carbon monoxide. By replacing the reference electrode with a more stable electrode (for example Ir/IrO, Pb/PbO), TTI has developed an electrochemical hydrogen sensor that is immune to the typical baseline drift. Additionally, incorporation of a proprietary membrane has greatly reduced interferences from potential interferences such as CO, ethylene. The sensor is specified to 100% H2 by the manufacturer. Testing of this sensor at IIT yielded excellent results from 0-8% hydrogen, as well as immunity to variations in oxygen concentration. 7.3.2. CO sensor for Reformer Stream Application (NexTech): A test plan for this sensor was prepared in May, 2004. The sensor was received by IIT, but a Stop Work order was received from DOE, and testing put on indefinite hold. 7.3.3. H2S Sensor for Reformer Stream Application (NexTech): Nextech provided two alphatest devices to IIT for testing in the SSTUF apparatus. Details are presented in the report, attached in Appendix 3. Briefly, results were encouraging, as response to ppb levels of hydrogen sulfide were obtained. There were several operational issues which limited the testing, with only two tests being obtained from one sensor, and no response obtained from the second. The stability and repeatability of the sensor needs improvement; however, this is not unusual for early prototype devices. 15

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7.3.4. Nanoparticle-based Hydrogen Sensor (Nanomix) Nanomix provide specifications on a very promising hydrogen sensor, which IIT was planning to test whenever samples were available. As of 9/05, no samples were obtained from the company 7.3.5. MEMS/Nanoparticle-based Hydrogen Sensor (Transducer Technology, Inc.) TTI was developing a MEMS-based sensor under a separate DOE funded effort. Samples of the device were tested at TTI, but no samples were received for testing at IIT.

16

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Table 7.2.1.a: Candidate Fuel Cell Sensors Tested at IIT


Manufacturer Model Technology Application Test Dates Specifications Operating Operating Range Temp 0-1500ppm +60 to 120C 0-5000ppm +60 to 120C 0-4% 0-10% "ambient" "ambient"

Applied Sensors

AS-FHH-400 AS-FHH-450

MOSFET MOSFET Layered Pd Layered Pd Tin Oxide

Safety Safety Safety Safety Safety Safety Safety Safety Safety Safety Safety Safety Reformer

May-04 May-04 Oct-04 Apr-05 May-04 Jun-04 Apr-04 Jul-05 Dec-04 Apr-04 May-05 May-June 05 Jul-05

ATMI

T1ATBH (2nd gen)

T1ATBH (2nd gen) Figaro H2Scan RKI


TGS821, 2613

10-5000ppm -20 to +80C 0.5-100% 0-2% 0-2% 0-4% 0-100% 0-10% 0-100% n.d. -20 to +40C -10 to +80C -10 to +80C "ambient" 5-45C -20 to +70C 0 - 50C n.d.

"Robust Sensor" Pd Alloy film SD-750HB SD-750HB Ceramic Catalyst Ceramic Catalyst MOS EC "Pellistor" TCD Ceramic

Synkera TTI Nemoto C-Squared Nextech Nextech

LEL H2 Sensor P-Series NP-AHS H2 Analyzer Alpha prototype

Hydrogen Sulfide Carbon Monoxide


Not tested due to programmatic issues. GC In-situ Jun-05 .5ppb-100% -13 to +30C Peak Laboratories PERFORMER 1

17

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TABLE 7.2.1.b: Summary of Test Results for Sensors Tested at IIT


Summary of SSTUF Facility Sensor Testing, 2004-2005
Mfg Hydrogen Results Linear Range (at 1 atm) n.d. nd ATMI 0-2.5% 2-10% Figaro H2Scan RKI Dynamic Range 0 to <0.5% 0-5000ppm 0-4% 0-10% tested <10 sec <10 sec no data no data no data 29 19 60 <20 sec <20 sec Resp Time (T10-90) ext test in SSTUF nd 45 45 <60 <60 148 80 40 41 n.d. n.d. n.d. n.d.
O2 effect on 2%H2? (%Range over H2S response CO Response Repeatability Pressure Effect (1 std dev as %signal) (20 and 100ppb) (equiv H2 resp to 100ppm CO)

Temp Effect

RH Effect (@23C and 1atm)

Applied Sensors

<4% <4% not tested not tested <4% yes; <16% <4% <4% yes; 0-40%
no (for 5 min exp)

nd nd >5% >5% <2% <2% <2%

not tested not tested not tested


20ppm poisons sensor

no response no response no response no response no response no response not tested no response ~3% H2 not tested not tested no response n.d.

no quantifiable effect at 5psig no quantifiable effect at 5psig not tested not tested no quantifiable effect at 5psig
prop'l to H2 partial pressure, 1-2 atm

not tested not tested not tested not tested not tested not tested

not tested not tested not tested not tested not tested not tested

n.d. 0-0.5% 2-8% 2-8% (0-8% tested) (0-8% tested) 0-6% tested
0-2%, sat'd at 4%

not tested not tested no response

0-6% tested
0-2%, sat'd at 4%

not tested
no meas effect, 1- no meas effect; 3 atm 23-75C not tested prop'l to H2 part press no meas effect; 050% RH

Synkera TTI Nemoto C-Squared

non-linear 0-8% tested 2-10% 0-8% tested

0-15% 0-8% tested 0-10% tested 0-8% tested

0.27% no response 10% decr with each consec exposure not tested 1.97% <5% n.d. n.d. not tested not tested no response NA

not tested not tested not tested no effect 2345C n.d.

not tested not tested not tested

0-16% tested
-2%sig/%O2; 0-16% tested

not tested
not tested

BL shift 0.5% H2 over 0-85% RH; no effect on span

Hydrogen
Nextech n/a n/a y n.d. g <60 sec* n.d. p to BL on first exposure, did not respond on subsequent. n.d. n.d.

Carbon
Nextech Peak Laboratories 0-1% tested 0-1% tested 2 min NA none <2% none NA
not tested

not tested

no effect 0-50%?

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8. CONCLUDING COMMENTS

The status of chemical sensors for fuel cell safety applications is encouraging. There are several sensors commercially available which meet the requirements for safety applications. In the area of fuel reformer and fuel streams, however, substantial work needs to be done. None of the sensors tested for reformer applications met all the specified requirements as packaged. There are several sensors, however, that has the performance criteria needed, if it can be packaged to meet the temperature range. The RKI sensor exhibits excellent performance over the range of conditions for which it was tested (0-2% Hydrogen, ambient-750C, 0- 95% RH [non-condensing], and 1-4 atmospheres). There were no visible effects of temperature, humidity, or pressure over this range, and no response to CO or hydrogen sulfide. This sensor should perform as an excellent safety sensor. For reformate and in-stream applications, the sensor in principle should be able to be made suitable: The ceramic catalyst is amenable to high temperatures. The packaging could be redone to replace the plastic and other ambient condition materials with materials compatible with high temperatures, and the linear range could be extended by appropriate geometry of the exposure/diffusion path. Several other sensors provided suitable performance for safety applications of hydrogen, but none were designed to handle the higher temperatures and low oxygen levels of the fuel stream. No sensors were found to be ready for OTC-use for H2S or CO measurements. The Peak Laboratories GC yielded excellent results for CO in a high hydrogen background, but this was a complete instrument requiring carrier gas, not a sensor.

9. REFERENCES Sensor Needs and Requirements for Proton Exchange Membrane Fuel Cell Systems and Direct-Injection Engines - Report by Lawrence Livermore National Laboratory, May 2000, UCRL-ID-137767. Chemical Sensors for Automotive Fuel Cells Market Survey on Available Technologies for Hydrogen and CO - Kapil Gupta, Saeweon Roh, Joseph R. Stetter, William R. Penrose, William J. Buttner; Partial Fulfillment of the Subcontract Award to IIT from UTRC Through DOE Contract Number DE-FC04-01AL67616 (January, 2004).

16

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APPENDICES

17

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APPENDIX IIT-1:

Market Survey

Chemical Sensors for Automotive Fuel Cells


Market Survey on Available Technologies for Hydrogen and CO
by

Kapil Gupta and Saeweon Roh Joseph R. Stetter, William R. Penrose, William J. Buttner
Sensor Research Group BCPS Department Illinois Institute of Technology 3101 S. Dearborn Street Chicago, IL 60616

delivered to

Brian Knight
United Technology Research Corportation January 21, 2004

In Partial Fulfillment of the Subcontract Award to IIT from UTRC Through DOE Contract Number DE-FC04-01AL67616

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Chemical Sensors for Automotive Fuel Cells Market Survey on Available Technologies for Hydrogen and CO
Introduction: The Sensor Research Group (SRG) at the Illinois Institute of Technology (IIT) and member of the IIT Center for Electrochemical Science and Engineering has performed a market survey of available sensor technologies for UTRC in support of the Department of Energys (DOE) commitment to the development of a viable fuel cell technology1. This market survey was a part of a major DOE initiative with United Technology Research Corporation (UTRC) to develop reformer-based fuel cells for automotive applications. The survey should have direct application to other fuel cell sensor requirements. Sensor technologies for carbon monoxide and hydrogen were surveyed. The focus was on sensor types currently commercially available or those devices at a mature level of development such that production could be expected in the near future. In this survey, vender-supplied sensor specifications were compared to performance requirements for use in fuel cells. The fuel cell requirements were developed by DOE and were based on operating parameters that prevail in functional fuel cells. As other sensor types enter the market place and are identified, the listings in this report will be updated. The results of this market survey and the follow-up benchmarking performance testing by the SRG will be used by the prime contractor (UTRC) in the design and optimization of reformer-based fuel cells. It should be noted that manufacturers are hesitant to participate in such studies without the provision for confidentiality of data. While every attempt was made to include all possible vendors for this technology, there will be some that need to be added as this study progresses. In these cases, we identified the key technology and possibilities. But , in fact, the focus for this work is on sensors that can contribute in the near term. And, our intent is to provide positive feedback, in confidence, to the vendors about the performance of their sensors so they can be improved as well as validate one or more sensors for use in current fuel cell applications.

Industrial providers of sensor technology were identified through the WEB, open literature, personal contacts, and technical publications. Over 70 commercial sensor types (or mature developing technologies) were identified for hydrogen. Of these, five hydrogen sensor designs were identified that meet or most closely meet deployment requirements for fuel cells. A comparable number of carbon monoxide sensor types were surveys, but, of these, only two developing technologies met the deployment requirement. The most common failure mode was the inability to selectively measure trace carbon monoxide in the presence of hydrogen and the ability to meet temperature specifications over the expected temperature range.

Support provided through DOE Contract Number DE-FC04-01AL67616

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Requirements (Hydrogen) The sensor requirements for PEM fuel cells have been specified [1]. Through interaction with UTRC and DOE personnel, the requirements for the hydrogen and CO sensors were defined [2]. Two major applications exist for hydrogen sensors. A feedback control sensor is required for use in the reformer of the fuel cell. This sensor must operate internal to the fuel process stream. In addition, a second critical application is the need for an ambient air monitor for use as a safety monitor. Table 1 specifies the hydrogen sensor requirements for fuel cell application.

Table 1: Performance specifications for deployment of hydrogen sensors in reformer based fuel cells Specifications Fuel Processor Ambient Air (safety)
H2 Concentration Range Operational Temperature Response Time (sec) Environment (inside the fuel cell) 1 100% 70 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS (for passenger chamber) 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed) 5% FS 5 year lifetime

Accuracy

Survey Details Over 70 commercial sensor types (or mature developing technologies) were identified for hydrogen (see Appendix 3). Of these, less than twenty hydrogen sensor designs were identified that meet or nearly meet the deployment requirements for at least one application for fuel cells, although the availability of some sensor designs is not clear (e.g., the new hydrogen sensor recently announced from Nanomix). Of these only five devices closely meet the required specifications for the reformer application (three developing technologies were also identified). The fuel cell application requires hydrogen sensors for dual purpose for use in the fuel processor and for monitoring the concentration of hydrogen in the car cabin (safety purposes). Therefore, the sensors were surveyed for a relatively wider range of specifications listed above.

Numerous sensor technologies were identified that meet the safety requirements. The limiting technical requirement for the safety application was the ability of the sensor technology to monitor hydrogen in the presence of interfering gases. The hydrogen sensor for deployment within the reformer presents a greater challenge due to the harsh environment, and accordingly, fewer technologies were identified for that application. Selectivity and ability to operate throughout the required temperature range were the most challenging factors for the sensors. The inability to 2

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operate in high concentrations of hydrogen was also a main cause for rejection of sensors. Nevertheless, eight promising technologies for hydrogen monitoring have been identified. The sensor types for both applications are listed below, and are identified by their manufacturer/developer. When engineering data was available, the critical performance specifications are also presented in the list. Those sensors listed below without specifications were identified from marketing literature and often the manufacturers engineering specifications were not available or provided to the SRG. The marketing literature did claim to have performance characteristics relevant to the indicated application. In some cases, vender specifications did not quite meet the fuel cell requirements, but were sufficiently close to warrant inclusion in the lists below. Frequently for these cases the devices were simply not tested under conditions that prevail in the fuel cell. Thus the vender could not guarantee that the device would work, but felt confident that it would or that there is significant possibility for operation under the desired conditions in the near term. These devices were selected for further consideration.
Fuel Processor H2 Scan o H2 Conc. Range from 0.5 to 100% o No oxygen requirement, no interference with other gases o Promising Technology Thin-film Pd alloy resistor

Applied Sensors o Temp. Range : - 40 to 120 deg. C (typically 140 C ) o No cross sensitivity to N2, Ar, CxHx, CO, CO2, NOx. Low for NH3. o No influence from humidity at all o Pd transistor technology. Makel Engineering o H2 Concentration Range 10 ppm 100% o Temp Range : -70 to 125 deg C o 0-100 % RH , Air or inert background gas o SiC structures with Pd activation layers as resistors or Schottky diodes. NGK- Japan o No information available was obtained on this sensor. ATMI ( no sensor specs available) o No sensor specifications o Pd/rare-earth composite structure on hotplates technology.

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Three additional sensors appeared to have promise for the fuel processor application. Nanomix, Inc and a division of NanoProprietary are currently investigating a new nanotechnology approach for hydrogen sensing. The earliest reports of these sensors have appeared in the literature. It is unclear what final specifications will be achieved. The most troublesome feature is that all tests to date appear in air matrix and the need for oxygen may preclude operation in the fuel process stream. The third technology is available from Transducer Technology, Inc. and incorporates selective membranes and conductive nanocomposite designs for very low cost but may not meet response time and temperature requirement even though operation in 100% hydrogen has been demonstrated. Both of these technologies will be monitored during the year and included in tests as far as possible for either process applications or the safety application discussed below.
For Safety Sensor The safety application has less stringent specifications than for the reformer. The following companies have sensor technologies with performance specifications close to those listed in Table 1: H2Scan, Applied Sensors Makel Engineering Applied Nanotech Drager Safety Inc Nemoto Environmental Technology Figaro NGK TTI

We were also ready to consider Nanomix , Nano-Proprietary, and other technologies for this part of our investigation as the information and technology becomes available.
Requirements (Carbon Monoxide) The sensor requirements for PEM fuel cells have been specified [1]. There exists one major applications for CO gas sensors in the Fuel Cell application. CO is a notorious catalyst poison, and even the presence of low ppm levels of CO will dramatically degrade current efficiency. It is critical that the hydrogen feed gas be CO free, or at worse, that the CO concentration is at low ppm levels. To assure this in the Fuel Cell during operation, a CO sensor is required that can operate in the presence of high hydrogen levels. Table 2 specifies the CO sensor requirements for fuel cell application. CO Sensors Nextec Comag IR

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Table 2: Performance specifications for deployment of CO sensors in reformer based fuel cells Application Specification Reformate Medium Conc. Low Conc.
CO Concentration Range Operational Temperature Response Time (sec) Environment 1 100 ppm <150oC 0.1 - 1 high humid 30-75% H2 CO2 CO N2 H2O 1-3 ATM 1-10% FS 100 1000ppm 250oC 0.1 1 high humid 30-75% H2 CO2 CO N2 H2O 1-3 ATM 1-10% FS 0.1 2% 250-800oC 0.1 1 high humid 30-75% H2 CO2 CO N2 H2O 1-3 ATM 1-10% FS

Accuracy

Comag IR website : www.comag-ir.com Figaro : CO TGS203, CO TGS2442 website : www.figarosensor.com

There are also sensors for CO available from city technologies but these only work in low levels of hydrogen [<1000 ppm] and will not meet current temperature specifications. TTI has a version of its sensor for CO in the presence of hydrogen and may be possible to test by the time these investigations begin. We have seen respots in the literature for other hig temperature CO sensors but these are not close to commercial availability. See Appendix for sensor lists and specifications available.
Sensor Acquisition The devices listed above were identified as potentially viable detection technologies in the UTRC fuel cell program. This assessment was based on vendersupplied specifications; it is critical that these specifications now be validated. In some cases, vender specifications did not quite meet the fuel cell requirements, but were sufficiently close to warrant investigation. Frequently for these cases the devices were not tested under conditions that prevail in the fuel cell. The vender could not guarantee that the device would work, but felt confident that it would.

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Samples of the various sensor technologies are now being acquired. The manufacturers are being apprised of the goals of the project and are given the opportunity to participate in the assessment. Conversely, the manufacture may decline to have their technology evaluated in this DOE-Funded assessment. A generic copy of the letter describing our interest in the various sensor technologies is included in Appendix 2. Implementation of tests of the sensors is now being started. Our intent is to share results with our sponsors and as feedback to the companies but not necessarily to share details from company to company. In this manner, we encourage participation, provide informative feedback to possible vendors, and get the results we need for the fuel cell program.
Description of Technologies a) H2 Scan H2Scan purchased the hydrogen sensor, developed by researchers at Sandia National Laboratories, which detects hydrogen as low as 30ppm. Refer to Appendix for specification details. The sensor technology was initially marketed by DCH Tech and the sensor was termed as a robust hydrogen sensor specifically suitable for fuel cell applications. IIT SRG is in the process of procuring the sensors for testing and evalution. Sensing Function: Electronic Sensor (Change of Resistance or conductance) (http://www.h2scan.com/technology.html) The sensor contains a thin film of a palladium-nickel (Pd/Ni) resistor deposited on a silicon substrate that changes resistance in the presence of hydrogen. The lattice inherent in the Pd/Ni absorbs hydrogen molecules. As the number of hydrogen molecules in the lattice increases, the resistance of the Pd/Ni increases in direct correlation. H2scan systems interpret this change in resistance and display the hydrogen concentration to the operator, while also generating an analog signal that can be sent to external monitoring systems. No other gasses or environmental controls are necessary for these measurements; no oxygen is required for a reading. In addition to the Pd/Ni resistor, some units also feature a Palladium Field Effect Transistor (FET) that enables the unit to detect concentrations as low as 10 parts per million. In this unit, the Pd/Ni acts as the gate function for the FET based on a dipole formed at the silicon interface. The sensor also features a temperature sensing diode and two on-board FET heaters. Using these, H2scan systems maintain the sensor substrate at a constant temperature. This elevated, controlled temperature assures that sensor operation is unaffected by ambient temperature. b) Applied Sensors The AS-FHH450 sensor by Applied Sensor is based on Metal-OxideSemiconductor Field-Effect Transistors, MOSFETs, with a catalytic gate metal. As per the information provided by the OEM, the sensor specifications seem suitable for the use inside the fuel processor. Therefore the sensors have been procured and are being tested by the SRG at the IIT test facility.

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Sensing function: Hydrogen molecules interacts with the gate the transistor characteristics will shift the turn on voltage of the transistor. (http://www.appliedsensor.com/modules.php?name=Treepages&pa=showtreepage&pid= 23) Makel Engineering The smart hydrogen microsensor by Makel Engineering has promising specifications, both for use as a safety sensor and for use in fuel processor, as per the information provided by the OEM. Refer to Appendix for specification details. These sensors would also be tested and evaluated at IIT if they can be provided. Sensing function: (http://www.grc.nasa.gov/WWW/RT1999/5000/5510hunter.html) Two palladium chrome (PdCr) hydrogen detection devices were included in each sensor package: A Schottky diode for low concentrations and a resistor for high concentrations. These devices change electrical properties when hydrogen gas is present and the output is appropriately monitored. d) Nemoto Co & Ltd., Japan [To Come] Upto 4% H2 detection for industrial application. Sensing Function: (http://www.nemoto.co.jp/product_e.html) Catalytic type sensor (Tin oxide type)- output resistance change by sample gas. No detailed interference data is available but we will continue to request and gather information on this sensor. RKI sensor by Argus Group: RKI sensors are customized for use as a safety sensor in the passenger chamber of vehicles operating on fuel cell. The compact size, vibration and water resistant design makes it a potential candidate for deployment. Refer to Appendix for specification details. Sensing Function: (http://www.fuelcellsensor.com/) Catalytic diffusionoutput potential changes when hydrogen is present in the sample gas. The catalytic sensor is heated and most versions respond to any combstible gas. The processor without oxygen will not be possible but the safety sensor application is possible for this technology. f) Transducer Technology Inc. Sensing function: 3 Electrode type Electrochemical gas sensor. (http://www.transducertech.com/); Several unique modifications will allow this sensor to respond to H2 in the presence of CO and vice versa. Also, the sensor signals are uniquely stable in high hydrogen concentrations. These sensor warrant further investigation if samples can be obtained. References: e) c)

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

1.

Sensor Needs and Requirements for Proton Exchange Membrane Fuel Cell Systems and Direct Injection Engines Sponsored by the Department of Energy, Energy Efficiency and Renewable Energy, Office of Automotive Technologies, Edited by Robert S. Glass, JoAnn Milliken, Ken Howden, and Roglieo Sullivan, Lawrence Livermore Laboratory (2000). Sensor Needs and Requirements for Proton Exchange Membrane Fuel Cell Systems and Direct Injection Engines; William Penrose, Letter Report on the Project Kickoff Meeting October 15, 2002.

2.

Supporting Documents Appendices 1and 3 provide additional information on the identified technologies. Sensor performance specifications on promising technologies is presented in Appendix 1. Appendix 3 lists the various manufacturers that were screened in this survey.

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

APPENDIX 1
Sensor Performance Specifications for Hydrogen and CO sensor Identified for use in Fuel Cell applicatons

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number:

Primary Gas and Vender Specified Application

Company Information
Name Address AppliedSensor, Inc. 400 Lanidex Plaza Parsippany, NJ 07054 (973) 887-6900 www.appliedsensor.com
Application Fuel Processor Ambient Air (safety)
(inside the fuel cell) 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS (in the vehicle) 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed) Accuracy 5% FS 5 year lifetime

Contact Information
Name and title Address Thomas Aiken, COO

Phone FAX Email WEB site

Phone FAX Email

(973) 887-5900 Tom.aiken@appliedsensor.com


Application Fuel Processor Ambient Air (safety)

Specifications (looking for)


H2 Concentration Range Operational Temperature Response Time (sec) Environment

Vender Specifications
0-5% -40 120 oC 140 oC typical

<2s (T75), <5s (T90) <1s (T90) with algorithm No cross sensitivity to N2, Ar, CxHx, CO, CO2, NOx. Low for NH3.
no influence from humidity

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

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COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Stability: Span Drift Stability: Background/Zero Drift Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air required Other Operating Requirements

Range
5% < 1s (T90) . -40 120oC -

Measurement Conditions/Comments
Bad - Its either Fuel processor or Ambient Air (safety) No data available When algorithm is used. Otherwise: < 2s (T75), < 5s (T90) No data available No data available No data available No data available No data available. Span as function temp. ? No data available. Baseline as function of temp? No data available No data available. ? See above See above ? More then 5 years ? More then 10 years ?

Years Years 80 mW at 140oC Voltage, U0-U = 0 1 V <1s Field Effect Yes No

No data available. (We might (predict) relevant data) No data available. (We might (predict) relevant data) No data available. (We might (predict) relevant data) Module?

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number: 6809185

Primary Gas and Vender Specified Application

Company Information
Name Address Drager Safety Inc.

Contact Information
Name and title Address Tom Fleming

Phone FAX Email WEB site

412-787-8383 412-787-2207
Application Fuel Processor Ambient Air (safety)
(inside the fuel cell) 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS (in the vehicle) 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed)

Phone FAX Email


Vender Specifications
0-2000ppm -20oC - 50oC 90% response in <20 sec 10-90% RH 20.7 38.4 inches Hg <+/-5% of measured value

Specifications (looking for)


H2 Concentration Range Operational Temperature Response Time (sec) Environment

Application Fuel Processor Ambient Air (safety)

Accuracy

5% FS 5 year lifetime

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection
Cross-Sensitivities: Positive - CO, NO, SO2, H2S, HCN, PH3, Ethylene, Acetylene, Methanol Negative Cl2 and NO2

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air requirements Other Operating Requirements

Range

Measurement Conditions/Comments

3-6 months

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HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number: Various

Primary Gas and Vender Specified Application


H2scan produces products only for hydrogen gas detection.

Company Information
Name Address H2Scan, LLC.
25133 Anza Drive, Unit B Valencia, CA 91355

Contact Information
Name and title Address Nate Speer
25133 Anza Drive, Unit B Valencia, CA 91355

Phone FAX Email WEB site

661-775-9575 www.h2scan.com
Application Fuel Processor Ambient Air (safety)
(inside the fuel cell) 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM (in the vehicle) 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed)

Phone FAX Email

661-775-9575 nspeer@h2scan.com
Application Fuel Processor Ambient Air (safety)
0.5 100% -20C - 40C 0C - 100C 1% to 40% 3s Calibrated at 1 atm (Needs to be compensated for other pressures) 0.5 50% -20C - 40C 0% to 3% 7s

Specifications (looking for)


H2 Concentration Range Operational Temperature Response Time (sec) Environment

Vender Specifications
Range Ambient temp. for Elect. Gas temp. T90 from: Not affected by other gases. Oxygen not required to operate. Water content affects performance at 30% and higher.

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616 Accuracy 1-10% FS 5% FS 5 year lifetime

Final Report December 5, 2005 Multiple breakpoint curve enveloping accuracy. 5 year life.
+/- 0.20% H2 @ 0.5%, +/- 0.15% H2 @ 1.0%, +/- 0.20% H2 @ 2.0%, +/- 0.25% H2 @ 3.0%, +/- 0.50% H2 @ 5.0%, +/- 1.0% H2 @ 10%, +/- 2.0% H2 from 50% to 100%

COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection This is our current technology (RHS). See second form submitted for technology in development. Power req.:2W nominal consumption, avail: instrument only at this time, no O2 required, principle of detection: thin film palladiumalloy resistor (see attached description of tech.)

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit)

Range
0-100% H2 0.1% H2 T90 of 7 seconds @ 3% H2 0 See above See above Less than 866 ppm/mo. Less than 866 ppm/mo. None None See above None required None 5 years 5 years 2W @ 12-24 VDC nominal Digital and analog 0-5V or 4-20mA 6-12 months 15 minutes Solid-stat Pd alloy film See attached H2scan is OEM $2500

Measurement Conditions/Comments
Near LFL Zero output when concentration less than 0.5% H2

Digitally compensated system Digitally compensated system

10 years expected 10 years expected Full scale set per customers specification (1% to 100% H2)

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616 Oxygen/air requirements Other Operating Requirements None

Final Report December 5, 2005

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number: Various

Primary Gas and Vender Specified Application


H2scan produces products only for hydrogen gas detection.

Company Information
Name Address H2Scan, LLC.
25133 Anza Drive, Unit B Valencia, CA 91355

Contact Information
Name and title Address Nate Speer
25133 Anza Drive, Unit B Valencia, CA 91355

Phone FAX Email WEB site

661-775-9575 www.h2scan.com
Application Fuel Processor Ambient Air (safety)
(inside the fuel cell) 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS (in the vehicle) 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed)

Phone FAX Email

661-775-9575 nspeer@h2scan.com
Application Fuel Processor Ambient Air (safety)
10 ppm 100% -20C - 40C 0C - 100C TBD 10 ppm 100% -20C - 40C TBD

Specifications (looking for)


H2 Concentration Range Operational Temperature Response Time (sec) Environment

Vender Specifications
Range Ambient temp. for Elect. Gas temp. T90 from: Not affected by other gases. Oxygen not required to operate. Water content affects performance at 30% and higher. TBD 5 year life

Accuracy

5% FS 5 year lifetime

10

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COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection This is our pending technology (WRS) in development.

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air requirements

Range
100% H2 TBD TBD TBD See above See above TBD TBD None None TBD None required None 5 years 5 years TBD Digital and analog V or mA TBD TBD Solid-stat Pd alloy film See attached H2scan is OEM TBD None

Measurement Conditions/Comments

Digitally compensated system Digitally compensated system To incorporate pressure compensation 10 years expected 10 years expected Full scale set per customers specification (1% to 100% H2)

11

United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616 Other Operating Requirements

Final Report December 5, 2005

12

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HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number: Smart Hydrogen Microsensor

Primary Gas and Vendor Specified Application

Company Information
Name Address 1585 Marauder St. Chico, CA 95973 Phone FAX Email WEB site Tel: 530.879.2770 Fax: 530.895.2777 Makel Engineering, Inc.

