Hydrogen Sensors: Ensuring Safety in Hydrogen Deployment

1. Overview of the U.S. DOE Hydrogen Safety, Codes and Standards Program--Part 4: Hydrogen Sensors W. Buttner, C. Rivkin, R. Burgess National Renewable Energy Laboratory Golden ,Colorado 80401 E. Brosha and R. Mukundan Las Alamos National Laboratory Los Alamos, NM 87545 J. Keller Zero Carbon Energy Solutions Oakland, CA 94602 Will James DOE/EERE/FCTO/SCS Washington, DC 20585 Presented to International Conference on Hydrogen Safety October 18-21, 2015 The Energy Systems Integration Facility NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

2. Provide critical safety factor Alarm at unsafe conditions Ventilation activation Automatic shutdown Bad things can happen when sensors are not used (properly)[www.h2tools.org/lessons] “Gaseous Hydrogen Leak and Explosion” Lack of H2 detection: “Hydrogen Explosion and Iron Dust Flash Fires in Powdered Metals Plant” No combustible gas monitoring or training “Two False Hydrogen Alarms in Research Laboratory” Nonspecific sensors alarmed twice ($10,000 fine) H2 specific sensors are now installed Mandated by code NFPA 2 (Sections 10.3.19.1 and 3.3.219.2.2) IFC (Repair garages, other indoor operations) NFPA 2 is referenced in IFC Relevance: Role of Sensors for Safe H2 Deployment Sensors Hydrogen dispenser equipped with wall-mount and internal sensors

3. Relevance: Why Develop and Evaluate H2 Sensors “H2 Sensors Don’t Work” Not true Not totally untrue 1/3 of sensors tested out of spec. Unacceptable failure rate in the field Wrong sensor for application Self-fulfilling attitude Emerging Markets New applications (end-users) New sensor technology (manufacturers) Expectations of Performance Sensors can be used improperly Matrix Effects User expertise/attitude Critical Gaps Guidance on placement/location Cost of ownership How to properly qualify sensors Codes & Standards ISO 197 TC 197 UNECE GTR 13 (Hydrogen Vehicles) H2 Sensors required by NFPA 2, IFC SAE FCSTF (SAE J3089) A sensor will work only if used properly • Historical EVENT • (Abandoned Computer Center) • Battery room for back up power (severe damage) • Hydrogen sensor was in audible alarm (ignored) • http://www.cholarisk.com/Files/Risk%20Note%20on%20Explosion%20Risks%20in%20Battery%20Rooms.pdf

4. SCS Program Commitment to Hydrogen SafetyHydrogen Sensors • Past Success Stories • Advanced Technologies • On-Going Programs • The Future

5. Short History of H2scanA Technology Transfer Success Story With several tens of millions of dollars of investment in development of the sensor for practical applications, achieved the “Schedule A” certification from UOL (Honeywell) for use in process streams containing H2S and CO. The Hy-Alerta brand of safety sensor has been deployed globally in many applications environments successfully. DOE’s INL is a major user of the area monitor which has been adopted in a different configuration by Meggitt Safety Systems for nuclear power station monitoring, globally. The scientific work of DOE’s Sandia laboratories has been advanced with the latter’s cooperation to a stage at which the other types of Hydrogen sensing technology fall short in cost, stability, durability and adaptation to environmental challenges. Dennis Reid purchased assets of DCH Technology, Inc. Retained the exclusive license from DOE for the Hughes et al patent for a Wide Range Sensor, incorporating both a MOSFET charge device and a resistive device to enable a range of Hydrogen from <100 ppm to 100%. Retained Sandia under a CRADA from 2003-2013. 20022010 2012 2014 2015 H2scan refined the design and obtained 27 patents, and patents pending for improvements and basic configuration changes, enabling the sensor to operate in refinery process streams, operate embedded in transformer oil and as area monitors and safety sensors. The first major transformer oil sensor application was secured in 2010 from a major transformer monitoring OEM. H2scan has secured exclusive supply agreements with 8major transformer monitoring OEMs and Transformer manufacturers as well as with 3 major process gas monitoring OEMs as well as most major oil companies and independent refiners for use in various refinery applications and in gas generation companies. Slide provided by James Litton, President H2Scan

6. H2Scan Hydrogen Monitor Applications Safety Devices HY-ALERTA 500 Petrochemical Process Sensors, Measurement of H2 in Natural Gas Pipelines HY-OPTIMA 2700 Industrial Gas Generation Systems HY-OPTIMA 700 Power and Distribution Transformer Fault Monitoring Sensors OEM Product Hydrogen Storage in Methane Pipelines HY-OPTIMA 1700 Hydrogen Cooled Generator Monitoring Systems HY-OPTIMA 1700 DOD Nuclear Facilities, High End Production Facilities HY-ALERTA 1610 Battery Room Monitoring , Wireless Transmitter Sites, Submarine Fuel Cell Applications, Sonobuoys, Hydrogen Production Slide provided by James Litton, President H2Scan HY-ALERTA 600

