Advanced doping techniques and dehydrogenation properties of transition metal-doped LiAlH 4 for fuel cell systems

by Jie Fu

Institution: Technische Universität Dresden
Department: Fakultät Maschinenwesen
Degree: PhD
Year: 2015
Record ID: 1108383
Full text PDF: http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-159024


Hydrogen is an efficient, carbon-free and safe energy carrier. However, its compact and weight-efficient storage is an ongoing subject for research and development. Among the intensively investigated hydrogen storage materials, lithium aluminum hydride (LiAlH4) is an attractive candidate because of its high theoretical hydrogen density (volumetric: 96.7g H2/l material; gravimetric: 10.6 wt.%-H2) in combination with rather low decomposition temperatures (onset temperature <100°C after doping). Although the reversible dehydrogenation of LiAlH4 must be carried out with the help of organic solvent, LiAlH4 can serve as single-use hydrogen storage material for various special applications, for example, hydrogen fuel cell systems. This thesis deals with transition metal (TM)-doped LiAlH4 aiming at tailored dehydrogenation properties. The crystal structure and morphology of TM-doped LiAlH4 is characterized by XRD and SEM respectively. The positive effects of four dopants (NiCl2, TiCl3, ZrCl4 and TiCl4) on promoting the dehydrogenation kinetics of LiAlH4 are systematically studied by thermal analysis. Based on the state of each TM chloride (solid or liquid), three low-energy-input doping methods (1. ball-milling at low rotation speed; 2. manual grinding or magnetic stirring; 3. magnetic stirring in ethyl ether) are compared in order to prepare LiAlH4 with the maximum amount of hydrogen release in combination with fast dehydrogenation kinetics. The dehydrogenation properties of the TM-doped LiAlH4 powders are measured under isothermal conditions at 80°C at a H2 pressure of 1 bar, which is within the operating temperature range of proton exchange membrane (PEM) fuel cells, aiming at applications where the exhaust heat of the fuel cell is used to trigger the dehydrogenation of the hydrogen storage material. Furthermore, the mid-term dehydrogenation behavior of TM-doped LiAlH4 was monitored up to a few months in order to test its mid-term storability. In addition, the pelletization of TM-doped LiAlH4 is investigated aiming at a higher volumetric hydrogen storage capacity. The effects of compaction pressure, temperature and the H2 back-pressure on the dehydrogenation properties of TM-doped LiAlH4 pellets are systematically studied. Moreover, the volume change through dehydrogenation and the short-term storage of the TM-doped LiAlH4 pellets are discussed in view of practical applications for PEM fuel cell systems. Wasserstoff ist ein effizienter, kohlenstofffreier und sicherer Energieträger. Jedoch die kompakte und gewichtseffiziente Speicherung ist ein permanentes Forschungs- und Entwicklungsthema. Unter den intensiv untersuchten Materialien für die Wasserstoffspeicherung ist aufgrund der hohen theoretischen Speicherdichte (volumetrisch: 96,7 g H2/L, gravimetrisch: 10.6 Gew.%-H2) in Kombination mit sehr niedrigen Zersetzungstemperaturen (Anfangstemperatur < 100°C nach Dotierung) Lithium Aluminiumhydrid (LiAlH4) ein vielversprechender Kandidat. Obwohl die reversible Dehydrierung von LiAlH4 mit Hilfe von organischen…