Contact Information
Name and title Address Jeffrey Stroh, Sales Manager 1585 Marauder St. Chico, CA 95973 Phone FAX Email Tel: 415.345.1247, 530.879.2770 Fax: 530.895.2777 jdstroh@standardhydrogen.com
Application Fuel Processor Ambient Air (safety)
.1 100% 70 to +125 oC 0.1 1 initial response H2O (10 30%) CO2 N2 1-3 ATM 0.1 10% -30 to +80 oC <1 initial response 10 - 98% RH HC (as needed) Vacuum to 20 ATM (typical range, higher pressures available)

http://www.makelengineering.com Application Specifications Fuel Processor Ambient Air (safety) (inside the fuel cell) (in the vehicle) (looking for)
H2 Concentration Range Operational Temperature Response Time (sec) Environment 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed)

Vendor Specifications
10ppm 100% -55 to +125 oC <1 initial response Air or Inert background gas 0-100% RH

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616 Accuracy 1-10% FS 5% FS 5 year lifetime

Final Report December 5, 2005 .1-10%FS (application defined) 1-10% FS 5% FS 5 year lifetime

COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Stability: Span Drift Stability: Background/Zero Drift Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air required Other Operating Requirements

Range
100% <1 sec for initial response -55 to +125 oC

Measurement Conditions/Comments

Significantly higher temp range is in development

Vacuum to 20 ATM 0-100% RH

10 years 10 years 1-1.3 watts 0-5 VDC, 4-20 mA 6-12 mos <3 seconds Pd Alloy Microsensors

Significantly lower power consumption is in development

Variable based on application Oxygen/air not required

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HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number: NP-AHS

Primary Gas and Vender Specified Application


Hydrogen Monitoring in air for safety purposes

Company Information
Name Address Nemoto Environmental Technology

Contact Information
Name and title Address David Bone Director Rayne House 3, The Street, Rayne,, Braintree, Essex CM77 6RH UNITED KINGDOM +44 (0)1376 560763/4 (Two Lines) +44 (0)1376 560550 david.bone@nemototech.com
Application Fuel Processor Ambient Air (safety)
YES

Rayne House 3, The Street, Rayne,, Braintree, Essex CM77 6RH UNITED KINGDOM Phone +44 (0)1376 560763/4 (Two Lines) Phone FAX +44 (0)1376 560550 FAX Email david.bone@nemototech.com Email WEB site www.nemototech.com Application Vender Specifications Fuel Processor Ambient Air (safety) Specifications (inside the fuel cell) (in the vehicle) (looking for)
H2 Concentration Range Operational Temperature Response Time (sec) Environment 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed) Accuracy 5% FS 5 year lifetime 0-5000ppm -20 70oC

Measured as what? Ours is T90 - <8s 0-99% (Non condensing) ? +/- 200ppm

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COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Stability: Span Drift Stability: Background/Zero Drift Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air required Other Operating Requirements

Range
4% Hydrogen in Air +/- 2% FSD T90 <8 secs +/- 200ppm -20 - +7- deg C -20 - +70 deg C <+/- 1%FSD / month <+/- 40ppm / month N/A <9ppm/deg C 800-1200mBar N/A AS ABOVE! AS ABOVE! None 3-5 years 6 months 1.6V, draws 140mA 75mV/1% Hydrogen in air Recommended 3 months 20 secs Catalytic pellistor Potential ignition source N/A N/A $20-30 Air N/A

Measurement Conditions/Comments
(100% LEL)

Depends on application and working environment Standard Wheatstone Bridge Circuit Dependent on Application and accuracy required Sensor should be housed behind flame arresting sinter (Frit) Sensor can be supplies as complete Explosion proof assembly (P/No NET-22-AHS)

Dependent on quantities Will work in Oxygen concentrations >2%

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HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number:

TGS821

Primary Gas and Vender Specified Application


Transformer maintenance, Batteries, Steel industry usage

Company Information
Name Address Figaro USA, Inc. 3703 West Lake Avenue, Suite 203 Glenview, IL 60025, USA (847)832-1701 (847)832-1705 figarousa@figarosensor.com
Application Fuel Processor Ambient Air (safety)
(inside the fuel cell) 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS (in the vehicle) 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed) Accuracy 5% FS 5 year lifetime

Contact Information
Name and title Address Taro Amamoto VP, Engineering Same as in the left

Phone FAX Email WEB site

Phone FAX Email

Same as in the left amamoto@figarosensor.com


Application Fuel Processor Ambient Air (safety)

Specifications (looking for)


H2 Concentration Range Operational Temperature Response Time (sec) Environment

Vender Specifications
10 - 5000 ppm -20 -- 80 oC 10 - 60 10 - 95% RH

10 - 20 % FS 5 year lifetime

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COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air requirements Other Operating Requirements

Range
5000 ppm 10% FS 10 - 60 secs. 80 deg. C 100 deg. C

Measurement Conditions/Comments

natural environment 5 years 1 year 660 +/- 55 mW DC 1 - 5V no maintenance 5 min. Metal oxide semi-conductor Explosion-proof SUS mesh

@US$33 at 100 pcs. natural environment

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HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number:
Hydrogen Sensor

Primary Gas and Vender Specified Application


Fuel cell application

Company Information
Name Address Fuel Cell Sensor

Contact Information
Name and title Address Jay Fitzgerald

Argus Group 46400, Continental Drive Chesterfield Township MI 48047 Phone 1-800-873-0456 Phone FAX 586-840-3201 FAX Email info@fuelcellsensor.com Email jfitzgerald@argus-group.com WEB site www.fuelcellsensor.com Application Vender Application Specifications Fuel Processor Ambient Air (safety) Specifications Fuel Processor Ambient Air (safety) (inside the fuel cell) (for passenger chamber) (looking for)
H2 Concentration Range Operational Temperature Response Time (sec) Environment 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed) Accuracy 5% FS 5 year lifetime 0-10,000 ppm -10 to 80 C <= 10 sec to reach 90%

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COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air requirements Other Operating Requirements

Range

Measurement Conditions/Comments

0-95% RH (n-condensing)

1watt at 12V D.C 0.5 to 4.5 V D.C. proportional to the detector range Catalytic Diffusion

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HYDROGEN (H2) Gas Sensor Data Table


Sensor Information
Part Number:
HD-PSW-A1

Primary Gas and Vender Specified Application


Hydrogen

Company Information
Name Address Applied Nanotech, Inc. 3006 Longhorn Blvd. Suite 107 Austin, TX 78758

Contact Information
Name and title Address Kwok Ng 3006 Longhorn Blvd. Suite 107 Austin, TX 78758

Phone FAX Email WEB site

512-339-5020 Phone 512-339-5020 512-339-5021 FAX 512-339-5021 zyaniv@appliednanotech.net Email kng@appliednanotech.net http://www.nano-proprietary.com Application Vender Application Specifications Fuel Processor Ambient Air (safety) Fuel Processor Ambient Air (safety) Specifications (inside the fuel cell) (in the vehicle) (looking for)
H2 Concentration Range Operational Temperature Response Time (sec) Environment 1 100% 70 - 150oC 0.1 - 1 H2O (10 30%) CO2 N2 1-3 ATM 1-10% FS 0.1 10% -30 80oC <1 10 - 98% RH HC (as needed) Accuracy 5% FS 5 year lifetime 0.5 100% -20 170 oC < 1s H2O O2 N2 CO2 N/A 0.5 100% -20 170 oC < 1s H2O O2 N2 CO2

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COMMENTS: (available as OEM, power requirements, size requirements; available as detector only or instrument system, oxygen requirements, principle of detection

Other Details/Specifications:
Maximum Concentration Precision/Repeatability Response Time Background/Zero Reading Temp. Range: Continuous Temp. Range: Intermittent Stability: Span Drift Stability: Background/Zero Drift Temp. Coefficient: Span Temp. Coefficient: Baseline Operating Pressure Total Water Vapor Pressure Position Sensitivity Expected Lifetime Storage Life Power Requirements Output Signal (type/range) Calibration Frequency Warm-up Time Technology Safety (explosive, radioactive etc) Mech.(drop test, size) EMI OEM Cost (per unit) Oxygen/air requirements Other Operating Requirements

Range
100% < 1s Zero current -20 170 oC -20 170 oC None at room temperature None at room temperature 1 atm > 1 year > 1 year 0.1 1V 0 0.1 mA N/A Palladium alloys nanoparticles arrays N/A

Measurement Conditions/Comments

N/A

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COMAGIR CO Sensor Specifications The digital InfraRed, extended calibration gas sampler for Carbon Monoxide, Hydrocarbons and Acetylene in industrial safety and HVAC systems Lab-quality infrared gas detection available for professional and domestic applications in demand control ventilation and environmental safety appl's.
Sensor type: Technical data: Measurement range Options Characteristics: Accuracy of gas measurement 15 ppm in 15 to 30C range 40 ppm outside Repeatability 5 ppm Resolution 2 ppm (CO) / 5 ppm (HC) Warm up time < 60 seconds Response time < 1 second Air pressure correction - 0.13% of reading / mm Hg Measurement range temperature - 30 to +50 C, digital Temperature accuracy < 0.5 C @ 5 - 40 C Temperature repeatability < 0.2 C Functions: Sampling interval 30 sec standard 3 sec - 4 hours, user selectable Standard output RS232 ,0-4V analog Alarm relay output General: Material Size Weight Color Supply voltage Current consumption Wiring On/Functional Sheet metal, 24 gauge (LxWxH) 172 x 158 x 42 mm 860 g Bone 12VDC <1.5W ave. < 0.5A sample - 0.12A idle Terminal block, Phoenix type Green LED, steady/flashing 0 - 800 ppm standard (0 - 0.08%) Other ranges on custom order Microprocessor controlled fully digital, non-dispersive dual wavelength infrared, temperature compensated

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- Extended calibration, High resolution, Special performance - No calibration gas ever required - BacNet version available

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616

Final Report December 5, 2005

APPENDIX 2 Cover letter sent by the SRG to vendors requesting samples of sensors for Benchmark Testing

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APPENDIX 3

List of companies surveyed, but the products were either not found acceptable or venders were not able to provide sufficient information or declined to provide any sensors or support:
1. ECD - Energy Conversion Devices, Inc. -MI 2. Element 1 Power Systems Inc. - CA 3. EPI - Energy Partners, Inc. - FL 4. FCE - FuelCell Energy, Inc. - CT 5. Global Thermoelectric - AB, CANADA 6. Hydrogenics Corporation - ON, CANADA 7. JLG Industries, Inc. - PA 8. Magnetek - CA 9. Plug Power - NY 10. Dais-Analytic Corporation - FL 11. Avista Labs WA 12. Fuel Cell Safety Systems MI 13. Fuel Cell Sensor- MI 14. Air Instruments And Measurements, Inc. - AIM - CA 15. Ametek - PA 16. Analytical Industries, Inc. - CA 17. Analytical Technology, Inc. (ATI) - PA 18. AppliedSensor Inc. - NJ 19. Aqualytic - GERMANY 20. Biosystems - CT 21. BW Technologies - AB, CANADA 22. . NJ 23. Comag IR Inc. - MN 24. Conspec Controls Inc. - PA 25. Crowcon Detection Instruments Ltd UK 26. Datatest, Inc. PA 27. Detcon, Inc. - TX 28. Dijita Controls Ltd. - BC, CANADA 29. Dryden Aqua - UK 30. Eco Sensors, Inc. NM 31. Gas Tech, Inc. - CA 32. GLI International WI 33. Hanna Instruments - RI 34. Ion Optics Inc. MA 35. Lumidor Safety Products - FL 36. ME Grisard GMBH - GERMANY 37. Mettler-Toledo, Inc. - OH 38. MicroChemical Systems SA - SWITZERLAND 39. Monitor Labs Inc. - CO 40. Nemoto & Co.,Ltd - JAPAN 41. Net Safety Monitoring Inc. - AB, CANADA 42. Rae Systems Inc. - CA 43. Scott Instruments - PA 44. Sencera Company Ltd. -

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United Technologies Corporation. DOE Contract No. DE-FC04-01AL67616


45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75.

Final Report December 5, 2005

Sensidyne Inc. - FL Sierra Monitor Corporation - SMC - CA Telaire - CA TPS Pty Ltd - AUSTRALIA TSI Incorporated - MN Uniloc Division Fisher-Rosemount - CA Vaisala - MA Vernier Software & Technology - OR ATEQ Corp - MI TPI Test Products International - OR UView Ultraviolet Systems - ON, CANADA Yokogawa Corp. Of America - GA Zellweger Analytics / Astro / Polymetron / Sieger / Solomat GA ATC Inc. - IN Industrial Test Equipment NY CEA Instruments, NJ Applied Analytics Alpha Omega Instruments Corp. AltOptronic AB Amercian Innovations Amtek Inc (PA) Anarad Inc Armstrong Monitoring Corp Bascom-Turner Instruments Control Instruments Corp. NJ Delphian Corporation- NJ Delta Instruments LLC NJ Drager Instruments Inc. NJ CODEL International Inc- PA Advanced Instruments Inc CA HRL laboratories - CA

List of Companies Contacted For Carbon Monoxide Sensors


Comag IR Fluke Nextec (http://www.nextechmaterials.com/) Figaro (http://www.figarosensor.com/) TTI

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APPENDIX IIT-2: SSTUF Facility Operators Manual

IIT SSTUF Users Manual.doc

IIT\Users Manual\Bill of Materials SSTUF-09

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APPENDIX IIT-3: Test Reports Double click icon to open file; close file to return to main report document. A3-1: Applied Sensors AS-FFH-400 A3-2: Applied Sensors AS-FFH-450 A3-3: ATMI; October, 2004 A3-4: ATMI; April, 2005 A3-5: C-Squared A3-6: Figaro TGS821 A3-7: Figaro TGS2613 A3-8: H2Scan; November, 2004 A3-9: Nemoto A3-10: Nextech H2S Sensor A3-11: Peak Laboratories (CO) A3-12: RKI; April, 2004 (Safety) A3-13: RKI; July, 2005 (Gas stream environment) A3-14: Synkera A3-15: TTI Hydrogen Sensor

AppliedSensorsRepor t-AS-FHH-400-G08-04

AppliedSensorsRepor t-AS-FHH-450-NH3_0

ATMI OCTOBER04.doc

ATMI Report-APR2005.doc

C squared report 080805.doc

FigaroReport--May2 004_TGS821.doc

FigaroReport--May2 004_TGS2613.doc

H2Scan_Report-Nov 04.doc

Nemoto Report-MAY2005.doc

NEXTECH 050704 CO Test Plan-NEXTECH d

Nextech Summary-Initial Testin

Nextech Summary-Second Tes

Peak Report--July 2005.doc

RKI sensor 2nd round tests 0705.doc

RKIReport--April200 4a (1).doc

SynkeraLELH2Sensor sPN7000003testresul

TTI Report - April 2004.doc

sensor test summary.xls

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Appendix III Development of Sensors for Automotive PEM-based Fuel Cells Final Report
Frank DiMeo, Jr. Philip Chen Barry Chen Jeffrey Neuner Jim Welch ATMI, Inc. 7 Commerce Dr. Danbury, CT 06810 203-794-1100

September 28, 2005

Prepared for UTRC/IFC & The United States Department of Energy Under Cooperative Agreement No. DE-FC04-02AL67616

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1.

Introduction

Effective hydrogen gas detection and monitoring will be required for the safe, efficient, and reliable utilization of fuel cell technology in mobile, hydrogen-based vehicles and stationary hydrogen-derived power sources. Fuel cells require two types of sensors; the first monitors the quality of the hydrogen feed gas, and the second for life safety leak detection. A fast speed of response is a critical requirement for life safety monitoring. It is also necessary for real time control of processes that run on rapid duty cycles. For industrial applications, sensors must be hydrogen-selective and immune to impurity gases, such as sulfur, that are commonly present in hydrogen feedstock. Existing gas sensors, such as catalytic bead or electrochemical, are not adequate, either technically or from a cost standpoint. To address this, we have developed MEMS (Micron-Electro-Mechanical System) based solid-state sensor arrays for the detection of H2, and hydrogen sulfide (H2S) gases. There are several forces driving the development of micro-machined sensor platforms for fuel cell applications. Primary among these are the need to minimize device size and power consumption, and the need to produce large quantities of sensors at low cost. In this project, we have developed a new type of MEMS based sensor for hydrogen and H2S gas detection. The MEMS platform, known as a micro-hotplate, is a suspended thermal isolation structure with an embedded heater element. The ability to elevate the local temperature above ambient in a controlled manner makes the micro-hotplate platform particularly useful for gas sensing applications based on chemical reactions.

2.

Project plan

The goal of this project was to develop MEMS based solid state sensors for gas detection in the multi-component environments found in fuel cell applications. This project was divided into three tasks, based on the chemical composition of the detected gases. Task 1:Develop H2 sensors using metal hydride systems. Task 2:Demonstrate sensors for sulfur compounds using ultra-thin metal films. Task 3: Demonstrate sensors for NH3 using metal hydride and metal sulfide thin films. During the course of this study ammonia was no longer considered to be a problem due to improvement of the quality in feed gas. Consequently, limited efforts in the development of NH3 sensors were employed. Both tasks 1 and 2 were carried out in close collaboration with UTRC/IFC in order to ensure the sensors were developed and tested in relevant environments.

2.1 Technical approach


Micromachined thin film hydrogen gas sensors developed at ATMI are built upon a microhotplate platform. Our embodiment of the micro-hotplate is a micromachined thermal isolation structure with an embedded polysilicon resistive heater where elevated temperature can be achieved with ease. The micro-hotplate layered stack is fabricated via a CMOS-compatible

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foundry process and has been described elsewhere.2 The as-received micro-hotplate platforms were subsequently etched at ATMI to create suspended thermal isolation structure. A rare earth metal thin film over-coated with a palladium-based cap layer serves as the active sensing layer. The metal-insulator transition induced by hydrogenation of rare earth metals is a known phenomenon, and detection of hydrogen using rare earth metal hydride has been proposed as far back as 1973.3 However, the proposed approach was specific to steel industry and not adaptable for other applications. The recent discovery of spectacular changes in optical and electrical properties of thin film rare earth metals upon hydrogenation4 sparked great interest in these materials. We immediately recognized the technological advantages in using these novel thin film materials for hydrogen sensing.5 With the support of the DOE Hydrogen Program, we have continued to develop micro-hotplate based hydrogen gas sensors incorporating rare earth metal coatings as the active sensing layer. These new sensors incorporate novel rare earth metal coatings that react with hydrogen upon exposure, leading to a change in electrical resistance that scales with hydrogen concentration in the gas phase. The reaction is reversible and the reaction kinetics can be engineered by the micro-hotplate temperature. We have previously demonstrated fast speed of response (< 1 second), large signal range (120% resistance change at 0.25% H2), and low-level sensitivity (< 200 ppm). In this program, we further exploited various protective coatings for detection of high-levels of hydrogen, and demonstrated long sensor life time with barrier layer protection for rare earth sensing layer. We have also investigated ultra thin metallic films on the microhotplate platform for H2S sensing. A chemical-mechanical planarization (CMP) process was also developed to obtain a flat surface on the hotplate allowing the deposition of ultra thin sensing films

2.2 Technical objectives


This program was focused on achieving the following two objectives 1) Develop H2 sensors using metal hydride systems. 2) Demonstrate sensors for hydrogen sulfide using ultra-thin metal films.

2.2.1 Hydrogen sensor development


We have tailored our hydrogen sensor technology to the two separate hydrogen environments as specified in the DOE solicitation. The first environment examined the detection of H2 in ambient (life safety) conditions, while the second environment was for the H2 sensing in the fuel processor. In order to efficiently achieve the stated objectives, the following three tasks were identified and executed: (1) Modification of the precious metal protective layer for high concentration
2 S. Semancik, R.E. Cavicchi, M.C. Wheeler, J.E. Tiffany, G.E. Poirier, R.M. Walton, J.S. Suehle, B. Panchapakesan, D.L. DeVoe, Microhotplate platforms for chemical sensor research, Sensors and Actuators B 77, 579-591 (2001). 3 S.M. Toy and A. Phillips, Rare earth hydrogen detector, U.S. Patent 3,732,076 (1973) S.M. Toy, Hydrogen detection means, U.S. Patent 3,768,975 (1973). 4 J.N. Huiberts, R. Griessen, J.H. Rector, R.J. Wijngaarden, J.P. Dekker, D.G. de Groot, N.J. Koeman, Yttrium and lanthanum hydride films with switchable optical properties, Nature 380, 231 (1996). 5 G. Bhandari and T.H. Baum, Hydrogen sensor utilizing rare earth metal thin film detection element, U.S. Patent 6,006,582 (1999); F. DiMeo and G. Bhandari, Micro-machined thin film hydrogen gas sensor, and method of making and using the same, U.S. Patent 6,65,222 (2001).

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hydrogen detection, and (2) Development of diffusion barrier layers and examination of sensor long-term behavior.
2.2.1.1 Modification of the protective layer We have successfully developed fuel process (stack) sensors based on various precious metal protective layers for high concentration H2 detection. Both Rh and Ir were used to replace the Pd protective layer for sensing high hydrogen concentrations with various degrees of success. Thereafter, with the incorporation of oxidation protective layer in the Pd based sensors we have further improved the stack sensor properties and met the stringent requirements for fuel cell applications. 2.2.1.2 Improvement of long-term sensor performance There are many inputs to the short- and long-term stability of theses sensors: design and fabrication of micro-hotplate platform, materials science of the functional layer, sensor packaging, to name a few. We sought to develop an understanding of these mechanisms and to feed this knowledge back for design/fabrication improvement. Based on these studies, we have developed barrier layers in the metal hydride system and demonstrated life safety H2 sensors with long life time and fast response.

2.2.2 Hydrogen sulfide sensor development


We have developed a CMP process in planarizing the microhotplate platform to allow the deposition of ultra thin films. We have investigated various metallic thin films, such as Rh, Ir, Cu and Cr. Although only the Rh film reacted with the H2S gas, we have achieved the detection of 10 ppb concentration H2S through the optimization of film thickness and operating temperature.

3. Experimental results
3.1. Device design and fabrication

3.1.1 Device design


The micro-hotplate structure, developed at the National Institute of Standards and Technology (NIST) has been described in detail in the literature. The structure is shown in Figure 1. Typical physical characteristics of these devices are listed in Table 1.

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SiO 2

Al SiO2

Al

SiO2

Poly -Si

SiO2

Figure 1. Structure of the NIST developed micro-hotplate.

Table 1. Typical physical characteristics of the micro-hotplates.

Feature Suspended Mass Suspended Area Maximum Surface Temperature Thermal rise time, fall time Efficiency

Measure ~0.2 g 50 m x 100 m, 550 C 1-3ms, 3-4 ms ~12 C / mW

Comment Low thermal mass Small size High Temperature Operation > 105 C/s Low Power Consumption

The microhotplate structure employed in this study permits measurement of electrical resistance of the gas-reactive coating via the top contacts as a function of temperature, which is controlled using the embedded poly-silicon heater. The micro-machining step creates the suspended structure, which is thermally isolated from the substrate. This, together with the small thermal mass, enables extremely rapid heating and cooling while using minimal power. The microhotplate can then be used as a gas sensor by depositing a gas-reactive coating. The response of the gas-reactive coating is typically a function of the gas concentration, temperature and time. The rapid thermal response of the micro-hotplate permits the measurement of transient responses that cannot be realized by any other means.

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3.1.2 Device fabrication


The microhotplate platform layout and layer construction were produced by a commercial foundry. Computer aided designs were submitted electronically to the foundry and fabricated using a CMOS process. The fabricated chips were etched to preferentially remove exposed silicon and form the suspended micro-bridge. After this process, the gas sensing elements were functionalized by the deposition of the active layer(s). Figure 1 shows the micro-hotplate design used for this study. The silica frames surrounding the aluminum via were removed with chemical-mechanical planarization (CMP) process to obtain a flat surface on the hotplate for the deposition of sensing films. Figure 2 shows the surface profiles of the micro-hotplate before and after the CMP process. The polished microhotplates were subsequently released by gaseous XeF2 etching to remove the silicon from underneath the microhotplate platform and its surrounding areas. An e-beam evaporation process was then used to deposit the sensing layers. The processed dies were then diced and each individual sensor was packaged onto TO-5 header.
20 Scan Height (Angstrom) 0 -20 -40 x10 20 0 -20 -40x10 100
3 3

'Before CMP' 'After CMP'

150

200

250

300

350

400

Scan Distance (micron)

Figure 2. Surface profiles of the micro-hotplate before and after CMP process.

3.1.3 Device temperature measurement


Temperature control is an important aspect of sensor performance. The microhotplate employs an embedded polysilicon resistor as the heating element. Polysilicon has a significant temperature coefficient of resistivity , which can be useful towards relative temperature measurement. The polysilicon resistance can be expressed as a function of joule power: R = Rambient [1 + (T Tambient )] Rambient (1 + WH ) where Rambient is the heater resistance at ambient temperature (i.e., at zero joule power), is the heater efficiency, and WH is the joule power delivered to the heating element. The microhotplate temperature can then be inferred from the measured heater resistance:
T Tambient + 1 (R Rambient 1)

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or, alternatively, the applied joule power: T Tambient + WH This heater efficiency depends on the deposition conditions and therefore can vary from process to process. To minimize the variation in temperature coefficient, only one batch of sensors (T1ATBH) was used for this program. Placing the microhotplate device in an environmental chamber and measuring the polysilicon heater resistance at temperatures from 40 to 140 C yielded a temperature coefficient of resistivity of approximately 0.000655/C for the chosen foundry process, as shown in Figure 3. Based on this technique, the heater efficient of the hydrogen sensor was determined to be around 12 C/mW.

Polysilicon Heater Resistance 3.3 3.25 3.2 3.15 3.1 3.05 3 2.95 2.9 2.85 2.8 2.75 -50 0 50 Temperature (C) 100 150

Resistance (Kohm)

43-34A 34-24A 38-25B 33-23A 37-33B 41-28A

Figure 3. Polysilicon heater resistances of T1ATBH sensors measured from 40 to 140 C.

The heater resistance data, as shown in Figure 3, display a slightly higher slope at temperatures between 80 and 140 C. This is not surprising, as the resistance of polysilicon is known not to be increased linearly with temperature. Figure 4 shows the heater resistances of a microhotplate at temperatures between 20 and 300 C. The value (slope) for this device was calculated to be 0.000736 and 0.00099/C, respectively, for temperatures ranged from 20 to 150 and 200 to 300 C. Consequently a temperature coefficient measurement derived at the specific temperature range is needed for using this heater efficiency technique in sensor temperature determination.

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3700 Resistance (ohm) 3600 3500 3400 3300 3200 3100 50 Alpha = 0.000736 100

Alpha = 0.00099

150 200 Temperature (C)

250

300

Figure 4. Heater resistance of a micro-hotplate at various temperatures. The temperature coefficient of resistivity increases significantly at temperatures between 200 and 300 C.

The sensor operating temperature can also be determined with the power consumed using a temperature-based heating efficiency assessment. This technique is believed to give a more accurate heater temperature measurement than the temperature coefficient technique, as it does not involve the measurement of temperature coefficient of heater resistance. Considering that constant temperature and constant resistance are equivalent provided that the resistance has a one-to-one relationship with temperature (even if it's non-linear), one has the following relation, Ta = Top W where Ta and Top are ambient temperature and hotplate operating temperature, respectively. If one plots the ambient temperature versus joule power, the data should present a straight line. The intercept gives hotplate operating temperature and the slope gives (negative) heating efficiency. The same sensor used for heater resistance measurement, as shown in Figure 4, was placed in a furnace that was maintained at a fixed temperature of 300 C. After the resistance measurement, the furnace temperature was sequentially reduced and the power consumption required to maintain the heater resistance at the 300 C value was measured. Figure 5 shows the power required at temperatures between 100 and 250C for maintaining a sensors heater resistance at 300C value. The slope gives a heating efficiency of about 10.77 C/mw for this micro-hotplate.

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350 300 Temperature (C) 250 200 150 100 50 0 5 10 Power (mw) 15 20 y = -10.767 x + 302.43

Figure 5. Power consumptions at various temperatures for achieving the equivalent heater resistance at 300 C. The slope yields sensors heater efficiency.

3.2

Hydrogen sensors

3.2.1 LEL (lower explosion limit) application


With domestic natural gas, sulfur-containing mercaptan gases are introduced in order to alert the consumer to a gas leak. This approach is not possible for hydrogen usage in fuel cell applications, as the fuel cell catalysts can be poisoned. Consequently, hydrogen sensors are needed to monitor the environment around the fuel cell for hydrogen leaks, as hydrogen is highly combustible with a lower explosion limit (LEL) of 4.0% in air.

3.2.1.1 Sensing material The LEL hydrogen sensors developed in this program employ rare earth yttrium metal thin films as the active sensing layer, and coated with a palladium overlayer for oxidation protection and dissociation of hydrogen molecules, as shown in Figure 6. Electron beam evaporation was used to deposit yttrium and palladium layers without breaking vacuum. The nominal thicknesses were 250 nm for the yttrium layer and 25 nm for the palladium overlayer, respectively. The microhotplate platform was not intentionally heated during the evaporation of either layer. Functionalized dies were packaged in a standard chip carrier and connected electrically by wire bonding.

In the presence of gaseous hydrogen, dissociated hydrogen atoms diffuse through the palladium layer to react with the yttrium hydride layer. This new sensor uses the reversible hydrogenation of yttrium hydrides as the sensing mechanism. Initial hydrogenation of the yttrium metal is an irreversible formation of the di-hydride phase. Further hydrogenation of the yttrium induces a continuous and reversible transition between the di-hydride and tri-hydride phases. Significant changes in the optical and electrical properties of these materials accompany this transformation. In particular, the electrical resistance can increase several orders of magnitude, making it a very sensitive transduction mechanism.

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H2 Pd YHx Al SiO2

Figure 6. Schematic of the yttrium hydride based micro-hotplate sensor.

The response time of these bilayers is rather slow at room temperature, but can be greatly enhanced with moderate heating. Thus the combination of micro-hotplate and rare earth metal thin film has resulted in hydrogen sensors with a greatly reduced response time. Long term response test of these Pd/Y bilayer sensor yielded significant baseline drift, which was attributed to the oxidation of the yttrium layer. Metallic diffusion barriers of Ta and Cr were then added to the top and bottom of the yttrium layer, respectively, for oxidation protection.

3.2.1.2 Sensor testing manifold A gas manifold, as shown in Figure 7, was used to examine sensor performance with sub-second time resolution. The gas manifold was constructed using low-volume 4-way gas chromatography valves in combination with 1/8 stainless steel tubing leading to a small volume chamber (approximately 2 cm3). The small volumes of all gas handling parts facilitated fast purge during gas switching even at low flow conditions; e.g., 8 chamber volumes are exchanged in under 1 second at a flow rate of 1000 sccm. To measure electrical resistance of the sensor element, a small sensing current of 0.1 mA was employed to minimize possible in-plane electromigration of negatively charged H species. The ambient gas used for the experiment was either filtered compressed air with a dew point of 40C or dry nitrogen from a liquid nitrogen source. Hydrogen was blended with the clean, dry air to achieve the designated concentration using mass flow controllers. The hydrogen concentration in the gas ambient quoted is taken from the ratio of the hydrogen flow readout to total flow readout. No separate concentration measurement was in place.

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To Vent To UHP Hydrogen Source Single Stage Regulator Filter 4 Filter 3 Filter 2 Manual Valve

Manual Valve Manual Valve

To Compressed Dry Air Source. Filter 1

All piping used is 1/4" stainless steel. The GC valve has 1/8" connections. All 1/4" pipe is then converted to 1/8" pipe at the GC valve. The pipe to the sensor after the GC valve is 1/8" stainless steel.

Figure 7. Schematic of the H2 sensor testing manifold.

3.2.1.3 Alpha bi-layer LEL Sensor Response Characteristics

3.2.1.3.1

Sensor response as a function of temperature

As previously mentioned the response time of the micro-hotplate based sensor is strongly depended on the sensor operating temperature due to the nature of the hydrogen diffusion mechanism. A higher temperature will improve the sensor response time, but too high a temperature may degrade the sensor and limit the lifetime. Pd/Y bi-layer sensor was operated under various degrees of power to determine the optimum (minimum) operating temperature, and Figure 8 shows the response of a H2 sensor under powers between 4 to 6.5 mw with 0.4 and 1.4% H2 exposures. An operating power of about 7 mw, or a temperature of about 110 C appears to be needed to achieve a fast response.

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100 80 60 40 20 Resistance (ohm) 100 80 60 40 20 100 80 60 40 20 2.0 1.5 1.0 0.5 0.0 0 1000 2000 3000 4000 Time (sec) 5000

'% H2' '4.02 mw' '5.21 mw' '6.52 mw' 6000 7000

% H2

Figure 8. Pd/Y bi-layer sensor responses under various power to the heater. A power of about 7 mw is required to achieve the optimum performance.

3.2.1.3.2 Sensor response as a function of hydrogen concentration in air


Sensitivity and response time are prominent characteristics of interest for sensor applications. For life safety scenarios, early detection is critical to damage prevention and personnel survival. The sensor signal strength and response time were examined as functions of hydrogen concentration in the gas ambient. The response characteristics at several hydrogen concentrations are summarized in Figure 9 and Figure 10. From a baseline of 32.5 in the absence of hydrogen, one derives signal strength of 300% at 1% hydrogen in air. The response to 242-ppm hydrogen is shown in greater detail in Figure 11. At this low concentration, the sensor exhibits a fast response time of 1.54 seconds after valve switching, or a 0.28 second delay for the signal onset from the baseline reading.
160 140 120 RS () 100 80 60 40 20 0 20 40 60 80 100 Time (minutes) 120 140 160 1% 0.5% 0.25% 0.12% 555 ppm 242 ppm

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Figure 9. Sensor resistance response of a Pd/YHx hydrogen sensor to several hydrogen concentrations as a function of time. The sensor exhibits fast response and sufficient signal strength at 240 ppm for life safety applications.

100 80 RS () 60 40 20 0
2 3 4 5 6 7 8 9

10

7 8 9

H2 (ppm)

10

Figure 10. Sensor signal response of a Pd/YHx hydrogen sensor as a function of hydrogen concentration in air ambient.

39 38 37 RS () 36 35 34 33 32 300 200 100 0 -10 0 10 20 30 Time (seconds) 40 50 60 H 2 (ppm) 0.28s apart

Figure 11. Sensor resistance response of a Pd/YHx hydrogen sensor to 242 ppm hydrogen concentration as a function of time. This low-level hydrogen concentration is approaching the control limits of the mass flow controllers, as evidenced by the presence of quantization noise. The sensor exhibits fast response and sufficient signal strength at this low concentration.

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3.2.1.3.3 Sensor long-tern stability


3.2.1.3.3.1 Sensor long-term response

Long-term stability is an important requirement for any type of sensor. To test the stability of stability, hydrogen sensors were connected to a long-term gas manifold and exposed to hydrogen over a three-month period. The temporal sequence of the gas stream included a 24-hour dry air purge followed by a 10-minute exposure to 1% H2. Figure 12 shows this long-term test result. Although the sensor remained fully functional at the end of experiment, there is a noticeable upward drift in the baseline resistance, which was attributed to the gradual oxidation of the rare earth layer, as yttrium is prone to oxidation due to a large Gibbs free energy gain upon reaction.
35

30 Resistance(Ohms) H2 Conc (%)

25

20

15

10 1.0 0.8 0.6 0.4 0.2 0.0 0 10 20 30 Time(days) 40 50 60 70

Figure 12. Two-wire resistance response of a micro-hotplate based hydrogen gas sensor over a threemonth period under repeated exposure to 1% H2.

3.2.1.3.3.2 Sensor baseline drift Figure 6 shows a schematic of the layered construction of the sensor stack. The Pd top layer is intended to prevent oxidation, as well as dissociate hydrogen molecules. At the bottom interface between yttrium and SiO2, thermodynamic calculation indicates a favorable oxidation reaction of Y due to transfer of oxygen from SiO2 to Y. This reaction is desired as it helps the adhesion of the yttrium layer to SiO2. However, the observed excess resistivity drift warranted a reassessment of the sensor design.

Two Pd/Y/SiO2/Si specimens were prepared on planar wafers (i.e., no hotplate structure). They were deposited with Pd and Y of nominally identical thickness, and stored in room air for one (#1) and six months (#6), respectively. Four point probe measurements indicated that the sheet resistance of specimen #1 increased only marginally after aging for one month, and that of #6

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increased by 10% over a six-month period. Samples from both wafers were sent out for Auger Depth Profile analysis and the results are shown in Figure 13.
100 80 Composition (%) 60 40 20 0 0 1000 2000 3000 Sputter Depth (nm) 4000 5000 Pd/Y/SiO2, one month aging O1 Si4 Y1 Pd1_ls2

(a)
100 80 Composition (%) 60 40 20 0 0 100 200 300 400 Sputter Depth (nm) 500 600 Pd/Y/SiO2, 6-month aging

O1 Si4 Y1 Pd1

(b)
Figure 13. Auger depth profile of aged Pd/Y/SiO2/Si specimens as a function of sputter depth. (a) one month (b) 6 month aging.

There was already extensive intermixing of yttrium and oxygen (out-diffused from SiO2 dielectric) after one month of aging, and more than half of the yttrium layer was consumed by oxidation after 6 month. These results support the hypothesis that loss of active material is responsible for the resistance drift observed on the sensor platform. The extent of inter-diffusion indicated that the kinetics were relatively fast and persisting, contrary to our initial assumptions. Furthermore, for specimen #6, oxygen apparently broke through the Pd cap layer and reacted with yttrium. The inter-diffusion between yttrium and SiO2 must be deterred to achieve a reasonable sensor lifetime.
3.2.1.3.3.2.1 Bottom Barrier layer proof of concept Yttrium and oxygen species have exhibited high diffusivity when yttrium is in intimate contact with SiO2, leading to the consumption of the active yttrium layer. To preserve sensor

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functionality, it is necessary to separate yttrium and SiO2 spatially by a diffusion barrier. After considering various factors such as oxidation resistance and process compatibility, we chose aluminum and chromium as leading candidates for barrier layer materials. Thermodynamically, aluminum in intimate contact with SiO2 will take oxygen away from silicon, potentially forming an aluminum oxide passivation layer. Chromium, on the other hand, should remain metallic; if oxygen were to diffuse into and react with chromium however, the resulting chromium oxide would also be a passivation layer and thus prevent oxygen from reaching the yttrium layer. An experimental matrix of 32 cells was carried out to verify the proposed barrier layer function. The 3 variables for this matrix were 1) the choice of substrate (SiO2 or Al2O3), 2) the hydride state of the yttrium phase (metal or dihydride), and 3) the choice of annealing atmosphere(air or N2). Planar sapphire and quartz were chosen as substrates representing SiO2 and Al2O3. Half of the samples were first annealed in hydrogen for 30 minutes at 100C to convert yttrium metal to yttrium hydride. This split was conceived to verify the result from thermodynamic analysis that yttrium hydride is more oxidation resistant than yttrium metal. Lastly, the samples were split upon annealing for 24 hours in either air or N2. In the case of air, oxygen is present in both the top and bottom interfaces; in the case of N2, the sole oxygen source is the substrate. The results are summarized in Table 2.
Table 2. Sheet resistance (in / ) of specimens at various post-processing steps. The samples are identified by a three-letter code: A(l2O3) or S(iO2), H(ydride) or M(etal), and A(ir) or N(itrogen) anneal. The last row is the increase in sheet resistance upon annealing.