7. ORNL H2 sensor based on nanostructured Pd filmAdanced Sensor Technology with Remote Interrogation Transducer schematic Position Sensitive Detector (PSD) Bench-scale prototype VCSEL Array 200µm Cantilever Array Nanostructured Pd film Patton, Lavrik, Joy, Hunter, Datskos, Smith, and Sepaniak, Nanotechnology 23 (2012) 465403 Patton, Hunter, Sepaniak, Datskos and Smith, Sens. Actuators A: Phys. 163, 464-470 (2010) Slide provided by Barton Smith, ORNL

8. ORNL H2 sensor based on nanostructured Pd film Sensor response to common interferents and carrier gases (CO2, CH4, H2O, N2, He, CO) was at least an order of magnitude smaller than that observed for H2 at similar concentrations. MEMS-based H2 sensor met all but the most stringent requirements for automotive sensing applications (in 2011) Winner of a 2011 R&D 100 Award Slide provided by Barton Smith, ORNL

9. Versatile Low-Cost Hydrogen Indicators Leak Detection Application Visual H2-sensitive indicator • Developed in different configurations (Element One, Inc.) • 10 foot rolls • Pale color in air, turns black when exposed to hydrogen • reversible and irreversible formulations • Ideal leak detector around fittings and enclosures • Wraps around fittings for visual inspection/verification of integrity • Deployment study within NREL H2 operations (under MOU) • Located a hydrogen leak within a H2 R&D laboratory • Product prototypes are available ~ 6 inches

10. LANL Project timeline leading up to 2015 field trials work 2011 2009-2010 2008 Pre-commercial mixed potential sensor in thick film version on ESL fabricated platform (LANL specs). Power requirements: 6.5V, 0.75A. 1st Generation device – tape cast using ITO electrode and controlled interface approach. Externally-heated with tube furnace (30lbs): 120V, 8A. 1” Pre-commercial ceramic packaging/sensor supported by 4 posts. Power requirements: 5.0V, 0.65A. Pre- commercial prototype easily handled. 1st devices sent to NREL for Round 1 testing. 2013 2012 2014 Sensor and signal / heater electronics integrated into a single unit with wireless communications. Search for commercial testing partner. Round 2 NREL testing. Begin developing sensor electronics with Custom Sensor Solutions. Round 3 NREL testing. Prototype sensor heater control board developed and tested. Slide provided by Eric Brosha, LANL

11. Experimental - Field trials unit designed around NEMA-8 enclosure and commercially sourced componentry. Omega Engineering wireless system selected because of limited space within H2F explosion proof conduits.

12. Experimental: Desired heater power was selected and locked-in and an H2 calibration performed. Resulting logarithmic fit was entered into Labview™ data logging program. Calibration run data Calibration data used in field trials software Resistance of sensor Pt heater loop and hence temperature of the sensor element. Heater resistance during calibration Slide provided by Eric Brosha, LANL

13. Field Trials Unit Installed in H2F Dispenser Island LANL/LLNL unit #2 installed on 11-5-14. Cal gas exposure testing before leaving site. Conduit for 24V DC power Commercial H2 sensor Activated charcoal canister Slide provided by Eric Brosha, LANL

14. Field trials testing results show a stable and sensitive device. 4.20 Kg dispensed 11/7 17:36 – 17:48 MST 4.01 Kg dispensed 11/8 3:03 – 3:15 MST Thursday 11-7-14 6.80 Kg dispensed 11/7 15:01 – 15:13 MST 5.47 Kg dispensed 11/7 14:35 – 14:43 MST 2.39 Kg dispensed 11/8 14:46 – 14:53 MST 2.29 Kg dispensed 11/8 15:06 – 15:13 MST 1.80 Kg dispensed 11/8 14:19 – 14:24 MST 9:48 MST 15:00 MST 2.17 Kg dispensed 11/8 15:48 – 15:55 MST 10:03 MST 14:34 MST 7.37 Kg dispensed 11/7 9:48 - 9:59MST 6.99 Kg dispensed at 10:03 – 10:08 MST • Comparison of H2 filling station logs and sensor output show excellent correlation to station activities: e.g. filling fuel cell vehicles produces H2 releases. • No false positives encountered during field trials testing. • Sensor baseline stability confirmed in the field.

