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DOE Hydrogen Program FY 2009 Annual Progress Report

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DOE Hydrogen Program FY 2009 Annual Progress Report IV.H.3 NaSi and Na-SG Powder Hydrogen Fuel Cells* Technical Barriers Michael Lefenfeld (Primary Contact), This project addresses the following technical Andrew Wallace barriers of the Storage section of the Hydrogen, Fuel SiGNa Chemistry Inc. Cells and Infrastructure Technologies Program Multi- 530 East 76th Street 9E New York, NY 10021 Year Research, Development and Demonstration Plan: Phone: (212) 933-4101; Fax: (212) 208-2605 (A) System Weight and Volume E-mail: [email protected]; [email protected] (B) System Cost (J) Thermal Management DOE Technology Development Manager: Grace Ordaz Phone: (202) 586-8350; Fax: (202) 586-9811 Technical Targets E-mail: [email protected] The developed sodium silicide technology is DOE Project Officer: Katie Randolph specifically focused on portable power applications such Phone: (303) 275-4901; Fax: (303) 275-4753 as back-up power, mobile workstations, and emergency E-mail: [email protected] responders. The target range includes applications from 50 to 500 W. The developed technology is expected to Contract Number: DE-FG36-08G088108 be scalable to at least 1 kW for applications such as lawn mowers that are known to be highly polluting. Subcontractors: • Trulite Inc., El Dorado Hills, CA The developed technology will likely not meet all • University of Texas, CEM, Austin, TX DOE technical targets for automotive applications, but there is a significant focus on customer attributes such as Project Start Date: August 1, 2008 fast starting, rapid restarting, low pressure, and ease of Project End Date: January 31, 2010 use. The specific technical targets are discussed below. *Congressionally directed project The primary focus of the current effort is to establish system technology using sodium silicide. SiGNa anticipates the development of advanced silicides with comparable system control architectures which will Objectives further increase performance metrics. The specific energy can reach up to 1,734 W-hr/kg (lower heating • Develop and demonstrate a controllable hydrogen value) including all reaction water, power and packaging generation system based on sodium silicide powder for the current commercial sodium silicide material. for portable fuel cell applications. Further research is required to understand and optimize • Develop specific reaction control mechanisms which the over-stoichiometric water required in the silicide encompass water feeding, thermal management, and reaction. Advanced silicides, which are currently under reaction site maximization. development, will yield a specific energy of up to 2,125 • Verify operation of all core balance of plant and W-hr/kg. reaction control components in a laboratory setup. The cost will approach DOE targets even for small • Design, fabricate, and assemble a prototype system portable applications. The cost is expected to reach packaged in a professional manner which generates $4.47/kW-hr. Further cost reductions are possible which controlled hydrogen with minimal user intervention. may be enabled by manufacturing scale up and the • Demonstrate operation with a fuel cell system industrial usage demands of sodium silicate. capable of 250 W. • Conduct core research to evaluate the potential for ultra-high performance sodium silicide materials. Accomplishments • Develop the appropriate manufacturing methods to Significant progress has been made in the readily scale production of sodium silicide in follow- development of a standalone hydrogen generation on activities. system for fuel cell applications. These accomplishments are summarized by the following: • Completed laboratory system and demonstrated key performance attributes: >9 wt% hydrogen yield on a DOE Hydrogen Program 792 FY 2009 Annual Progress Report Michael Lefenfeld – SiGNa Chemistry Inc. IV.H Hydrogen Storage / Cross-Cutting powder basis, multiple re-starts with up to 1 week of or other reaction tuning parameters. In practice, off-time, and controlled generation (~3 slpm) at low a micro-spray water distribution system has been pressures (~30 psi). developed to increase the active reaction area. For a • Have successfully completed bench top testing and “single-start” reaction, this distribution system is not sustained operation of a 300 W fuel cell-powered necessary as the bed will self-churn and fully react large electric bicycle. quantities of powder. To rapidly start a cold, partially • Developed a hydrogen purity filtration system and reacted solution, the micro-spray system serves to spray verified results with gas chromatography verifying water streams on un-reacted powder throughout the 99.99% hydrogen purity. chamber. • Completed design of stand alone hydrogen SiGNa first developed a series of clear reaction generation development unit. vessels to visualize the reaction and optimize the parameters. This series of breadboard test vehicles is used to test the various control components and G G G G G demonstrate the core reaction characteristics. The results of these experiments are being incorporated to Introduction