SHA SHN SMA SMN As-deposited 3.93082 4.0450 3.99934 4.1173 6 5 Hydrogenated 2.79986 2.84931 2.74305 2.8224 9 Air anneal 2.9921 4.4637 2.9901 4.65 N2 anneal 2.8486 4.6252 2.8464 4.7205 R 0.4166 0.0239 0.19224 -0.0007 6 0.5102 0.24705 1 0.65066 0.60315 For comparable conditions, film stacks on sapphire always exhibited less change in resistance, R, than those on quartz, and hydride films exhibited less R than metal films. These results suggest that Al2O3 probably serves well as a diffusion barrier material, and yttrium hydride is indeed more oxidation resistance than yttrium metal. For hydride films on sapphire, no resistance increase was observed when annealed in N2, and the observed increase upon air anneal is apparently caused by oxidation from oxygen in the ambient air. Auger analysis of the SHA sample, as shown in Figure 14, confirms the efficacy of the Cr barrier layer.

AHA AHN AMA AMN 3.96982 4.03651 4.04704 4.115

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100 Pd/Y/Cr/SiO2 80 Composition (%) 60 40 20 0 0 100 200 300 400 Sputter Depth (nm) 500 600 'O1 ls3' Si4 'Cr2 ls5' 'Y1 ls1' 'Pd1 ls2'

Figure 14. Auger depth profiles of the SHA sample indicated that the Cr bottom layer successfully prevents the inter-diffusion of yttrium and oxygen between YH2 sensing layer and SiO2 substrate.

3.2.1.3.3.2.2 Top Barrier layer proof of concept Auger results of the Pd/Y/SiO2/Si indicated the break through of oxygen through the Pd caplayer and reacted with yttrium after a 6-month storage in air, as shown in Figure 13. A thin layer of Ta was proposed to prevent this top layer oxidation, as Group VB elements were reported to have higher hydrogen permeability than palladium. Furthermore, Ta does not alloy with yttrium under the process and operating conditions. Similar to the consideration for the bottom interface barrier, ideally one would choose a thickness that is minimal to retain signal strength but large enough to deter inter-diffusion. We chose to first experiment with 5 and 10 nm barrier thickness. The Pd/Y/Cr trilayer was nominally 25 nm/250 nm/7.5 nm for all stacked structures. Half of the samples were first annealed in 0.5% H2 for 30 minutes at 80C to convert yttrium metal to yttrium hydride. The accelerated degradation was carried out for 24 hours at 100C in either room air or N2. For specimens with tantalum barrier, an additional 64 hours in room air was performed subsequently to confirm barrier function. The resistivity figures taken from the resistivity tool (RESMAP) are in unit of /, and an accuracy of 0.5% specified by the tool vendor. For ease of comparison, the results are shown as conductivity () and summarized in Table 3. Resistance degradation corresponds to conductivity loss, or a positive . Ideally, one prefers a small or zero .
Table 3. Sheet conductivity (in /) of specimens at various post-processing steps.

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Pd/Ta/Y/Cr/SiO2/Si Annealing Air N2 ambient 0 5 10 0 5 10 Thickness (nm) 0.3332 0.2974 0.3448 0.3291 0.2982 0.3443 As-deposited 0.3016 0.3467 Post 24hr-anneal 0.2801 0.3052 0.3599 -0.0034 -0.0024 from metal 0.0531 -0.0077 -0.0151 0.3048 0.3633 Post 88hr-anneal 0.0004 -0.0034 from 24hr Pd/Ta/YH2/Cr/SiO2/Si Annealing ambient Thickness (nm) As-deposited Hydrogenated Post 24hr-anneal from metal Post 88hr-anneal from 24hr Air N2

0 5 10 0 5 10 0.3280 0.2874 0.3396 0.3261 0.2929 0.3449 1.1352 1.0639 1.1732 1.1237 1.0576 1.1799 1.1334 1.0854 1.2265 1.1278 1.0905 1.2129 0.0018 -0.0215 -0.0534 -0.0041 -0.0329 -0.0330 1.1016 1.2120 -0.0162 0.0145

The results indicated that the insertion of a tantalum barrier layer between palladium and yttrium was effective in reducing conductivity loss. The barrier was effective at a thickness of 5 nm and did not depend on whether yttrium layer had been hydrogenated. It should be noted that, unlike chromium, tantalum does react with hydrogen to form tantalum hydride. Alloying between palladium and tantalum cannot be entirely excluded because the existence of intermetallic phases. These chemical reactions may explain the observed negative conductivity loss (or equivalently, conductivity gain). Two Pd/Ta/Y/Cr specimens on SiO2/Si wafers were sent for Auger depth profiling. The two specimens had nominally the identical layer stack as-deposited: 25 nm Pd/10 nm Ta/250 nm Y/7.5 nm Cr on SiO2/Si. One specimen was first annealed in 0.5% H2 for 30 minutes at 80C to convert yttrium metal to yttrium hydride. Both specimens subsequently underwent accelerated degradation, which was carried out for 88 hours at 100C in room air. Their depth profiles are shown in Figure 15. There was some extent of intermixing between Cr and SiO2 as was observed before. Oxygen was found in chromium layer but not into the yttrium layer yet, reaffirming that the chromium layer maintained its function as an oxygen diffusion barrier. Tantalum layer, on the other hand, still let a very small amount of oxygen through. The oxygen inflow was higher for Pd/Ta/YHx/Cr than for Pd/Ta/Y/Cr even though we had shown earlier that YHx is less prone to oxidation than Y. The postulation is that the Pd/Ta bilayer was stressed when the underlying yttrium underwent hydrogenation and expanded in volume. The Pd/Ta bilayer is not ductile and therefore some micro-cracks could have happened which would become conduits for oxygen diffusion. The unhydrogenated specimen did not have this expansion history and therefore the Pd/Ta barrier 33

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function was better maintained. A possible process route to circumvent this drawback is to hydrogenate yttrium prior to subsequent depositions.
100 80 Composition (%) 60 40 20 0 0 100 200 Sputter Depth (nm) 300 Pd/Ta/YH/Cr/SiO2

'O1 ls6' Si4 'Cr2 ls4' 'Y1 ls3' 'Pd1 ls1' 'Ta1 ls2'

(a)
100 80 Composition (%) 60 40 20 0 0 50 100 150 200 Sputter Depth (nm) 250 300 'O1 ls6' Si4 'Cr2 ls4' 'Y1 ls3' 'Pd1 ls1' 'Ta1 ls2' Pd/Ta/Y/Cr/SiO2

(b)
Figure 15. Auger depth profiles of (a) Pd/Ta/YHx/Cr on SiO2/Si wafer and (b) Pd/Ta/Y/Cr on SiO2/Si wafer.

3.2.1.4 Beta quad-layer sensor response characteristics

3.2.1.4.1

Sensor response time

The newly developed Pd/Ta/Y/Cr quad-layer structure was used to fabricate micro-hotplate H2 sensors. The main concerns with these quad-layer structure sensors in sensor performance were the effects of Cr bottom barrier on the sensor baseline drift and the Ta top barrier on sensor response time, even though Ta was known to have a higher permeability for H2 than that of palladium. Sensors with a 7.5 nm Ta layer and 10 nm Cr layer were fabricated and tested at 95 C with a train of 0.5% H2 pulses in clean, dry air. The results are shown in Figure 16. The sensor responded to hydrogen with good signal strength and response speed, but the signal level 34

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was not stable until after 3 pulses later. Similar break-in behaviors have been observed for bilayer sensors, and therefore it cannot be conclusively attributed to the presence of a tantalum barrier layer. The sensor achieved a steady state within the test period, and there was no noticeable loss of signal strength or response speed. Figure 17 shows the expanded response with a fast response time of 2.14 seconds after the valve switching, and a 0.6 seconds delay for the signal onset from the baseline.
80 Response (ohm) 70 60 50 40 30 % H2 20 0.5 0.0 0 1000 2000 3000 Time (sec) 4000 5000 '% H2' 'Sensor B' BH-76-26B-1, 95 C, Air

Figure 16. Temporal sensor response sequences to 0.5% H2 in clean, dry air.

80 Response (ohm) 70 60 50 40 30 % H2 20 0.5 0.0

BH-76-26B-1, 95 C, Air

0.6 sec apart

'% H2' 'Sensor B'

2980

2990

3000 Time (sec)

3010

3020

Figure 17. Sensor resistance response of a Pd/Ta/YHx/Cr hydrogen sensor to 0.5% H2 in air exposure.

3.2.1.4.2

Quad-layer sensor baseline drift

The Pd/Ta/YHx/Cr quad-layer sensors were fabricated and tested under a nominal heater voltage of 5V. Figure 18 shows the resistance responses of these quad-layer hydrogen sensors at room air for 180 days. The average sensor baseline drift of the operating sensors was determined to be 2.68% + 1.09 %/month. Figure 19 shows the effect of sensor operating temperature on 35

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baseline drift of a batch of quad-layer sensors. Surprisingly, higher operating temperatures did not cause a greater drift. The low operating sensor temperature indicates low heater efficiency, and poor sensor response. It also tends to yield abnormal drift rate. This wide spread of sensor operating temperature was attributed to a poor control in the XeF2 etching process that caused the variation in heater efficiency. We have subsequently monitored the heater efficiency of each sensor in process and adjusted the XeF2 etching process accordingly to narrow down the heater efficiency spread.
BH-108, 5V Sensors Baseline Drift

Series1 Series2 Series3 Series4 Series5 Series6 Series7 Series8 Series9 Series10 Series11 Series12 Series13

12 10 Response (ohm) 8 6 4 2 0 0 50 100 Time (day) 150 200

Series14 Series15

Figure 18. Baseline drift profiles of normal heater efficiency quad-layer LEL sensors under 5V operation. The average drift rate per month was about 2.68%.
BH-108, 5V Sensors 16 14 12 10 8 6 4 2 0 -2 0 -4 -6

Drift Rate (%/month)

50

100

150

200

Temperature (C)

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Figure 19. Effect of heater temperature on baseline drifts of quad-layer sensors. High operating temperature did not equate to high drift rate, and abnormal drift rates were associated with poor heater efficiency.

3.2.1.4.3

IIT results

3.2.1.4.3.1 Testing protocol The Pd quad-layer sensors were tested at IIT Sensor Research Group with Shared Sensor Test User Facility (SSTUF) under specific test conditions using ATMI provided sensor testing electronics board. The ATMI board was designed to output a digital response proportional to device resistance that can be read on a computer through a terminal emulator program. The sensors were tested with the following test protocol: 1. A repeatability test consisting of five sequential exposures to 2% hydrogen in air

2. 3.

A linearity test from 0 to 4% hydrogen at 0.5% increment steps A second series of exposures to 2% hydrogen that included effect of 100 ppm CO interference

All exposures were 5 minutes duration followed by a five-minute recovery in air. The gas mixtures were generated by mixing 10% hydrogen in nitrogen with air or using 100 ppm CO in air without dilution. The actual compositions of the background gas ranged from 20% N2/ 80% O2 to 48% N2/48% O2 for hydrogen concentrations of 0 to 4%, respectively. This variation in oxygen concentration did not affect the sensor performance. Figure 20 shows the gas mixture and resistance response profiles of a Pd quad layer sensor.
100
Sensor Response

ATMI H2 Sensor
8.0V %H2

CO

60 40 20 0 0 50 100 150 200


TIME (Approximate Minutes)

Figure 20. Gas mixture and sensor resistance response profiles of a Pd quad-layer sensor tested at IIT.

3.2.1.4.3.2 Sensor response characteristics The Pd quad-layer sensor exhibits a fast, reversible response under 2% hydrogen exposures. Figure 21 shows the resistive response profiles of a Pd quad-layer sensor under 2% hydrogen exposures at 8 and 8.5 V. The t90 response time at 8.5 V was calculated to be about 2 seconds. The response profile indicates good signal repeatability with the identical 5-minute exposure cycles to 2% hydrogen.

37

Gas Composition

80

5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 250

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100 80
Sensor Response

ATMI: Device T1AT-BH-76-6

60 40 20
8.0V

0 0 5 10 15 20 25 30 35 40 45 50
TIME (approxim ate m inutes)

100 80
Sensor Response

ATMI: Device T1AT-BH-76-6

60 40 20
8.5V

0 0 5 10 15 20 25 30 35 40 45 50
TIME (approxim ate m inutes)

Figure 21. Resistive response profile of a Pd quad-layer sensor under 2% hydrogen exposures.

The dynamic range (range in which a change in concentration induces a measurable change in signal) of the Pd quad-layer sensor was obtained by plotting the net responses as shown in Figure 22 vs. hydrogen concentration. Figure 23 shows the results. The sensor shows a dynamic range of about 0- 3 % H2 with good linearity exists in the entire range. Figure 24 shows that the Pd quad-layer sensor yields no detectable response or suffers any adverse effect from the exposure of 100 ppm CO.

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90 80 Sensor Response 70 60 50 40 30 20 10 0 0 15 30

T1AT-BH-76-6 (Vh = 8.5)

45 60 75 90 105 Time (approximate minutes)

120

135

150

Figure 22. Sensor response to 0 to 4% hydrogen at 0.5% increment steps, in ascending and descending orders.
Tt1AT-BH-76-6; 8.5V 60 Net Sensor Response 50 40 30 20 10 0 0 0.5 1 1.5 2 % H2 2.5 3 3.5 4 ascend descend

Figure 23. Net sensor response for a Pd quad-layer sensor under various hydrogen concentration exposures.
ATMI H2 Sensor aat 8.5Vh (CO interferance)
#15 #6 2% H2 100ppmCO

100 80
Sensor reposne

5
Gas Composition

4 3 2 1 0 0 5 10 15 20 25 30 35 40 45 50 Time (approximate minutes)

60 40 20 0

Figure 24. Resistive response of a Pd quad-layer sensor to a series of 2% hydrogen/air exposures and a single exposure to 100 ppm CO in air.

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3.2.2 Stack application


Monitoring the H2 content in the feed gas is critical for the successful implementation of fuel cell technology. The H2 concentrations of these feed gases can range from 40 to 99.9%, depending on the fuel cell design. The Pd quad-layer sensors developed in this program for hydrogen leakage detection was explored for the stack application. Modifications of the Pd protective layer thickness and sensor operating temperature were used to improve the sensors performance in stack environment. Quad-layer sensors based on other precious metals, such as Rh and Ir, were also fabricated and tested for stack applications.

3.2.2.1 Pd quad-layer sensor

3.2.2.1.1

Preliminary test results

Testing of the Pd quad-layer LEL sensor under stack conditions (in N2 background, instead of air) resulted in an incomplete recovery. Figure 25 shows the heater resistance and sensor responses of a Pd quad-layer sensor under 60% hydrogen balance nitrogen exposures. This incomplete recovery was attributed to poor hydrogen out diffusion due to lack of oxygen. When operated in air at temperatures around 100 C, the oxygen in air appears to act as a getter that enhances the out diffusion of hydrogen. Without this oxygen pull, the hydrogen cant be released in a timely fashion, and the residual hydrogen causes the elevation of baseline response.

Resistance(Ohms) [H2] (%)

60 50 40 30 20 Rh(Ohms) 0

7920 7880 7840 7800 50 0

10

15 20 Time(min)

25

30

35

Figure 25. Response profile of a Pd quad-layer LEL sensor under 60% H2/N2 exposures. Lack of oxygen prevents a complete recovery.

3.2.2.1.2

Stack sensor response as a function of temperature

As previously mentioned, temperature is a critical aspect of the sensor performance. This is especially true for the Pd quad-layer sensor in stack application. To expedite the out diffusion of absorbed hydrogen in the oxygen deprivated environment, the sensor needs to be operated at a much higher temperature. Figure 26 shows the resistive responses of a Pd quad-layer sensor 40

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with repetitive 40% H2/N2 exposures at various operating temperatures. Increasing the sensor operating temperature significantly improved the recovery, and a complete recovery was achieved at around 200 C. Figure 27 shows the expanded response of this sensor with a fast response time of 1.4 seconds after the valve switching, and a 0.7 seconds delay for the signal onset from the baseline. An improved Pd quad-layer sensor with a better e-beam control for Pd evaporation yielded a probably thinner Pd protective layer and a lower temperature required for complete recovery, as shown in Figure 28. Figure 29 shows the expanded response of this improved sensor with a slightly longer 2.1 seconds after the valve switch and a 1.4 seconds delay for the signal onset from the baseline. This reduction in operating temperature is critical in achieving sensor longterm stability that will be discussed later in the baseline drift section.
100 BH-76-26B, N2

Response (ohm)

80

60

40 '% H2' '95 C' '130 C' '165 C' '200 C' 0 1000 2000 3000 Time (sec) 4000 5000

20 50 40 30 20 10 0

% H2

Figure 26. Resistive responses of a Pd quad-layer sensor under various operating temperatures. An operating temperature of about 200 C is needed for complete recovery. The apparent time shift in response at 95 C was due to variation in the logging frequency, which depends on other on-going computer operations.

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80 Response (ohm) 70 60 50 40 30 20 40 20 0 2210 % H2

BH-76-26B, 200 C, N2

0.7 sec apart

'% H2' 'Sensor B'

2215

2220

2225 Time (sec)

2230

2235

2240

Figure 27. Expanded resistive response of a Pd quad-layer stack sensor at 200 C.

30 Response (ohm) 25 20 15 10 5 0 40 20 0 0 % H2

BH-99-34A

'% H2' '130 C' '165 C' 1000 2000 3000 Time (sec) 4000 5000

Figure 28. Resistive responses of an improved Pd quad-layer sensor under various operating temperatures. An operating temperature of about 165 C is sufficient for complete recovery.

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30 Response (ohm) 25 20 15 10 5 0 40 20 0 2210 2215 2220 2225 Time (sec) 2230 2235 2240 % H2 1.4 sec apart BH-99-34A, 165 C, N2

Figure 29. Expanded resistive response of a Pd quad-layer stack sensor at 165 C.

3.2.2.1.3

Stack sensor response as a function of hydrogen concentration

The calibration (concentration) curve of the Pd-quad-layer stack sensor at 200 C operation was constructed with repeating exposures of hydrogen concentration from 1.25 to 40% in balanced N2. The expose and recovery times were fixed at 7.5 and 10 minutes, respectively. Since the resistive responses of these Pd quad-layer sensors tend to decrease gradually in the first couple cycles as indicated in Figure 26, the responses of the third cycle was used for the construction of concentration curve. Figure 30 shows the response profiles of a standard Pd quad-layer sensor with various hydrogen exposures, and Figure 31 shows a concentration curve derived from the third responses of the hydrogen exposures. An over 300% response (R/R) was achieved with this sensor at 40% H2/N2 exposures, with a dynamic and linear range detected between 1.25 and 40% H2 in N2.

40 BH -78-33A,200 C , N 2 Response (ohm) 30

20

'% H2' '40% H2' '30% H2' '20% H2' '10% H2' '5% H2' '2.5% H 2' '1.25% H2'

10

0 1.2 0.8 0.4 0.0 0 500 1000 1500 T ime (sec) 2000 2500 3000

H2 on/off

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Figure 30. Response profiles of a standard Pd quad-layer sensor at 200 C with hydrogen exposures from 1.25 to 40%.

400 BH-78-33A, N2, 200 C 300 Delta R/R (%)

200

100

0 0 10 20 % H2 30 40 50

Figure 31. Concentration curve of a standard Pd quad-layer sensor.

Figure 32 and Figure 33 show the response and calibration curve, respectively, of an improved Pd quad-layer sensor at 165 C. At a lower operating temperature of 165 C, the degradation in sensor response during the first couple exposure cycles appears to be minimized. However, the response (R/R) of this sensor was significantly less than those of the standard Pd quad-layer sensor. This lower response of improved sensor was attributed to a higher baseline resistance, as the net response (R) was not much different from those of the standard sensor. The dynamic range of this improved Pd quad-layer sensor was also reduced to around 30% hydrogen, and nonlinearity was detected in the concentration curve.
30 Response (ohm) 25 20 15 10 5 H2 on/off 0 1.0 0.0 0 1000 2000 3000 Time (sec) 4000 '% H2' '40% H2' '30% H2' '20% H2' '10% H2' '5% H2' '2.5% H2' 5000 BH-99-26, 165 C

Figure 32. Response profiles of an improved Pd quad-layer sensor at 165 C with hydrogen exposures from 2.5 to 40%.

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200 180 160 Delta R/R (%) 140 120 100 80 60 0 10 20 % H2/N2 30 40 50

Figure 33. Calibration curve of an improved Pd quad-layer sensor.

3.2.2.1.4

Moisture effect on stack sensor performance

3.2.2.1.4.1 Humidity generation The stack application necessitates the testing of sensors in a humid environment ranged from 0 to 100% relative humidity (RH). To fulfill this requirement, an evaporator consists of 3/8 O.D. copper tubing coils was fabricated to generate water vapor for the screening of stack sensors under humid nitrogen. The copper coil evaporator was filled with water (at midpoint) and placed inside an oven at controlled temperatures. Various N2 flows were then used to carry away the water vapor and generate moist N2 gas. The amount of water evaporated was controlled with the N2 flow used and oven temperature, and the relative humidity of the generated N2 stream was measured at room temperature with a humidity sensor sitting on a Tee. High relative humidity flow can be generated with this evaporator for wet test of stack sensors. 3.2.2.1.4.2 Calibration of the evaporator A Sensirion SHT75 humidity sensor was used to monitor the relative humidity and temperature of the N2 flow. Temperature monitoring is critical, as relative humidity depends strongly on the temperature of the flow. The evaporator was initially left inside the oven for over 2 hours before initiation of experiment to allow the water reaches the desired temperatures. Nitrogen flow was then introduced and the induced humidity and temperature changes indicated by the humidity sensor were recorded. Figure 34 shows the evaporator set-up inside the oven, while Figure 35 shows the calibration curves of the bottom coil between 5 and 20 C with 500 sccm of N2 flow. The relative humidity of the N2 flow reaches a steady state in about 30 minute, and a relative humidity of about 70% was achieved on an oven temperature of 20 C. However, it was latter discovered that the 2-hour hold was insufficient for the water temperature to reach the steady state, as duplicated tests based on increase and decrease oven temperature yielded two different sets of humidity data (with decrease temperature run yielded higher humidity).

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The evaporator was then left inside the oven for overnight to allow the water temperature to have sufficient time to equilibrate with the oven temperature. A nitrogen flow of 500 sccm was first introduced and the induced humidity and temperature changes indicated by the humidity sensor were recorded. After the humidity level off at around 30-minute mark, the flow rate was reduced to 300 sccm and then 100 sccm and the experiment was repeated.

Figure 34. Evaporator set-up inside the oven.

100

80 Relative Humidity (%)

'-5 C' '0 C' '5 C' '10 C' '15 C' '20 C'

500 scc m N2 F low

60

40

20

0 0 5 10 15 T im e (m inutes) 20 25 30

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Figure 35. Calibration curves of the evaporator at temperatures between 5 to 20 C under 500 sccm flow of N2.

Since the measured relative humidity depends strongly on the temperature difference between the evaporator and N2 purging gas, efficiency (RH measured/RH theoretical) rather than theoretical humidity was used to characterize the evaporator performance. The theoretical humidity was calculated by dividing the vapor pressure at the oven temperature to the vapor pressure at the room temperature. Figure
36 shows the efficiency of the evaporator at temperatures of 10, 15 and 20 C with N2 flows of 500, 300

and 100 sccm. The relatively insensitivity of efficiency to the flow indicates that humidity generation is not limited by the evaporation with flows less than 500 sccm, while the slightly higher efficiency at lower evaporator temperature may be attributed to a larger temperature difference between the incoming N2 gas and water inside the evaporator. However, there appears to be no significant difference in the efficiency between 10 and 15 C. Similarly, the reduction of efficiency at 100 sccm may be attributed to less thermal energy from the lower N2 flow available for water evaporation. Finally, no difference in the performance was detected between the top and bottom coils when tested at 20 C.
100

Evaporator Efficiency (%)

95

90

85

'20 C' '15 C' '10 C'

80 0 100 200 300 N2 F low (s cc m) 400 500

Figure 36. Efficiency of the evaporator.

3.2.2.1.4.3 Moisture effects on Pd quad-layer stack sensors performance The effects of moisture on the improved Pd quad-layer stack sensor performance were determined with the sensor operated at 165 C, the optimum operating temperature. The hydrogen concentration was fixed at 10%, as this stack sensor yield large response with 10% hydrogen exposure, while the environmental chamber that houses the evaporator was fixed at 15C. With a room temperature of 22C, the theoretical humidity generates was calculated to be about 64.5%. Since the total flow was fixed at 500 sccm (efficiency of the evaporator was previously determined to be about 95%) the relative humilities for the exposure and recovery cycles were determined to be about 60%. Sensors were first screened without moisture to establish the response baseline, and then screened again with the moisture. A second dry run was then repeated to confirm the effect of

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moisture, as the responses of these relatively fresh sensors may decrease gradually. Figure 37 shows the response profiles of a Pd quad layer sensor under dry and wet conditions. The addition of moisture appears to only reduce slightly the resistive response of Pd quad-layer sensor.
25 Response (ohm) 20 15 10 5 10 0 0 1000 2000 Time (sec) 3000 4000 '% H2' 'Second Dry' '55% RH' 'First Dry' BH-99-35, 165 C

% H2

Figure 37. Resistive responses of a Pd quad-layer sensor tested at 165 C under dry and wet conditions.

3.2.2.1.5

Stack sensor baseline drift

The baseline drift of the Pd quad-layer stack sensor under 4% H2 balanced N2 exposure was monitored using a long-term test manifold consists of a series of connected Swagelok union tee fittings. The responses of the sensors were monitored with ATMI Gen III testing board and recorded with a PC. Figure 38 shows the 20-day drift profiles of standard Pd quad-layer sensors at 200 C with 4% H2/N2 exposure. Two distinguish drift profiles were detected, one with minor while the other with significant drift. This large baseline drift is not attributed to YH2 oxidation but rather to the instability of the sensing material at this relatively high operating temperature, as the sensors were not exposed to oxygen during the test. However, it is not clear what causes the difference in drift response. Furthermore, this initial minor drift phenomenon was only temporary, as further exposure resulted in a significant increase in baseline resistance. Figure 39 shows the 60-day drift profiles, with interruptions at 18, 33 and 46-day, of another two standard Pd quad-layer sensors at 200 C. The 16B sensor showed an initial flat response, but subsequent exposure resulted in large drift. Figure 40 shows the degradation in response of this sensor after exposures of 18, 33 and 46 days. The net response (R) increased after the 18day exposure, but speed of response was significantly reduced (t90 time increased). And after the 33 days of exposure, both the net response and speed of response were significantly reduced. Figure 41 shows a similar degradation of response on 20A sensor.

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100 Response (ohm)

BH-78, 4% H2/N2, 200 C

80

60

'BH-78-29A' 'BH-78-29B' 'BH-78-33A' 'BH-78-33B'

40

10 Time (day)

15

20

Figure 38. Drift profiles of standard Pd quad-layer stack sensors under 4% H2 balanced N2 exposure at 200 C.
120 BH-78, 200 C, 4% H2/N2 Drift 100 Response (ohm)

80

60 'BH-78-16B' 'BH-78-20A' 0 10 20 30 Time (day) 40 50 60

40

Figure 39. Drift profiles of a standard Pd quad-layer stack sensors under 4% H2 balanced N2 exposure at 200 C.

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100 Response (ohm) 80 60 40 20 0 40 20 0 0

BH-78-16B, 200 C, 4% H2/N2

1000

2000 3000 Time (sec)

'% H2' 'Before Drift' 'After 18 days' 'After 33 days' days' 4000 'After 465000 'After 60 days'

Figure 40. Sensor (BH-78-16B) responses after the long-term hydrogen exposures.

100 Response (ohm) 80 60 40 20 0 40 20 0 0

% H2

BH-78-20A, 200 C, 4% H2/N2

1000

2000 3000 Time (sec)

'% H2' 'Before Drift' 'After 18 days' 'After 33 days' 4000 'After 46 days' 'After 60 days'

% H2

Figure 41. Sensor (BH-78-20A) responses after the long-term hydrogen exposures.

The improved Pd quad-layer sensors that were successfully operated at 165 C yielded minimum drifts in baseline resistance under 4% H2/N2 exposure, as shown in Figure 42. It also showed little or no performance degradation after the drift test, as shown in Figure 43.

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100 BH-99, 4% H2/N2 Drift, 165 C 80 Response (ohm)

60

40 BH_99_35A BH_99_35B BH_99_31B

20

0 5 10 15 20 25 Time (day) 30 35 40

Figure 42. Drift profiles of an improved Pd quad-layer stack sensors under 4% H2 balanced N2 exposure at 165 C. The lower operating temperature reduces significantly the drift in baseline resistance.
40 BH-99-35A, 165 C, 4% H2/N2 drift

Response (ohm)

30

20

10

0 50 40 30 20 10 0 0 1000 2000 3000 Time (sec) 4000

'% H2' 'before drift' 'after 21 days' 'after 42 days'

% H2

5000

Figure 43. Resistive response of an improved Pd quad-layer sensor after 4% H2/N2 exposure at 165 C. Sensor suffered little degradation after 42 days of drift test.

3.2.2.2 Ir quad-layer sensor Our earlier hydrogen sensor study, based on light ball platform, indicated a much more stable response from Ir protective layer sensor to high hydrogen concentration than those with Pd. Consequently, Ir quad-layer sensors with film thickness of Ir protective layer, Ta top barrier layer, Y sensing layer, and the Cr bottom barrier layer of 25, 7.5, 250 and 10 nm, respectively, were also fabricated on microhotplates for stack sensor applications.

3.2.2.2.1

Sensor response as a function of temperature

Figure 44 shows the resistive responses of an Ir quad-layer sensor tested at various temperatures with 40% H2/N2 exposures. Sensor performed best at around 165 C, and the speed of response 51

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was much slower than those of Pd quad-layer sensors. At 200 C, the sensor was unstable and it speed of response was significantly reduced. This inferior performance may be attributed to a slower diffusion rate of hydrogen in Ir. Reduction of the Ir protective layer thickness to 10 nm improved the speed of response, as shown in Figure 45. However, these thin Ir quad-layer sensors suffered a large baseline drift at 175 C.
200 B Q -6 -18 B

Response (ohm)

150

100

50

0 50 40 30 20 10 0 0 500 100 0 150 0 T ime (s e c) 2000 2500

% H2

'% H 2' '100 C' '130 C' '165 C' '200 C' 3 000

Figure 44. Resistive responses of a standard (25 nm thick) Ir quad-layer sensor tested at various temperatures.

7000 6000 Response (ohm) 5000 4000 3000 2000 1000 0 50 40 30 20 10 0 0 1000 '% H2' '125 C' '150 C' '175 C'

BX-36-24B

% H2

2000

3000 Time (sec)

4000

5000

Figure 45. Resistive responses of a thin (10 nm thick) Ir quad-layer sensor tested at various temperatures.

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3.2.2..22

Moisture effect on sensors performance

As in the Pd quad-layer sensor, these Ir quad-layer sensors were first screened without moisture to establish the response baseline, and then screened again with the moisture. A second dry run was then repeated to confirm the effect of moisture. Figure 46 shows the response profiles of a standard Ir (25 nm) quad layer sensor under dry and wet conditions. In contrast to the Pd quadlayer sensors, the addition of moisture did not appear to affect the resistive response of Ir quadlayer sensors.
200 Response (ohm) 180 160 140 120 100 10 0 0 1000 2000 Time (sec) 3000 4000 '% H2' 'Firat Dry' '55% RH' 'Second Dry' BQ-6-22B, 165 C

% H2

Figure 46. Resistive responses of a standard Ir quad-layer sensor tested at 165 C under dry and wet conditions.

3.2.2.3 Rh quad-layer sensor Rhodium, with a thickness of 25 nm, was also used to replace the protective Pd layer for quadlayer sensor fabrication. The thickness of the barriers layers of Ta and Cr and sensing Y layer remained unchanged.

3.2.2.3.1

Sensor response as a function of temperature

Figure 47 shows the resistive responses of a standard Rh quad-layer sensor at various operating temperatures with 40% H2/N2 exposures. These Rh quad-layer sensors exhibit a large response (R/R), but their speeds of response are much slower than those of Pd quad-layer sensors. Furthermore, the sensor does not completely recover even at 200 C. A thinner Rh protective layer was then tried to improve the sensors recovery. Figure 48 shows that reducing the Rh thickness to 10 nm significantly improves the sensors speed of response, and an operating

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temperature of 160 C was sufficient for achieving a full recovery.


14x10 Response (ohm)
3

BH-75-16A

12 10 8 6 4 2 0 50 40 30 20 10 0 0 1000 2000 3000 Time (sec) 4000 '% H2' '95 C' '130 C' '165 C' '200 C' 5000

% H2

Figure 47. Resistive responses of a standard (25 nm thick) Rh quad-layer sensor tested at various temperatures.

250 Response (ohm) 200 150 100 50 40 20 0 0 % H2

BH-109-33A

1000

2000

3000 Time (sec)

4000

'% H2' '95 C' '130 C' 5000 C' '160

Figure 48. Resistive responses of a thin (10 nm thick) Rh quad-layer sensor tested at various temperatures.