15. The NREL Sensor Laboratory The NREL Sensor Testing Facility The ultimate goal of the Hydrogen Sensor Testing Laboratory is to ensure that end-users get the sensing technology they need • Commissioned in 2009 • Assessment of H2 sensing element, sensor, detection apparatus performance • Interact with manufacturers to improve sensor performance to meet targets, e.g., ISO 26142, DOE, specialized applications • Support hydrogen sensor codes and standards development (national and international) • Safety Committees/Panels • Support end-users • “Topical Studies”—information on sensor use • Direct collaborationswith the H2 Community • Infrastructure, Vehicles, SDOs, Hydrogen Panels, Developers and Manufacturers

16. Approach: NREL SCS Project Structure The NREL Sensor Testing Laboratory is an integral part of the NREL Safety Codes and Standards Group

17. Collaborations: Strategic Partnerships Photograph used with permission Much of the sensor laboratory activity is in direct support of end-users and deployment Industrial Partnerships • Multiple formalized agreements • Primary: Direct support of deployment • Vehicle OEM and Infrastructure • Secondary: Sensor technology development Government Agencies (National/International) • NREL-JRC/IET (MOA, DOE-EU Common Call) • National Laboratories “Ad Hoc” Support/Collaboration • US DOT-NHTSA (support of the FMVSS) • Federal Institute for Materials Research and Testing (BAM) Berlin • Water Electrolysis Safety (H2 limits in O2 stream) • NASA (Breathing Air) • Giner (H2 Production)

18. Support of Standards and Code Development (Working with SDOs) • Collaborative effort among SDOs • UL and CSA co-authors • Input from ETL, FM Global and ANSI • Overview • Identified standard types for H2 sensors • Identification and description of relevant standards • Guidance to protect from fraudulent certification claims • Distinction between a code and standard • Sensor requirements specified in codes (IFC, NFPA 2) • Certification process and crucial definitions

19. Definitions (as provided by SDOs & ANSI) Certification: Process by which the product design undergoes specific evaluation and testing procedures to ensure that the design meets all of the requirements detailed in a standard and is with respect to a specific standard. Listed: Refers to the list published by a CB or NRTL of products certified to a specific standard. Label: Mark that is displayed on products to indicate that it is certified to a specific standard Approved - ANSI: Refers a standard that it recognizes - Means or authority for an AHJ to use products that are not certified (e.g., “ approved by AHJ) - Not synonymous with CERTIFIED* *Not universally accepted by all SDOs (e.g., FM Global) Photo used with permission, CSA Group Elements of the Label - Certification Body (CB) or NRTL marking - Standard(s) to which product is certified - Other qualifying information.

20. Develop guideline for qualifying sensors considered for automotive applications GTR Does NOT require on-board sensors Sensors are just an option to verify compliance to GTR requirements NREL Sensor laboratory is working with OEMs Side meeting at JARI on October 23 Working with International SDOs SAE J3089 IS NOT A STANDARD - provides guidance and proposed test methods for hydrogen sensors – There are no pass/fail criteria It does not dictate that sensors are required on-board vehicles

21. On-going since 2008 Formalized in 2010 by MOA Synergize respective laboratory activity Over 30 joint publications (formal presentations, articles, and reports) FCH JU and DOE (NREL) Common Call 1stUS –EU project with common objectives E.U. Team: BAM & JRC, working with industry under auspices of H2Sense U.S. Team headed primarily from NREL Facilitate the safe use of H2 by ensuring correct use of hydrogen detection devices. International PartnershipsNREL-JRC Collaboration

22. Gap Analysis of hydrogen Sensors In Development for publication (ACS Sensors) Deployment Maintenance/calibration cost Sensor Placement Network/WMA Lifetime/Sensor Stability Impact of environment Mode of failure Accelerated life test End of life indication Novel applications Power to Gas GTR Requirements Electolyzers DOE National Laboratory-JRC Sensor Laboratory CollaborationsOn-going and Proposed Activity

23. Organized Experts Group --Guideline for Sensor Placement Sensor placement and deployment guidance identified as a critical gap Established team of sensor, CFD and Risk Assessment experts Goal: guidance document for the deployment of hydrogen sensors (e.g., an annex to model code) On-going Topical Studies Development of an Analyzer for the verification of the GTR 13 tailpipe emission requirements Power to Gas (H2 sensors in Natural Gas) Sensor Failure Mechanisms (impact of poisons) Sensor Test Protocols Pending Publications WHEC Abstracts (on “topical studies) Gap Analysis on Hydrogen Sensors in ACS Sensors Annex to Standards DOE National Laboratory-JRC Sensor Laboratory CollaborationsOn-going and Proposed Activity

24. Authors Thomas Hubert, BAM William Buttner, NREL Lois Boon-Brett, JRC Contributions from Eveline Weidner, JRC Valerio Palmisano, formerly JRC Ulrich Schmidtchen, BAM Bernd Fellmuth, Physikalisch-Technische Bundesanstalt Accomplishments and Progress Coming soon from the CRC Press (in press)

25. THANK YOU Support provided Department of Energy, FCTO SCS Program, Program Manager: Will James For more information William Buttner william.buttner@nrel.gov (303) 275-3903 http://www.nrel.gov/hydrogen/facilities_hsl.html (or Google “NREL Sensor Laboratory”)