develop a standalone hydrogen generation system. This system will be tested in conjunction with a fuel cell/ SiGNa Chemistry, Inc. is developing a unique battery hybrid system against a range of operational hydrogen storage mechanism utilizing SiGNa’s air-stable scenarios. sodium silicide powder derivatives (e.g. NaSi). SiGNa’s stabilized powders have been shown to produce up to The materials to date have only been manufactured on a lab scale. SiGNa is currently working with an 9.8 wt% H2. The primary goal is to develop a prototype system including all balance-of-plant components established toll manufacturer with expertise in alkali which generates hydrogen in a controlled manner metals to develop the next generation manufacturing based on usage requirements. SiGNa Chemistry will process. initially target a hydrogen generation system yielding approximately 3 slpm. This level of hydrogen generation Results can support a wide range of applications such as: supplemental hydrogen for diesel trucks for improved Three different breadboard reactors have been fuel efficiency and reduced emissions, primary power fabricated and tested in a range of ~60 to ~1,200 ml. for small vehicles (i.e. scooters, mini-bikes), emergency The primary areas of development and testing have responder stations, backup power, surveillance, and been: water feeding and distribution, hydrogen separation, control system and balance-of-plant other off-grid applications. For reference, 3 slpm of H2 will net approximately 250 W in fuel cell applications. components, and the hydrogen purity system. While numerous chemistries have been explored The water feed and distribution system primarily for hydrogen production for portable systems such as consists of the pump and micro-nozzle network. In sodium borohydride or methanol reforming, hydrogen practice, there are significant challenges in getting a far storage commercialization has been limited to high reaching spray at very low water flows (< 1 ml/min). pressure tanks and metal hydrides both of which have The water distribution network is almost exclusively significant usability issues. SiGNa’s newly developed required for re-start conditions. The laboratory systems class of sodium silicides such as, NaSi, rapidly react with have shown the ability to rapidly restart after storage at water to form hydrogen and a benign waste product, room temperature for 7 days (Figure 2). In this test, the sodium silicate. reactor was tested for a total of five starts with each run generating about 1/5 of the total available hydrogen. It is also required near the end of the reaction to ensure 2NaSi(s) + 5H2O(l) 5H2(g) + Na2Si2O5(aq) maximum powder reactivity. The water feed system SiGNa has developed systems implementation was also modified to incorporate the spray nozzles technology to facilitate this reaction in a manner that directly over the separation membrane to minimize filter is highly controllable with high flow capability at low clogging. pressures with excellent re-start characteristics. A significant amount of work was done early in the project with the small reactors in the selection Approach of separation membranes. For the small reaction chambers, significant foaming could readily cause The overall approach is summarized in Figure 1. filtration clogging. A filter spray system was developed The basic architecture is straightforward; simply add to breakdown the foaming. This enabled significant water to powder. Water solutions, such as salt water, improvements in the separation membrane pressure may also be employed for lower temperature operation drop (Figure 3). The developed separation membrane FY 2009 Annual Progress Report 793 DOE Hydrogen Program IV.H Hydrogen Storage / Cross-Cutting Michael Lefenfeld – SiGNa Chemistry Inc. FIGURE 1. Development Approach Including Laboratory Test Systems and Controlled Hydrogen Generation After 7-Day Restart Membrane Resistance With System Pressure (PSI) Water Flow (x10 mL/min) H2 Flow (slpm) and Without Filter Cleaning Spray ) 12 0.4 in 90 Restart after ) /m ) 10 m 80 I L 7 Days at Room Temp 0.3 S lp m P 8 s 70 ( 0 ( 1 e r 60 w (x 6 Water Flow 0.2 u o s l w 50 s F o 4 e l r 2 F 0.1 40 P r 2 H e t 30 a 0 0 (PSI/SLPM) W 20 5 6 789 10 11 12 13 10 Delta Pressure/Flow Time (min) 0 0 0.5 1 1.5 2 (H flow starts at 10 PSI due to back-pressure regulator) 2 Time (Minutes) FIGURE 2. Restart Example After 7 Days at Room Temperature With Filter Spray Without Filter Spray FIGURE 3. Impact of Filter Spray and Separation Membrane Resistance DOE Hydrogen Program 794 FY 2009 Annual Progress Report Michael Lefenfeld – SiGNa Chemistry Inc. IV.H Hydrogen Storage / Cross-Cutting included a sandwich of multiple layers. The much larger reactors have had very little foaming issues as the surface tension forces are typically insufficient to develop foam over the larger reactor area. However, the developed components are still utilized on the larger canisters for robustness and to ensure operation in non-typical operating scenarios such as vibration, upside down storage, etc. The balance-of-plant components including check valves, on/off valves, sensors, and pumps have been selected and tested.
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