3.2.2.3.2

Sensor response as a function of hydrogen concentration

The calibration (concentration) curve for the thin Rh-quad-layer stack sensor at 160 C operation was constructed with repeating exposures of hydrogen concentration from 2.5 to 40% in balanced N2. The expose and recovery times were fixed at 7.5 and 10 minutes, respectively. Again the responses of the third cycle were used for the construction of concentration curve. Figure 49 shows the response profiles of a thin Rh quad-layer sensor with various hydrogen exposures, and Figure 50 shows a concentration curve derived from the responses of the third

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exposures. An over 200% response (R/R) was achieved on this sensor for 40% H2/N2 exposure with a dynamic and linear ranges between 2.5 and 40% H2.
120 Response (ohm) 100 80 60 40 H2 on/off 1.0 0.0 0 500 1000 1500 2000 Time (sec) 2500 'H2 on/off' '2.5% H2' '5.0% H2' '10% H2' '20% H2' '30% H2' 3000 '40% H2' BH-109-33A, 160 C

Figure 49. Response profiles of a thin (10 nm thick) Rh quad-layer sensor at 160 C with hydrogen exposures from 2.5 to 40%.

250 BH-109-33A, 160 C 200 Response (%)

150

100

50 0 10 20 % H2 in N2 30 40 50

Figure 50. Calibration curve of a thin (10 nm thick) Rh quad-layer sensor at 160 C.

3.2.2.3.3

Sensor baseline drift

The baseline drift of the thin Rh quad-layer stack sensor under 4% H2 balanced N2 exposure was monitored using the long-term test manifold. The responses of the sensors were again monitored with an ATMI Gen III testing board and recorded with a PC. Figure 51 shows a minor negative baseline drift on the 16-day drift profiles of thin Rh quad-layer sensors operated at 160 C with 4% H2/N2 exposure. After the 16-day drift test the sensors were re-characterized with 40% H2/N2 exposures. Figure 52 and Figure 53 show two distinguish sensor responses after the drift test. The 27A sensor showed a significant increase in sensor resistance response and sensor degradation after the 1655

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day test, but not the 28A. The drift test was continued and Figure 54 shows the 30-day drift profiles. Both sensors show a significant jump in sensor resistance after the 16-day interruption. These two sensors were again characterized with 40% H2/N2 exposures after the 30-day drift test. The 27A sensor showed a further jump in resistance and the 28A sensor failed after the 30-day drift.

240 4% H2/N2 Drift, 160 C 220 Response (ohm) 200 180 160 140 120 100 0 2 4 6 8 Time (day) 10 12 14 'BH-109-27A' 'BH-109-28A'

Figure 51. Drift profiles of thin Rh quad-layer stack sensors under 4% H2 balanced N2 exposure at 160 C.

1200 BH-109-27A, 160 C Response (ohm) 1000 800 600 400 200 150 100 50 0 40 20 0 0 1000 2000 Time (sec) 3000

% H2

'% H2' 'Before Drift' 'After 16 days' 'After 30 days' 4000

Figure 52. Sensor (BH-109-27A) responses after the long-term hydrogen exposures.

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200 BH-109-28A, 160 C Response (ohm) 150 100 50 0 40 20 0 0 1000 2000 Time (sec) 3000 '% H2' 'Before Drift' 'After 16 days'

% H2

Figure 53. Sensor (BH-109-28A) responses after the long-term hydrogen exposures.

1400 1200 Response (ohm) 1000 800 600 400 200 0 0

BH-109, thin Rh quad-layer, 4% H2/N2 drift

'BH-109-27A' 'BH-109-28A'

10

15 Time (day)

20

25

Figure 54. Drift profiles of thin Rh quad-layer stack sensors under 4% H2 balanced N2 exposure at 160 C.

The 4% H2/N2 drift test was repeated on another two thin Rh quad-layer sensors, and Figure 55 shows the results. Various degrees of baseline drift were detected on these thin Rh quad-layer sensors, but they all suffered large drop in net response, as shown in Figure 56 and Figure 57. Judging from these results, the thin Rh quad-layer sensor appears to be unstable under long term 4% H2/N2 exposure.

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350 300 Response (ohm) 250 200 150 100 0

Thin Rh quad-layer, 160 C drift test

'BH-109-22A' 'BH-109-22B' 'BH-109-23B' 5 10 15 Time (day) 20 25

Figure 55. Drift profiles of thin Rh quad-layer stack sensors under 4% H2 balanced N2 exposure at 160 C.

500 Response (ohm) 400 300 200 100 0 40 20 0 0

BH-109-22A, 165 C, 4% H2/N2 drift

% H2

'% H2' 'Before drift' 'After drift' 1000 2000 3000 Time (sec) 4000 5000

Figure 56. Sensor (BH-109-22A) responses after the long-term hydrogen exposures.

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400 Response (ohm) 300 200 100 0 40 20 0 0 1000

BH-109-22B, 165 C, 4% H2/N2 drift

% H2

'% H2' 'Before drift' 'After drift' 2000 3000 Time (sec) 4000 5000

Figure 57. Sensor (BH-109-22B) responses after the long-term hydrogen exposures.

3.2.2.3.4

Moisture effect on sensors performance

As in the Pd quad-layer sensor, these thin Rh quad-layer sensors were first screened without moisture to establish the response baseline, and then screened again with the moisture. A second dry run was then repeated to confirm the effect of moisture. Figure 58 shows the response profiles of a thin Rh quad layer sensors under dry and wet conditions. The thin Rh quad-layer sensor is probably not sensitive to moisture, as both the wet and second dry runs displayed a slight drop in response.
250 Response (ohm) 200 150 100 50 0 10 0 0 1000 2000 Time (sec) 3000 4000 '% H2' 'Second Dry' '55% RH' 'First Dry' BH-109-16B, 165 C

% H2

Figure 58. Resistive responses of a thin Rh quad-layer sensor under dry and wet conditions.

3.2.2.4 IIT results

3.2.2.4.1

Test protocol

Preliminary evaluations of the ATMI sensor for stack applications were performed using a series of well-defined tests in nitrogen background. The series of tests consisted of: A repeatability test consisting of six sequential exposures to 10% hydrogen A linearity test from 0 to 10% hydrogen. 59

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A second repeatability of six exposures to 10% Hydrogen.

All exposures were 5 minutes duration followed by a five-minute recovery in nitrogen. The gas mixtures were generated by mixing 10% hydrogen in nitrogen with 100% nitrogen. Figure 59 shows the sequence of gas exposure with Labview program.
Sequence of Gas exposure 10%H2 in N2 6 5 4 3 2 1 0
0 1200 2400 3600 4800 6000 7200 8400 9600 10800 12000

100% N2

time (sec)

Figure 59. The sequence of gas exposure with Labview program.

3.2.2.4.2

Sensor response characteristics

The standard Pd quad-layer sensor exhibits a fast, reversible response at 200 C under nitrogen background, as shown in Figure 60. Table 4 shows the response times of these standard Pd quad-layer stack sensors. These data was obtained from the first exposure of the series. Figure 61 shows the sensor responses to 2 to 10% concentrations of hydrogen in ascending and descending orders. The BH-76-23B sensor shows good linearity while the 19A and 30A sensors show small net response between 2 to 10% H2, as shown in Figure 62.

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ATMI T1AT-BH-76-19A 35 30 response (ohm


response (ohm) 50 45 40 35 30 25 20 15 10 5 0
0 300 600 900

ATM T1AT-BH-76-23B I

25 20 15 10
0 300 600 900 1200 1500 1800 2100 2400 2700 3000

aR

bR

1200 1500 1800 2100 2400 2700 3000

tim (approx. sec) e

tim (approx. sec) e

ATMI T1AT-BH-76-30A
31 29

response (ohm

27 25 23 21 19 17 15 0 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300

aR

time (approx. sec)

Figure 60. Standard Pd quad-layer stack sensor repeatability test results. Sensors were exposed to 10% hydrogen at 8 V heater voltage (200 C).

Table 4. Response times (t90) of the Pd stack sensors tested at IIT. Sensor Name Net Response response
T1AT-BH-76-19A (Vh=8V) T1AT-BH-76-23B (Vh=8V) T1AT-BH-76-30A (Vh=8V)

10 TO 90%

5 TO 95%

recovery 52 47 101

response 12 24 24

recovery 87 79 102

11.31 28.71 10.53

7 16 17

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ATMI T1AT- BH- 7 19A- - Vh=8V 629 27 response (ohm) response (ohm) 25 23 21 19 17 15
0 600 1200 1800 2400 3000 3600 4200

ATMI T1AT- BH- 7 23B- - Vh=8.0V 645 40 35 30 25 20 15 10 5 0 0 600 1200 1800 2400 3000 3600 4200 23B

19A

time (approx. sec)

time (approx. sec)

ATMI T1AT- BH- 76- 30A- - Vh=8.0V

29 27 response (ohm) 25 23 21 19 17 15 0 600 1200 1800 2400 3000 3600 4200 time (approx. sec) 30A

Figure 61. Response of the Pd quad-layer stack sensors to exposures of 2, 4, 6, 8, and 10% H2 at 200 C in ascending and descending concentrations.

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ATMI T1AT- BH- 76- 19A 12 Net response (ohm) Net response (ohm) 11 10 9 8 7 6 2 4 6 8 10 %H2 in N2 8 6 4 2 ascend descend 26 24 22 20 18 16 14 12 2 4 6

ATMI T1AT- BH- 76- 23B

asc end des cend

10 %H2 in N2

ATMI T1AT- BH- 76- 30A 11 Net respo nse (ohm) 10.5 10 9.5 9 8.5 8 7.5 7 2 4 6 8 10 2 %H2 in N 8 6 4 2 ascend descend

Figure 62. Linearity ranges of the Pd quad-layer sensors tested. The 23 B sensor shows the most sensitive response among the sensors tested.

Figure 63 shows the sensor responses to repeated 10% and 2 to 10% concentrations of hydrogen (in balanced nitrogen) in ascending and descending orders of an improved Pd quad-layer sensor operated at 7 V (165 C). The BH-99-29 sensor shows good linearity between 2 to 10% H2, as shown in Figure 64. Table 5 shows the t90 times of the BH-99-29 sensor at 7V operation with 10% H2/N2 exposure. The t90 response time of 29A sensor was about 1 second, a significant improvement over the about 7 seconds, as shown in Table 4, for the standard Pd quad-layer sensor that was operated at 200 C.
ATMI T1AT-BH-99-29, 04-17-05 a, 7V, 10% H2-0-10-0% H2-10% H2

20 18 16

Response (ohm)

14 12 10 8 6 4 2 0
0 600 1200 1800 2400 3000 3600 4200 4800 5400 6000 6600 7200 7800 8400 9000 9600 10200

aR bR

time (sec)

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Figure 63. Resistive responses of the improved Pd quad-layer sensors at 165 C (7 V).

BH-99-29A, 165 C 12 10 8 6 4 2 0 0 5 10 % H2 in N2 15 ascending descending

BH-99-29B, 165 C 12 10 8 6 4 2 0 0 5 10 % H2 in N2 15 ascending descending

Figure 64. Net response of the improved Pd quad-layer sensors at 165 C.

Table 5. Response times (t90) of the improved Pd stack sensors tested at IIT. Sensor Name Net Response

Net Response (ohm)

Net Response (ohm)

10 TO 90% (sec)
response recovery 5 7 1 3

T1AT-BH-99-29A (Vh=7V) T1AT-BH-99-29B (Vh=7V)

10.3 ohm 11.3 ohm

3.3 H2S Sensor


Various H2S sensing materials have been developed for detecting H2S in air based on semiconducting oxides. These semi-conducting oxides based solid state sensors cant be used for H2S detection in fuel cell applications due to their cross sensitivity to hydrogen. Ultra thin noble and transition metals, such as Rh, Ir, Co, Cr and Cu, were instead chosen as the sensing materials for H2S. Of all the materials studied, only Rh sensed H2S.

3.3.1 Rh based H2S sensor


The sensing mechanism of Rh is based on the reversible, sulfide-induced transition from the metallic Rh to the Rh sulfide. This is represented by the following equation involving rhodium: 2Rh + 3H2S Rh2S3 + 3H2 64

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The change in the electrical resistivity as the material goes from the pure Rh to the Rh sulfide is the basis of the proposed sensors. Sensor response and recovery were found to be temperature dependent and a minimum temperature of around 160 C is needed for H2S sensing.
3.3.1.1 Preliminary test results Thin Rh films, with thickness of 25 nm and 50 nm, were deposited onto the micro-hotplate sensor using e-beam evaporation. A few 50 nm thick Rh sensors were functional and all 25 nm thick Rh sensors were electrically open. The 25 nm Rh was apparently too thin for continuous coverage and the 50 nm Rh suffered from poor adhesion with the SiO2 substrate. Nevertheless the survived 50 nm thick Rh sensors were sent to MST, an ATMI subsidiary in Germany, for H2S test while the in-house H2S manifold was under construction. The measured responses of the gas sensors were the changes in resistance that occurred in the active layer film when exposed to H2S, where the resistance of the film increased with increasing H2S concentration. Figure 65 shows the response of this sensor at 160 C with 180 ppm H2S exposure in a 4% H2/N2 background. This initial test result indicated that thin Rh films reacted with H2S and they showed no cross sensitive to H2.
120 Resistance (ohm) 115 110 105 100 95 90 150 100 50 0 4 3 2 1 0 0 5 10 Time (min) 15 '% H2' '% H2S' 'Sensor Response'

% H2

H2S (ppm)

20

25

Figure 65. Initial H2S testing results on Rh sensor with 180 ppm H2S exposure in 4% H2/N2 background at 160 C. Sensor showed no cross sensitivity with H2.

3.3.1.2 Sensor testing manifold In order to achieve fast gas switching speeds, the gas handling manifold used low volume gas chromatography valves in combination with 1/8 tubing and a small test chamber size. A schematic diagram of the system is shown in Figure 66. Nitrogen make-up was taken from facility liquid nitrogen system, and transported through the house N2 system. As a test gas, certified 5.4 ppm or 1.0 ppm H2S doped Grade 5.0 (99.999%) N2 were used and blended with Grade 5.0 hydrogen using mass flow controllers with ranges of 200 and 100 sccm respectively. A Grade 5.0 of 4% H2 balanced N2 forming gas was used for the off cycles. The total gas flows for these tests were limited to between 200 and 500 sccm. A PC controlled automated system was constructed and data acquisition cards were used for data collection.

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Manual Valve H2 100 sccm MFC Chamber Check Valve ppmH2S/N2 200 sccm MFC 4-way Valve

Vent

H2S Scrubber

N2

1000 sccm MFC

MFC = Mass Flow Controller

4% H2/N2

1000 sccm MFC

Figure 66. Schematic of the H2S test manifold.

3.3.1.3 Sensor fabrication improvement To improve the adhesion of the thin Rh film with the micro hotplate, a thin layer of Cr was deposited before the Rh evaporation without breaking the vacuum. This 7.5 to 10 nm thick Cr significantly improved the adhesion of Rh film and subsequently the sensor yield. The optimum Rh film thickness was determined to be about 35 nm, as several trials with 30 nm Rh on top of 10 nm Cr failed to produce conductive sensor. 3.3.1.4 Sensor response as a function of temperature Since operating temperature is critical for sensor performance, the optimum sensor operating temperature was first determined. Figure 67 shows the responses of a H2S sensor at temperatures between 245 and 330 C. In this experiment, the sensor was cyclically exposed 6 times to 5.2 ppm H2S in 4% H2 balanced N2. The exposure time was 10 minutes and the time between exposures was 12 minutes. The 90% response times (t90) for 290 and 245C were determined to be about 1 and 3 minutes, respectively. At 330C, the sensor showed a significant drift (2.9% per hour) in baseline. Consequently, all subsequent tests were operated at 290C.

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90 BH-70-29 Response (ohm) 85 80 75 70 65 H2S (ppm) 60 5 0 0 2000 4000 Time (sec) 6000 H2S '245 C' '330 C' '290 C'

Figure 67. Resistive responses of a release-first Rh/Cr sensor to 5.2 ppm H2S exposures at various temperatures. The film thickness of Rh and Cr were 40 and 10 nm, respectively.

3.3.1.5 Sensor response as a function of H2S concentration Figure 68 shows the resistive responses of the same micro-hotplate H2S sensor with exposures of 0.1, 0.5, 1.0 and 5.2 ppm H2S at 290C. The higher baseline resistance at lower H2S concentrations was attributed to an increase in contact resistance. The sensor exhibited detectable responses to a level as low as 0.1 ppm.
82 Response (ohm) 80 78 76 74 72 H2S on/off 70 1.0 0.8 0.6 0.4 0.2 0.0 0 2000 4000 Time (sec) 6000 H2S '5.2 ppm' '1 ppm' '0.5 ppm' '0.1 ppm' BH-70-29A, 290 C

Figure 68. Resistive responses of a Rh/Cr sensor at 290 C with various concentrations of H2S exposure.

Figure 69 shows the response of a similar microhotplate to various concentrations of H2S at 290C. The sensor was exposed 3 times at each concentration. The exposure time was 17.5 67

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minutes and the time between exposures was also 17.5 minutes. The sensor exhibited detectable responses down to 10 ppb H2S concentration. Figure 70 is a plot of the responses from Figure 69 as a function of logarithmic H2S concentrations. The response follows a linear dependence on the log H2S concentration, in line with the typical logarithmic response observed for solid-state sensors.
480 BH-70-34A, 290 C

Response (ohm)

475

470

465

H2S on/off

460 1.2 0.8 0.4 0.0 0 1000 2000 3000 Time (sec) 4000

H2S '0.01 ppm' '0.05 ppm' '0.16 ppm' '0.5 ppm' '0.96 ppm' 5000

Figure 69. Resistive responses of a Rh/Cr sensor at 290 C with various concentrations of H2S exposure.

14 12 Delta R (ohm) 10 8 6 4 2 0 0.01

BH-70-34A, 290 C

6 7 8 9

0.1 H2S (ppm)

6 7 8 9

Figure 70. Response of a Rh/Cr sensor as a function of H2S concentrations.

3.3.1.6 Sensor stability Long-term stability is an important requirement for any type of sensor. Although no long-term exposure has been performed on these Rh based H2S sensors, the data presented in Figure 69 were obtained after over 100 exposures of various H2S concentrations, including air exposures. These Rh based sensors did not detect H2S in air due to oxidation of Rh sensing films, but the sensor recovered upon hydrogen exposure at 290C, as shown in Figure 71 and Figure 72.

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140 Response (ohm) BH-70-34A, Air 130 120 110 H2S (ppm) 100 5 0 0 1000 2000 3000 Time (sec) 4000 5000 6000 'H2S (ppm)' '200 C' '290 C'

Figure 71. Resistive responses of a standard release-first H2S sensor at various temperatures with 5.2 ppm H2S exposures in air. Sensor fails to detect H2S due to a much more favorable oxidation reaction.
130 Response (ohm) BH-70-34A, 290 C, 4% H2/N2 120 110 100 H2S (ppm) 90 1.0 0.0 0 1000 2000 3000 Time (sec) 4000 5000

Figure 72. Resistive response of a micro-hotplate H2S sensor at 290C with background of 4% H2/N2 after testing in air. Sensor recovered upon hydrogen exposure.

3.3.1.7 Moisture effect The Rh H2S sensors were first screened without moisture to establish the response baseline, and then screened again with the moisture. A second dry run was then repeated to confirm the effect of moisture. Figure 73 shows the resistive responses of a H2S sensor under both dry and wet conditions. The initial sensor response was noisy and very unstable, as indicated by the sudden drop in response during the second exposure cycle. Upon switching to wet test, the response was not only stabilized but also turned much smoother. When the humidity was removed, in the second dry run, the smooth response returned to noisy. Thermodynamic analysis indicates that moisture should not react with the Rh metal; however, moisture appears to improve the stability of thin Rh film based H2S sensor.

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190 Response (ohm) 185 180 175 170 0.10 0.00 0

BH-70-30A, 290 C

H2S 'First Dry' '55% RH' 'Second Dry'

H2S (ppm)

1000

2000

3000 Time (sec)

4000

5000

Figure 73. Resistive responses of a Rh/Cr sensor under dry and wet conditions.

3.3.2 Other H2S sensors

Metal/Cr thin film based MEMS hotplate sensors were fabricated, with Ir, Cr, Co and Cu metals, for H2S detection. The thicknesses of the metal sensing and Cr adhesive films were fixed at 40 and 10 nm, respectively. Table 6 lists the Gibbs free energies of the metal sulfide formation from reactions between metal thin films and H2S gas. A slight negative Gibbs energy is desired, as it favors a reversible reaction that is essential for H2S sensing. However, no detection of H2S was achieved with Ir or Cu sensors at 290 C, as shown in Figure 74 and Figure 75. Furthermore, Figure 76 and Figure 77 show that neither the Co nor the Cr thin film reacts with H2S at 330 C.
Table 6. Gibbs free energies of the metal sulfide formations from metal and H2S gas reactions at 300 C.

Reaction Rh + 1.5 H2S(g) = 0.5 Rh2S3 + 1.5 H2(g) Ir + 1.5 H2S(g) = 0.5 Ir2S3 + 1.5 H2(g) Cr + 1.5 H2S(g) = 0.5 Cr2S3 + 1.5 H2(g) Co + H2S(g) = CoS + H2(g) Cu + 0.5 H2S(g) = 0.5 Cu2S + 0.5 H2(g)

Delta G (kcal) at 300 C -13.389 -6.313 -28.145 -12.500 -6.259

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135

T1ATBH-81-26, 290 C, 4% H2/N2 '% H2S' 'Sensor A' 'Sensor B'

H2S (ppm)

Response (ohm)

130

125

120

115 6 4 2 0 0 1000 2000 Time (sec) 3000 4000

Figure 74. Resistive responses of an Ir/Cr sensor with 5 ppm H2S exposures at 290 C in 4% H2/N2 back ground.
100 Bh-82-34-1, 290 C, 4% H2/N2 Response (ohm) 80 60 40 20 H2S (ppm) 0 5 0 0 1000 2000 Time (sec) 3000 H2S 'Sensor A' 'Sensor B'

Figure 75. Resistive responses of an Cu/Cr sensor with 5 ppm H2S exposures at 290 C in 4% H2/N2 back ground.
4400 Response (ohm) 4200 4000 3800 3600 3400 3200 H2S (ppm) 3000 1.0 0.0 0 1000 2000 3000 Time (sec) 4000 'ppm H2S' 'Sensor B' T1ATBH-85-16B-1, 4% H2/N2, 330 C

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Figure 76. Resistive responses of a Co/Cr sensor with 1 ppm H2S exposures at 330 C in 4% H2/N2 back ground. Co does not react with H2S at 330 C.
120 Response (ohm) 110 100 90 80 H2S (ppm) 70 1.0 0.0 0 1000 2000 3000 Time (sec) 4000 5000 H2S Sensor_B BH-84-32B, 4% H2/N2, 330 C

Figure 77. Resistive responses of a Cr sensor with 1 ppm H2S exposures at 330 C in 4% H2/N2 background. Cr does not react with H2S at 330 C.

3.4 Ammonia sensor


Ammonia was one of the possible contaminants for the feed gas that necessitate constant monitoring. However, during the course of this study ammonia was no longer considered to be a problem due to improvement of the quality in feed gas. Consequently, only limited tests were performed. Figure 78 and Figure 79 show the resistive responses of a copper and Cr sensor, respectively, to 20-pm ammonia exposures in N2 background. Neither the copper, nor the Cr reacts with the ammonia. Furthermore, addition of 4% H2 to the test failed to improve the ammonia detection.
30 Response (ohm) 25 20 15 10 5 NH3 (ppm) 0 20 10 0 0 1000 2000 Time (sec) 3000 'ppm NH3' 'Sensor A' 'Sensor B' T1ATBH-82-24-3, Copper, 290 C, No H2

4000

Figure 78. Resistive responses of a copper/Cr sensor with exposures of 20 ppm NH3 in N2.

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620 T1ATBH-84-33A-1, Cr, 290 C Response (ohm) NH3(ppm) 610 600 590 580 20 10 0 0 500 1000 1500 Time (sec) 2000 2500

Figure 79. Resistive responses of a Cr sensor with exposures of 20 ppm NH3 in N2.

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Conclusions

The goal of this project was to develop MEMS based solid state sensors for gas detection in the multi-component environments found in fuel cell applications. This project was initially divided into three tasks, based on the chemical composition of the detected gases: the development of H2 sensors (for both life safety and fuel cell stacks) using metal hydride systems; the development of sensors for sulfur compounds using ultra-thin metal films; and the demonstration sensors for NH3 using metal hydride and metal sulfide thin films. During the course of the program, the NH3 sensor became less critical to the overall objectives the larger fuel cell program, and was deemphasized. This project has achieved substantial success in each of its primary tasks

Life Safety Hydrogen Sensors


Multiple generations of rare earth hydride MEMS sensors were developed and successfully. As shown in this report, these sensors substantially meet the performance targets, especially with respect to speed and sensitivity of response.

Fuel Cell Stack Hydrogen Sensors


Much of the knowledge gained in the development of life safety sensors was readily applied to the development of fuel stack sensors, and multiple generations of new sensors were investigated. This included new sensor materials stacks consisting of Pd, Ir, and Rh quad-layer sensors. Of these new designs, the Pd quad stack operated at a temperature that is elevated with respect to the life safety sensor has been recommend as the leading candidate. This configuration substantial meet the performance targets

Similarly, the knowledge gained in the development of hydrogen sensors was readily applied to the development of H2S sensors, and multiple generations of new sensors were investigated. Through the use of ultrathing films of Rh, we have demonstrated demonstrated the detection of 10 ppb H2S. This exceeded the original program goals, and even exceed the new target of 50 ppb that was suggested during one of our program review meetings. In summary, this program has been successfully concluded and has made significant contributions to the development of sensor technologies for future fuel cell automobiles.

H2S Sensors

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Appendix IV

Development of Sensors for Automotive PEM-based Fuel Cells

Final Report
Reporting Period: 3/2002-9/2005 Principal Authors: Scott Swartz, Chris Holt, and Steve Cummings Date of Report: November 11, 2005 DOE Contract No. DE-FC26-02NT41576 NexTech Materials, Ltd. 404 Enterprise Dr. Lewis Center, OH 43035. Phone: (614) 842-6606 Fax: (614) 842-6607 swartz@nextechmaterials.com

Disclaimer

This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise.

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Table of Contents Table of Contents ...........................................................................................................................2 Abstract...........................................................................................................................................4 Introduction ....................................................................................................................................4 Results and Discussion...................................................................................................................6

Sensor Characterization .......................................................................................................6 Carbon Monoxide Sensors ...................................................................................................8 Hydrogen Sulfide Sensors..................................................................................................23 Ammonia Sensors ..............................................................................................................33 Sensor Prototype Development..........................................................................................36
Conclusions ...................................................................................................................................43 Bibliography .................................................................................................................................45 Appendix A. H2S and Carbon Monoxide Sensor Summary with Lab-book Numbers .................46 Appendix B. Heater Type and Formulation Summary for Prototypes .........................................62 List of Tables Table 1. DOE Sensor Requirements and NexTech Technical Status ............................................6 Table 2. Response summary of pre-treatment on best performing NexTech sulfur sensor .........25 List of Figures Figure 1. Sensing model of a semi-conducting material ................................................................5 Figure 2. NexTechs automated sensors stand for testing CO sensors ..........................................7 Figure 3. NexTechs stand for measuring intrinsic sensor response time .....................................7 Figure 4. Schematic of a chemi-resistive sensor on an alumina substrate with Au-electrodes .....9 Figure 5. Schematic of Fuel Cell and mixed-potential mode carbon monoxide sensors ...........9 Figure 6. Microstructures of CuCl thick-film sensors .................................................................10 Figure 7. XRD of as deposited CuCl from acetonitrile................................................................10 Figure 8. Response of CuCl to 5000ppm CO in dry N2/H2 .........................................................11 Figure 9. CuCl response with second phase metal oxide to 5000ppm CO in N2/H2 ...................12 Figure 10. XRD showing slight conversion of CuCl to hydrated copper chloride ......................13 Figure 11. Capacitance to frequency converter for interfacing CO chemical capacitor ..............13 Figure 12. Mixed potential response of NexTech sensor to 5ppm CO in humidified H2/N2.......15 Figure 13. Response of single layer electrode system to 25 ppm CO in humidified H2/N2 ........16 Figure 14. Microstructure of the Inert Electrode in the NexTech M.P. CO sensor .....................17 Figure 15. Microstructure of the Active electrode of the NexTech M.P. CO sensor ..................17

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Figure 16. Figure 17. Figure 18. Figure 19. Figure 20. Figure 21. Figure 22. Figure 23. Figure 24. Figure 25. Figure 26. Figure 27. Figure 28. Figure 29. Figure 30. Figure 31. Figure 32. Figure 33. Figure 34. Figure 35. Figure 36. Figure 37. Figure 38. Figure 39. Figure 40. Figure 41. Figure 42. Figure 43. Figure 44. Figure 45. Figure 46. Figure 47.

Quantitative response of bi-layer mixed potential sensor ..........................................18 Inert vs. inert electrode on GDC electrolyte (5 days of testing) .................................19 Response of coarsened bi-layer sensor to multiple cycles of CO...............................19 YSZ fuel cell mode sensor response to 333 ppm CO tested at 400oC........................20 YSZ fuel cell mode sensor response to 333 ppm CO tested at 450oC........................21 YSZ fuel cell mode sensor response to 333 ppm CO tested at 550oC........................21 Quantitative response of GDC fuel cell sensor at 250oC............................................22 Quantitative response to 2.5 and 5ppm H2S in syngas ...............................................24 Response of NexTech sulfur sensor to 0.5 ppm H2S in syngas ..................................24 Enhancement in sensitivity after high temperature sulfur treatment ..........................26 Response of pre-treated sulfur sensor to 50-500 ppb H2S in humidified H2/N2.........27 Response of pre-treated sulfur sensor to 25-50 ppb H2S in humidified H2/N2...........27 Microstructure of the NexTech H2S sensor showing a high degree of porosity ........28 Microstructure of the NexTech H2S sensor showing sub-micron grain-size .............28 Cycling performance in automated test stand.............................................................29 Long-term (250 hour) cycling behavior of the composite sulfur sensor ....................29 Response of ABO4 system to 0.25 and 0.5ppm H2S in N2/H2/H2O background .......30 ABO4 based sensor exhibiting fast response time to 250 ppb H2S ............................31 Response of H2S sensor to 500 ppb in humidified methane/hydrogen ......................32 Long term stability of the ABO4 sensor after 400 hours of operation ........................32 Response of CuBr thick film to 10 ppm ammonia in dry nitrogen ............................33 Response of CuBr to ammonia in dry N2/H2 at 75oC .................................................34 SEM micrograph of thick film CuBr showing columnar structure ............................34 XRD spectrum of AgCl showing reduction to Ag after running in N2/H2 .................36 CO fuel cell sensor test module ..................................................................................37 Chemi-resistor and Mixed-Potential test module .......................................................38 Furnace controller for IDE heaters used in alpha prototypes .....................................39 Alpha prototype with heater rod-cartridge heater mounted on backside....................40 C2-type heater mounted on IDE shows even heat distribution ..................................40 Old and new IDE substrate with Swagelok tee and small NiCr filament heater ..41 Heater electronics for varying sensor duty cycle........................................................42 Heater dynamics at low and high duty cycle with and without cooling load .............42

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Abstract

The following report summarizes work conducted by NexTech Materials, Ltd. during the DOE sponsored program Development of Sensors for Automotive PEM-based Fuel Cells under contract No. DE-FC04-02AL67616. For automotive PEM fuel cells operating on reformed domestic fuels (i.e. gasoline), chemical sensors will be needed to protect the various fuel cell system components. This report discusses the development of carbon monoxide, sulfur, and ammonia chemical sensors as well as the electronic system platform for integration into automotive hardware systems. UTC Fuel Cells and its team consisting of UTRC, NexTech Materials. ATMI and IIT were tasked with developing physical and chemical sensors for automotive PEM fuel cell power plants, targeting low costs (<$20 / sensor) at 200k quantities. Specifically, NexTech Materials was tasked with developing chemical sensors for the detection of carbon monoxide (CO), hydrogen sulfide (H2S), and ammonia (NH3) for the protection of PEM fuel cell systems. In this program, NexTech investigated multiple platforms for the detection of carbon monoxide, sulfur and ammonia. For ammonia, a planar substrate with interdigitated electrodes and deposited thick films of various metal-halides were used to detect ammonia selectively in syngas compositions. For CO, chemical resistors (using similar IDE platform as used with ammonia), chemical capacitors, mixed potential and fuel cell sensors were developed for detecting CO in both dry and humidified hydrogen rich environments. For sulfur, both mixed potential and chemical resistor formats were investigated. The mixed potential format was not successful in detecting H2S, however, strategies using threephase mixtures of active metal oxides proved to be successful in measuring H2S at the 25 ppb level.
Introduction

Power generation systems based on fuel cells require sensors to detect numerous volatiles at extremely low levels (0.1-1 ppm) in the presence of hydrogen and other gaseous components (N2, CO2, methane and steam). In the case of PEM fuel cells presence of carbon monoxide, ammonia and sulfur-bearing species in the gas stream is undesirable, as these are known to poison the Pt anode. The automotive fuel cell application requires a sensor to detect low levels of carbon monoxide and ammonia (~1-100 ppm CO) in order to protect the fuel cell and control the fuel processor. The monitoring of sulfur at low levels (~0.1 ppm) is perhaps more critical due to issues of sulfur tolerance of not only the anode and, but the catalyst reactor components. However, their monitoring in a hydrogen-rich reformate (~40% hydrogen) is a challenging task and standard combustion based sensors will no longer work in environments lacking oxygen. The measurement becomes more daunting in presence of appreciable amount of carbon dioxide, and water vapor in the reformate gas. In a PEM-based fuel cell, knowledge of the CO, H2S, and NH3 concentration after the various reaction stages is of paramount importance to any PEM-based power generation systems. For example, CO sensors would provide two primary benefits: (1) The sensor can provide feedback to the PROX reactor; this will allow an optimum and regulated air-feed into the PROX reactor (and minimize any wasted hydrogen) and,

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(2) The sensor will protect the PEM fuel cell stack; when a high CO content is detected the reformate gas would be diverted from the stack (with power being provided by a battery) until the CO level returns to tolerable levels. Knowledge of sulfur breakthrough of the liquid phase or high temperature zinc oxide sorbents would enable protection of both the PEM fuel cell anode and the catalysts used in the various fuel reforming stages. The same argument applies to detecting ammonia in the gas stream, though its measurement and detection are of lower priority since its generation would only apply to systems using CPOX and autothermal reforming during the initial stages of fuel processing. Existing sensors for carbon monoxide and sulfur cannot meet the requirements of the PEM fuel cell system. Commercial CO and sulfur sensors, typically based on semiconducting oxides (e.g., tin oxide), operate on the basis of a resistance change due to the chemisorption of oxygen from the ambient and oxidation of CO and H2S to CO2 and H2/SOx, respectively [1-3]. The typical response of most semi-conducting oxides to volatile gases is a result of the combustion reactions that occur of at the surface of the ceramic crystal grain and grain boundaries. Initially, the adsorption of oxygen at the neck region of the grain boundaries results in an electron depletion layer a few atomic layers thick. These surface reactions between combustibles (CO, H2 and H2S) and oxygen result in a generation of electrons which result in a corresponding resistance change. Figure 1 shows an example of this model mechanism with CO combustion to CO2 as an example. These types of sensor cannot work for the fuel cell application because of the absence of oxygen in the reformate gas. While scientists have demonstrated the use of metal-halide thin films to detect ammonia in nitrogen containing environments [4], there use in reducing atmospheres had not been established before this program.

Figure 1. Sensing model of a semi-conducting material showing the depletion region and energy barrier (qVs) at the intergranular contact.

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Target specifications for the sensors to be developed by NexTech are provided in Table 1. NexTech was able to develop sensor technology that was selective to the analytes of interest. Specifically, methods for measuring CO in dry-hydrogen showed a response time of less than 4 seconds. While methods for measuring CO using a mixed-potential sensor while showing high sensitivity to CO over hydrogen had a longer response time on the order of minutes. For sulfur, materials were identified that exhibited high sensitivity to concentrations as low as 25 ppb sulfur. Other materials sets while showing lower detection limits (500 ppb), showed response times of less than 1 minute as needed. NexTech has identified multiple metal-halide systems that exhibited sensitivity to ammonia in the 1-10 ppm in dry N2/H2 containing backgrounds, however, upon introduction of humidified syngas streams, all sensitivity to ammonia was lost. Due to a change in priorities, no further work was done to investigate the possibility of modifying the metal-halides to impart selectivity to ammonia over water vapor.

Table 1. Target specifications for various gases to be monitored in fuel cell gas stream. Concentration Range Temperature Range

Gas

t90
0.1-1 s 0.1-1 s 0.1-1 s < 1min. seconds

Priority*

CO (pre-stack) CO (WGS outlet) CO (reformer outlet) Sulfur compounds (H2S/SO2) NH3 * 1: highest, 3: lowest

1-100 ppm 100-1000 ppm 0.1-2% 0.5-0.01 ppm 1-10 ppm

< 150C < 250C 250-800C < 400C 70-150C

1 2 or 3 3 1 or 2 3

Results and Discussion Sensor Characterization

Over the course of this program, multiple test stands were fabricated to provide quick screening of sensor material compositions. Two fully functional automated stands were designed to cycle sensors over the course of hundreds of hours in order to assess the issues of baseline drift (see Figure 2). In order to investigate intrinsic response time of the sensors, test modules with low test volumes (<100ml) were fabricated to remove system response time effects due to dead test volume (see Figure 3).

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Figure 2. NexTechs automated sensor stand for testing CO sensors (automated H2S not shown).

Figure 3. NexTechs stand for measuring intrinsic sensor response time.

Special precautions were taken in designing the test stands for the H2S sensor. Since H2S is a poisonous and toxic gas, great care was taken to establish a protocol for its safe handling, delivery and disposal. The simulated gas mixtures were produced from standard compressed gas cylinders containing various levels of H2S in adequately humid H2, CO, CO2 in N2 background by metering proper flows of various gases through analog and electronic mass flow controllers (MFCs), which in turn were controlled by a Sierra Control Box. In order to generate a moist environment, the mixture was passed through a water bath on a hot-plate at controlled temperatures to create a desired level of humidity. The sensor was located in the uniform temperature zone of a tube furnace that was heated to the desired temperature (1C) at which electronic measurements were conducted. In the case of sulfur sensor development, the exhaust stream from the test capsule was passed through reagent bottles containing aqueous solutions of silver nitrate, before it was discharged to the atmosphere through a fume hood. The H2S in the gaseous stream was neutralized by this reagent to form silver sulfide. For the automated stands a LabVIEW interface was designed to utilize various instruments for data acquisition and control. An Agilent 34401 was used for making voltage, current, and resistance measurements on the various sensors. Temperature of the test furnace was monitored using the National Instruments (NI) FieldPoint (FP) hardware. The FP hardware was used for

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on/off control of the gas flow using relay modules. An RS485 card was used to communicate to the FP hardware and the Applied Test Systems (ATS) high temperature test furnace temperature controller. A Brooks controller was used to control the electronic mass flow controllers. The Brooks Smart DDE software enabled the LabVIEW software to monitor and control valve set points, flow rates and override parameters. For the quick screening stands an Agilent 34401A digital multimeter connected via serial port to a desktop computer was utilized to make electrical voltage and/or resistance measurements. Agilent Benchlink software was used to read the resistance/voltage data serially and the data was formatted automatically for easy analysis in Microsoft Excel. The sensor was heated to a given temperature in a Swagelok fixture housed in a tube furnace and steady-state resistance (chemical resistors) or open circuit voltage (fuel cell and mixed potential) were measured as a function of analyte level in the gas stream. Various gas concentrations and mixes were controlled using Matheson analog flow meters. To obtain lower gas concentrations, pre-mixed cylinders of a few ppm of CO, Sulfur or ammonia balanced with nitrogen or hydrogen were obtained from BOC and Matheson gas companies. During the measurements, the analyte of interest was injected into the sensor test module using a Swagelok valve. After the electrical response reached the steadystate condition in the analyte of interest, the valve was turned off and recovery of the sensor to the original baseline was measured.
Carbon Monoxide Sensors

NexTech investigated multiple sensing platforms for measuring CO in syngas environments. These included; metal-halide chemical resistors where thick films of copper chloride (CuCl), copper bromide and composites thereof were deposited on an alumina substrate with gold interdigitated electrodes (Figure 4). This platform is the bases for all chemical resistor (both CO and H2S) work conducted at NexTech during this program. Pellets of metal-halides dispersed on high surface area (>400m2/g) fumed silica were used as chemical capacitors. However, the sensitivity of the sensors was much lower than obtained in a chemical resistor mode. NexTech also developed a mixed potential sensor and sensors operating in fuel cell mode to detect CO. These sensors were better suited for operation in humidified syngas when compared to thick film metal halides. Fuel cell and mixed potential mode CO sensor platforms are shown in Figure 5. Our use of thick-film metal-halides as the active sensing material was based on previous research, which showed the cuprous chloride is capable of selectively adsorbing carbon monoxide from multiple component syngas mixtures [5-7]. Upon exposure to CO, CuCl is known to form the copper carbonyl complex Cu(CO)Cl over a wide range of temperatures. With formation of this phase and underlying change in the electrical properties of the material was expected to occur.

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Figure 4. Schematic of a chemi-resistive sensor on an alumina substrate with Au-electrodes.

Figure 5. Schematic of Fuel Cell and mixed-potential mode carbon monoxide sensors.

Under a previous Phase I STTR program, multiple methods were identified to prepare copper chloride thick films. These ranged from adding the copper chloride from acetonitrile solution drop-wise to a hot-substrate at approximately 90C, where evaporation of the film would leave residual CuCl crystals on the interdigitated alumina substrate [8]. Other techniques involve the deposition of the film using terpineol vehicles. The process route with the highest sensitivity to carbon monoxide was based on a solvent evaporation method. First, 50 mg of copper chloride was dissolved in 5 ml of acetonitrile. The interdigitated electrode substrates were then submerged into the solution, where the solvent (acetonitrile) was removed in a vacuum oven. This was found to leave a highly porous lamellar structure that resulted in enhanced gas sensitivity (Figure 6). Control of the microstructure and morphology of the sensor film is a critical factor in enhancing the sensor performance, since surface reactions dictate overall performance. As shown in Figure 6, the sub-micron crystals offer high surface area for reactions to take place. In all methods of CuCl thick-film deposition on the IDE, the cuprous chloride exhibited the standard nantokite structure (Figure 7). The alumina and gold peaks in Figure 7 are from the underlying IDE substrate. Figure 8 shows a typical response of the CuCl to 5000ppm CO in dry N2/H2 baselines. The resistance is seen to increase rapidly with the introduction of 5000ppm CO.

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Figure 6. (A) Microstructure of CuCl thick-film sensor obtained through drop-wise on hot substrate. (B) Microstructure of sensor with enhanced response to CO obtained with vacuum solvent evaporation.

CuCl Au CuCl

Intensity

Al2O3

CuCl

Al2O3

Al2O3

Au

20

30

40

50

Degrees 2 (deg)

Figure 7. XRD of as deposited CuCl from acetonitrile.

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16 15
N2/H2 N2/H2 N2/H2 N2/H2

Resistance (k)

14 13 12 11 10 9 8 0 50 100 150 200 250 300


5000ppm CO

Time (sec)
Figure 8. Response of CuCl to 5000ppm CO in dry N2/H2.

The response of CuCl is believed to be due to carbonyl complex formation. The primary species contributing to conduction in CuCl is believed to be holes. Formation of Cu2+ on the surface during film preparation is believed to impede hole migration across the grains. However upon introduction of CO, the complex formation results in a loss of the Cu2+ barrier, increasing hole mobility and therefore increasing conduction as shown in Figure 8. Response time is significant for the PEM protection application. As shown in Figure 8, the Sensor exhibits a rapid response to the presence of 5000ppm CO. Addition of high surface metal oxides as second phase components was found to increase the magnitude of the copper chloride response (see Figure 9). The baseline resistance was also observed to increase an order of magnitude, possibly due to the insulative nature of the second phase metal-oxide. This does not present problems for application of the composite device since spacing between the IDE electrodes could be shortened to decrease geometric resistance. The enhancement in sensitivity is a result in the increased surface to volume ratio achieved by using a high surface area metal oxide support as a platform for CuCl re-crystallization from solvent evaporation. However, upon humidification of the N2/H2 environment, all sensitivity to CO was lost, possibly due complexation competition between CO and H2O species with copper vacancies. XRD of sensors tested in humidified environments showed hydration of the CuCl films (see Figure 10).

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2.5 2.3 2.0

N2/H2

Resistance (M)

1.8 1.5 1.3 1.0 0.8 0.5 0.3 0.0 0 250 500 750 1000 1250 1500 1750 2000

5000 ppm CO

Time (sec)

Figure 9. CuCl response with second phase metal oxide to 5000ppm CO in nitrogen hydrogen background.

Under a DOE-SFAA program, multiple strategies were investigated to remove the effects of humidity cross-sensitivity [9]. Including, hydrophobic coatings, molecular sieves (zeolites) and operating the device above the condensation point. Addition of hydrophobic coatings limited condensation issues, but resulted in a sluggish response and the sensor was only responsive over a few cycles. Ultimately, none of these strategies proved successful in limiting H2O crosssensitivity. Chemical capacitors were also studied as a means to impart selectivity to CO over water in reducing gas backgrounds. Hydrophobic fumed silica was chosen as a platform for copper chloride. It was theorized that the hydrophobic surface groups of the fumed silica may screen possible cross-sensitivity to H2O. The insulative nature of fumed silica was not amenable to a chemical resistor approach and this required the use of capacitive measurements for the detection of CO. The circuit shown in Figure 11 was used to determine the changes in sensor capacitance (labeled C1) by recording the frequency of pulses from a 555 timer chip.

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a = CuCl b = CuCl2-2H2O c = CuCl2-3Cu(OH)2 a

Intensity

a b,c c

a b

10

20

30

40

50

60

Degrees 2- (deg)

Figure 10. XRD showing slight conversion of CuCl to hydrated copper chloride.

F=

1.44 ( R1 + 2 R 2)C1

Figure 11. Capacitance to frequency converter for interfacing CO chemical capacitor.

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Changes in resistor values R1 and R2 allow the measurement frequency range to be modified from a few thousand hertz to 100s of kilohertz. While the sensors did show small changes in capacitance with introduction of 4000 ppm CO in dry/syngas of 170 hz on a baseline of 6000 hz (S~3%), no observable sensitivity was recorded in the presence of humidified syngas. It was recognized early in the program that copper chlorides use in the fuel processing application is limited. This is due mainly to cross-sensitivity to water vapor and issues of run to run reproducibility of the sensors. Thus, NexTech and UTRC decided to shift focus of CO development efforts from chemical resistors and capacitors based on metal-halides to fuel cell and mixed-potential sensors. The non-Nernstian mixed potential technique combines the advantages of semiconducting oxide-based sensing with galvanic measurement, where the preferential catalytic behavior of a semiconducting oxide-based electrode is advantageously exploited to generate a non-Nernstian response to the presence of an active gas. Essentially, at the surface of a semiconducting oxide, a potential gradient is developed as a consequence of the chemisorption of oxygen forming ionic species (O2-ads). If there is no other reactive species in the ambient, this potential will be identical on either electrode and hence the classical Nernst equation would not generate any EMF across the solid electrolyte. However, in the presence of a reactive gas, the number and concentration (and hence the surface coverage) of such species is lowered from the equilibrium value to a steady-state value. This is dictated by the rate constants of the combustion reaction and re-adsorption of fresh oxygen (which in turn leads to the formation of ionized oxygen species on the surface). Hence the developed EMF is a measure of the reducing gas concentration [10-11]. The voltage generated from the mixed potential sensor is the difference between the voltages developed at the two electrodes, which in turn are dependent on the oxygen adsorption rate and surface area coverage. Depending on the nature of the gas phase, an emf is generated across the electrolyte. For a given gas (CO, HC, H2S, etc.) the difference of reaction rate (dissociative/ associative adsorption) generates a concentration difference of the oxygenated charged species at the two electrode-electrolyte interfaces. This difference arises due to the different electrocatalytic characteristics of the electrodes which has a chemical and physical (particle size, morphology) basis. Consequently, it gives rise to a gradient of the conducting species of the ionic conductor and hence the development of an emf proportional to the concentration of the gas in the ambient. For the fuel cell environment the mixture of H2O and H2 creates a PO2 partial pressure (albeit low). This PO2 partial pressure difference between the electrodes results in the measurable EMF on the mixed potential sensors developed by NexTech. With proper selection of electrode materials, preferential adsorption of CO at one electrode (active electrode) versus second (inert electrode) results in a kinetic limitation of oxygen adsorption and thus, different concentrations of ionized oxygen at electrodes which results in a change in the EMF. Operation at elevated temperatures results in reversible CO adsorption/desorption. The operation of the fuel cell sensor is basically the same as described for the mixed potential sensor, except, the fuel cell sensor actually has an air reference which results in a much higher baseline voltage. Introduction of CO in the humidified fuel results in a change in the open circuit voltage due to poisoning of the active electrode. The key is the temperature of operation results in reversible CO adsorption/desorption. However, with the fuel cell sensor, sealing of the air reference is critical since air leakage would result in a change in the oxygen partial pressure in the fuel chamber, resulting in interference of the CO response.

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For the mixed potential sensor, multiple electrolyte materials were investigated as potential platforms. These included, yttria-stabilized zirconia (YSZ), Scandia-stabilized zirconia (ScZ), and gadolinium doped cerium oxide (GDC). The electrolyte powders were prepared by hydrothermal synthesis techniques to achieve a reactive high surface area (>100m2/g) powder amenable to densification during sintering of electrolyte discs. Multiple electrode materials were evaluated as possible sensing electrodes in the mixed-potential and fuel cell sensors. These electrode powders were prepared by chemical precipitation techniques to attain high surface area powders. The as prepared powders were pre-calcined before inking in terpineol to stabilize the surface area and minimize spalling during the adhesion step to the electrolyte. The powders were ball milled in isopropanol for 8 hours, dried and made into homogenous viscous slurry by mixing with an organic vehicle and terpineol, so as to give about 60-70% solid loading in the resulting ink. These inks were used to form the active metal films on the mixed-potential sensors. The inks were painted onto dense electrolyte discs and slowly fired in air to the optimum temperature to form an adherent film. Commercial platinum paste (Engelhard) was also applied to the surface of the electrolyte disc in close proximity to the active electrodes and fired at 900C for 1 hour. Silver wires were attached to both the electrodes with Alfa Aesar silver paste by first curing at ~100C for few minutes followed by firing at ~300C for 30 minutes in air.

-16

-17

Cell Potential (mV)

5 ppm CO
-18

5 ppm CO

5 ppm CO

-19

-20

-21

34% H2/ 66% N2/ 3% H2O

-22 0 1 2 3 4 5 6

Time (min)

Figure 12. Mixed potential response of NexTech sensor to 5 ppm CO in humidified H2/N2.

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Studies were conducted to evaluate the impact of calcine temperature on electrode stability and reactivity (sensitivity) to the carbon monoxide. One electrode material in particular showed a reversible response to CO in humidified reducing environments. Modifications in sensitivity were possible by using multiple electrode layers of coarse and fine powders. The bi-electrode (coarse/fine) approach proved beneficial in lowering the detection limit to CO. By maximizing electrode surface area while maintaining electrode adhesion integrity, sensitivities to CO at the 5 ppm level were established as shown in Figure 13. A single layer electrode of the same material calcined at high temperature was able to detect CO, but with much smaller change in signal (Figure 14). The response in Figure 12 is reversible and approximately 30 seconds in duration. The magnitude of the signal is roughly 1mV change at 5 ppm CO. With proper selection of instrumentation, this signal is easily amplified to a 0-5V output using standard strain gauge circuitry. Figure 13 shows the response of the mixed potential sensor to 25 ppm CO in humidified N2/H2. This sensor generated a signal change of 2mV with 25 ppm CO, proving that the bi-layer electrode approach results in higher sensitivity. Figure 14 shows the microstructure of the inert electrode of the best performing mixed potential sensor. Figure 15, shows the microstructure of the active sensing electrode. As shown in Figure 14 and 15, the size of the grains of the active electrode compared to the inert electrode are much smaller. The agglomerated grains in the inert electrode are on the order of 10-20 microns, while the grain size of the active electrode is on the order of 1 micron. This physical property alone could result in a difference in EMF. Coupled with the difference in chemical activity (dissimilar electrodes) results in improved sensitivity to CO.

-44 -46

Cell Potential (mV)

25 ppm CO

-48 -50 -52 -54 -56

34 H2/66N2/ 3 H2O

200

400 Time (min)

600

800

Figure 13. Response of single layer electrode system to 25 ppm CO in humidified N2/H2.
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Figure 14. Microstructure of the Inert Electrode in the NexTech M.P. CO sensor.

Figure 15. Microstructure of the Active electrode of the NexTech M.P. CO sensor.

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The bi-layer mixed potential sensor while exhibiting sensitivity at the lower concentrations also could be used as a quantitative device as shown in Figure 16. The improved performance of the bi-layer electrode versus the single layer is believed to be due to the use of a stable base electrode material with low surface area to form an adherent layer. This adherent layer acts as a support for a second high surface area layer which can be fired at a much lower temperature minimizing active surface area loss, resulting in improved CO sensitivity. The sensor is shown to generate a reversible quantitative response in the range of 100-500 ppm CO. One of the issues during the early stage of mixed potential sensor development was baseline drift. The sensors tended to drift from low negative (0 to -10mV) potential to high negative potential (-40 to -60mV). Initially, this was believed to be due to the nature of the electrolyte system (GDC). It was thought that the GDC was possibly reducing during the operation of the sensor. Tests of similar inert electrodes showed that the baseline drift was mainly due to the active electrode and not the GDC electrolyte (Figure 17). One strategy to address electrode drift is to age or coarsen the active electrode. Tests on low surface are electrodes resulted in slight baseline drift as shown in Figure 18. However, after multiple cycles, another problem was identified. While the sensor initially shows a quantitative response, there appears to be some irreversible poisoning of the electrode after multiple cycles. As shown in Figure 18, the response to 500ppm initially resulted in a change in voltage of approximately 20 mV. Multiple cycles in CO at 250, 100, and back to 500 showed that the sensor was not able to recover to full signal strength (20mV vs. 7mV).

0 T= 250C -20 CO 500 ppm Cell Potential (mV) -40 CO 250 ppm CO 100 ppm

-60 50 N2: 50 H2: 3H2O -80

-100 0 50 100 150 200 250 Time (min)

Figure 16. Quantitative response of bi-layer mixed potential sensor.

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30 20 10 0 -10

5 mV Total Drift

Cell Potential (mV)

34H2/66N2/3H2O
-20 -30 -40 500 2000 3500 5000 6500 8000

Time (min)

Figure 17. Inert vs. inert electrode on GDC electrolyte (5 days of testing)

30

500ppm
20 10 0

Cell Potential (mV)

-10 -20 -30 -40 1000

250ppm

100ppm

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

Time (min)

Figure 18. Response of coarsened bi-layer sensor to multiple cycles of CO.

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It should be noted that this would be considered a very aggressive test and it is unlikely that a PEM fuel cell system would ever see a breakthrough of 500ppm CO. In fact, breakthrough of a few ppm would probably result in significant PEM fuel cell degradation. As mentioned previously, the loss in sensor performance was believed to be due to irreversible CO poisoning. Cycling the sensor 100-200 degrees above the operating temperature resulted in a limited recovery of the sensor performance, but maximum sensitivity during initial cycling was never fully recovered. Tests of syngas cross-sensitivity on the best performing sensors showed that they did not suffer from cross-sensitivity to methane or carbon-dioxide. The issue of sensor poisoning would probably limit the sensor to a one shot device. This may be possible due to the low cost of the sensor platform (>$10) in high volume. Feasibility of fuel cell mode test sensors was also evaluated. Dense electrolytes of GDC, YSZ, and ScZ were used at the test electrolytes. Initial tests of fuel cell sensors focused on active electrodes on YSZ electrolytes. Inks of high surface are materials of test electrodes were prepared as described previously. Once both electrodes were adhered onto the electrolyte disc, the disc was finally sealed to an open-ended alumina tube with an aqueous base Aremco sealant, with Pt cathode exposed to air. The other end was designed to accommodate the inlet and outlet for the gas mixture. The use of YSZ electrolytes necessitated the operation of the sensor typically above 400C. The YSZ sensor did show a change in OCV with introduction of CO in humidified hydrogen, however, the response was typically erratic and the sensor suffered from baseline drift as shown in Figures 19-21. Similar results were obtained with ScZ electrolytes. Though the temperature of operation was lowered due to the enhanced conductivity of the ScZ electrolyte, the sensors still suffered from baseline drift. One advantage of the sensors operated in fuel cell mode was the ability to screen multiple electrode formulations in one single test. Electrodes showing promise at high temperature were tested on GDC at lower temperature.

940 920 900 880 Anode 1 860 840 333 ppm CO 820 0 20 40 Time (minutes) 60 80 humidified syngas

Anode 2

Figure 19. YSZ fuel cell mode sensor response to 333 ppm CO tested at 400C (format figure).
Development of Sensors for Automotive PEM-based Fuel Cells

OCV (mV)

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940 920 900 OCV (mV) Anode 1 880 860 840 820 0 20 40 60 80 100 Time (minutes) humidified syngas Anode 2

333 ppm CO

Figure 20. YSZ fuel cell mode sensor response to 333 ppm CO tested at 450C (format figure).

940 920 900 OCV (mV) 880 860 840 333 ppm CO 820 0 40 Time (minutes) 80 120 humidified syngas Anode 1

Anode 2

Figure 21. YSZ fuel cell mode sensor response to 333 ppm CO tested at 550C (format figure).

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Figure 22 shows the response of a GDC sensor at 250C with the best electrode formulation showing reversible and quantitative operation to 250 and 500 ppm CO in humidified syngas. While the sensor still suffers from limited baseline drift, the response is much more stable when compared to YSZ fuel cells operated at higher temperature. The lower OCV of the GDC fuel cell sensors is believed to be due to the reducibility of the GDC electrolyte. The use of the fuel cell sensor in a PEM fuel cell system will require significant miniaturization and package integrity of the prototypes produced in this program. Because the fuel cell sensor requires an air reference, integrity of the electrolyte and seals to leaks is of critical importance. However, fuel cell sensors based on GDC with active electrodes do show promise because of magnitude of the response (25 mV at 500ppm) and the possibility of regenerating the electrode via reverse biasing of the fuel cell sensor. In cases of CO poisoning, the sensor could be cleaned by pumping oxygen into the test chamber to re-oxidize the CO to CO2.

0.40

S500 = 9.27%
Cell Potential (Volts)
0.35

S250 = 4.61%
250 ppm CO

0.30

0.25

500 ppm CO

500 ppm CO

0.20 0 20 40 60 80 100 120 140 160

Time (minutes)

Figure 22. Quantitative response of GDC fuel cell sensor at 250C.

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Hydrogen Sulfide Sensors

Initially, NexTech had proposed to use an electrochemical based H2S sensor using -alumina solid electrolyte. However, these sensors proved to be unstable in the reducing syngas environment. NexTech tested multiple galvanic cells using Ag+ -alumina electrolyte discs/tubes with pure metallic Ag and a mixture of FeS2+FeS+Ag2S as a reference electrode. Problems of reference electrode isolation were the biggest issue and hydrogen leakage resulted in the conversion of silver sulfide to silver and hydrogen sulfide. In the case of hydrogen sulfide, a novel formulations were devised based on research conducted under a SECA core technology project. This consisted of two oxide components: one that could tolerate the reducing environment and exist as a stable phase and the other that could form a sulfide reversibly in the presence of H2S in the gas stream. The selection of second and thirdphase oxides were based on a rigorous thermodynamic analysis of the energetics involved in the macroscopic and reversible formation of metal sulfides/oxysulfides from their corresponding oxides in a H2/H2S mixture. The sensor consisted of these reactive metal-oxide compositions used as thick films in a planar chemiresistor format (films deposited onto alumina substrates with interdigitated gold electrodes printed on them) for monitoring H2S in H2-rich gas stream. In this format, the films responded reversibly to the presence of H2S via a change in the film resistance. The sensors with different chemistries have been tested in the temperature range of 300-550C over several cycles and in backgrounds containing up to 40 vol. % H2. The precursor powders consisted of nano-scale ceramic powder in which second and third phases were homogeneously dispersed. The sensors response was measured as the film resistance changed upon exposure to 0.25-10 ppm of H2S. The sensors were cycled several times in the above temperature range during continuous testing (in some cases multiple days). Figure 20 shows the response of a single representative sulfur sensor to 2.5 and 5 ppm H2S in a N2/H2/CO2/H2O background at 500C. Figure 23 shows that the sensor has 91 and 124% sensitivity to 2.5 and 5ppm H2S in syngas. Figure 24 shows the response of a similar sensor to 500ppb H2S in syngas. The sensitivity S is defined as the change in resistance for a given concentration divided by the baseline resistance in the background gas composition: S = ((Rgas Rbackground)/Rbackground)100 As mentioned previously, multiple formulations were tested for sulfur sensitivity and the results of these tests are summarized in Appendix A. During the course of the research NexTech evaluated various pre-treatments and discovered that these pre-treatments can have a dramatic impact on device sensitivity. These experiments were done as a result of earlier discovery that the sensors tend to improve with cycling time. Table 2 shows the sensitivity and changes in response time of the best performing sensor composition processed under various pre-treatment temperatures (to sulfur in the presence of syngas.

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20 16 Resistance (k) 12 8 4 0
0 75 150 225 300 375 Syngas and 2% H2O at 500 C 2.5 ppm H2S 5 ppm H2S

Time (Minutes)

Figure 23. Quantitative response to 2.5 and 5ppm H2S in syngas.

10 0.5 ppm H2S 9 Resistance (k) 8 7 6 5 0 10 20 30 40 50 Time (minutes) Syngas and 3% H2O at 500C S= 0.098

Figure 24. Response of NexTech sulfur sensor to 0.5 ppm H2S in syngas.

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Table 2. Response Summary of Pre-Treatments on Best Performing NexTech Sulfur Sensor

T = 350 deg C Cell Preparation 450 Deg C, 30 min 500 Deg C, 15 min 500 Deg C, 30 min 500 Deg C, 60 min 550 Deg C. 30 min 600 Deg C, 30 min No prep Min/Max/Min T = 400 deg C Cell Preparation 450 Deg C, 30 min 500 Deg C, 15 min 500 Deg C, 30 min 550 Deg C. 30 min 600 Deg C, 30 min No Prep Min/Max/Min T = 450 deg C Cell Preparation 450 Deg C, 30 min 500 Deg C, 15 min 550 Deg C. 30 min 600 Deg C, 30 min No Prep Min/Max/Min 90th Time Up (min) 89.463 52.899 32.627 32.961 54.943 32.627 Sensitivity 275.32% 226.64% 80.84% 596.18% 302.64% 596.18% 90th Time Down (min) 65.579 62.37 49.278 32.639 62.904 32.639 Delta R (K) 0.73 1.62 18.21 32.82 0.55 90th Time Up (min) 32.379 52.542 22.638 21.519 33.519 46.377 21.519 Sensitivity 84.72% 139.36% 56.69% 30.70% 68.49% 145.40% 145.40% 90th Time Down (min) 42.962 45.477 22.023 28.049 29.853 42.692 22.023 Delta R (K) 32.85 125.05 41.4 46.14 90.46 46.19 90th Time Up (min) 31.317 59.541 32.204 43.049 29.982 34.842 45.219 29.982 Sensitivity 41.18% 56.01% 55.36% 66.97% 30.43% 51.99% 59.70% 66.97% 90th Time Down (min) 41.913 41.099 28.422 48.201 35.847 44.28 33.512 28.422 Delta R (K) 69.22 416.33 325.69 325.12 134.99 362.46 99.46

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A repeat of the 600C treatment (596% sensitivity) obtained a similar result, though the response time was much longer ~90 minutes. As shown in Table 2, there does not appear to be a correlation between response time and sensitivity. The long response times are due to deadspace in the sensor test bed. Figure 25 graphically shows the change in sensitivity for the high temperature treatments for a sensor tested at 450C compared to a sensor without the pretreatment. Using high temperature pre-treatment conditions, NexTech was able to detect sulfur in the range of 25-500 ppb (see Figures 26 and 27). Figure 28 shows the microstructure of the as deposited active sulfur sensor film. The microstructure is show to have a high degree of porosity which is typical of sensitive sensor films. Figure 30 shows the average grain-size of the film to be at the sub-micron level. Long-term cycling of the sensor in the automated test-stand showed the sensor to be responsive over multiple cycles at 500 ppb (Figure 30). The cycling tests were conducted by injecting the H2S for 3 minutes and removing for 5 minutes. As shown in Figure 30 the sensor responds to H2S with each cycle. Even after cycling the sensor for 200 hours, there appears to be no issue with baseline drift (Figure 31). The increase in the response after 200 hours is due injecting the sulfur for a longer period of time (3 hours on, 5 hours off).

50 T=450C 40 Resistance (k) 5 ppm H2S 5 ppm H2S

30

S = 596%

20

10 S = 130% 34%H2/ 66%N2/ 3%H2O 0 0 25 50 75 100 125 150 175 Time (min)

Figure 25. Enhancement in sensitivity after high temperature sulfur treatment.

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1.4 1.2 Resistance (M) 1.0 0.8 0.6 0.4 0.2 0.0 0

500 ppb H2S

100 ppb H2S 50 ppb H2S

BASELINE: 33.6% H2, 66.4% N2 (wet 3%)

10

Time (hours)

Figure 26. Response of pre-treated sulfur sensor to 50-500ppb of H2S in humidified hydrogen.

1000

800 Resistance (k) 50 ppb H2S 600 50 ppb H2S 25 ppb H2S

400

Baseline: H2/N2 (3% H2O)

200 0 1 2 3 4 Time (hours) 5 6 7 8

Figure 27. Response of pre-treated sulfur sensor to 25-50 ppb H2S in humidified hydrogen.

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Figure 28. Microstructure of the NexTech H2S sensor showing a high degree of porosity.

Figure 29. Microstructure of the NexTech H2S sensor showing sub-micron grain-size.
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640
Resistance

80 70 60 50

620

H2S Flowrate

600

40 30 20

580

560

5 min. BASELINE: 33.6% H2; 66.4% N2 (wet 3%) -100sccm 20.20 20.40 20.60 20.80

10 0

540

20.00

-10 21.00

Time (hr)

Figure 30. Cycling performance in automated test stand.

800

700

Resistance (k)

600

500

400 0 50 100 150 200 250

Time (hours)

Figure 31. Long-term (250 hour) cycling behavior of the composite sulfur sensor.

H2S Flowrate (sccm)

3 min.

Resistance (k)

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Single component mixed oxide of the form (ABO4) was also investigated as a sulfur sensor materials. These types of materials were found to exhibit a response to sulfur in reducing environments and its viability as a thick film sensor was tested in this program. The various ABO4 compositions were fabricated via solid-state reaction by ball-milling pre-cursor materials in 100-ml of isopropanol in a 500-ml Nalgene bottle. Approximately 200-grams of 3-mm round zirconia media were used. The material was ball-milled for 12 hours, and the material was decanted and dried at 80-100 C in a stainless steal pan. The dried powder was placed into a 100-ml high alumina crucible and calcined to 1000 C for 4 hrs. The powder was crushed and sieved through 60-mesh, and then the powder was vibratory-milled in a 250-ml Nalgene powder in isopropanol for one hour. Again, the powder slurry was decanted and dried at 80-100C in a stainless steal pan. The ABO4 inks were synthesized by combining ~30-grams of powder with 8-grams of JohnsonMatthey (#63-2) ink vehicle in a Nalgene straight-side, wide-mouth jar. A handheld ultrasonic probe was used to disperse the powder into the ink vehicle. Additional powder was added slowly into the ink in order thicken the ink to a viscosity ~8000 cp. The ink was screen-printed onto an inter-digitated electrode and the sensor films were adhered at temperatures between 800 and 900C. Figure 32 shows the response of one ABO4 system to 0.25 and 0.5 ppm H2S. The response is seen to be quantitative with changes is sensitivity corresponding with changes in gas concentration. It should be noted, that the long response times shown for the sulfur sensor are due to dead-space in the quartz reactor test bed. Tests in the low volume Swagelok test stand for measuring intrinsic response time confirmed this (Figure 33).

400 350 300 Resistance (k) 250 200 150 100 50 0 0 50 100 150 200 250 300 350 Time (min) 34 H2/ 66 N2/ 3H2O

500 ppb H2S

250 ppb H2S

Figure 32. Response of ABO4 system to 0.25 ppm and 0.5 ppm H2S in N2/H2/H2O background.

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11 0.25 ppm H2S

Resistance (k)

10

212 s t90= 40 s

9
34 H2/ 66 N2/ 3 H2O Gas input 172 s

8 0 200 400 600


Time (sec)

800

1000

1200

Figure 33. ABO4 based sensor exhibiting fast response time to 250 ppb H2S.

This binary oxide system was also found to perform in the presence of high volumes of methane (Figure 34). The performance in methane shows the versatility of this material to be used in fuel processors for both PEM and SOFC systems. In most SOFC based systems that derive energy via direct oxidation of hydrocarbon based fuels, it is important to detect sulfur in gas streams other than hydrogen rich streams. During long term cycling of the ABO4 sensors, NexTech discovered potential baseline drift issues (Figure 35). While the sensor does suffer from serious baseline drift issues, there is no loss in sensitivity with cycling. This drift could be possibly due to the aging or grain growth of the ceramic material with long-term operation at temperature. In order for the ABO4 system to be realized in a commercial device, it will be necessary to age or conduct periodic calibrations of the sensor during operation in the field. The initial cycles were conducted at 0.5 and 5 ppm sulfur and the remaining cycles were ran at 500, 250, and 100 ppb sulfur in wet N2/H2.

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4.0 3.5 3.0 Resistance (M) 2.5 2.0 1.5 1.0 0.5 0.0 0 1 2 3 4 Time (hours) 5 6 7 8 50% CH4/ 34% H2/ 16% N2 (3% H2O) 500 ppb H2S

Figure 34. Response of H2S sensor to 500ppb in humidified methane/hydrogen.

5 4.5 4
5 ppm

Resistance (M)

3.5 3 2.5 2 1.5 1 0.5 0 0-10 hours


0.5 ppm 0.5 ppm 0.25 ppm 0.1 ppm

403-409 hours 307-315 hours 68-75 hours

Time (hr)

Figure 35. Long term stability of the ABO4 sensor after 400 hours of operation.

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Ammonia Sensors

NexTech platform for measuring ammonia consisted of a planar chemical resistor format as described above. Previously, researchers have demonstrated the use of metal-halides to detect ammonia with high sensitivity in non-oxidizing atmospheres. It is well known that halides are particularly reactive with ammonia vapors and copper ions specifically are known to form stable amine complexes with ammonia [4]. NexTech investigated multiple metal-halide single phase and composite systems as ammonia sensors. Thick films of AgCl and CuBr exhibited sensitivity at the 1-10 ppm range in dry hydrogen/nitrogen environments. However, upon introduction of humidity all sensitivity to ammonia was lost. CuBr samples prepared by solvent removal techniques were shown to be sensitive to ammonia at the ppm level. At ambient temperature, resistance increased when ammonia was introduced and decreased in the absence of ammonia. The sensor exhibited very high sensitivity (average ~ 8) in the presence of dry nitrogen. However, it was observed that the baseline was increasing constantly (see Figure 36). At higher temperatures of 50oC and 75oC and in the presence of hydrogen, the sensors stilled show sensitivity to ammonia (see Figure 37). At both temperatures, the same trend was observed however sensitivity decreased and response time lengthens. Also, the baseline increased with temperature. Examination of the microstructure by SEM showed columnar poly-crystals with sub micron features (Figure 38).

300 250 Resistance (K) 200 150 100 50


N2 N2

N2/10 ppm NH3

T=25C

S=800%

N2

N2

0 100

200

300

400

500

600

Time (Minutes)

Figure 36. Response of CuBr thick film to 10 ppm ammonia in dry nitrogen.

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90 5ppm NH3 85 Resistance (K) 80 75 70 65 60 0 20 40 60 80 100 Time (Minutes) N2/H2 N2/H2 N2/H2

Figure 37. Response of CuBr to ammonia in dry N2/H2 at 75C.

Figure 38. SEM micrograph of thick film CuBr showing columnar structure.

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In order to increase sensitivity of CuBr film, the films were pre-conditioned with ammonia. This was shown by other researchers to improve copper bromides sensitivity to ammonia. The basic premise that pre-treatment with ammonia will enhance conductivity by adsorption of ammonia at grain boundaries and creating vacancies. Thus, following the treatment, with exposure to ammonia gas, transfer of copper ions would be hindered due to interfacial resistance will result and hence resistance increases. Films prepared by these treatment methods still showed a response to ammonia, in dry nitrogen and hydrogen, however, no increase in device sensitivity were noted at high temperature. Silver chloride was also tested as a possible ammonia sensor. In our studies, AgCl was highly insulative until temperatures in excess of 150C are reached. Films prepared by dispersing AgCl in terpineol did show some sensitivity to ammonia in N2/H2 at temperatures between 150-200C. However, sensitivities were lower than CuBr materials. In order to enhance the sensitivity a couple of approaches were investigated. The first method investigated used potassium chloride (KCl) as a second phase component. A review of the KCl/AgCl phase diagram shows at low temperature eutectic melting point of 306C at 30mol% KCl in AgCl. Thick films of AgCl/30%KCl were prepared at temperatures of 295C and the second phase of KCl was leached by water dissolution. The basic idea was to remove the KCl to form a porous microstructure, which should provide enhanced ammonia gas diffusion to the AgCl grain boundaries. The second method was based on the results obtained by other researchers which showed that AgCl made by decomposition of Ag(NH3)2Cl resulted in enhanced conductivity [12]. Ammonia is known to complex with silver ions and hence introduce vacancies which will increase conductivity. However, while the films both showed improved sensitivity to ammonia, stability of the AgCl was an issue. Upon removing the films from the testing apparatus, a change in color of the film was noted. Further investigation via X-ray diffraction showed a slight reduction of the AgCl to Ag (see Figure 39). Other metal halide systems of AgI and AgBr were added to the AgCl system in order to improve conductivity. This was done to reduce the resistivity of the films in order to lower the operating temperature and thus, lower the driving force for AgCl reduction in hydrogen. However, upon addition of second phase dopants, the response to ammonia was not ideal between 50 and 300C, where continuous baseline drift (increase in resistance) was observed. Silver promoted molybdenum oxide was also investigated as a possible ammonia sensing material. Sputtered molybdenum oxide was shown to exhibit high sensitivity and selectivity to ammonia between the temperature ranges of 230-280C [13]. Thick films of molybdenum oxide were prepared by dispersing nano-scale molybdenum oxide prepared by soft chemistry routes in standard terpineol ink vehicles. The deposited thick-films were cured in pure oxygen to ensure adherence to the substrate. While the MoO3 films prepared at NexTech did show a response to methane in N2/H2, the intrinsic sensitivity was much lower than the metal-halide systems. In all metal halide systems investigated, no response to ammonia was recorded in the presence of even the smallest amount of water vapor. Thus, the sensors as prepared will need a hydrophobic coating in order to be operating in-situ in a fuel processing system. Since ammonia was the lowest priority sensor, a decision was made to stop all work on ammonia by NexTech in order to focus on sulfur and carbon monoxide sensors.

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AgCl

Intensity

Ag Formation AgCl

AgCl

20

25

30

35 2 theta

40

45

50

Figure 39. XRD spectrum of AgCl showing reduction to Ag after running in N2/H2 background at 150C. SENSOR PROTOTYPE DEVELOPMENT

Face to face meetings were held at IIT and UTRC to determine the specific hard-ware requirements of the prototypes to be tested at each facility. NexTechs engineers were invited to Chicago to tour the IIT test facility and to work out potential test issued during alpha and beta prototype tests. The IIT setup appeared to be capable to test sensors in simulated re-formate environments at gas temperatures no greater than 150C. The low temperature test capability was the first point of discussion, since NexTechs sensors operate between 200 and 500C, depending on the device. NexTechs CO sensor operates between 300-400C (the mixed potential sensor at the lower end, the fuel cell sensor at the higher end). NexTechs chemiresistors operate at 400-500C (for H2S) and 150-200C (for ammonia). It was agreed that the IIT test furnace could operate at 400C and the CO sensor tests should not be a problem, however, the chemi-resistor sulfur devices will need their own heater element. The IIT test stand consisted of a single furnace with 4-5 MFCs to control flow from multiple gases. During testing, the system is pressurized the to 3 atmospheres gauge pressure (~30 PSI). For the NexTech fuel cell sensor, it will be necessary to check the pressure tolerance of the ceramic bonding agent and electrolyte used to isolate the fuel side from the air reference side. Multiple drawings were made of possible test housings that could be easily configured into their system. Two designs were agreed upon, one for the fuel cell sensor testing (Figure 40), and a second for the chemi-resistor and mixed potential device testing. For the chemi-resistor and

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mixed potential devices, a -3/4 ceramic tube was connected to a steel flange (Figure 41). Seals were made at the cold end for the electrical lead-wire, and thermocouple feed throughs. A second ceramic cup will be placed over the sensor in the tube, to maintain a practical sensor test volume. IIT supplied a drawing of the flange so that NexTech would be able to machine a fixture that could be used for the chemi-resistor testing. The steel flange made a leak tight fit to a gasket on the steel sensor furnace housing. The fuel cell sensor was sealed onto a ceramic tube -3/4 diameter, and fuel with analyte was passed on the inside of the tube and air reference was maintained in the furnace with one end open. Of all the prototypes shipped to IIT, only the sulfur sensor was able to be tested due to program slow downs and release of fund issues. The results of the sulfur testing are summarized later in this section. Two alpha CO prototypes and an alpha and beta sulfur prototype with integrated heater were delivered to UTRC during the program for testing and characterization in their automated test facility. In almost all cases, the sensors operate at a temperature above the fuel stream temperature where the device would be potentially located in a fuel processor. This necessitated the design of an integrated heater on the backside of the IDE substrate or electrolyte disc. Numerous, methods were investigated for heating the backside of the sensor substrate. These included platinum and ruthenium oxide thick films, miniature rod heaters, and small NiCr filaments. The ruthenium and platinum thick films were problematic in that they suffered from uniformity issues which resulted in hot-spots and cracking of the sensor substrate. For the miniature rod heaters, a 15 Watt (SUNROD) cartridge heater was attached to IDE alumina substrates. For the first prototype Aremco 552VFG (a fine, 1-part alumina paste) was used to form the heater body and adhesive for attaching itself and thermocouple to the IDE substrate. It worked but did not reach a high enough temperature. This limit was later extended by greater hot zone utilization of the cartridge heaters (See "C2" type heaters Appendix B).

Figure 40. CO fuel cell sensor test module

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Figure 41. Chemi-resistor and Mixed-Potential test module

During the next few months, we designed and built small temperature-and-power controllers, approximately 8"W x 6"D x 3"H, capable of controlling a variety of heaters from very low power up to 1600 Watts between 0 and 1200C, with a high degree of precision (1C). Figure 42 shows a picture of the controller units built in house for controlling the alpha-prototype onboard heaters. During the alpha prototype stage of development, NexTech tested 2 basic types of heater assemblies:
1. Those designed to be precisely the same shape and size as the IDE substrates (~1 square cm); and 2. Those utilizing pre-manufactured cartridge-type heaters thermally joined to the IDE with various materials.

In both these categories, NexTech tested heating capability in still air and in moving air (~0.3 m/sec). NexTech also tested the assemblies with and with out insulation. In summary, while the highest heat-per-watt rating was achieved with the flat film heaters applied directly to substrate, problems with fabrication led to localized hot spots which cause heater burnout, and films being too thick or too thin. The flat-film type design was deselected, since it was not our intention to develop a new heater technology, instead rather a system capable of high temperature, accurate control in a small, affordable package.

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Figure 42. Furnace controller for IDE heaters used in alpha prototypes.

With a rating system arbitrarily based on maximum temperature divided by wattage used to achieve that temperature, one of the graphite cast flat heaters scored the highest. While it may be determined thru future testing that graphite can be utilized for this purpose, concern over carbon oxidation and contamination of surrounding / adjacent systems rules this out for now. The flat-film type design was deselected, since it was not our intention to develop a new heater technology, instead rather a system capable of high temperature, accurate control in a small, affordable package. The final decision for the alpha prototype heaters was based on the "C2" assemblies (2 of 15Watt cartridge heaters), because they were the only systems capable of repeated cycling and smooth control to 500C in a moving airstream. A thermocouple and IDE substrate were cemented to the thermal mass using an even volumetric mixture of 552VFG, Pyro-Putty, and Cotronics #907 (mica-based cement); the result was a highly thermally conductive, high strength bond which married the thermal mass together. A final coat of 552VFG was applied to the heater side because of the following properties; it fills in cracks and voids, provides additional protection to thermocouple, can be heat-cured to purposely form bubbles (or voids) to make it a low-mass insulator, and it is pure white, which is a poor heat radiator. Figure 43 shows the finished alpha prototype with rod-heaters attached by the bonding agent. As these C2 heaters reach temperatures of visible glowing (~ 550C in a dark room) the glow is uniformly distributed across the entire IDE sensor surface, which means more even heat distribution, more control, and more heater longevity (Figure 44).

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Figure 43. Alpha prototype with heater rod-cartridge heater mounted on backside.

Figure 44. C2-type heater mounted on IDE shows even heat distribution, starting around 550C

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Due to the high power consumption, sensor platform footprint and requirements for bulky temperature controller, it was decided that applying a small filament element to backside of the sensor IDE. The filament, when attached with a thermal bonding agent provided the most robust design in terms of simplicity and overall device volume. However, the Cotronics ceramic bonding agent while providing excellent adherence to the substrate and protection against volatiles in the fuel process stream added extra volume to the package. Thus, it was decided fairly early in the heater development effort, that the IDE platform would need to be shrunk from 15x15mm to 5x5mm in order to package the sensor with heater into a -3/8 Swagelok tee package (Figure 45). The electronic circuitry for controlling the NiCr filament is simple and low-cost (Figure 46). Using a variable resistor the pulses from the 555 timer can be varied which varies the on/off time or duty cycle of the sensor. The resistance and capacitance values in the circuit control the frequency of the pulses and the time on (T1) and time off (T2). The time T1 and T2 values are given by the following equations: T1 = 0.693*(R1+R2)*C1 T2 = 0.693*(R2)*C1 Using a 6 Volt power supply and 4 ohm filament heater (for a total power of 9 Watts) the filament heater was able to be cycled from room temperature to temperatures in excess of 500C. The capability of heating the substrate under flow was testing by using a small fan displacing 4.5 CFM of cool air over the hot substrate. As seen in Figure 47, the heater system was still capable of maintaining a substrate temperature of 450C under these conditions. Also, the sensor is able to cycle between room temperature and target temperature relatively quickly (within 2 minutes).

Figure 45. Old and new IDE substrate with Swagelok tee and small NiCr filament heater.

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Figure 46. Heater electronics for varying sensor duty cycle [14].

Figure 47. Heater dynamics at low and high duty cycle with and without cooling load.

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Conclusions
During the course of this program, NexTech developed multiple techniques and materials sets for measuring ammonia, CO, and H2S in syngas environments. Numerous sensing platforms were developed for monitoring carbon monoxide. These included, mixed potential, chemical capacitor and resistor, and fuel cell sensors which all showed changes in signal output with changes in various CO concentrations. With proper selection of electrodes, the fuel cell and mixed potential sensors enabled the measurement of CO in simulated syngas environments between 250 and 500C. Chemical resistors and capacitors based on copper chlorides, bromides and alloys thereof were used to detect CO in dry nitrogen, hydrogen and syngas mixtures at temperatures between 40-100C. By compositing the metal-halides with high surface area metaloxides, enhancements in the sensitivity were achieved. However, all measurements in humid hydrogen, nitrogen and syngas mixtures resulted in a loss of sensitivity. Since the UTRC application required the detection of CO in humid syngas environments and removal of the water from the system would result in an increase in system complexity, all work with metal-halides was abandoned early in the program. However, during the later stages of research, it was suggested that it may be necessary to monitor CO in dry hydrogen due to the reactive nature of the most feasible hydrogen storage media. Thus, it appears that the metal-halide sensors may play a role in future hydrogen filling stations. Results from the mixed potential and fuel cell CO sensor development were much more promising. NexTech identified two key electrodes which exhibited a quantitative and reversible response to carbon monoxide in humid reducing environments. The lower limit detection limit of the mixed potential sensor was found to be 5 ppm, which is well within the required detection range for the PEM protection application. The fuel cell sensor while showing a high change in voltage with introduction of carbon monoxide actually has lower sensitivity when normalized to the baseline voltage. The use of YSZ requires a higher temperature of operation, but leads to issues of baseline drift due to electrode sintering (look through the report for words). The critical issues with the carbon monoxide mixed-potential sensors include:
o Response time, which may be improved through device miniaturization and electrode optimization (small crystallite size). o Baseline drift issues during device operation, possibly due to electrode sintering. o Poisoning issues with multiple cycles at high CO concentration.

As noted above, the miniaturization of the CO sensor and reduction of the electrode size may result in faster response times. However, it is important to optimize crystallite size such that issues of baseline drift related to electrode sintering do not adversely affect the sensor performance. The poisoning issue is believed to be a result of the multiple exposures to high concentrations of CO. It is expected that the sensor will not be required to monitor this range of CO concentrations (500ppm) for the PEM fuel cell protection application since concentrations as a high as 10 ppm are known to poison the cell. Cross-sensitivity tests to methane and CO2 showed the sensor to be impervious to coking, making its use in the fuel processing application a real possibility.

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During the program NexTech developed an optimized three-phase ceramic sensor capable of detecting hydrogen sulfide in various syngas compositions. The sensor when treated with sulfur at high temperature exhibited even higher sensitivity when compared to sensors not treated at high temperature with H2S. The surface enhancement due to high temperature sulfur treatments resulted in a sensor capable of detecting H2S at the 25ppb level in wet syngas environments. In most cases, the sulfur sensor appeared to show a quantitative response to a wide range of H2S concentrations suggesting its feasibility as an analytical device. During the research, NexTech discovered a second system based on metal oxides of ABO4 which showed sensitivity to concentrations as low as 250ppb H2S. This system exhibited a fast response (<1 min) when compared to the three-phase system, but also suffered from a high degree of baseline drift during 500 hours of operation. In general the three phase device appeared to have much better baseline stability than the ABO4 systems. The ABO4 system showed instability in methane backgrounds. The three phase system appeared to be stable and sensitive to H2S in methane backgrounds as high as 50%, suggesting its possible use in SOFC stack monitoring. NexTech was also successful in developing an on-board heater technology which proved critical in enabling the project partners to test the beta-prototypes. The critical issues with the sulfur sensors include:
o Sluggish response and recovery time, which may be improved through device miniaturization and electrode optimization (small crystallite size). o The H2S sensor requires a high temperature of operation (~450C) for optimum response to H2S. This will require the use of an on-board heater to control substrate temperature. An on-board heater will increase system complexity and require parasitic system power. o Limited baseline drift requiring periodic calibration of the device.

Based on discussions with other fuel cell system designers, the NexTech sulfur sensor will most likely find use in the sorbent breakthrough monitoring application. The slow recovery of the sensor is not an issue for sorbent breakthrough since the sensor has plenty of time to recover between sorbent bed cycling. NexTech spent a limited amount of time developing the ammonia sensor technology. However, in this limited of time, a few key breakthroughs were realized. These include:
o Demonstrated platform for monitoring ammonia in dry H2/N2 environments. o Developed sensor is capable of detecting ammonia at the 5ppm NH3 level in N2/H2. o Developed sensor operates in a temperature range necessary for PEM anode protection (~75C).

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Bibliography

1. M.J. Madou and S.R. Morrison, Chemical Sensing with solid State Devices, Academic Press, San Diego, CA, 1989. 2. A.-M. Azad and E.D. Wachsman, Solid State Chemical Sensors for CO Gas, in: Proceedings of the 198th Meeting of the Electrochemical Society: Solid State Ionic Devices II, Ceramic Sensors, October 23-27, 2000, Phoenix, AZ, Eds. E.D. Wachsman, W. Weppner, E. Traversa, M. Liu, P. Vanysek and N. Yamazoe, vol. 2000-32, pp. 455. 3. L. Jianping, W. Yue, G. Xiaoguang, M. Qing, W. Li, H. Jinghong, H2S sensing properties of the SnO2-based thin films, Sensors and Actuators B 65 (2000) 111-113. 4. P. Lauque, M. Bendahan, C. Jacolin, J.-L. Seguin, M. Pasquinelli, P. Knauth, Electrical properties and sensor characteristics for NH3 gas of sputtered CuBr films, Sensors and Actuators B 59 (1999) 216-219. 5. C.T. Holt, A.-M. Azad, S.L. Swartz, R.R. Rao, and P.K. Dutta, Carbon monoxide sensor for PEM fuel Cell systems, Sensors and Actuators B 87 (2002) 414-420. 6. P.K. Dutta, R.R. Rao, S.L. Swartz, and C.T. Holt, Sensing of carbon monoxide in reducing environments, Sensors and Actuators B 84 (2002) 189-193. 7. X.D. Peng, T.C. Golden, R.M. Pearlstein, R. Pierantozzi, CO adsorbents based on the formation of supported Cu(CO)Cl complex, Langmuir 11 (1995) 5241. 8. NexTech Materials, Ltd., DOE Contract No. DE-FG02-99ER86099. 9. Subcontract to Nuvera Fuel Cells, under DOE Contract No. DE-FC02-99EE50580.
10. H. Okamoto, H. Obayashi and T. Kudo, Solid State Ionics, 1, 319 (1980); ibid., 3-4, 453 (1981). 11. G. Lu, N. Miura and N. Yamazoe, Ionics, 7, 16 (1998).

12. U. Lauer, J. Maier, and W. Gpel Conductance Effects of Ammonia on Silver Chloride Boundary Layers Sensors and Actuators B 2, 125-131 (1990). 13. M. Ferroni, V. Guidi, G. Martinelli, P. Nelli, M. Sacerdoti, and G. Sberveglieri, Thin Solid Films, 307 (1997) 148-151. 14. F. Mims, Timer, Op Amp & Optoelectronic Circuits & Projects, Radio Shack books, pg. 11.

Appendix A: H2S and Carbon Monoxide Sensor Summary with Lab-book Numbers.

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H2S Sensor Summary


Date Length of Run Sample ID IDE Mixed Potential Mixed Potential Mixed Potential Mixed Potential 15mm Cure Temp. Baseline Gas Composition
33.4%H2 - 22.2%CO2 - 4.4%CH4 -

Sample Prep.

Test Temp.

Average Baseline

H2S Conc.

Average Response

Sensitivity

Relative Sensitivity

8/20/02

1 day

101-17

800

C 40%N2 -

250 C

NA

5 ppm

NA

Electrode reduced Ag2S reduced Ag2S Reduced CuS Reduced Too insulative

1/2/03 1/28/03 2/25/03 2/17/03

1 day 1 day 1 day 1 day

101-73 101-86 101-90 101-92

825 825 1050 1050

C 40%N2 C 40%N2 C 40%N2 C

33.4%H2 - 22.2%CO2 - 4.4%CH4 33.4%H2 - 22.2%CO2 - 4.4%CH4 33.4%H2 - 22.2%CO2 - 4.4%CH4 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 -

250 C 250 C 250 C 300 C

NA NA NA NA

5 ppm 5 ppm 5 ppm 5 ppm

NA NA NA NA

3/10/04

2 days

157-011A

15mm

17%CO2-3.7%CH4-25%H2-50%N2wet 3% None

350 oC 425 oC 500 oC

23.5 M 5.77 M 4.1 M

500 ppb 500 ppb 500 ppb 500 ppb 500 ppb 500 ppb 500 ppb 1 ppm 2.5 ppm 5 ppm 1 ppm 5 ppm 5 ppm 2.5 ppm 1 ppm 0.5 ppm 5 ppm 5 ppm 2.5 ppm 1 ppm 0.5 ppm 5 ppm 2.5 ppm 1 ppm 0.5 ppm 1 ppm 1 ppm 1 ppm 0.5 ppm 1 ppm 0.5 ppm 1 ppm 1 ppm 1 ppm 0.5 ppm 1 ppm 0.5 ppm 1 ppm 0.5 ppm 5 ppm 5 ppm

1.68 M 0.35 M 0.0778 M 42.8 k -30.4 k 57.5 k 0.409 k 0.476 k 0.665 k 1.88 k 18.206 k 4.86 k 1.12 k 1.48 k 0.74 k 0.74 k -0.25 k 32.9 k 73.1 k 55.8 k 44.2 k 0.23 M 0.64 M 0.64 M 0.44 M -0.0295 k -6.608 k 1.436 k 1.42 k 1.41 k 0.905 k 0.154 M 8.94 k 0.751 k 0.806 k 0.589 k 1.522 k 0.988 k 0.93 k 4.93 k 1.41 k

7.15% 6.07% 1.90% 7.10% -10.57% 16.29% 7.45% 8.67% 12.11% 34.24% 2.81% 0.75% 20.48% 20.03% 9.50% 10.12% -2.90% 10.47% 10.29% 7.13% 5.50% 2.04% 3.86% 3.76% 2.60% -1.31% -1.36% 9.77% 8.11% 5.30% 3.32% 6.06% 1.12% 6.53% 6.08% 3.66% 7.62% 1.12% 1.02% 5.31% 2.13%

14.30% 12.13% 3.80% 14.20% -21.14% 32.58% 14.90% 8.67% 4.85% 6.85% 2.81% 0.15% 4.10% 8.01% 9.50% 20.25% -0.58% 2.09% 4.12% 7.13% 10.99% 0.41% 1.54% 3.76% 5.21% -1.31% -1.36% 9.77% 16.23% 5.30% 6.63% 6.06% 1.12% 6.53% 12.16% 3.66% 15.24% 1.12% 2.05% 1.06% 0.43%

3/11/04

1 day

157-011B

15mm

3/12/04

2 days

147-087A

15mm

17%CO2-3.7%CH4-25%H2-50%N2wet 3% None 17%CO2-3.7%CH4-25%H2-50%N2wet 3% 17%CO2-3.7%CH4-25%H2-50%N2wet 3% None

500 oC 602.9 k 500 oC 287.6 k 350 C 500 oC 500 oC 500 oC 500 oC


o

353 k 5.49 k 5.49 k 5.49 k 5.49 k

3/16/04

3 days

147-092A

15mm

17%CO2-3.7%CH4-25%H2-50%N2wet 3% None

350 oC 647.4 k 350 oC 647.4 k 500 oC 500 oC 500 oC 500 oC 5.47 k 7.39 k 7.79 k 7.31 k 8.63 M

3/18/04

3 days

147-095B

15mm

17%CO2-3.7%CH4-25%H2-50%N2None 800 oC wet 3%

350 oC

500 oC 314.3 k 500 oC 710.1 k 500 oC 782.9 k 500 oC 804.2 k 400 oC 400 oC 400 oC 400 oC 3/23/04 2 days 147-092B 15mm 17%CO2-3.7%CH4-25%H2-50%N2800 oC wet 3% None 350 oC 11.3 M 16.6 M 17 M 16.9 M 2.26 M

400 oC 485.3 k 500 oC 500 oC 17%CO2-3.7%CH4-25%H2-50%N2wet 28% 17%CO2-3.7%CH4-25%H2-50%N2800 oC wet 3% None 500 oC 500 oC 3/25/04 2 days 147-105B 15mm 350 oC 14.7 k 17.5 k 26.6 k 27.3 k 2.54 M

400 oC 801.4 k 500 oC 17%CO2-3.7%CH4-25%H2-50%N2wet 28% 17%CO2-3.7%CH4-25%H2-50%N2800 oC wet 3% None 11.5 k

500 oC 13.26 k 500 oC 16.09 k 500 oC 19.97 k 3/29/05 5 days 147-110A 15mm 500 oC 500 oC 500 oC 550 oC 88.6 k 90.9 k 92.9 k 66.3 k

Development of Sensors for Automotive PEM-based Fuel Cells

Page 61

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

550 oC 550 oC

68.4 k 67.6 k

1 ppm 0.5 ppm 5 ppm 1 ppm 5 ppm 1 ppm 5 ppm 1 ppm 5 ppm 1 ppm 5 ppm 1 ppm 5 ppm 5 ppm 1 ppm 5 ppm 1 ppm 5 ppm 1 ppm 5 ppm 1 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm

0.333 k 0.71 k 189.7 k 40.25 k 58.4 k 5.09 k 28.1 k 17.8 k 48.8 k 10.1 k 34.9 k 9.8 k 45.6 k 4.7 k 2.1 k 2.11 k 0.614 k 1.46 k 0.059 k 0.304 k 0.045 k 0.14 k 0.28 k 0.72 k -0.08 k 0.138 k 0 k 0 k 0 k 0 k 0.032 k 0.13 k 6.85 k 7.7 1.04 k 4.81 5.9 k 1.94 k 22.1 4.58 1058 k 2.42 k

0.49% 1.05% 41.19% 4.86% 22.73% 1.33% 10.43% 8.69% 27.92% 5.74% 21.20% 6.21% 27.59% 50.05% 24.28% 34.20% 8.45% 42.57% 2.16% 13.51% 1.89% 0.77% 2.14% 3.65% -5.39% 7.50% 0.00% 0.00% 0.00% 0.00% 2.09% 0.31% 45.97% 0.89% 8.20% 4.97% 6.24% 39.27% 4.22% 98.92% 304.99% 100.00%

0.49% 2.10% 8.24% 4.86% 4.55% 1.33% 2.09% 8.69% 5.58% 5.74% 4.24% 6.21% 5.52% 10.01% 24.28% 6.84% 8.45% 8.51% 2.16% 2.70% 1.89% 0.15% 0.43% 0.73% -1.08% 1.50% 0.00% 0.00% 0.00% 0.00% 0.42% 0.06% 9.19% 0.18% 1.64% 0.99% 1.25% 7.85% 0.84% 19.78% 61.00% 20.00%

450 oC 460.5 k 450 oC 828.6 k 460 oC 256.9 k 460 oC 382.4 k 470 oC 269.4 k 470 oC 204.8 k 480 oC 174.8 k 480 oC 176.1 k 490 oC 164.6 k 490 oC 157.7 k 4/6/04 3 days 147118C 15mm 17%CO2-3.7%CH4-25%H2-50%N2None 800 C wet 3%
o

400 C 165.3 k 450 oC 450 oC 460 oC 460 oC 480 oC 480 oC 500 oC 500 oC 9.39 k 8.65 k 6.17 k 7.27 k 3.43 k 2.73 k 2.25 k 2.38 k

???

1 day

147-143

15mm

17%CO2-3.7%CH4-25%H2-50%N2800 oC wet 3% None 17%CO2-3.7%CH4-25%H2-50%N2None 600 oC wet 3% 17%CO2-3.7%CH4-25%H2-50%N2N/A oC wet 3% None 17%CO2-3.7%CH4-25%H2-50%N2None 600 oC wet 3% 17%CO2-3.7%CH4-25%H2-50%N2C wet 3% None

485 oC 18.15 k 500 oC 13.1 k 19.7 k

???

1 day

147-143

15mm

488 oC

353 oC 1.485 M 5/11/04 5/25/04 1 day 1 day 166-057 147-149B 15mm 15mm 500 oC 1.84 M

295 oC 61.52 k 353 oC 11.58 k

5/26/04

1 day

166-033

15mm

N/A

395 oC 443 oC

3.39 k 1.39 k 1.53 k 41.6 k 14.9 k 862

5/27/04 5/28/04 6/2/04 6/3/05 6/7/05

1 day 1 day 1 day 1 day 1 day

147-151A 147-151E 147-151F 147151D 147-149B

15mm 15mm 15mm 15mm 15mm

17%CO2-3.7%CH4-25%H2-50%N2C wet 3% 17%CO2-3.7%CH4-25%H2-50%N2o C wet 3% 17%CO2-3.7%CH4-25%H2-50%N2600 oC wet 3% 17%CO2-3.7%CH4-25%H2-50%N2600 oC wet 3% 17%CO2-3.7%CH4-25%H2-50%N2600 oC wet 3%
o

None None None None None

500 oC 485 oC 432 C 500 oC


o

355 oC 12.68 k 500 oC 96.71

6/10/04 6/11/04 6/23/04

1 day 2 days 2 days

147-143 147151H 147175C

15mm 15mm 15mm

17%CO2-3.7%CH4-25%H2-50%N2600 C wet 3% None 17%CO2-3.7%CH4-25%H2-50%N2None 600 oC wet 3% 17%CO2-3.7%CH4-25%H2-50%N2600 oC wet 3% None


o

492 oC 495 oC

94.6 k 4.94 k

498 oC 523.1 355 oC 4.63 M

399 oC 346.9 k 450 oC 5ppm H2S for 17%CO2-3.7%CH4-25%H2-50%N2- 30 min @ 600 oC wet 3% 500oC 2.42 k

6/28/04

2 days

147-175A

15mm

500 oC

92.6

5 ppm 5 ppm 5 ppm

7.67 k 328.2 k 41.4 k

8.28% 49.92% 56.48%

1.66% 9.98% 11.30%

355 oC 657.5 k 407 oC 5ppm H2S for 17%CO2-3.7%CH4-25%H2-50%N2- 60 min @ 600 oC wet 3% 499oC 5ppm H2S for 17%CO2-3.7%CH4-25%H2-50%N2- 25 min @ 511oC 600 oC wet 3% 17%CO2-3.7%CH4-25%H2-50%N2- Mid-run 600 oC wet 3% @ 500oC 73.3 k

7/1/04

1 day

147-175A

15mm

500 oC 350 oC

93 468 k

5 ppm 5 ppm

16.8 317 k

18.06% 67.74%

3.61% 13.55%

7/1/04

1 day

147-175A

15mm

500 oC 354 oC

183 21.7 k 89.7 k 24.2 k

5 ppm 5 ppm 5 ppm 5 ppm

70.5 0 k 7.05 k 3.2 k

38.52% 0.00% 7.86% 13.22%

7.70% 0.00% 1.57% 2.64%

7/6/04

1 day

147-175A

15mm

350 oC 400 oC

Development of Sensors for Automotive PEM-based Fuel Cells

Page 62

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

450 oC 500 oC 350 oC 400 oC 450 oC 5ppm H2S for 30 min @ 450oC

6.95 k 97.6 862 k 109 k 746 k

5 ppm 5 ppm 5 ppm 5 ppm 5 ppm

0.77 k 14.4 407 k 125.1 k 1615 k

11.08% 14.75% 47.22% 114.77% 216.49%

2.22% 2.95% 9.44% 22.95% 43.30%

7/12/04

1 day

147-175A

15mm

600 oC

350 oC 190.7 k 400 oC 450 oC 36.8 k 279

5 ppm 5 ppm 5 ppm

68.9 k 32.8 k 725

36.13% 89.13% 259.86%

7.23% 17.83% 51.97%

7/12/04

1 day

147-175A

15mm

600 oC

5ppm H2S for 30 min @ 550oC

350 oC 601.7 k 400 oC 450 oC 143 k 42.3 k

5 ppm 5 ppm 5 ppm

8.13 k 21 k 1.38 k

1.35% 14.69% 3.26%

0.27% 2.94% 0.65%

7/15/04

1 day

147-175A

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

5ppm H2S for 30 min @ 550oC 5ppm H2S for 30 min @ 600oC

350 oC 258.5 k 400 oC 113.9 k

5 ppm 5 ppm

29.5 k -1.51 k

11.41% -1.33%

2.28% -0.27%

7/15/04

2 days

147-175A

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

350 oC

753 k

5 ppm 5 ppm 5 ppm 2.5 ppm 2.5 ppm

362 k 89.7 k 28.8 k 13.4 k 42.8 k

48.07% 67.29% 449.30% 241.44% 29.93%

9.61% 13.46% 89.86% 96.58% 11.97%

400 oC 133.3 k 450 oC 450 oC 400 oC 5ppm H2S for 30 min @ 550oC 6.41 k 5.55 k 143 k

7/22/04

2 days

166-102A

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

350 oC 400 oC 450 oC

475 k 151 k 24.8 k 124 174 k 38.3 k 179 735 k 282 k

5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm

146 k 46.1 k 18.3 k -2.54 99 k 46.1 k 548 k 1221 k 379 k

30.74% 30.53% 73.79% -2.05% 56.90% 120.37% 306.15% 166.12% 134.40%

6.15% 6.11% 14.76% -0.41% 11.38% 24.07% 61.23% 33.22% 26.88%

7/23/04 7/26/04

1 day 2 days

166-102A 166-102A

15mm 15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3% 600 oC 33.6% H2 - 66.4% N2 - wet 3%

None None

450 oC 350 oC 400 oC 450 oC

7/29/04

1 day

147-185

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

None 5ppm H2S for 30 min @ 500oC 5ppm H2S for 30 min @ 500oC 5ppm H2S for 30 min @ 500oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC

350 oC 400 oC

8/2/04

1 day

147-185

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

350 oC 400 oC

1132 k 252 k

5 ppm 5 ppm

1068 k 343 k

94.35% 136.11%

18.87% 27.22%

8/4/04

1 day

166-102A

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

350 oC 400 oC

860 k 170 k

2.5 ppm 2.5 ppm

174 k 53 k

20.23% 31.18%

8.09% 12.47%

8/9/04

1 day

166-102A

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

500 oC

117

5 ppm

4.04

3.45%

0.69%

8/11/04

2 days

166-102A

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

605

5 ppm

171

28.26%

5.65%

8/16/04

9 days

166-102A

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

475 oC 300 oC 300 oC 300 oC 300 oC 300 oC 300 oC 300 oC 300 oC 300 oC

167 3540 k 4288 k 3900 k 4185 k 4056 k 4050 k 4085 k 4138 k 5719 k 12.8 M

5 ppm 5 ppm 2.5 ppm 1 ppm 0.75 ppm 0.5 ppm 0.25 ppm 0.5 ppm 0.25 ppm 0.5 ppm 5 ppm

105 2270 k 1347 k 215 k 195 k 1180 k 653 k 837 k 850 k 1177 k 8.14 k

62.87% 64.12% 31.41% 5.51% 4.66% 29.09% 16.12% 20.49% 20.54% 20.58% 63.59%

12.57% 12.82% 12.57% 5.51% 6.21% 58.19% 64.49% 40.98% 82.17% 41.16% 12.72%

9/1/04

8 days

162-136A

15mm

900 oC 33.6% H2 - 66.4% N2 - wet 3%

None

350 oC

Development of Sensors for Automotive PEM-based Fuel Cells

Page 63

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

400 oC 420 oC 420 oC 420 oC 420 oC 420 oC 9/13/04 1 day 162-136A 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 385 oC 385 oC 9/17/04 1 day 101-105B 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 102 oC 215 oC 293 oC 9/20/04 1 day 101-105A 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 445 oC 465 oC 9/23/04 1 day 166-164 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 500 oC 450 oC 9/23/04 9/29/04 1 day 1 day 166-164 101105C 15mm 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% 900 oC 33.6% H2 - 66.4% N2 - wet 3% None None 454 oC 150 oC 200 oC 10/5/04 10 days 162-136A 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 420 oC 325 oC 325 oC 325 oC 325 oC 325 oC 322 oC 322 oC 322 oC 322 oC 415 oC 370 oC 325 oC 10/6/04 1 day 166-177 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 545 oC 545 oC 10/11/04 3 days 166-183 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 446 oC 472 oC 462 oC 496 oC 10/14/04 6 days 166-190 15mm 900 C 33.6% H2 - 66.4% N2 - wet 3%
o

2.31 M 207 k 170 k 141 k 120 k 104 k 9.68 k 8.87 k 971 43 13 227 k 31.3 k 3.95 M 25.1 M 4.74 M 61.7 30.2 k 8.66 k 75.8 k 84.9 k 195 k 116 k 143 k 122 k 113 k 121 k 117 k 10.9 k 25.4 k 55.9 k 494 k 547 k 176 k 90.2 k 108 k 56.7 k 22.4 M

5 ppm 5 ppm 2.5 ppm 0.5 ppm 0.25 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 2.5 ppm 1 ppm 5 ppm 0.5 ppm 5 ppm 2.5 ppm 5 ppm 2.5 ppm 5 ppm 5 ppm 1 ppm 5 ppm 0.5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 2.5 ppm 5 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.5 ppm 5 ppm 2.5 ppm 5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.5 ppm 0.25 ppm 0.1 ppm 5 ppm 2.5 ppm

1.86 k 372 k 191 k 192 k 37.8 k 157 k 2.53 k 1.38 k 0 0 0 18.7 k 2.27 k 0 M 0 M 0.53 k 0 k 0 k 35.2 k 10258 k 9775 k 9205 k 7893 k 222 k 15.8 k 19.8 k 23.6 k 30.1 k 0.48 k 1.92 k 3.5 k 31.7 k 8.3 k 232 k 13.3 k 108 k 2.4 k 10.5 M 1.72 M 0.64 M 0.43 M 0.13 M 0.75 M -0.55 k 0.38 k 174 k 179 k 122 k 73.8 k 65.8 k 65 k 119 k 121 k 123 k 40.2 k 33.3 k

80.52% 179.71% 112.35% 136.17% 31.50% 150.96% 26.14% 15.56% 0.00% 0.00% 0.00% 8.24% 7.25% 0.00% 0.00% 11.18% 0.00% 0.00% 406.47%

16.10% 35.94% 44.94% 272.34% 126.00% 301.92% 52.27% 62.23% 0.00% 0.00% 0.00% 16.48% 14.50% 0.00% 0.00% 2.24% 0.00% 0.00% 81.29%

13532.98% 2706.60% 11513.55% 4605.42% 4720.51% 4720.51% 6804.31% 1360.86% 155.24% 12.95% 17.52% 19.50% 25.73% 4.40% 7.56% 6.26% 6.42% 1.52% 131.82% 14.75% 100.00% 4.23% 46.88% 16.65% 6.82% 5.74% 1.94% 5.80% -4.20% 2.97% 150.00% 99.44% 153.07% 82.55% 102.17% 310.49% 2.59% 7.01% 3.90% 10.29% 0.88% 1.51% 6.26% 1.28% 3.03% 26.36% 2.95% 20.00% 0.85% 9.38% 3.33% 2.73% 1.15% 3.88% 11.60% -16.81% 5.94% 30.00% 39.78% 30.61% 165.10% 408.70%

None

500 oC

520 oC 10.33 M 520 oC 520 oC 520 oC 9.39 M 7.49 M 6.7 M

500 oC 12.93 M 500 oC 13.09 k 500 oC 10/15/04 8 days 166-185 15mm 600 oC 33.6% H2 - 66.4% N2 - wet 3% None 395 oC 395 oC 414 oC 414 oC 414 oC 414 oC 400 oC 400 oC 400 oC 450 oC 450 oC 12.8 k 116 k 180 k 79.7 k 89.4 k 64.4 k 62.5 k 120 k 128 k 132 k 7.56 k 8.21 k

104.00% 1040.00% 99.17% 94.53% 93.18% 531.75% 405.60% 198.33% 378.13% 931.82% 106.35% 162.24%

Development of Sensors for Automotive PEM-based Fuel Cells

Page 64

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

450 oC 500 oC 500 oC 500 oC 500 oC 10/20/04 2 days 192-004 15mm 600 C 33.6% H2 - 66.4% N2 - wet 3%
o

9.32 k 100 97.3 93.6 87.4 k 15.1 k

1 ppm 5 ppm 2.5 ppm 0.5 ppm 0.1 ppm 5 ppm 5 ppm 5 ppm 0.5 ppm 5 ppm 0.5 ppm 0.1 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.3 ppm 0.5 ppm 0.25 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.5 ppm 0.25 ppm 0.5 ppm 0.25 ppm 0.5 ppm 0.25 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 5 ppm 5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.25 ppm 0.1 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.25 ppm 5 ppm

30 k 30.3 15.6 15.5 5.9 k 87 k 0 k 0 k 0 k 0 k 0.162 k 0.089 k 0.0826 k 0.0635 k 0.0508 k 0.94 k 4.06 k 193 k 29.5 k 18.6 k 73 k 43.5 k 11.2 k 5.17 k 4 k 3.63 k 5.09 k 4.34 k 3.42 k 3.2 k 0.88 k 1.04 k 2.6 k 0.27 k 0.028 k 0 k 2.89 k 20.6 k 13.8 k 0 k 4.5 k 0.125 k 0.0836 k 0.0672 k 0.0545 k 0 k 0.047 k 0.093 k 0.0684 k 0.0532 k 0.359 k 0.2221 k 9.33 46.4 k 34.7 k 571 k

321.89% 30.30% 16.03% 16.56% 6.75% 576.16% 0.00% 0.00% 0.00% 0.00% 70.74% 37.87% 55.81% 41.78% 33.64% 4.09% 4.38% 57.44% 6.07% 29.62% 162.95% 102.59% 63.64% 44.57% 33.06% 29.51% 136.46% 94.76% 142.50% 124.51% 60.27% 66.67% 63.73% 15.98% 2.75% 0.00% 50.70% 293.45% 223.30% 0.00% 44.12% 70.62% 48.05% 37.97% 47.81% 0.00% 45.63% 83.04% 50.67% 36.94% 244.22% 111.61% 9.96% 44.19% 23.45% 348.17%

321.89% 6.06% 6.41% 33.12% 67.51% 115.23% 0.00% 0.00% 0.00% 0.00% 141.48% 378.72% 111.62% 167.11% 336.42% 8.17% 8.77% 114.88% 24.28% 98.73% 325.89% 410.38% 127.27% 89.14% 132.23% 295.12% 272.92% 379.04% 285.00% 498.05% 120.55% 266.67% 127.45% 31.95% 5.49% 0.00% 101.40% 58.69% 44.66% 0.00% 88.24% 141.24% 192.18% 379.66% 191.23% 0.00% 91.26% 166.07% 202.67% 369.44% 48.84% 223.22% 19.91% 88.38% 93.78% 69.63%

None

400 oC

450 oC 0.978 k 500 oC 0.227 k 10/21/04 2 days 166-181 15mm 600 oC 33.6% H2 - 66.4% N2 - wet 3% None 103 oC 4.78 k

159 oC 0.475 k 10/25/04 2 days 166-185 15mm 600 C 33.6% H2 - 66.4% N2 - wet 3%
o

None

420 oC 0.229 k 420 oC 0.235 k 430 oC 0.148 k 430 oC 0.152 k 430 oC 0.151 k

10/25/04

3 days

192-008

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

None

415 oC 375 oC 330 oC 330 oC

23 k 92.6 k 336 k 486 k 62.8 k 44.8 k 42.4 k 17.6 k 11.6 k 12.1 k 12.3 k 3.73 k 4.58 k 2.4 k 2.57 k 1.46 k 1.56 k 4.08 k 1.69 k 1.02 k 1.17 k 5.7 k 7.02 k 6.18 k 5.98 k 10.2 k

75% H2 - 25% N2 - dry 10/27/04 7 days 192-011 15mm 600 oC 33.6% H2 - 66.4% N2 - wet 3% None

330 oC 273 oC 273 oC 300 oC 325 oC 325 oC 325 oC 365 oC 365 oC 390 oC 390 oC 425 oC 425 oC

10/29/04

1 day

166-185

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

None

400 oC 420 oC 440 oC

11/2/04

4 days

192-007

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

None

440 oC 375 oC 375 oC 420 oC 420 oC 395 oC

11/4/04

6 days

192-007

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

None

430 oC 0.177 k 430 oC 0.174 k 430 oC 0.177 k 450 oC 0.114 k 450 oC 0.106 k 450 oC 0.103 k 445 oC 0.112 k 445 oC 0.135 k 445 oC 0.144 k 440 oC 0.147 k 440 oC 0.199 k

11/10/04 11/11/04

1 day 1 day

192-041 162-136A

15mm 15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3% 900 C 33.6% H2 - 66.4% N2 - wet 3%


o

None None

420 oC 415 oC 415 oC 415 oC

93.7 105 k 148 k 164 k

Development of Sensors for Automotive PEM-based Fuel Cells

Page 65

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

425 oC 188.7 k 425 oC 425 oC 11/16/04 1 day 192-046 15mm 600 oC 33.6% H2 - 66.4% N2 - wet 3% None 350 oC 315 oC 11/17/04 3 days 192-047A 15mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 410 oC 410 oC 410 oC 400 oC 400 oC 11/22/04 2 days 192047C 15mm 900 C 33.6% H2 - 66.4% N2 - wet 3%
o

0.5 ppm 0.25 ppm 0.1 ppm 0.5 ppm 5 ppm 0.5 ppm 5 ppm 0.25 ppm 0.5 ppm 5 ppm 0.5 ppm 5 ppm 0.5 ppm 5 ppm 5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 0.5 ppm 5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 5 ppm 0.5 ppm 0.25 ppm 5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 5 ppm 5 ppm 5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.5 ppm 5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.5 ppm

48.8 k 24.5 k 7.4 k 0 k 5.26 k 14.1 k 62 k 5.4 k 14.5 k 10.6 k -4.59 k 9.3 k 0 m 0 m 0 m 235 k 87.7 k 0.0708 k 0.013 k 0 k 0 k 0 k 0 m 113 k 61.5 k 93.2 k 47.8 k 29.2 k 17.9 k 626 k 118 k 62.9 k 33.6 k 178 k 34.7 k 18.3 k 3955 k 393 k 285 k 96 k 76 1102 1505 k 680 k 555 k 254 k -2.67 k -49 k 192 k 475 k 668 k 600 k 316 k 81 k 720 k

25.86% 13.32% 4.93% 0.00% 28.28% 15.16% 67.03% 6.12% 15.78% 11.57% -5.09% 10.50% 0.00% 0.00% 0.00% 32.68% 23.77% 28.66% 5.20% 0.00% 0.00% 0.00% 0.00% 116.62% 31.22% 55.81% 37.05% 26.31% 15.70% 377.11% 35.98% 18.28% 9.11% 130.88% 22.98% 10.11% 342.42% 21.13% 17.17% 5.78% 18.86% 156.76% 199.34% 42.42% 27.96% 13.51% -0.44% -8.35% 17.04% 61.29% 86.53% 103.63% 60.08% 16.04% 135.08%

51.72% 53.26% 49.33% 0.00% 5.66% 30.32% 13.41% 24.49% 31.56% 2.31% -10.18% 2.10% 0.00% 0.00% 0.00% 65.37% 47.53% 57.33% 20.80% 0.00% 0.00% 0.00% 0.00% 23.32% 62.44% 11.16% 74.11% 105.23% 157.02% 75.42% 71.95% 73.14% 91.06% 26.18% 45.96% 40.44% 68.48% 42.26% 68.67% 57.83% 3.77% 31.35% 39.87% 84.84% 111.84% 135.11% -0.87% -1.67% 34.07% 122.58% 173.06% 207.25% 240.30% 160.40% 270.17%

184 k 150 k 13.7 k 18.6 k 93 k 92.5 k 88.2 k 91.9 k 91.6 k 90.2 k 88.6 k 661 m 662 m 792 m 719 k 369 k

None

434 oC 434 oC

11/22/04

1 day

192-065

15mm

800 C 33.6% H2 - 66.4% N2 - wet 3%

None

420 oC 420 oC 500 oC

11/24/04

7 days

192-007

15mm

900 oC 33.6% H2 - 66.4% N2 - wet 3%

None

400 oC 420 oC

11/30/04

2 days

166-185

15mm

600 C 33.6% H2 - 66.4% N2 - wet 3%

None

430 oC 0.247 k 430 oC 0.25 k 48 k 46.6 k 7.2 k 926 m 96.9 k 197 k 167 k 129 k 111 k 114 k 166 k 328 k 344 k 369 k 136 k 151 k 181 k 1155 k 1860 k 1660 k 1660 k 403 703 755 k 1603 k 1985 k 1880 k 613 k 587 k 1127 k 775 k 772 k 579 k 526 k 505 k 533 k

12/2/04

1 day

192-067

15mm

700 oC 33.6% H2 - 66.4% N2 - wet 3%

None

230 oC 230 oC 325 oC 425 oC

12/3/04

7 days

162-136A

15mm

900 oC 33.6% H2 - 66.4% N2 - wet 3%

None

425 oC 425 oC 435 oC 435 oC 435 oC 435 oC

12/10/04

7 days

162-136A

15mm

900 oC 33.6% H2 - 66.4% N2 - wet 3%

None

420 oC 420 oC 420 oC 420 oC

12/20/04

11 days

166-185

15mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

None

366 oC 366 oC 366 oC

1/10/05

8 days

162-136A

5mm

900 oC 33.6% H2 - 66.4% N2 - wet 3%

None

420 oC 420 oC 420 oC 420 oC

1/5/05

3 days

192-104

15mm

800 oC 33.6% H2 - 66.4% N2 - wet 3%

None

400 oC 350 oC

1/18/05

18 days

162-136A

5mm

900 oC 33.6% H2 - 66.4% N2 - wet 3%

None

420 oC 420 oC 420 oC 420 oC

2/8/05

2 days

162-136A

5mm

33.6% H2 - 4%CH4 - 66.4% N2 - wet 900 C 3% None


o

420 C 420 oC

2/10/05 2/15/05

6 days 23 days

162-136A 162-136A

5mm 5mm

33.6% H2 - 4%CH4 - 62.4% N2 - wet 900 C 3% None


o

420 C 420 oC 420 oC 420 oC 420 oC 420 oC

900 oC 33.6% H2 - 66.4% N2 - wet 3% None 33.6% H2 - 1%CH4 - 65.4% N2 - wet 3% 33.6% H2 - 5%CH4 - 61.4% N2 - wet 3%

33.6% H2 - 10%CH4 - 56.4% N2 wet 3%

420 oC

Development of Sensors for Automotive PEM-based Fuel Cells

Page 66

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

420 oC 420 oC 33.6% H2 - 20%CH4 - 46.4% N2 wet 3% 33.6% H2 - 50%CH4 - 16.4% N2 wet 3% 192133C 420 oC 420 oC 420 oC 420 oC 2/21/05 9 days 5mm 1000 oC 33.6% H2 - 66.4% N2 - wet 3% None 430 oC 430 oC 430 oC 430 oC 3/4/05 4 days 192167A1 5mm 600 oC 33.6% H2 - 66.4% N2 - wet 3% None 210 oC 200 oC 107 oC 241 oC 297 oC 3/8/05 2 days 192-172 5mm 500 oC 33.6% H2 - 66.4% N2 - wet 3% None 420 oC 420 oC 3/10/05 1 day 192-171B 5mm 900 oC 33.6% H2 - 66.4% N2 - wet 3% None 5ppm H2S for 30 min @ 600oC 535 oC 535 oC

516 k 471 k 561 k 697 k 545 k 1080 k 13.5 M 21.7 M 22.5 M 16.9 M 6.85 6.87 6.86 8.04 24.5 619 k 345 k 37.7 M 37.4 M

0.25 ppm 0.1 ppm 0.46 ppm 0.25 ppm 0.5 ppm 0.1 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.08 ppm 0.5 ppm 0.5 ppm 5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 5 ppm 0.5 ppm 5 ppm

257 k 155 k 929 k 553 k 2171 k 295 k 4.63 M 4.1 M 0.64 M 0.473 k 0 0.113 0.4 0.37 1.3 145 k 2325 k 0 M 1.9 M

49.81% 32.91% 165.60% 79.34% 398.35% 27.31% 34.30% 18.89% 2.84% 2.80% 0.00% 1.64% 5.83% 4.60% 5.31% 23.42% 673.91% 0.00% 5.08%

199.22% 329.09% 359.99% 317.36% 796.70% 273.15% 68.59% 75.58% 28.44% 34.99% 0.00% 3.29% 1.17% 9.20% 10.61% 46.85% 134.78% 0.00% 1.02%

3/11/05

15 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC 450 oC 450 oC

29.2 k 47.2 k 51.5 k

0.5 ppm 0.25 ppm 0.1 ppm

46.1 k 12.9 k 8.5 k

157.88% 27.33% 16.50%

315.75% 109.32% 165.05%

3/25/05

1 day

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

3/28/05

2 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

3/28/05

30 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC

450 oC

18.3 k

0.5 ppm

0 k

0.00%

0.00%

450 oC

3.09 k

0.5 ppm

0 k

0.00%

0.00%

400 oC 400 oC

1363 k 1442 k

0.5 ppm 0.25 ppm 0.5 ppm 0.25 ppm 0.1 ppm 0.5 ppm 0.25 ppm

3953 k 1817 k 1.82 M 1.46 M 0 M 5.79 M 4.62 k

290.02% 126.01% 17.64% 14.31% 0.00% 22.44% 16.99%

580.04% 504.02% 35.27% 57.25% 0.00% 44.88% 67.94%

98% CH4 - 2% H2

400 oC 10.32 M 400 oC 400 oC 350 oC 350 oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC None None 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC 10.2 M 10.8 M 25.8 M 27.2 k

3/30/05

3 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

103 k

0.5 ppm

0 k

0.00%

0.00%

4/5/05

3 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

1.65 k

0.5 ppm

0 k

0.00%

0.00%

4/11/05

4 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

616

0.5 ppm

0.00%

0.00%

4/14/05 4/18/05 4/18/05

2 days 1 day 1 day

166-102A 166-102A 162-136A

5mm 5mm 5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3% 600 oC 33.6% H2 - 66.4% N2 - wet 3% 900 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC 1.085 k 450 oC 420 oC 3.77 k 1407 k

0.5 ppm 0.5 ppm 0.5 ppm

0 k 0 k 0 k

0.00% 0.00% 0.00%

0.00% 0.00% 0.00%

4/20/05

2 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

139

0.5 ppm

0.00%

0.00%

4/22/05

4 days

192-176

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

8.01 k

0.5 ppm

0.093 k

1.16%

2.32%

4/27/05

9 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3% 98% CH4 - 2% H2

450 oC 450 oC 450 oC

36 k 2246 k 2640 k

0.5 ppm 0.5 ppm 0.25 ppm

59 k 305 k 194 k

163.89% 13.58% 7.35%

327.78% 27.16% 29.39%

Development of Sensors for Automotive PEM-based Fuel Cells

Page 67

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

450 oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC

2560 k

0.1 ppm

78 k

3.05%

30.47%

4/28/05

2 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

345 k

0.5 ppm

45 k

13.04%

26.09%

4/29/05

3 days

192-176

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

53.3 k

0.5 ppm

inconclusive k 5.57 k 2.6 k 0.7

N/A

N/A

5/3/05

8 days

210-007

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC 450 C
o

93.9 k 85.4 k

0.5 ppm 0.25 ppm 0.1 ppm

5.93% 3.04% 0.61%

11.86% 12.18% 6.05%

450 oC 115.7 k 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC

5/6/05

2 days

210-007

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

919

0.5 ppm

14 k 744 k 718 k 427 k 252 k 126 k 545 k 292 k 380 k 420 k 225 k 200 k 128 k 90 k 447 k 229 k 0.7 k 25.8 k 12 k 92.1 k 40 k 36 k 21 k 9.55 k 0 k 26 k 32.8 k 13 k 35 k 27 k 410 k 270

1.52%

3.05%

5/9/05

33 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC 450 C 450 oC 450 oC 450 oC


o

425 k 473 k 600 k 548 k 577 k 259 k 317 k 1990 k 1970 k 1968 k 2260 k 2335 k 2340 k 253 k 268 k

500 ppb 250 ppb 100 ppb 50 ppb 25 ppb 100 ppb 50 ppb 500 ppb 250 ppb 100 ppb 500 ppb 250 ppb 100 ppb 250 ppb 100 ppb

175.06% 151.80% 71.17% 45.99% 21.84%

350.12% 607.19% 711.67% 919.71% 873.48%

33.6% H2 - 66.4% N2 - dry

450 oC 450 oC

210.42% 2104.25% 92.11% 1842.27% 19.10% 21.32% 11.43% 8.85% 5.48% 3.85% 176.68% 85.45% 38.19% 85.28% 114.33% 17.70% 21.93% 38.46% 706.72% 854.48%

98% CH4 - 2% H2 - dry

450 C 450 oC 450 oC

98% CH4 - 2% H2 - wet 3%

450 oC 450 oC 450 oC

33.6% H2 - 66.4% N2 - wet 3% 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC 5ppm H2S for 30 min @ 600oC

450 C 450 oC

5/11/05

2 days

210-007

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC

52.9 k

0.5 ppm

1.32%

2.65%

5/13/05

3 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC 450 C
o

460 k 431 k

0.5 ppm 0.25 ppm

5.61% 2.78%

11.22% 11.14%

5/18/05

10 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC 450 oC 450 oC

720 k 758 k 771 k 1388 k

0.5 ppm 0.1 ppm 0.05 ppm 0.5 ppm

12.79% 5.28% 4.67% 1.51%

25.58% 52.77% 93.39% 3.03%

98% CH4 - 2% H2 - wet 3%

450 oC Heat to 300oC then heat w/ NiCr Heat to 300oC then heat w/ NiCr 5ppm H2S for 30 min @ 600oC

6/7/05

4 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

395 oC

26.5 k

0.5 ppm

36.04%

72.08%

6/16/05

8 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

~400 oC ~400 oC

385 k 302 k

0.1 ppm 0.5 ppm

0.00% 8.61%

0.00% 17.22%

~450 oC ~451 C 450 oC 450 oC


o

195 k 241 k 216 k 219 k

0.5 ppm 0.25 ppm 0.25 ppm 0.1 ppm

16.82% 5.39% 16.20% 12.33%

33.64% 21.58% 64.81% 123.29%

6/27/05

2 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

5ppm H2S for 30 min @ 600oC

450 oC 450 oC

1650 k 1840 k

0.5 ppm 0.25 ppm

24.85% 14.67%

49.70% 58.70%

Development of Sensors for Automotive PEM-based Fuel Cells

Page 68

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005


k 40 k 190 k 142 k 38.5 k 7 k 137 k 9.15 k 35.5 k 100 k 121 13 311 48 k -1.25 k -30 k 0.25 k 0.03 k 0.05 1.7 10.5 k 0.28 k 0.15 k 0.026 M -0.9

~450 oC 450 oC 5ppm H2S for 30 min @ 600oC

1625 k 2230 k

0.5 ppm 0.5 ppm

2.46% 8.52%

4.92% 17.04%

6/30/05

7 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

450 oC ~450 oC ~450 C


o

612 k 235 k 225 k

0.5 ppm 0.5 ppm 0.25 ppm

23.20% 16.38% 3.11%

46.41% 32.77% 12.44%

7/20/05

3 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

5ppm H2S for 30 min @ 600oC

450 oC ~450 oC

762 k 19.3 k 166 k

0.5 ppm 0.5 ppm 0.5 ppm

17.98% 47.41% 21.39%

35.96% 94.82% 42.77%

7/27/05

3 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3%

8/1/05

5 days

166-102A

5mm

600 oC 33.6% H2 - 66.4% N2 - wet 3% 25% CO - 25% H2 - 50% N2 - wet 600 oC 3%

None 5ppm H2S for 30 min @ 600oC

450 oC

450 oC 450 oC

661 k 747 k 912 919 946 92.4 k 2230 k 2.54 k 2.85 k 20.2 k 120 118 1.76 k 1.85 k 1.77 k 37.9 M

0.5 ppm 0.5 ppm 0.5 ppm 5 ppm 2.5 ppm 0.5 ppm 5 ppm 0.5 ppm 5 ppm 5 ppm 0.5 ppm 5 ppm 5 ppm 1 ppm 0.5 ppm 0.5 ppm

15.13% 16.20% 1.43% 33.84% 5.07% -1.35% -1.35% 9.84% 1.05% 0.25% 1.42% 8.90% 15.91% 8.11% 1.47% -2.37%

30.26% 32.40% 2.85% 6.77% 2.03% -2.71% -0.27% 19.69% 0.21% 0.05% 2.83% 1.78% 3.18% 8.11% 2.94% -4.75%

8/8/05

3 days

166-102A

5mm

None

700 oC 700 oC 700 oC

8/11/05

2 days

192-045

5mm

25% CO - 25% H2 - 50% N2 - wet 800 oC 3% 25% CO - 25% H2 - 50% N2 - wet 800 C 3%
o

None

700 oC 450 oC

8/16/05

1 days

192-040B

5mm

None

700 oC 700 oC 450 oC

8/17/05

2 days

125-050A

5mm

25% CO - 25% H2 - 50% N2 - wet 700 C 3%


o

None

650 C 650 oC

8/23/05

2 days

147-149B

5mm

25% CO - 25% H2 - 50% N2 - wet 600 C 3%


o

None

650 C 650 oC 650 oC

8/31/05

2 days

210-098

5mm

25% CO - 25% H2 - 50% N2 - wet 700 oC 3%

None

700 oC

CO Sensor Summary

Development of Sensors for Automotive PEM-based Fuel Cells

Page 69

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

Date

Length of Run

Sample ID

Mode

Baseline Gas Composition

Sample Prep.

Test Temp

Avg. Baseline

CO Conc.

Average Response

Sensitivity

Relative Sensitivity

4/23/02 6/06/02

NA NA 3 days

42-187 42-188

resistive resistive

NA 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2

CuBr purification CuBr/CuCl alloy

NA 65 60 48

NA 9 Kohm 12 Kohm 21 Kohm NA OVLD 10 kohm 1.7 Mohm


o

NA 400 400 400 ppm ppm ppm

NA 400 ohms

NA 4% 11% 13% NA NA NA Kohm mV mV mV mV mV mV 40 NA 0.00% 2.56%

NA

1320 ohms 2793 ohms NA NA NA 700 NA NA 23

6/10/02 6/17/02 10/7/02 12/20/02 9/3/02 9/6/02 9/13/02 10/29/02

1 day 1 day 1 day 1 day 1 day 1 day 1 day 1 day

42-190 42-192 104-17 104-133 101-023 101-030 101-039 101-060

resistive resistive resistive resistive Fuel Cell Fuel Cell Fuel Cell Fuel Cell

33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3% 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3% 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3% 60% H2 - 40% N2

CuBr-MO TEOS CuCl-MO CuBr/CuCl alloy CuCl/MO None None Heated to 300 C in dry H2; then switch to syn gas None
o

65 65 150 55 300 C 300 C 400 C 250 C 350 C


o o o o

4000 ppm 400 ppm

NA NA

5000 ppm 5000 ppm 400 400 400 ppm ppm ppm ppm ppm ppm

820 mV 232 mV 900 mV 700 mV mV mV

NA 0.00% 3.19%

10/29/02 12/16/02 12/28/02

1 day 1 day 1 day

101-060 104-028

Fuel Cell Resistive

33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3% 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2

None None None

300 C

104-032A Capacitance

100 C 150 C
o

14.2 pF 15.3 pF 22.6 pF 22.6 pF 15.3 pF 18.8 pF 18.8 pF 18.8 pF 18.8 pF 19.6 pF 35.3 pF 804 mV 859 mV 876 mV 863 mV 877 mV 906 mV 883 mV 863 mV

400 400 400

ppm ppm ppm

0 0.1 -0.1 -0.4 0 0 0 0 0 -0.3 2

pF pF pF pF pF pF pF pF pF pF pF

0.00% 0.65% -0.44% -1.77% 0.00% 0.00% 0.00% 0.00% 0.00% -1.53% 5.67% -0.28% 3.11% 1.97% 3.19% 0.41% 0.85% 0.39% 0.94%

0.00% 0.82% -0.55% -0.22% 0.00% 0.00% 0.00% 0.00% 0.00% -1.91% 7.08% -0.42% 4.67% 2.97% 4.78% 0.62% 1.28% 0.58% 1.41%

12/31/02

1 day

104-032B Capacitance

33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2

None

60 C 60 C
o

4000 ppm 400 400 ppm ppm

1/2/03

2 days

104-036

Capacitance

33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2

None

30 C 65 C 65 C 85 C 85 C 100 C
o o o o o

4000 ppm 400 ppm

4000 ppm 400 400 333 333 333 333 333 333 333 333 ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm

1/5/03 1/21/03

1 day 2 days

101-074 104-054

Capacitance

H2/N2

Heat in BL to o 100 C then cool to o 60 C None

60 C 350 C 400 C 450 C 550 C


o o o o

Bi-anode Fuel Cell Humid syngas

-2.27 mV 26.7 17.3 27.5 3.6 7.7 3.43 8.12 mV mV mV mV mV mV mV

1/21/03

2 days

104-054

Bi-anode Fuel Cell Humid syngas

None

350 C 400 C 450 C 550 C


o o o

1/22/03 1/22/03 2/8/03

2 days 2 days 1 day

104-061 104-061 104-084

Bi-anode Fuel Cell Humid syngas/Humid N2/H2 Bi-anode Fuel Cell Humid syngas/Humid N2/H2 Bi-anode Fuel Cell Humid syngas

None None None 450 C 500 C


o o

791 mV 877 mV 767 mV 924 mV 887 mV

500 500 500 500 500

ppm ppm ppm ppm ppm

-9.33 mV -2 mV

-1.18% -0.23% -2.83% -0.61% -0.45%

-1.18% -0.23% -2.83% -0.61% -0.45%

2/8/03

1 day

104-084

Bi-anode Fuel Cell Humid syngas

None

450 C 500 C
o

-21.7 mV -5.6 -4 mV mV

2/23/03

1 day

104-109

28%H2 - 18.6%CO2 - 3.7%CH4 Bi-anode Fuel Cell 50%N2 - wet 3%

None

450 C

Development of Sensors for Automotive PEM-based Fuel Cells

Page 70

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616


28%H2 - 18.6%CO2 - 3.7%CH4 50%N2 - wet 3%

Final Report November 11, 2005

2/23/03 2/25/03

1 day 1 day

104-109 104-111

Bi-anode Fuel Cell

None None

450 C 450 C 500 C 550 C


o o o

912 mV 917 mV 978 mV 989 mV 967 mV 993 mV 989 mV 814 mV 909 mV 628 mV 697 mV 986 mV 1007 mV 835 mV 636 mV 829 mV 516 mV 638 mV 940 mV 985 mV 680 mV 761 mV 743 mV 743 mV 862 mV 460 mV 466 mV 573 mV 812 mV 497 mV 732 mV 820 mV 560 mV 765 mV 885 mV 882 mV 470 mV 627 mV 678 mV 404 mV 597 mV 655 mV 684 mV 667 mV

500 500 500 500 500 500 500 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400

ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm

8 1.75 3 5.5 11.5 7 4.5 0.2 45.4 -10 3.93 -1.9

mV mV mV mV mV mV mV mV mV mV mV mV

0.88% 0.19% 0.31% 0.56% 1.19% 0.70% 0.46% 0.02% 4.99% -1.59% 0.56% -0.19% -0.03% 0.00% 4.32% 8.38% 1.94% 3.21% 0.59% 0.29% 0.15% 1.51% -1.14% 0.13% 0.07% 0.08% 1.29% 1.83% 1.23% 0.80% 0.41% 2.93% -1.96% 0.98% -1.02% 1.36% -1.38% -0.96% 0.44% -0.74% -1.42% -1.68% -1.17% 0.08%

0.88% 0.19% 0.31% 0.56% 1.19% 0.70% 0.46% 0.03% 6.24% -1.99% 0.70% -0.24% -0.03% 0.00% 5.40% 10.48% 2.42% 4.02% 0.73% 0.37% 0.18% 1.89% -1.43% 0.17% 0.09% 0.10% 1.61% 2.29% 1.54% 1.01% 0.51% 3.66% -2.46% 1.23% -1.27% 1.70% -1.73% -1.20% 0.55% -0.93% -1.78% -2.10% -1.46% 0.10%

Bi-anode Fuel Cell 55%H2 - 45%N2 - wet3%

2/25/03

1 day

104-111

Bi-anode Fuel Cell 55%H2 - 45%N2 - wet3%

None

450 C 500 C 550 C


o o

2/27/03

2 days

104-116

Bi-anode Fuel Cell

33.3%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3%

None

350 C 400 C 250 C 300 C 450 C 500 C 300 C


o o o o o o

-0.27 mV 0 27.5 69.5 10 20.5 5.5 2.9 1 11.5 -8.5 1 0.6 0.37 6 10.5 10 4 3 24 -11 7.5 -9 12 -6.5 -6 3 -3 -8.5 -11 -8 0.55 mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV mV

2/27/03

2 days

104-116

Bi-anode Fuel Cell

33.3%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3%

None

350 C 400 C 250 C 300 C 450 C 500 C 300 C


o o o o o o

2/28/03

1 day

104-120

Bi-anode Fuel Cell Humid Syngas

None

250 C 300 C 350 C 400 C


o o o

2/28/03

1 day

104-120

Bi-anode Fuel Cell Humid Syngas

None

250 C 300 C 350 C 400 C


o o o

3/13/03

1 day

104-137

Bi-anode Fuel Cell Humid syngas

None

250 C 300 C 350 C 250 C 300 C 350 C 400 C


o o o o o o

3/13/03

1 day

104-137

Bi-anode Fuel Cell Humid syngas

None

250 C 300 C 350 C 250 C 300 C 350 C 400 C


o o o o o o

3/17/03

1 day

104-144

Bi-anode Fuel Cell Humid Syngas

None

250 C

Development of Sensors for Automotive PEM-based Fuel Cells

Page 71

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

300 C 350 C 3/17/03 1 day 104-144 Bi-anode Fuel Cell Humid Syngas None 250 C 300 C 350 C 3/31/03 2 days 104-159 40%H2 - 26.7%CO2 - 5.33%CH4 Bi-anode Fuel Cell 28%N2 - wet 3% None 350 C 400 C 250 C 300 C 350 C 150 C 3/31/03 2 days 104-159 Bi-anode Fuel Cell 40%H2 - 26.7%CO2 - 5.33%CH4 28%N2 - wet 3% None 350 C 400 C 250 C 300 C 350 C 150 C 3/03 3/03 8/13/03 1 day 1 day 2 days 101-093 101-093 125-060 Bi-anode Fuel Cell Bi-anode Fuel Cell Resistive 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3% 33.4%H2 - 22.2%CO2 - 4.4%CH4 40%N2 - wet 3% 60.9% N2 - 27.1% H2 - 10% CO2 - 2% H2 O None 300 C 300 C 350 C 500 C 8/18/03 2 days 125-063C Resistive 60.9% N2 - 27.1% H2 - 10% CO2 - 2% H2 O None 350 C 350 C 350 C 350 C 8/20/03 6 days 125-063B Resistive 60.9% N2 - 27.1% H2 - 10% CO2 - 2% H2 O None 350 C 500 C 8/25/03 9/3/03 9/5/03 9/9/03 5 days 2 days 4 days 7 days 125-063A Resistive 125-082C Resistive 125-082E Resistive 125-082D Resistive 60.9% N2 - 27.1% H2 - 10% CO2 - 2% H2 O 60.9% N2 - 27.1% H2 - 10% CO2 - 2% H2 O 60.9% N2 - 27.1% H2 - 10% CO2 - 2% H2 O 60.9% N2 - 27.1% H2 - 10% CO2 - 2% H2 O None None None None 350 C 350 C 350 C 350 C 500 C 10/23/03 2 days 125-117A Mixed Potential 50% H2 - 50%N2 - wet 3% Heat to 550 C in BL then cool to o 200 C to test
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

878 mV 947 mV 779 mV 933 mV 977 mV 992 mV 1016 mV 637 mV 937 mV 1003 mV 33.3 mV 1007 mV 1011 mV Unsta ble 1022 mV 1029 mV 58.4 mV 648 mV 521 mV k 24.4 k 762 k 694 k 1044 k 1066 k 487 k 3.15 k 1220 k 2920 k 238 k 269 k 2.22 k

400 400 400 400 400 280 280 280 280 280 280 280 280 280 280 280 280 400 400 609 609 609 300

ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm

2.5 6 15.8 32 20 29 2.1 7 -5 3.3 0.53 9.4 3

mV mV mV mV mV mV mV mV mV mV mV mV mV

0.28% 0.63% 2.03% 3.43% 2.05% 2.92% 0.21% 1.10% -0.53% 0.33% 1.59% 0.93% 0.30%

0.36% 0.79% 2.54% 4.29% 2.56% 5.22% 0.37% 1.96% -0.95% 0.59% 2.84% 1.67% 0.53%

-2 3 -2.6 -8 -9

mV mV mV mV mV k

-0.20% 0.29% -4.45% -1.23% -1.73%

-0.35% 0.52% -7.95% -1.54% -2.16%

0.43

1.76% -2.24% -2.67% -3.83% -0.68% 2.16% -7.75% -1.07% 3.66% -3.76% -2.23% 0.23% 1327.94% 6.23% -4.41% -3.14% 3.17% -10.64% -3.86% -2.98% -3.25% -4.16% -4.07% -4.01%

1.45% -1.84% -4.44% -0.31% -0.56% 1.77% -6.36% -0.87% 3.01% -3.09% -1.83% 0.18% 1327.94% 6.23% -4.41% -3.14% 3.17% -10.64% -3.86% -5.96% -6.50% -4.16% -4.07% -4.01%

-17.1 k -18.5 k -40 -7.3 10.5 k k k

6090 ppm 609 609 609 609 609 609 609 609 500 500 500 500 500 500 500 250 250 500 500 500 ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm

-0.244 k -13 107 k k

-8.95 k -6 k

0.005 k 0.903 mV 0.24 mV

200 C -0.068 mV 200 C


o

3.85 mV -2.04 mV -1.59 mV 0.473 mV -2.34 mV -5.13 mV -5 mV -5.08 mV -5 mV -5.04 mV -63.4 mV

10/28/03

8 days

125-117B Mixed Potential

50% H2 - 50%N2 - wet 3%

Heat to 550 C in BL then cool to o 200 C to test

300 C 250 C 200 C 250 C 300 C 300 C


o o o o o

-0.09 mV -0.05 mV 0.015 mV -0.249 mV -0.198 mV -0.149 mV -0.165 mV -0.208 mV -0.205 mV -2.54 mV

50% H2 - 50%N2 - wet 28% 50% H2 - 50%N2 - wet 28% 50% H2 - 50%N2 - wet 3% 11/11/03 3 days 125-127A Mixed Potential 50% H2 - 50%N2 - wet 3% Heat to 450 C in BL; reduce CuO @ o 450 C; cool to test
o

300 C 300 C 300 C 300 C


o o o

Development of Sensors for Automotive PEM-based Fuel Cells

Page 72

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

350 C 11/25/03 1 day 125-145A Resistive 50% H2 - 50%N2 - dry None Heat to 550 C in BL; reduce NiO overnight; cool to test
o

-196 mV

500 500

ppm ppm

-0.027 mV

-0.01%

-0.01%

300 C
o

12/16/03

8 days

125-132A Mixed Potential

50% H2 - 50%N2 - wet 3%

300 C
o

-14.9 mV

500

ppm

-1.46 mV

-9.80%

-9.80%

300 C 300 C 12/29/03 10 days 125-127B Mixed Potential 50% H2 - 50%N2 - wet 3% Heat to 200 C in BL Reduce CuO @ o 450 C overnight o Heat to 550 C in BL; reduce NiO; cool to test None
o o

-23 mV -29.4 mV -3.12 mV -7.93 mV -92.1 mV 855 mV 599 mV 583 mV 316 mV 494 mV 493 mV 471 mV 413 mV 354 mV 486 mV 481 mV 565 mV 622 mV 523 mV 516 mV 487 mV 511 mV 320 mV 805 mV 800 mV 809 mV 312 mV 282 mV 223 mV 189 mV 183 mV 179 mV 174 mV 172 mV 172 mV 676 mV 871 mV 832 mV 810 mV 806 mV 786 mV 53.4 mV 104 mV 84 mV 135 mV 744 mV 813 mV 683 mV 969 mV 537 mV 11.7 mV 12.4 mV 21.6 mV -30.5 mV -37.6 mV -36.6 mV -36.6 mV 396 mV 301 mV

50 500 500 500 500

ppm ppm ppm ppm ppm

-0.977 mV 0.424 mV 2.34 2.09 mV mV

-4.25% 1.44% 75.00% 26.36% -0.51% 0.38% 0.00% 0.09% 1.13% 0.53% 0.04% 0.25% 0.08% -1.75% -0.94% 0.35% 0.32% 0.50% -0.55% -0.88% -0.63% 0.04% -0.91% -0.05% 0.01% 0.35% -9.94% -4.65% -8.07% -2.98% -0.40% -6.48% -4.06% -0.60% 0.47% 1.11% 0.73% 0.65% 0.99% 0.69% 1.31% -8.52% -3.84% -5.43% -3.24% -1.84% -0.17% 0.00% 0.00% 1.13% -0.09% 0.00% 5.28% 26.16% 7.85% 3.01% 8.50% -2.98% -6.61%

-42.48% 1.44% 75.00% 26.36% -0.51% 0.38% 0.00% 0.18% 1.13% 0.53% 0.09% 0.25% 0.08% -1.75% -0.94% 0.69% 0.32% 0.50% -0.55% -0.88% -0.63% 0.04% -0.91% -0.05% 0.01% 0.35% -9.94% -9.29% -8.07% -5.96% -4.04% -6.48% -8.13% -2.99% 1.55% 1.11% 0.73% 0.65% 0.99% 1.38% 1.31% -8.52% -3.84% -5.43% -3.24% -1.84% -0.17% 0.00% 0.00% 1.13% -0.09% 0.00% 5.28% 26.16% 15.69% 15.03% 8.50% -2.98% -6.61%

200 C 200 C 300 C 300 C 250 C 250 C


o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

1/8/04 3/31/04

7 days 3 days

125-132B Mixed Potential 157-051B Fuel Cell

50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3%

-0.468 mV 3.25 mV 0.004 mV 8 0.52 mV 3.57 mV 2.61 mV 0.21 mV 1.16 mV 0.33 mV -6.18 mV -4.59 mV 1.668 mV 1.79 mV 3.08 mV -2.89 mV -4.55 mV -3.08 mV 0.22 mV -2.9 mV -0.4 mV 0.11 mV 2.82 mV -31 mV -13.1 mV -18 mV -5.63 mV -0.74 mV -11.6 mV -7.07 mV -1.03 mV 0.8 mV 7.47 mV 6.36 mV 5.37 mV 8.01 mV 5.55 mV 10.3 mV -4.55 mV -3.99 mV -4.56 mV -4.37 mV -13.7 mV -1.36 mV 0 mV 0 mV 6.08 mV -0.01 mV 0 mV 1.14 mV 7.98 mV 2.95 mV 1.1 mV 3.11 mV -11.8 mV -19.9 mV

500 ppm 500 ppm 250 ppm 500 ppm 500 ppm 250 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 500 ppm 250 ppm 50 ppm 500 ppm 250 ppm 100 ppm 150 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 100 ppm 500 ppm 500 ppm 500 ppm

4/5/04

3 days

157-052A

Fuel Cell

50% H2 - 50%N2 - wet 3%

None

250 C 300 C 300 C 275 C 250 C 225 C

4/8/04

3 days

157-057A

Fuel Cell

50% H2 - 50%N2 - wet 3%

None

250 C 250 C 275 C 300 C 325 C 350 C 375 C 300 C 250 C

4/12/04

6 days

166-001B

Fuel Cell

50% H2 - 50%N2 - wet 3%

None

250 C 275 C 250 C

Reduce CuO @ o 450 C/1hr

250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C

4/15/04

2 days

166-005

Fuel Cell

50% H2 - 50%N2 - wet 3%

None

250 C 300 C 325 C 350 C 350 C 375 C

4/16/04

5 days

166-007A

Mixed Potential

50% H2 - 50%N2 - wet 3%

N2 on 100 C; H2 on o 450 C; cool at min. value

250 C 275 C 225 C 250 C


o o o o o o o o o o o

4/20/04

2 days

157-079

Fuel Cell

50% H2 - 50%N2 - wet 3%

None Reduce CuO in BL @ 450oC/1hr Reduce CuO in BL @ 450oC/1hr None N2 on 100 C; H2 on o 200 C Reduce CuO in BL o @ 450 C/1hr
o

250 C 300 C

4/26/04

1 day

166-012C

Fuel Cell

50% H2 - 50%N2 - wet 3%

250 C 300 C

4/26/04 4/26/04

2 days 1 day

166-012D 166-022

Fuel Cell Mixed Potential

50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3%

250 C 300 C 250 C

4/26/04 4/27/04

2 days 4 days

166-019A 166-012B

Mixed Potential Mixed Potential

50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3%

250 C 250 C 250 C 250 C 250 C


o o o o o o

4/30/04

10 days

166-025A

Fuel Cell

50% H2 - 50%N2 - wet 3%

Reduce CuO in BL @ 450oC/2hrs Reduce for an

250 C 250 C

Development of Sensors for Automotive PEM-based Fuel Cells

Page 73

NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616


additional hour at o 450 C 260 C 270 C 240 C 245 C 250 C 5/4/04 5/5/04 5/7/04 1 day 2 days 1 day 166-025B 166-039A 166-051A Fuel Cell Mixed Potential Mixed Potential 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% Reduce CuO in BL o @ 450 C/2hrs None None Reduce CuO in BL o @ 450 C/2hrs None None Reduce CuO in BL o @ 450 C/2hrs Reduce CuO in BL o @ 450 C/1hr 250 C 250 C 250 C 255 C 255 C 5/11/04 5/12/04 5/13/04 5/13/04 1 day 2 days 2 days 2 days 166-048A 166-051B 166-025A 166-048B Fuel Cell Mixed Potential Fuel Cell Fuel Cell 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% 250 C 250 C 250 C 250 C 275 C 5/14/04 1 day 166-062 Mixed Potential 50% H2 - 50%N2 - wet 3% 250 C 250 C 250 C 5/04 5/26/04 5/29/04 6/1/04 1 day 2 days 1 day 1 day 166-052C 166-052D 166-068 166-078 Mixed Potential Mixed Potential Mixed Potential Mixed Potential 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% 50% H2 - 50%N2 - wet 3% Reduce CuO in BL o @ 450 C/1hr None Reduce CuO in BL o @ 450 C/1hr Reduce CuO in BL o @ 450 C/1hr Reduce CuO in BL o @ 450 C/1hr 250 C 250 C 250 C 250 C 250 C 6/2/04 2 days 166-077C Mixed Potential 50% H2 - 50%N2 - wet 3% 250 C 250 C 250 C 250 C 250 C 6/4/04 1 day 166-077E Mixed Potential 50% H2 - 50%N2 - wet 3% N2 on @ 50 C; H2 o on @ 80 C; reduce o 1hr @ 450 C o N2 on @ 50 C; H2 o on @ 450 C; reduce 1hr @ o 450 C o N2 on @ 250 C; H2 o on @ 450 C; reduce 1.25hr @ o 450 C
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

Final Report November 11, 2005

346 mV 368 mV 278 mV 307 mV 306 mV 423 mV -149 mV -148 mV -66.3 mV -67.5 mV -2.89 mV 140 mV 291 mV 20.3 mV 212 mV -56.2 mV -56.2 mV -53.6 mV -96.4 mV -111 mV -39.9 mV -76.7 mV -69.2 mV -153 mV -152 mV -89.3 mV -92.7 mV -95.1 mV -86.3 mV

500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 500 ppm 250 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 100 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 500 ppm 250 ppm 500 ppm 250 ppm 100 ppm 500 ppm

-12.1 mV -5.03 mV -4.41 mV -4.04 mV 4.07 mV 0 mV 25 mV 18.9 mV 9.08 mV 8.68 mV 0.55 mV 1.82 mV 4.97 mV 1.83 mV -4.4 mV 19.7 mV 15.4 mV 10.7 mV 14.8 mV 26.1 mV 32.3 mV 22.9 mV 13.7 mV 12.7 mV 5.64 mV 14 mV 10.2 mV 5.6 mV 4.93 mV

-3.50% -1.37% -1.59% -1.32% 1.33% 0.00% 16.78% 12.77% 13.70% 12.86% 19.03% 1.30% 1.71% 9.01% -2.08% 35.05% 27.40% 19.96% 15.35% 23.51% 80.95% 29.86% 19.80% 8.30% 3.71% 15.68% 11.00% 5.89% 5.71%

-3.50% -1.37% -1.59% -1.32% 1.33% 0.00% 16.78% 25.54% 13.70% 25.72% 19.03% 1.30% 1.71% 9.01% -2.08% 35.05% 54.80% 99.81% 15.35% 23.51% 80.95% 29.86% 39.60% 8.30% 7.42% 15.68% 22.01% 29.44% 5.71%

250 C

6/5/04

1 day

166-077F

Mixed Potential

50% H2 - 50%N2 - wet 3%

250 C

-48 mV

500 ppm

20.2 mV

42.08%

42.08%

6/7/04

2 days

166-077B

Mixed Potential

50% H2 - 50%N2 - wet 3%

250 C 250 C 250 C


o o

-40.1 mV -41 mV -17.6 mV -32 mV

500 ppm 250 ppm 500 ppm 500 ppm

12 mV 8.53 mV 6.91 mV 5.9 mV

29.93% 20.80% 39.26% 18.44%

29.93% 41.61% 39.26% 18.44%

6/8/04

1 day

166-085

Mixed Potential

50% H2 - 50%N2 - wet 3%

6/04

1 day

166-087

Mixed Potential

50% H2 - 50%N2 - wet 3%

N2 on @ 275 C; H2 o on @ 450 C; reduce 1.25hr @ o 450 C o N2 on @ 250 C; H2 o on @ 450 C; reduce 1hr @ o 450 C

250 C

250 C 250 C 250 C


o o

-56.4 mV -61.7 mV -58.2 mV -42.3 mV

500 ppm 250 ppm 100 ppm 500 ppm

19.1 mV 15.8 mV 9.89 mV 4.09 mV

33.87% 25.61% 16.99% 9.67%

33.87% 51.22% 84.97% 9.67%

6/04

1 day

166-071C

Mixed Potential

32.7% H2 - 64.5%N2 - wet 3%

6/04

1 day

166-091

Mixed Potential

32.7% H2 - 64.5%N2 - wet 3%

6/23/04

1 day

166-094A

Mixed Potential

32.7% H2 - 64.5%N2 - wet 3%

6/24/04

1 day

166-094B

Mixed Potential

32.7% H2 - 64.5%N2 - wet 3%

6/28/04 6/29/04 7/1/04 7/4/04 7/26/04 7/27/04 7/28/04

1 day 1 day 1 day 1 day 1 day 1 day 1 day

166-94B 166-097C 166-097A 166-097E 166-097A 166-097B 166-097E

Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential

N2 on @ 250 C; H2 o on @ 430 C; reduce 1.25hr @ o 450 C o N2 on @ 250 C; H2 o on @ 430 C; reduce 1.25hr @ o 450 C o N2 on @ 250 C; H2 o on @ 450 C; reduce 1.25hr @ o 450 C o N2 on @ 280 C; H2 o on @ 450 C; reduce 1.25hr @ o 450 C o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min.

250 C

250 C

-34.3 mV

500 ppm

2.64 mV

7.70%

7.70%

250 C

32.5 mV

500 ppm

9.79 mV

30.12%

30.12%

250 C

21 mV

500 ppm

7.58 mV

36.10%

36.10%

250 C 250 C 250 C 250 C 250 C 250 C 250 C


o o o o o o

-39 mV -27.7 mV -34.5 mV 9.92 mV -3.97 mV 14.6 mV -2.92 mV

500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm

-1.54 mV -6.57 mV -1.04 mV -0.49 mV 1 mV 5.82 mV 0.22 mV

-3.95% -23.72% -3.01% -4.94% 25.19% 39.86% 7.53%

-3.95% -23.72% -3.01% -4.94% 25.19% 39.86% 7.53%

Development of Sensors for Automotive PEM-based Fuel Cells

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value 7/29/04 8/2/04 8/9/04 8/11/04 8/12/04 8/20/04 8/26/04 8/27/04 8/30/04 9/1/04 9/3/04 9/7/04 9/8/04 9/17/04 9/20/04 10/22/04 10/04 10/27/04 10/29/04 12/15/04 1 day 1 day 2 days 1 day 1 day 1 day 1 day 2 days 3 days 3 days 5 days 2 days 1 day 1 day 1 day 1 day 1 day 1 day 4 days 12 days 166-097D 166-097F 166-097B 166-097C 166-097D 166-097A 166-097B 166-132 166-132 166-132 166-132 166-132 166-132 166-150 166-150 166-150 166-132 166-132 166-132 166-132 Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential Mixed Potential 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value
o

Final Report November 11, 2005

250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C 250 C
o o o o o o o o o o o o o o o o o o o o o o o o

-50.2 mV -81.5 mV 36.3 mV -32.7 mV 10.9 mV mV mV 10 mV -12 mV -29 mV -49.5 mV -59 mV mV mV mV -7 mV 0 mV 0 mV -37 mV -17.6 mV -18.6 mV -15.3 mV -18.2 mV -22.4 mV -16.3 mV -22.3 mV 5 uA 0 mA -53 mV -99.8 mV -104 mV

500 ppm 500 ppm 500 ppm 50 ppm 500 ppm ppm ppm 500 ppm 100 ppm 50 ppm 25 ppm 10 ppm ppm ppm ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 250 ppm 100 ppm 50 ppm 50 ppm 500 ppm 50 ppm 50 ppm 500 ppm 500 ppm 500 ppm 0.5 ppm

7.08 mV -0.68 mV 5.46 mV 6.18 mV -1.68 mV mV mV 17 mV 5 mV 2 mV 1.1 mV 0.5 mV mV mV mV 0.5 mV No BL to see sensitivity No BL to see sensitivity 5 mV 8.5 mV 4.03 mV 1.48 mV 1.13 mV 0.83 mV 2.64 mV 0 mV 0 uA 0 mA 4 mV 0 mV 0 mV

14.10% -0.83% 15.04% 18.90% -15.41%

14.10% -0.83% 15.04% 188.99% -15.41%

170.00% 41.67% 6.90% 2.22% 0.85%

170.00% 208.33% 68.97% 44.44% 42.37%

7.14%

7.14%

13.51% 48.30% 21.67% 9.67% 6.21% 3.71% 16.20% 0.00% 0.00% 0.00% 7.55% 0.00% 0.00%

13.51% 48.30% 43.33% 48.37% 62.09% 37.05% 16.20% 0.00% 0.00% 0.00% 7.55% 0.00% 0.00%

2/8/05

1 day

166-132

Mixed Potential

33.6% H2 - 66.4%N2 - wet 3%

N2 on 250 C; H2 on o 450 C; cool at min. value

250 C 250 C
o o

2/18/05 2/11/05 2/15/05

1 day 2 days 1 day

192-146 166-132 166-132

Amperimetric Mixed Potential Mixed Potential

33.6% H2 - 66.4%N2 - wet 15% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value
o o

400 C 250 C 250 C 250 C


o o o

2/16/05 2/16/05 2/17/05 2/17/05

1 day 1 day 2 days 2 days

166-132 166-132 166-132 166-132

Mixed Potential Mixed Potential Mixed Potential Mixed Potential

33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3%

250 C 250 C 250 C 250 C 250 C


o o o o

1 mV -92 mV -15.6 mV -16.9 mV -16.5 mV

500 ppm 500 ppm 500 ppm 0.5 ppm 0.1 ppm

0 mV 2 mV 0.4 mV 0.25 mV 0.15 mV

0.00% 2.17% 2.56% 1.48% 0.91%

0.00% 2.17% 2.56% 1479.29% 4545.45%

2/21/05 2/21/05 2/23/05 2/24/05

1 day 1 day 1 day 1 day

166-132 166-132 166-132 192-159A

Mixed Potential Mixed Potential Mixed Potential Mixed Potential

33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3%

N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min.

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NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616


value 2/24/05 2/25/05 1 day 5 days 192-132A 192-160C Mixed Potential Mixed Potential 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value
o

Final Report November 11, 2005

250 C 250 C 250 C


o o

-25 mV -46 mV -47 mV

5 ppm 10 ppm 50 ppm

1.5 mV 0.5 mV 1 mV

6.00% 1.09% 2.13%

600.00% 54.35% 21.28%

3/3/05 3/4/05 3/9/05 4/8/05 4/20/05

1 day 6 days 13 days 1 day 1 day

192162B3 192162A3 192-168 192-146B

Mixed Potential Mixed Potential Fuel Cell Amperimetric

33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 15% 33.6% H2 - 66.4%N2 - wet 3%

N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o Heat to 400 C in N2/H2; hold 30min; o cool to 250 C None None

250 C 250 C 330 C 250 C 300 C


o o o o o o o o o o o o o

-40 mV 378 mV 0 mA 13.6 mV 31.2 mV 45 mV 45 mV -6 mV 6 mV 1.55 mV 1.45 mV -25 mV 100 mV 100 mV -24 mV

100 ppm 100 ppm

0 mV 5 mV

0.00% 1.32%

0.00% 6.61%

203-068A4 Solid Reference 203068A10

500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 500 ppm 50 ppm 500 ppm 50 ppm 500 ppm 500 ppm

0 mV 0 mV 0 mV 2 mV 0 mV -0.4 mV -0.1 mV -0.05 mV 0 mV 0 mV 0 mV -1 mV

0.00% 0.00% 0.00% 4.44% 0.00% -6.67% -6.45% -3.45% 0.00% 0.00% 0.00% -4.17%

0.00% 0.00% 0.00% 4.44% 0.00% -6.67% -6.45% -34.48% 0.00% 0.00% 0.00% -4.17%

4/25/05

3 days

Solid Reference

33.6% H2 - 66.4%N2 - wet 3%

None

250 C 300 C

4/28/05 5/12/05

1 day 5 days

203-068A9 Solid Reference 210-017 Mixed Potential

33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3%

None None

250 C 250 C 225 C 225 C

5/19/05 5/25/05

1 day 2 days

202-094A 202-094A

Solid Reference Solid Reference

33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3%

None None N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value N2 on 250 C; H2 on o 450 C; cool at min. value o N2 on 250 C; H2 on o 450 C; cool at min. value
o o

250 C 250 C 250 C

6/2/05 6/17/05 6/17/05 6/27/05

2 days 1 day 2 days 2 days

202-094A 210-045 210-045 210-046

Solid Reference Mixed Potential Mixed Potential Mixed Potential

33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3%

250 C

250 C 250 C 250 C


o o

-102 mV -3.5 mV -3.5 mV -14 mV -55 mV

500 ppm 500 ppm 50 ppm 50 ppm 50 ppm

-2 mV 0.25 mV 0.1 mV 0 mV 0 mV

-1.96% 7.14% 2.86% 0.00% 0.00%

-1.96% 7.14% 28.57% 0.00% 0.00%

6/29/05 6/30/05

1 day 2 days

210-046B 210-049

Mixed Potential Mixed Potential

33.6% H2 - 66.4%N2 - wet 3% 33.6% H2 - 66.4%N2 - wet 3%

250 C 250 C
o

Appendix B: Heater Type and Formulation Summary for Prototypes

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NexTech Materials, Ltd. DOE Contract No. DE-FC04-01AL67616

Final Report November 11, 2005

All Heaters: had their own individual type-K thermocouple attached with ceramic adhesives; the best thermocouple type were of 24AWG wire, due to the low thermal mass's quicker response. Graphite heaters: I cast several of Cotronics 931 graphite paste; they are made of paste spread onto IDE's and electroded with solder-wick (= multi-strand braided copper wire) SSF (Stainless Steel Foil): 2-mil thick SS-304 foil was electroded with silver wires, attached to foil with silver ink. Thermocouple and IDE were attached with a ceramic adhesive. Platinum thick film: IDE's were painted with platinum ink, baked in to 950C; then electroded with silver wires which were bonded to the platinum with silver ink. Pt-3: = modification of Pt-1 (I trimmed it down to the 1/2" NPT size requirement); re-electroded with silver wire & ink: It ran to the max power output of the solder gun; not enough power, being less than 7 Watts; NiCr1-L (Nichrome-1-L low impedance 0.07 ): This heater was fashioned by 10 parallel strands of 32 AWG nichrome wire, all paralleled across silver lead-busses; It worked but also reached the voltage limit of the solder gun; NiCr1-H (Nichrome-1-H high impedance 4.0 ): worked well up to 580C, where it burned open; I noticed the silver joints glowing orange right before it opened. NiCr1-H was fashioned by wrapping a continuous wind of 32AWG nichrome wire around an IDE to form a series loop; The wind was encapsulated in 552VFG alumina; a series of wire pairs were joined at each end using silver ink; the silver was baked in, encapsulated in 552VFG alumina, and the gold IDE side was cleared of it's wire by stripping with a hi-speed cutoff wheel; this formed a back and forth series of wire on one side of substrate, hence the higher impedance. Ru (Ruthenium Thick Film): constructed similar to platinum film, but with a thinner coating, that also only covered half the IDE sensor area ( 0.4 x 0.9 cm). One of these reached an impressive temperature, but then quickly burned open due to localized hot spot created by lack of thickness uniformity ( thin spot hot spot). C2 (2-cartridge heater) style IDE heaters: The C2 series was fashioned by joining 2 SUNROD 15 Watt, 12 Volt cartridge heaters into a common thermal node using PYRO-PUTTY, a stainless steel, one part putty; it has very high strength and thermal conductivity.

A thermocouple and IDE substrate were cemented to the thermal mass using an even volumetric mixture of 552VFG, Pyro-Putty, and Cotronics #907 (mica-based cement); the result was a highly thermally conductive, high strength bond which married the thermal mass together.

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